Environmental Protection Technology Series
INDUSTRIAL PROCESS  PROFILES fOh
   ENVIRONMENTAL USE:  Chapter  6.
                The  Industrial Organic
                    Chemicals  Industry
                 Industrial Environmental Research laboratory
                      Office of Research aii Development
                     U.S. Environmental Protection Agency
                             Cincinnati, Ohio 45268

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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency,  have been grouped  into five series. These five broad
categories were established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The five series are:

     1.    Environmental Health Effects Research
     2.    Environmental Protection Technology
     3.    Ecological Research
     4.    Environmental Monitoring
     5.    Socioeconomic Environmental Studies

This report  has been  assigned  to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to develop and
demonstrate instrumentation, equipment, and methodology to repair or prevent
environmental degradation from point and non-point sources of pollution. This
work provides the new  or improved technology required for the control  and
treatment of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                            EPA-600/2-77-023f
                                            February  1977
         INDUSTRIAL PROCESS PROFILES

            FOR ENVIRONMENTAL USE

                  CHAPTER 6

  THE INDUSTRIAL ORGANIC CHEMICALS INDUSTRY
                      by

       Raimond Llepins and Forest Mixon
          Research Triangle Institute
      Research Triangle Park, N.C.  27709

      Charles Hudak and Terry B. Parsons
              Radian Corporation
             Austin, Texas  78766
           Contract No. 68-02-1319
               Project Officer

               Alfred B. Craig
   Metals and Inorganic Chemicals Branch
Industrial Environmental Research Laboratory
           Cincinnati, Ohio  45268


INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
     OFFICE OF RESEARCH AND DEVELOPMENT
    U S. ENVIRONMENTAL PROTECTION AGENCY
           CINCINNATI, OHIO  45268

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                                 DISCLAIMER
       This report has been reviewed by the Industrial Environmental Research
Laboratory - Cincinnati, U.S. Environmental Protection Agency, and approved
for publication.  Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial products constitute endorsement
or recommendation for use.
                                      11

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                       TABLE OF CONTENTS
                                                               Page
INDUSTRY DESCRIPTION  	     6-1
INDUSTRY ANALYSIS   	     6-32
   SECTION I     -  BENZENE
        Process No. 1 - No. 52	     6-35
   SECTION II    -  BUTYLENES
        Process No. 53 - No. 75	     6-155
   SECTION III   -  SOURCES OF CRESYLIC ACIDS
        Process No. 76 - No. 82	     6-201
   SECTION IV    -  ETHYLENE
        Process No. 83 - No. 156	     6-219
   SECTION V     -  METHANE
        Process No. 157 - No. 207	     6-395
   SECTION VI    -  NAPHTHALENE
        Process No. 208 - No. 226	     6-513
   SECTION VII   -  PARAFFINS
        Process No. 227 - No. 249	     6-555
   SECTION VIII  -  PROPYLENE
        Process No. 250 - No. 323	     6-603
   SECTION IX    -  TOLUENE
        Process No. 324 - No. 358	     6-752
   SECTION X     -  XYLENES
        Process No. 359 - No. 364	     6-823
APPENDIX A  -  INDUSTRIAL CHEMICALS AND SOLVENTS GLOSSARY.     6-841
APPENDIX B  -  RAW MATERIALS	     6-957
APPENDIX C  -  CATALYSTS	     6-962
APPENDIX D  -  INDUSTRIAL ORGANIC CHEMICALS  	     6-966
APPENDIX E  -  INDUSTRIAL ORGANIC CHEMICAL PRODUCERS ...     6-977
                              iii

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                          LIST OF FIGURES
Figure                                                              Page
   1      Benzene Section Chemical Tree 	      6-36
   2      Benzene Section Process Flow Sheet  	      6-39

   3      Butylenes Section Chemical Tree 	      6-156
   4      Butylenes Section Process Flow Sheet  	      6-157

   5      Sources of Cresylic Acids Chemical Tree 	      6-202
   6      Sources of Cresylic Acids Process Flow Sheet  ....      6-203

   7      Ethylene Section Chemical Tree  	      6-220
   8      Ethylene Section Process Flow Sheet 	      6-226

   9      Methane Section Chemical Tree 	      6-396
  10      Methane Section Process Flow Sheet  	      6-398

  11      Naphthalene Section Chemical Tree 	      6-514
  12      Naphthalene Section Process Flow Sheet  	      6-515

  13      Paraffins Section Chemical Tree 	      6-556
  14      Paraffins Section Process Flow Sheet  	      6-557

  15      Propylene Section Chemical Tree	      6-604
  16      Propylene Section Process Flow Sheet  	      6-607

  17      Toluene Section Chemical Tree 	      6-753
  18      Toluene Section Process Flow Sheet  	      6-754

  19      Xylenes Section Chemical Tree	      6-824
  20      Xylenes Section Process Flow Sheet  	      6-825
                              iv

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                          LIST OF TABLES

Table                                                            Page

  1       General Statistic For Establishments, By Industry
          Specialization and Primary Product Class Speciali-
          zation:  1972	    6-6

  2       General Statistics, By Employment Size of Establish-
          ments:  1972	    6-7

  3       Products and Product Classes-Value of Shipments By
          All Producers:  1972 and 1967	    6-8

  4       Materials Consumed, By Kind:  1972   	    6-9

  5       Industrial Organic Chemicals:  General Statistics By
          Geographical Area	    6-11

  6       Fuels and Electric Energy Consumed in 1971 By Com-
          panies in SIC Codes 2865 and 2869	    6-13

  7       Toxicity of Selected Feedstocks For  the Industrial
          Organic Chemicals Industry   	    6-16

  8       The Most Significant Synthetic Organic Chemicals
          By Production Volume in 1973	    6-18

  9       The Most Significant Synthetic Organic Chemicals
          By Market Value in 1973 . . ,	    6-19

 10       Leading Chemical Companies in the U.S. During 1973.    6-21

 11       Industrial Organic Chemical Processes as Waste
          Sources	    6-25

A-l       Industrial Chemicals and Solvents Glossary   ....    6-841

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Chemical
INDEX TO INDUSTRIAL ORGANIC CHEMICALS
       DESCRIBED IN CHAPTER 6
                        	Process  Description  Numbers
Acenaphthene
Acetal
Acetaldehyde
Acetaldol
Acetamide
Acetanilide
Acetic acid
Acetic anhydride
Acetone
Acetone cyanohydrin
Acetonitrile
Acetophenone
Acetylene
Acrolein
Acrylamide
Acrylic acid
Acrylonitrile
Adipic acid
Alkylnaphthalenes
Allyl alcohol
Allyl chloride
m- or p-Aminobenzoic acids
Amino e thy1ethanolamin e
Amyl acetates
Amyl alcohols
Amyl amines
Amyl chlorides
Amyl mercaptans
Aniline
Aniline hydrochloride
                              208
                              123
                              84,124
                              85
                              128
                              17
                              101,  201,  227
                              101,  105
                              37,  227, 251B,  269,  270,  295
                              170
                              273
                              2, 37
                              173
                              250
                              274
                              276
                              273
                              45
                              208
                              251A, 289, 317
                              315
                              330
                              135
                              54
                              53,  244
                              243
                              242
                              245
                              9,  31,  300
                              33
                               vi

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               INDEX TO INDUSTRIAL ORGANIC CHEMICALS
                      DESCRIBED IN CHAPTER 6
Chemical
Process Description Numbers
Anisidines (ortho- and para-)
Anisole
Anthranilic acid
An thraquinone
310
302A.B
226
223, 224
Benzaldehyde
Benzamide
Benzene
Benzenesulfonic acid
Benzenedisulfonic acids
Benzil
Benzilic acid
Benzoic acid
Benzoin
Benzonitrile
Benzophenone
p-Benzoquinone
Benzotrichloride
Benzoyl chloride
Benzyl alcohol
Benzyl amine
Benzyl benzoate
Benzyl chloride
Benzyl dichloride
Biphenyl
Bisphenol A
Bromobenzene
Bromonaphthalenes
Butadiene
353
337
349
21
22
355
356
325
354
324
249
15
333
336
334
335
332
333
333
51
256
50
214
59, 240, 241
                               vii

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               INDEX TO INDUSTRIAL ORGANIC CHEMICALS
                      DESCRIBED IN CHAPTER 6
Chemical
Process Description Numbers
n-Butanol
n-Butenes
n-Butyl acetate
sec-Butyl acetate
tert-Butyl acetate
n-Butyl acrylate
sec-Butyl alcohol
tert-Butyl alcohol
sec-Butylamine
tert-Butylamine
n-Butyl amines
p-tert-Butylbenzoic acid
1,3-Butylene glycol
tert-Butyl hydroperoxide
p-tert-Butylphenol
p-tert-Butyltoluene
n-Butyraldehyde
n-Butyric acid
n-Butyric anhydride
Butyronitrile
97, 282
238
99
57
72
Til
55
67
58
71
284
70
86
68
73
69
88, 227, 278
89, 227, 233
283
232
Carbolic oil
Carbon disulfide
Carbon tetrabromide
Carbon tetrachloride
Cellulose acetate
Chloranil
Chloroacetic acid
Chloroanilines
p-Chlorobenzaldehyde
76
164
162
140, 160, 234
102
299
104
18
346
                               viii

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               INDEX TO INDUSTRIAL ORGANIC CHEMICALS
                      DESCRIBED IN CHAPTER 6
Chemical
Process Description Numbers
Chlorobenzene
Chlorobenzoic acids (o- and p-)
Chlorobenzoyl chlorides (o- and p-)
1,1,1-Chlorodifluoroethane
Chlorodifluoromethane
Bis(2-chloroethyl) ether
Chloroform
Chloronaphthalenes
Chloronitrobenzenes
Chlorophenols
m-Chlorotoluene
Chlorotoluenes (o- and p-)
m-Cresol
o-Cresol
p-Cresol
m,p-Cresols  (mixture)
Crotonaldehyde
Crotonic acid
Cumene
Cumene hydroperoxide
Cyanoacetic acid
Cyanogen chloride
Cyanuric acid
Cyanuric chloride
Cyclohexane
Cyclohexanol
Cyclohexanone
Cyclohexene
Cyclohexylamine
4
347
348
176
161
142
159
213
7
298
344
345
82
78, 82
80, 81, 82
78
87
98
36
294
111
168
186
169
44
46, 304
46, 305, 306
47
20, 48
                               ix

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               INDEX TO INDUSTRIAL ORGANIC CHEMICALS
                      DESCRIBED IN CHAPTER 6
Chemical
Process Description Numbers
Decahydronaphthalenes
Diacetone alcohol
3,5-Diaminobenzoic acid
Diaminotoluenes  (2,4- and 2,6-)
Dichloroanilines
Dichlorobenzenes
Dichlorodifluoromethane
Dichlorohydrin
Dichloronitrobenzenes
Dichloropentane
Dichloropropenes
Dicyclohexylamine
Diethylene glycol diethers
Diethylene glycol monoethers
Diethylene glycol monoether acetates
Diethyl ether
Diethyl sulfate
1,1-Difluoroethane
Diketene
N,N-Dimethylaniline
Dimethyl ether
N,N-Dimethylformamide
Dimethyl sulfate
Dimethyl sulfide
Dimethyl sulfoxide
Dimethyl terephthalate
Dinitrobenzene
Dinitrobenzoic acids (2,4- and 2,6-)
3,5-Dinitrobenzoic acid
Dinitrotoluene
216
257
328
343
11
5
163
253, 290
10
242
323
49
150
149
151
119, 127
125
175
263B
13
196
200
197
206
207
362B
26
342
327
340
                               x

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               INDEX TO INDUSTRIAL ORGANIC CHEMICALS
                      DESCRIBED IN CHAPTER 6

Chemical	Process Description Numbers
Dioxane                                      146
1,3-Dioxolane                                147
Diphenylamine                                34
Diphenyl oxide                               52
Diphenylthiourea                             32
Dodecene                                     264
Dodecylphenol                                313
Epichlorohydrin  -                            291
Ethanol                                      119, 227
Ethanolamines  (mono-, di-, tri-)             152
Ethyl acetate                                103, 227
Ethyl acetoacetate                           107
Ethyl acrylate                               122
Ethylamines  (mono-, di-, tri-)               120
Ethylbenzene                                 1, 359
Ethyl bromide                                83
Ethyl cellulose                              118
Ethyl chloride                               115
Ethyl chloroacetate                          110
Ethyl cyanoacetate                           113
Ethylene carbonate                           156
Ethylene dichloride                          131, 132
Ethylene chlorohydrin                        136
Ethylene diamine                             134
Ethylene dibromide                           114
Ethylene glycols (mono-, di-, tri-)          144, 203
Ethylene glycol mono- and diacetates         145
Ethylene glycol diether                      150
Ethylene glycol monoethers                   149
                              xi

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               INDEX TO INDUSTRIAL ORGANIC CHEMICALS
                      DESCRIBED IN CHAPTER 6
Chemical
Process Description Numbers
Ethylene glycol monoether acetates
Ethylene oxide
2-Ethylhexanol
Ethyl orthoformate
Ethyl oxalate
Ethyl sodium oxalacetate
151
143
90
167
121
129
Formaldehyde
Formamide
Formic acid
Fumaric acid
202
199
94, 227
24, 43
Glyceraldehyde
Glycerin (glycerol)
Glycerol tri(polyoxypropylene) ether
Glycine
Glyoxal
Guanidine
254
252, 255, 292, 318, 319
293
108
91
185
Heptenes
Hexachloroethane
Hexamethylenetetramine
Hexylene glycol
Hydrogen cyanide
Hydroquinone
62
236
205
258
166
16
Isoamylenes
Isobutenes (di- and tri-)
 246
 75
                               xii

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               INDEX TO INDUSTRIAL ORGANIC CHEMICALS
                      DESCRIBED IN CHAPTER 6

Chemical	Process Description Numbers
Isobutanol                                   279
Isobutyl acetate                             280
Isobutyraldehyde                             278
Isobutyric acid                              281
Isodecyl alcohol                             265
Isooctyl alcohol                             266
Isophorone                                   262
Isophthalic acid                             361
Isoprene                                     247, 248
Isopropyl acetate                            103
Isopropyl amine                              271
Isopropyl chloride                           268
Isopropyl phenols                            272
Ketene                                       263A
Maleic acid                                  41
Maleic anhydride                             38, 61
Malic acid                                   42
Mesityl oxide                                259
Methacrylic acid                             66, 171
Methacrylic esters                           172
Methacrylonitrile                            65
Methallyl alcohol                            64
Methallyl chloride                           63
Methyl acetate                               194, 227
Methyl acetoacetate                          195
Methanol                                     191, 227
Methylamines (mono-, di-, tri-)              192
                               xiii

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                INDEX TO  INDUSTRIAL ORGANIC CHEMICALS
                       DESCRIBED  IN CHAPTER 6
 Chemical
Process Description Numbers
 N-Methylaniline
 Methyl butynol
 Methyl chloride
 Methylcyclohexane
 Me thylcyclohexano1
 Methylcyclohexanone
 2-Methyl-l,3-dioxolane
 Methylene chloride
 Methylened ianiline
 Methyl ethyl ketone
 Methyl formate
 Methyl isobutyl carbinol
 Methyl isobutyl ketone
 Methyl pentynol
 Methylphenylcarbinol
 Methyl salicylate
 a-Methylstyrene
 Morpholine
12, 14
177
157, 193
350
351
352
148
158
204
56, 227
198
261
260
178
92
303B
296
153
Naphthalenes  (separation, desulfurization)   208, 209
1-Naphthalenesulfonic acid                   217
2-Naphthalenesulfonic acid                   218
1-Naphthol                                   212
2-Naphthol                                   219
1-Naphthylamine                              211
Neopentanoic acid                            74
o- and p-Nitroanilines                       29
Nitroanisoles (ortho- and para-)             309
Nitrobenzene                                 25
Nitrobenzoic acids (o-, m-, p-)              339
                               xiv

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               INDEX TO INDUSTRIAL ORGANIC CHEMICALS
                      DESCRIBED IN CHAPTER 6
Chemical
Process Description Numbers
m-Nitrobenzoic acid
Nitroparaffins (C^-C^
1-Nitronaphthalene
Nitrophenols (ortho- and para-)
Nitrotoluene
Nitroxylenes (o-, m-, p-)
Nonene
Nonylphenol
329
237
210
307
338
363
264
311
Octylphenol
Oxo alcohols
Oxo aldehydes
312
188
187
Paraldehyde
Pentaerythritol
Pentylenes
Perchloroethylene
Perchloromethyl mercaptan
Phenetidines (ortho- and para-)
Phenol
Phenolic pitch
Phenols (higher methylated)
Phenolsulfonic acids (ortho- and para-)
m-Phenylenediamine
o-Phenylenediamine
p-Phenylenediamine
Phosgene
Phthalic anhydride
Phthalimide
93
94
244
140, 180, 234, 235
165
308
8, 37, 78, 295, 326
78
82
314
27
28
30
189
220, 360
225
                              xv

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               INDEX TO INDUSTRIAL ORGANIC CHEMICALS
                      DESCRIBED IN CHAPTER 6
Chemical
ProcessDescription Numbers
Phthalonitrile
3-Picoline
Piperazine
Polybutenes
Polyethylene glycol
Polypropylene glycol
2-Propanol
Propionaldehyde
Propanoic acid
n-Propyl alcohol
n-Propyl amines
n-Propyl chloride
Propylene chlorohydrin
Propylene dichloride
Propylene glycols (mono- and di-)
Propylene oxide
Pyridine
222
100
154
239
155
288
267
229
126, 227
227
228, 231
230
285, 316
322
287
286, 320
100
Resorcinol
23
Salicylic acid (and methyl salicylate)
Sodium acetate
Sodium benzoate
Sodium carbolate (crude)
Sodium carboxymethyl cellulose
Sodium chloroacetate
Sodium formate
Sodium phenate
Sorbic acid
303A
106
331
77
112
109
190
301
96
                              xvi

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               INDEX TO INDUSTRIAL ORGANIC CHEMICALS
                      DESCRIBED IN CHAPTER 6

Chemical	Process Description Numbers
Styrene                                      3
Succinic acid                                39
Succinonitrile                               275
Sulfanilic acid                              35
Sulfolane                                    60
Synthesis gas                                181,  182
Terephthalic acid                            362A
1,1,2,2-Tetrachloroethane                    179
Tetrachlorophthalic anhydride                221
Tetraethyl lead                              116, 117
Tetrahydronaphthalene                        215
Tetrahydrophthalic anhydride                 40
p-Toluenesulfonamide                         358
Toluenesulfonic acids                        79
p-Toluenesulfonyl chloride                   357
Toluidines                                   341
2,4,6-Trichloroaniline                       19
Trichlorobenzenes                            6
1,1,2-Trichloroethane                        137, 138
Trichloroethylene                            140, 180
Trichlorofluoromethane                       163
1,2,3-Trichloropropane                       321
1,1,2-Trichloro-l,2,2-Trifluoroethane        141
Triethylene glycol monomethyl ether          149
Triethylene glycol dimethyl ether            150
Urea                                         183, 184
                              xvii

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               INDEX TO INDUSTRIAL ORGANIC CHEMICALS
                      DESCRIBED IN CHAPTER 6

Chemical	Process Description Numbers
Vinyl acetate                                95, 174
Vinyl chloride                               133
Vinylidine chloride                          139
Vinyl toluenes                               130
Xylenes (ortho-, meta-, para-)               349, 359
2,6-Xylenol                                  297
Xylenols                                     78, 82
Xylidines                                    364
                              xviii

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                           Acknowledgments




     Preliminary technical information used in preparing this catalog




entry was supplied to EPA by Monsanto Research Corporation, Dayton




Laboratory, under Contract No. 68-02-1320, Task 17.  Mr. William Hedley




was Project Leader.




     This catalog entry was prepared for EPA by Research Triangle




Institute under Contract No. 68-02-1325, Task 70.   The contributions




of Jefferson Surles, James J. Kearney, and Leila Z. Liepins are grate-




fully acknowledged.  Mr. Raimond Liepins was Project Leader and Forest




0. Mixon was the Program Manager.




     Radian Corporation prepared the Industry Description and Appendices




B, C, D and E.  Contributions by Charles E. Hudak and Terry B. Parsons of




Radian Corporation are gratefully acknowledged.
                                 XIX

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INDUSTRY DESCRIPTION
     6-1

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                   INDUSTRIAL ORGANIC CHEMICALS INDUSTRY






INDUSTRY DESCRIPTION




     A precise definition of the Industrial Organic Chemicals Industry is




difficult to formulate because of the close interrelationship between it




and other elements of the petrochemical industry in general.  For the




purpose of this study, industrial organic chemicals are defined as sol-




vents or chemical intermediates prepared from products of the Basic




Petrochemicals Industry (Chapter 5).  Industrial organic chemicals are




the product of at least one chemical reaction in this industry and will




undergo at least one additional treatment step in a downstream processing




industry.  Thus, these compounds are intermediate materials in the manu-




facture of such products as plastics, synthetic fibers, Pharmaceuticals,




and surfactants from basic petrochemicals such as olefins, aromatics and




paraffins.




     The Industrial Organic Chemicals Industry does not lend itself to




separation into various segments, but the chemical trees, flow sheets and




process descriptions are grouped according to feedstock.  This arrangement




according to feedstock results in ten groups of processes or sections:




benzene, butylene, cresol, ethylene, methane, naphthalene, paraffin, pro-




pylene, toluene and xylene.  Each section is preceded by a chemical tree




and flow sheets illustrating products and processing steps described.  The




chapter includes 364 processes describing the production of 442  industrial




organic chemicals.




     The principal feedstocks to the industry are the hydrocarbon products




(olefins,  paraffins, and aromatics) from the Basic Petrochemicals Industry
                                 6-2

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described in Chapter 5-  Many of these feedstocks come to the industry as




mixtures of olefins, paraffins and/or aromatics and must go through a




separation process such as distillation, extraction, absorption or crystal-




lization to separate the components.  The flow sheets and process descrip-




tions for this industry include separation processes as well as the conver-




sion processes used in manufacturing the organic chemicals.




     There are limited data available describing precisely the particular




group of companies defined in this chapter as producers of industrial organic




chemicals.  In a separate study performed under EPA Contract No. 68-02-1319,




Task 51, an intensive effort was made to characterize the industry defined




herein.  The 1976 Directory of Chemical Producers and additional sources of




information were used to compile data concerning production facilities for




some 358 industrial organic chemicals.  The product slate described in that




study differs only slightly from the one defined in this chapter.  The study




identified 260 companies with 544 plant sites for the manufacture of 442




industrial organic chemicals.  The product slate is given in Appendix D and




the list of producers in Appendix E.




     Because of the close functional and even physical relationships between




manufacturing establishments in the Basic Petrochemicals, industrial organic




chemicals and numerous downstream processing industries, classification of




industrial organic chemical manufacturers according to a single SIC code is




impossible.  The Index to Industrial Organic Chemicals (pages iv  through xix )




and the Industrial Chemicals and Solvents Glossary (Appendix A) indicate




that manufacturing establishments are classified in SIC codes 2865 and 2869-




However, tenancy in these classifications is shared with establishments
                                6-3

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 engaged  primarily  in manufacturing dyes and organic pigments  (Chapter 7),




 basic  petrochemicals  (Chapter  5), plasticizers  (Chapter 13),  and pesticides




 (Chapter 8).   The  only  available data on employment statistics and energy




 and  raw  materials  consumption  are compiled for  the groups of  companies




 classified  in  these SIC codes.




     Data published in  the  1972 Census of Manufacturers indicate there were




 173  establishments classified  in SIC code 2865  (Cyclic Crudes and Intermediates,




 Dyes and Organic Pigments).  Of these, 49 were  classified under product  code




 28651  (Cyclic  Intermediates) which is within the scope of the chapter.   The




 1972 Census of Manufacturers also indicates there were 514  establishments




 classified  in  SIC  code  2869  (Industrial Organic Chemicals,  not elsewhere




 classified).   Some 331  of these appear to produce chemicals defined as pro-




 ducts  of this  industry:  42 were producers of miscellaneous cyclic chemicals




 (product code  28691); 168 were producers of miscellaneous acyclic chemicals,




 except urea (product code 28692); 69 produced synthetic organic chemicals,




 not  elsewhere  classified, not  bulk (product code 28693); and  52 were producers




 of ethyl alcohol and other  industrial chemicals not elsewhere classified




 (product code  28695) .




     Figures given for  establishments classified in SIC codes 2865 and 2869




 include  establishments  producing materials outside the scope  of this study.




 Some establishments may  appear in any or all of the several industry and




 product  codes  cited above.  For these reasons,  no precise accounting of




 total industrial populations may be derived from SIC category data, either




by summation or by elimination.
                                 6-4

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     Information relating to the physical size of industrial organic chemical




manufacturing facilities is not available, because these operations are gen-




erally completely integrated with facilities classified in other industries.




     Employment statistics for manufacturing establishments classified in




SIC codes 2865 and 2869 are presented in Tables 1 and 2.  The caveat imposed




above applies also to data contained in these tables.  Employment statistics




for selected product classification codes are presented in Table 1.  Statis-




tics describing employment size of establishments specific for selected




product codes are not available, but composite statistics for SIC code 2865




and 2869 are contained in Table 2.




     Production data for materials classified under product codes 2865 and




2869 are presented in Table 3.  This table includes data reported not only




by establishments classified in SIC codes 2865 and 2869 but also by establish-




ments classified in other industries and shipping these products as "secon-




dary" products.  Certain of the data relating to products outside the scope




of this chapter are included in order to demonstrate the interrelationship




and convolutions of processes and products within the petrochemical industry




in general and the Industrial Organic Chemicals Industry in particular.  Data




for 1967 as well as 1972 production are presented and indicate an almost




universal pattern of growth.




     A tabulation of materials consumed in 1972 by establishments in SIC codes




2865 and 2869 is presented in Table 4.  This tabulation includes the consump-




tion of not only process chemicals and raw materials, but also other materials,




supplies and machinery necessary to the presentation of a product ready for




shipment.
                                 6-5

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                                         TABLE  1.    GENERAL  STATISTIC  FOR  ESTABLISHMENTS,  BY

                          INDUSTRY  SPECIALIZATION  AND  PRIMARY  PRODUCT  CLASS SPECIALIZATION:    1972
This table presents selected  statistics for establishments  according to their degree of  specialization in products  primary to their industry.  The measures
of plant specialization shown are  (1) industry specialization-the ratio of primary product shipments to total product shipments, primary plus  secondary, for
the establishments, and (2) product class specialization-the  ratio of the largest primary product class shipments to total product shipments,  primary plus
secondary, for the establishment.  See the source for method  of computing these ratios.  Statistics for establishments with specialization  ratios of less
than 75 percent are included  in  total lines but are not shown as a separate class.   In addition, data may not be shown, for some industries, product classes
or specialization ratios for  various reasons; e.g., to avoid  disclosure of individual company data.
Industry
   or
product
 class
 code
 Industry or product class
by percent of specialization
                              Establish-
                              ments
                                            (number)
                                                          All  employees
Number
                                           (1,000)
          Payroll
          (million
          dollars)
                                                                                  Production workers
                                                                Number
(1,000)
                                                                         Man-hours
                                                                                       (millions)
                                            Wages
(million
dollars)
Value
added by
manufac-
ture

(million
dollars)
                                                                Cost of
                                                                materials
(million
dollars)
                                                     Value of
                                                     shipments
(million
dollars)
Capital
expendi-
tures,
new

(million
dollars)
 2865
           Cyclic crudes and intermediates
           Entire industry	         173      28.2      317.6       18.7         38.4     190.9
           Establishments with 75% or more
             specialization	         141      16.8      181.1       11.1         22.7     108.6

28651      Cyclic intermediates
           (Primary product class of
             establishment)	          49      11.3      139.1        7.4         15.6      81.5
           Establishments with 75% or more
             specialization	          26       3.6       43.0        2.2          4.8      24.3

2869       Industrial organic chemicals,
             nee
           Entire industry	         514     101.7     1240.2       64.1        129.1     707.6
           Establishments with 75% or more
             specialization	         407      42.3      503.9       27.6         56.1     299.7

28691      Miscellaneous cyclic chemical
             products
           (Primary product class of
             establishment)	          42       5.7       61.1        3.7          7.5      35.9
           Establishments with 75% or more
             specialization	          21       1.8       19.8        1.0          2.1       9.7

28692      Miscellaneous acyclic chems.,
             exc. urea
           (Primary product class of
             establishments)	         168      78.6      981.3       50.2        101.6     570.6
           Establishments with 75% or more
             specialization                        93      17.1      215.5       11.4         23.0     129.2

28693      Synthetic organic chems., nee,
             not bulk
           (Primary product class of
             establishment)	          60       9.7      112.6        5.6         11.4      59.2
           Establishments with 75% or more
             specialization	          39       2.0       21.6        1.1          2.3      10.8

29695      Ethyl alcohol, other indust.
             organic chems., nee	
           (Primary product class of
             establishments)	          52       3.1       30.5        1.7          3.3     13.7
           Establishments with 75% or more
             specialization	          33       2.0       18.J	1.1	2.^     8.7

Source:   U.S.  Department  of  Commerce, Social and Economic  Statistics Administration,  Bureau of the Census,  "1972
         Industrial  Organic  Chemicals.  Sic Industry Group  286.
                                                                                                   925.2    1 109.7

                                                                                                   512.6      622.7
                                                                                                   504.4

                                                                                                   195.7
                                                                                                   190.4

                                                                                                    46.2
                                                                                                   288.6

                                                                                                    83.2
                                                                   659.3

                                                                   253.1
                                                                   187.8

                                                                    52.9
                                                                   431.3

                                                                   117.1
                                                      2 044.5

                                                      1 141.3



                                                      1 176.4

                                                        463.3
                                                                                                 4 965.1    4 209.5    9  179.1

                                                                                                 2 299.5    2 059.3    4  371.2
                                                         378.4

                                                         101.0
                                                                                                  4 080.7    3 298.7    7 399.4

                                                                                                  1 048.0    1 020.7    2 071.2
                                                         713.9

                                                         201.0
                                                                                                    66.9       85.8       152.3

                                                                                                    45.2       49.5        93.9

                                                                                                Census of Manufacturers",
                                              158.7

                                               80.4



                                              116.1

                                               45.5



                                              645.4

                                              224.3




                                               26.2

                                                8.3
                                                                                         508.1

                                                                                         120.7
                                               46.3

                                               15.2
                                                                                          5.7

                                                                                          5.0

-------
                        TABLE  2.    GENERAL  STATISTICS,  BYEMPLOYMENT  SIZE  OF  ESTABLISHMENTS:    1972
                     Item
                                               Establish-
                                               ments
                                               (number)
        All employees
                                                          Number
      (1,000)
                                                                   Payroll
      (million
      dollars)
                                                                               Production workers
                                                                            Number
      (1,000)
                                                                                    Man-hours
      (millions)
                                                                                                 Wages
                                                                                               (million
                                                                                               dollars
              Value
              added by
              manufac-
              ture

              (million
              dollars)
                                                     Cost of
                                                     materials
                 (million
                 dollars)
                                                      Value of
                                                      shipments
                    (million
                    dollars)
                    Capital
                    expendi-
                    tures,
                    new

                    (million
                    dollars)
                   End-of-
                   year
                   inven-
                   tories

                   (million
                   dollars)
2865—Cyclic crudes and Intermediates

      Establishments,  total	

      Establishments with an average of -
        1 to 4 employees	E7
        5 to 9 employees	E4
        10 to 19 employees	
        20 to 49 employees	
        50 to 99 employees	
        100 to 249 employees	
        250 to 499 employees	
        500 to 999 employees	
        1,000 to 2,499 employees	

      Estabs. covered  by admin,  record   .

2869—Industrial organic chemicals, nee

      Establishments,  total	

      Establishments with an average of -
        1 to 4 employees	E7
        5 to 9 employees	E2
        10 to 19 employees	El
        20 to 49 employees	
        50 to 99 employees	
        100 to 249 employees	
        250 to 499 employees	
        500 to 999 employees	
        1,000 to 2,499 employees	
        2,500 employees or more	

      Estabs. covered  by record1.
173


 23
 16
 17
 27
 29
 29
 17
  9
  6
 26
514


119
 50
 50
 82
 56
 77
 31
 24
 19
  6

 99
28.2


 (Z)
  .1
  .2
  .9
 1.9
 5.0
 6.1
 5.9
 7.9
  .1
                  317.6    .18.7
                                      38.4   190.9
                                                      925.2   1 109.7
  1.1
  2.4
  8.8
 20.3
 53.7
 64.5
 72.0
 94.3

  1.1
        101.7    1  240.2
  .2
  .3
  .7
 2.7
 4.0
12.0
11.1
16.6
30.4
23.5

  .3
  2.5
  3.6
  7.2
 28.6
 45.3
135.7
127.8
204.5
383.5
301.6
  2.7
 (Z)
  .1
  .2
  .6
 1.3
 3.0
 4.1
 3.8
 5.6
  .1
64.1


  .2
  .2
  .5
 1.6
 2.3
 7.4
 7.2
11.1
19.0
14.5
  .2
  .1
  .2
  .3
 1.2
 2.8
 6.4
 8.5
 7.8
11
   .3
   .7
  1.3
  5.2
 12.4
 29.3
 40.9
 39.7
 61.1
   .6
    1.2
    3.2
   11.1
   29.3
   60.6
  213.1
  239.4
  169.5
  198.0
    3.1
    1.5
    4.4
   18.6
   47.2
  104.1
  253.2
  291.2
  204.0
  185.4

    3.5
                                     129.1   707.6   4  965.1   4 209.5
  .3
  .4
  .9.
 3.3
 4.9
15.5
15.3
22.0
37.7
28.6

  .3
  1.3
  1.9
  3.9
 14.7
 23.5
 78.9
 77.4
124.0
217.7
164.6

  1.5
    7.9
   11.4
   22.7
  125.9
  195.5
  703.9
  550.0
  869.1
1 515.3
  963.4
    9.2
    5.9
   17.8
   31.2
  125.3
  260.0
  744.3
  586.4
  672.4
1 054.4
  711.8

    8.0
2 044.5


    2.7
    7.6
   29.4
   75.8
  165.7
  474.4
  529.5
  375.3
  384.1
    6.7
9 179.1

   13.7
   28.9
   54.6
  246.3
  457.7
1 429.4
1 139.7
1 542.5
2 580.3
1 686.1

   17.1
158.7


   .3
   .6
  1.1
  3.9
  5.3
 53.7
 53.4
                                                21.
                                                19.
    1
    3

   .9
355.6


   .5
  1.2
  4.8
 12.1
 25.2
 72.8
 78.7
 81.7
 78.6

  1.1
645.4   1 075.9


            2.1
            4.8
            5.2
           29.6
           49.4
          176.2
          120.4
          162.0
          277.6
          248.5
                                                                                       1.6
                                                                                                 2.3
(D) Withheld to avoid disclosing figures  for individual companies.  Data for this  item are included in the underscored  figures above.  (Z) Less than
    half of the unit of measurement  shown.
  1 Report forms were not mailed to  companies  that operated only one establishment—generally single-unit companies  with  less than 10 employees.  Payroll
    and sales for 1972 were obtained from administrative records supplied to other agencies of the Federal Government.  These payroll and sales d-ita were
    then used In conjunction with industry averages to estimate the balances of  the items shown in the table.   Data  are also included in the respective
    size classes shown for this industry.
Source:  U.S. Department of Commerce,  Social and Economic Statistics Administration, Bureau of the Consus, "1972 Census of Manufactures",
         Industrial Organic Chemicals. SIC Industry Croup 286.  See source for explanation of terms.

-------
                                            TABLE  3.    PRODUCTS  AND  PRODUCT  CLASSES-

                                 VALUE  OF  SHIPMENTS  BY  ALL  PRODUCERS:     1972  AND  1967
  (Includes quantity and value of  the products reported not only  by  establishments classified in this  industry, but also by establishments classified in other
  industries, and shipping these products as "secondary" products.   See source for explanation of term.
                                                                      1972
    1972
  product
    code
Product
Total product
shipments
including
interplant
transfers
                                        Commercial
                                        shipments
                                        only
Interplant
transfers
only
                                               (million dollars)   (million dollars)  (million dollars)
                                                                                                                              1967
Total product      Commercial       Interplant
shipments          shipments        transfers
including          only             only
interplant
transfers

(million dollars)   (million dollars)(million dollars)
  2865	  CYCLIC CRUDES AND INTERMEDIATES,
              TOTAL1	

  28651 11  Cyclic (coal tar) intermediates1
  28650 00  Cyclic crudes and intermediates,
              n.s.k., for companies with  10
              employees or more.  (See note).
  28650 02  Cyclic crudes and intermediates
              n.a.k., for companies with
              less than 10 employees.
              (See note)	

  2869	INDUSTRIAL ORGANIC CHEMICALS,
              N.E.C., TOTAL2	

  28691 11  Miscellaneous cyclic (coal tar)
              chemical products1	
  28692 13  Miscellaneous acyclic chemicals
              and chemical products, ex-
              cluding urea1 z	
  28693 —  Synthetic organic chemicals,
              N.E.C., except bulk surface
              active agents	
  28693 11      Flavor and perfume
                  materials 	
  28693 31      Rubber-processing chemicals1
  28693 51      Plasticizers1	
  28693 00      Synthetic organic chemicals,
                  n.e.c., n.s.k	
  28694 11  Pesticides and other synthetic
              organic agricultural chemicals,
              except preparations r	

  28695 —  Ethyl alcohol and other in-
              dustrial organic chemicals, n.e.c.
              Ethyl alcohol3	
  28695 11      Pure (natural)	
  28695 21      Denatured (special or com-
                  plete) , including natural
                  and synthetic for uses
                  other than rubbing	
  28695 31  Flavor oil mixtures and blends..
  28695 37  Reagent and high purity grades
              of organic chemicals refined
              from purchased technical
              grades	
  28695 51  Natural organic chemicals,
              n.e.c	
  28695 98  Other industrial organic
              chemicals	
  28695 00  Other industrial organic
              chemicals, n.s.k	

  28690 00  Industrial organic chemicals,
              n.e.c., u.s.k.,  for companies
              with 10 employees or more.
              (See note)	
  28690 02  Industrial organic chemicals,
              u.e.c.,  n.s.k.,  for companies
              with less than 10 employers.
              (See note)	
                               2,332.4

                               1,538.0
                                   6.7
                               7,465.7
                                 465.0
                               5,435.2
                                 723.0

                                 123.4
                                 228.2
                                 362.6
                                 489.3
                                 280.3
                                  35.0
                                  42.6
                                  34.7
                                  23.0

                                  60.4

                                  78.8

                                   5.6



                                  58.2



                                  14.7
                                (X)

                            1,151.7


                                (X)



                                (X)


                                (X)


                              417.0


                            4,107.4



                                (X)

                              116.3
                              190.8
                              306.5

                                (X)


                              434.1
                                (X)
                                (D)
                                (D)
                               34.7
                               22.0

                                 (D)

                                 (D)

                                 (X)




                                 (X)



                                 (X)
              (X)

            386.3


              (X)



              (X)


              (X)
          1,327.8


               (X)

              7.1
             37.4
             56.1

              (X)


             55.2
              (X)
              (D)
              (D)




              1.0

              (D)

              (D)

              (X)




              (X)



              (X)
          1,654.2

          1,066.1


             11.9
          5,539.4


            315.1


          4,052.2


            585.6

            119.0
            152.3
            309.2

              5.1


            308.2
            239.4
             33.6
             44.2
             27.9
              19.7

              44.0

              67.8

               2.2



              33.5
    (X)

  795.6


    (X)



    (X)


    (X)


  271.0


3,164.7


    (X)

    (D)
  137.1
  283.1

    (X)


  282.7
    (X)
    (D)
    (D)
   27.9
    19.7

     (D)

    64.4

     (X)



     (X)



     (X)
  (X)

270.5


  (X)



  (X)


  (X)


 44.1


887.5


  (X)

  (D)
 15.2
 26.1

  (X)


 25.5
  (X)
  (D)
                                                                                                                             (D)
  3.4

  (X)



  (X)



  (X)
    Note:  In the'1972 Census of Manufactures, shipments data for establishments of small companies, typically  those with fewer than 10 employees,  were
  estimated from administrative  record data rather than collected from respondents.  These shipments figures  (which are further discussed in the text)  are
  included in the code ending with  "002."  In both the 1972 and 1967 censuses  of manufactures, products which were not completely identified on the standard
  forms were coded  to the appropriate product-class code (5 digits)  followed by "00," or in some cases to the appropriate product-group code (4 digits)
  followed by "000."
    Represents zero.  (X) Not applicable.   (D) Withheld to avoid disclosing figures for individual companies.  (S) Withheld  because the estimate 'did not
meet publication standards either on the  basis of the associated standard error of estimate or on the basis of  a consistency review.   (X) Less than half
of the unit of measurement shown (less  than 0.1 when rounded).
    Data for quantities produced and values shipped for many of the synthetic  organic chemicals included in this grouping are shown in the U.S. Tariff
Commission's Annual Report,  "Synthetic  Organic Chemicals, United States Production and Sales."
  2 1967 and 1972 figures are not comparable.  The 1967 totals for code 28692  13 include the values for ureas.   Due  to revisions  in the Standard
Industrial Classification product classes, urea became code 28732 15 in 1972.
  3 For quantity information, refer to  the U.S. Treasury Department, Internal  Revenue Service publication:  Alcohol  and Tobacco-1972.  Excludes shipments
reported as rubbing alcohol  (primary to industry 2834, Pharmaceutical Preparations), and as antifreeze (primary to  industry  2899, Chemical Preparations,
N.E.C.).
  Source:  U.S.  Department of Commerce, Social and Economic Statistics Administration, Burea of the Census, "1972 Census of  Manufactures1'
           Industrial Organic Chemicals, SIC Industry Group 286.
                                                              6-8

-------
                                                                                   TABLE  4.    MATERIALS  CONSUMED,  BY  KIND:     1972

llll -—
281944
281946
287311
287410
281931
287312
281211
281996
281228
281238
286952
286920
286511
286552
286923
291165
291164
291166
291169
286555
286512
286513
286514
286533
147701
333348
131152
355911
970099
976000
Materials, containers, and supplies,
total 	
Inorganic chemicals:
Acids, except spent acids.
Hydrochloric acid 	

Nitric acid 	
Phosphoric acid 	
Sulfuric acid

Chloride . - .

Sodium hydroxide (caustic soda) 	
Organic chemicals:
Other alcohols, including amyl, butyl,
Aniline 	


Liquefied petroleum and refinery gases
for chemical feedstocks:






Phthalic anhydride 	
Crude materials :
Sulfur 	
Zinc and zinc-base alloy refinery shapes
Used as raw materials:
Parts and attachments for chemical Indus-

parts, containers, and supplies
Materials, containers, and supplies,
n.s.k.1 	
INDUSTRY 2865.— CYCLIC CRUDES AND INTERMEDIATES
Basis

100% BC1
100% UNO,
100%H;SO»
100% NH3
100% Cl
58% N!*Z0
100% NaOH

100% 	
100% CSH6
37% HCHO.




100%
100% 	
100% 	





Unit of
measure

1,000 s.
tons.
do
...do 	
do
do
...do 	
. do. .
...do 	
...do 	
do

Mil. gal.
Mil. lb..
...do 	
. . .do. . ..
do
. . .do. . .
do
do
do
do
...do 	
...do 	
1,000 s.
cons. . . .
1,000 long
tons
1,000 s.
tons.
Mil.cu.ft.


Total
consumption
of materials
(quantity)
(X)
50.8
(X)
589.5
(X)
800.7
191.9
(D)
(X)
42.0
474.3
(X)
53.7
(HA)
(D)
77.1
(D)
(X)
(D)
(NA)
213.5
438.9
61.9
19.2
(NA)
(X)
(X)
(X)
(X)
(X)
(X)
Consumption of materials
received from other
establishments
Quantity
(X)
43.5
(X)
101.4
(X)
331.0
191.9
331.8
(X)
42.0
474.3
(X)
53.7
79.7
1,100.3
77.1
(D)
(X)
(D)
(D)
(D)
12.0
46.4
19.2
1,299.5
163.5
.7
6,491.0
(X)
(X)
(X)
Delivered
cost
(million dollars)
945.8
2.0
(X)
7.2
(X)
9.3
7.4
16.4
(X)
2.2
20.7
1.0
9.3
12.0
35.2
2.2
(D)
(X)
(D)
(D)
CD)
.3
3.4
1.8
38.1
4.4
.3
3.0
29.4
630.9
41.0
Materials
made and
consumed in
same plant
(quantity)
(X)
7.3
(X)
488.1
(X)
469.7
(D)
(X)

m
(X)
(X)
(X)
(X)
INDUSTRY 2869. — INDUSTRIAL ORGANIC CHEMICALS, N.B..C.
Basis

100% HC1.
100% HF. .
100% HNOS
100% PjOs
100%H2SO»
100% KH3.
100% Cl. .
Technical
58% Na20.
100% NaOH

100% 	
100% CSH6
37% HCHO.





100% 	







Unit of
measure

1,000 s.
tons 	
...do 	
...do 	
...do 	
...do 	
. . .do 	
...do 	
...do 	
...do 	

Mil. gal..
Mil. lb...
...do 	
...do 	
. ..do 	
...do 	
...do 	
. . .do 	
...do 	
.. .do 	
...do 	
. ..do 	
...do 	
1,000 long
tons 	
Mil.cu.ft


Total
consumption
of materials
(quantity)
(X)
1,324.5
144.6
982.4
44.2
1,363.6
1,503.8
6,903.6
59.8
56.7
1,742.9
(X)
1,135.4
(NA)
3,168.6
2,416.3
11,275.9
(NA)
3,843.5
(RA)
612.8
(X)
464.2
443.7
(X)
(X)
(X)
(X)
(X)
(X)
(X)
Consumption of materials
establishments
Quantity
(X)
396.1
(D)
221.2
(D)
1,202.1
640.0
1,789.3
(D)
(D)
793.6
(X)
917.5
122.6
2,793.0
233.7
4,788.9
7,791.6
2,043.4
1,462.4
612.8
(X)
(D)
151.9
(X)
462.7
(X)
241,928.0
(X)
(X)
(X)
Delivered
cost
(million dollars)
3.436.5
14.8
(D)
15.9
(D)
25.3
25.4
76.4
(D)
(D)
38.3
39.8
122.4
15,9
80.0
5.2
154.9
98.2
54.6
173.3
27.8
(X)
(D)
11.2
(X)
13.1
(X)
64.8
114.0
2,096.9
104.9
Materials
made and
consumed in
same plant
(quantity)
(X)
928.4
(D)
761.2
(D)
161.5
863.8
5,114.3
(D)
(D)
949.3
(X)
217.9
(NA)
375.6
2,182.6
6,487.0
(NA)
1,800.1
(NA)
(X)
(D)
291.8
(X)
(X)
(X)
(X)
(X)
(X)
(X)
VD
     Represents zero.   (X) Not applicable.   (NA) Not available.  (D) withheld to avoid disclosing figures for individual c
the estimate did not meet publication standards, either on the basis of the associated standard error or on the basis of a
than half of the unit of measurement shown.   (n.e.c.) Not elsewhere classified.
   2 This item represents the total cost of  materials for establishments that did not report detailed materials data.   It ,
 companies that were not mailed report forms.

 Source:   U.S. Department of Commerce,  Social and  Economic  statistics  Administration, Bureau of  the Census, "1972 Census o
          Industrial Organic Chemicals, SIC Industry Group  286.
                                                                                                                     ianies.   (S) Withheld because
                                                                                                                   consistency review.  (Z) Less
                                                                                                                    Iso includes estimates for

                                                                                                                   f Manufacturers",

-------
      Although producing plants  for  industrial organic chemicals are scattered




 throughout  several  states, many are located near refineries which are located




 near  domestic sources  of  oil  or points of entry for imported oil.  Some of




 the petrochemical plants  border refineries, thus permitting an easy exchange




 of products.   This  results in a heavy concentration of chemical production




 along the Gulf coast and  the  east coast particularly in the area of New




 York,  New Jersey and Pennsylvania.   Additional concentrations occur along




 natural  gas pipeline routes and water transportation arteries throughout




 the central United  States and in the oil and gas fields of California.




 Significant organic chemical  production occurs in some 30 states.




      Table  5  presents  general statistical data by geographical area for




 establishments classified in  SIC codes 2865 and 2869.  The tabulated entries




 reflect  data  for certain  facilities  and products which are outside the scope




 of this  study,  so the  absolute  value stated for any particular parameter




 must be  considered  high.  Nevertheless, proportional relationships among




 the parameters and  relative geographic/economic influence may be considered




 typical  of  the Industrial Organic Chemical Industry.




     The industry has  experienced a  high growth rate almost since its begin-




 ning.  U.S. production of industrial organic chemicals has increased over the




 years  from  an  average  of  16 Tg  (35.3 billion pounds) during 1957 through 1959)




 to 25.7  Tg  (60.0 billion  pounds) in  1964, 47.3 Tg (104.3 billion pounds) in




 1969 and 62.9  Tg (138.7 billion pounds) in 1974.  However, the recent energy




 crisis has  doubly affected the  industry.  Refined petroleum products and




natural gas, traditional  feedstocks  for the production of the basic petro-




chemicals necessary to the industrial organic chemicals industry, are also
                                 6-10

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                                         TABLE  5.     INDUSTRIAL  ORGANIC  CHEMICALS:     GENERAL  STATISTICS  BY  GEOGRAPHICAL AREA

Geographic Area
UNITED STATES 	
NORTHEAST REGION 	
NEW ENGLAND DIVISION 	
MAINE 	
NEW HAMPSHIRE 	
MASSACHUSETTS . ...
RHODE ISLAND .

MIDDLE ATLANTIC DIVISION 	
HEW YORK
SEW JERSEY 	
PENNSYLVANIA, . ...
NORTH CENTRAL REGION 	
EAST NORTH CENTRAL DIVISION.
OHIO 	
INDIANA
ILLINOIS 	
MICHIGAN 	
WISCONSIN 	
CT> WEST NORTH CENTRAL DIVISION.
f IOWA
1 — l MISSOURI 	
1__1
SOUTH REGION
SOUTH ATLANTIC DIVISION 	
DELAWARE .... 	
MARYLAND . . . . ....
VIRGINIA
WEST VIRGINIA 	
NORTH CAROLINA 	
SOUTH CAROLINA

FLORIDA 	
•EAST SOUTH CENTRAL DIVISION.
KENTUCKY
TENNESSEE 	
ALABAMA ' .....
WEST SOUTH CENTRAL DIVISION.
LOUISIANA ... 	


MOUNTAIN DIVISION 	


CALIFORNIA 	
2865— CYCLIC CRUDES AND INTERMEDIATES
Establishments
Total
(number)
173
77
11
(NA)
(NA)
7
3
1
66
12
39
15
33
29
14

(1.000)
28.2
13.9
1.2
(NA)
(NA)
BB
CC
AA
12.7
2.6
8.3
1.8
5.7
FF
EE
(NA)
2.6
CC

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the prime sources for the energy required by an industrialized nation as well




as by  chemical production facilities.  With the demand placed on refinery




products and natural gas for use as fuels, there is little economic incentive




to increase production of refinery products and natural gas liquids to be




used as petrochemical feedstocks.  Thus, the industry has been affected not




only by increased costs but also by feedstock shortages.




     For this reason growth over the next several years is anticipated




to be  at a continuing slow rate and will probably be governed by improved




production technology and energy conservation techniques.  The continuity of




feedstock supply is almost more important than feedstock price.  As a result




the industry has been under considerable pressure to acquire its own sources




of raw material.  The need for such backward integration could lead not only




to the acquisition of basic petrochemical production facilities but even to




the acquisition of sources of raw materials for these and finally to control




of the well or mine.




     Table 6 presents data for fuels and electrical energy consumed by estab-




lishments classified in SIC codes 2865 and 2869 during 1971.  Specific data




relating to only those companies producing industrial organic chemicals as




defined herein were not found in the sources consulted for this study.  The




tabulation indicates that some on-site generation of electrical energy oc-




curred at facilities classified under these codes, but quantitative data




were not available.







Raw Materials




     The raw materials for the industry consist primarily of the products of




the Basic Petrochemicals Industry.  Thus, any adverse environmental impact
                                6-12

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                              Table 6.  FUELS AND ELECTRIC ENERGY CONSUMED IN 1971 BY

                                       COMPANIES IN SIC CODES 2865 AND 2869
                                                      SIC 2865
                                              SIC  2869
Coal

Distillate and Residual Fuel Oil

Natural Gas

Purchase Electric Energy

Total Energy Used for Heat and Power
(497,000 s  tons)  450.8  Gg

(4,748,100  bbl)  754.3 dam3

(69.4 x 109 ft3)  1.97 km3

                3.324 TWh

         40.3 TWh  equiv.
(5,036,600 s tons)  4,569 Tg

  (4,358,000 bbl)  692.4 dam3

(586.1 x 109 ft3)  16.59 km3

                   19.7 TWh

           286.0 TWh equiv.
Source:  U.S. Department of Commerce, Social and Economic Statistics Administration, Bureau of Census, "1972
         Census of Manufactures", Industrial Organic Chemicals, SIC Industry Group 286.

-------
associated with the production of raw materials for this industry is that




associated with production, transfer, and interim storage of olefins, aro-




matics, and paraffins.  Hydrocarbon emissions during raw material production




are estimated to range from 0.1 to 0.6 percent of plant throughput.  Non-




hydrocarbon pollutants include water treatment wastes, products from sulfur




and nitrogen removal processes, combustion and incineration products, catalyst




cleaning waste, spent catalysts and solid absorbents.  For a more complete




examination of pollutant and potential pollutant generation from raw materials




production, the reader is referred to Chapter 5.




     As noted above, the primary raw materials for this industry are olefins,




aromatics and paraffins.  Olefins are characterized by a highly reactive




double bond which renders them extremely useful in a variety of syntheses.




Ethylene surpasses all other hydrocarbons both in production volume and in




diversity of commercial use.  Ethylene production has grown from 136 Gg (300




million pounds) in 1940 to 2.27 Tg (5 billion pounds) in 1960 and to over




8.16 Tg (18 billion pounds) in 1970.  Propylene, though not produced in as




great a quantity as ethylene, is also an important raw material for this




industry.  In 1969, about 3.87 Tg (8.5 billion pounds) of propylene was con-




sumed to make chemicals.




     Benzene is the most important aromatic, second only to ethylene as a




building block for synthetic organic chemicals.  Figures for total consump-




tion of benzene by the industry are not available.  Data published in the




1972 Census of Manufacturers for those establishments classified in SIC code




2869 indicate a benzene consumption of 1.44 Tg  (3.17 billion pounds).  Toluenes




and mixed xylenes are likewise important feedstock materials,  though not  on
                                 6-14

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a level with benzene.  Napthalene and cresols comprise the balance of the




significant aromatic  feedstocks to this industry.




     The paraffins, or alkanes, are saturated hydrocarbons.  Methane, CHin




is the simplest member of this class, with subsequent members differing by




multiples of one carbon and two hydrogen atoms.  Paraffins containing one




to four carbons are gases at  standard temperature and pressure, while those




containing five or more carbons are liquids or solids.  Paraffins are the




least reactive of the hydrocarbons and all of the common processing methods




require elevated temperature  and pressures.  Paraffins with four or more




carbons can exist in  branched-chain forms, the number of possible isomers




increasing with the number of carbon atoms.  The principal paraffin feed-




stocks used by the industry are one- to five-carbon molecules.




     Toxicity ratings for selected hydrocarbons used as industry feedstocks




are shown in Table 7.  A complete list of raw materials used in the produc-




tion of the chemicals treated in this chapter is contained in Appendix B.




Chemicals which are listed as raw materials but which are also themselves




products of the industry and  for which process descriptions are included




in this chapter are identified with an asterisk.  Materials which function




as catalysts are listed in Appendix C.






Products




     Process descriptions for some 442 industrial organic chemicals are in-




cluded in this study.  These  chemicals are used as solvents or chemical inter-




mediates by downstream industries to produce organic chemical products estimated




by one source to number from  8,000 to 10,000.  During 1974 nearly 64 Tg (139




billion pounds) of cyclic and acyclic chemicals and chemical intermediates







                                 6-15

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 Table 7.  TOXICITY OF SELECTED FEEDSTOCKS FOR THE INDUSTRIAL
                  ORGANIC CHEMICALS INDUSTRY
ethylene
propylene
butylene

benzene

toluene

xylene

napthalene
cresols
ethane
propane
butane
n-pentane
isopentane
Low toxicity.
Low toxicity.
Butene-1, cis-butene-2, and trans-butene-2
isomers are asphyxiant gases; isobutene
isomer is non-toxic.
Highly toxic by ingestion, inhalation
and skin absorption; tolerance 25 ppm
in air.
Moderately toxic by ingestion, inhalation
and skin absorption; tolerance 200 ppm in
air.
Moderately toxic by ingestion or inhalation;
tolerance 100 ppm in air.
Moderately toxic; tolerance 10 ppm in air.
Moderate to highly toxic irritant; corrosive
to skin and mucous membranes; absorbed
through skin; tolerance 5 ppm in air;
22 mg/m3 in air; low toxicity.
Not available.
Non-toxic-
Asphyxiant gas.
Tolerance 500 ppm in air.
Low toxicity.
Source:  Hawley, Gessner, G.  Condensed Chemical Dictionary.
         Ed.   N.Y., Van Nostrand-Reinhold, 1971.
                                          8th
                            6-16

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with a value of approximately 7 billion dollars were produced in the United




States.  In general, the products of the Industrial Organic Chemical Industry




are used as feedstock to such downstream industries as adhesives; agricul-




tural chemicals; automotive chemicals; dyes; elastomers; explosives; paints




and protective coatings; refrigerants and propellant gases; petroleum pro-




duction and processing; Pharmaceuticals, plastics, resins and synthetic




fibers; solvents; surfactants; and others, including the chemical manufac-




turing industry itself.  Because of the number of processing steps from feed-




stock to end-product, intra-industry sales reach significant levels.




     Table 8 lists the 25 organic chemicals with the highest production




volume in 1973.  The chemicals listed accounted for 62.6 percent of the total




production of this industry for 1973.  Eighteen of the 25 chemicals listed




find direct application in the plastics, plasticizers and fibers industries.




Nine of the chemicals are used directly in the preparation of solvents and




as intermediates in the production of other organic chemicals.  Eight of the




chemicals find direct application in manufacturing of agricultural chemicals,




seven each in the preparation of dyes, Pharmaceuticals, and paints or other




protective coatings.  Twelve of the chemicals listed are used as primary or




alternate feedstocks for the production of other members of the list.




     A list of the 25 organic chemicals with the highest market value is




presented in Table 9-  Tetraalkyl lead compounds exclusive of tetraethyl




lead, for which no sales data were available, accounted for over 7.2 percent




of the total chemical sales in 1973 as reported to the U.S. International




Trade Commission.  During 1974 domestic consumption of these compounds dropped




by 12.4 percent.  The relative economic importance of tetraalkyl lead com-




pounds can be expected to diminish still further, as automotive gasoline





                                 6-17

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Table 8. THE MOST SIGNIFICANT SYNTHETIC ORGANIC CHEMICALS
BY PRODUCTION VOLUME IN 1973
Chemical
Ethylene dichloride
Urea
Methanol
Formaldehyde (37% by weight)
Styrene
Ethylbenzene
Vinyl chloride
Ethylene oxide
Ethylene glycol
Cumene
Dimethyl terephthalate
Acetic acid
p-Xylene
Phenol
Cyclohexane
Acetone
Ethyl alcohol
Isopropyl alcohol
Propylene oxide
Acetic anhydride
Adipic acid
Vinyl acetate
Acrylonitrile
o-Xylene
Carbon tetrachloride
Production
Gg
4215
3214
3204
2914
2710
2580
2427
1890
1487
1209
1163
1102
1055
1032
962.8
902.4
889.9
832.3
795.2
757.5
710.8
681.6
614.2
484.4
475.1
Sales Volume
Gg
613.0
3065
1743
1257
1288
188.3
1612
231.4
1283
635.4
594.9
276.1
711.8
595.2
900.2
702.0
689.6
408.1
NA
NA
69.28
436.7
218.0
351.5
448.8
Market Value
$1000
40,489
228,103
64,306
51,578
199,141
20,873
147,518
34,913
193,317
52,510
165,875
32,069
100,635
100,508
89,860
67,928
84,015
52,533
NA
NA
24,757
67,095
50,878
37,998
59,531
NA - Indicates data not available.
Source:  U.S. International Trade Commission.  Synthetic Organic Chemicals, United
         States Production and Sales, 1973.  ITC Publication 728.  Washington, GPO,
         1975.
                                       6-18

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               Table 9.  THE MOST SIGNIFICANT SYNTHETIC ORGANIC CHEMICALS

                                BY MARKET VALUE IN 1973
Chemical
Tetraalkyl lead compounds*
Urea
Styrene
Ethylene glycol
Dimethyl terephthalate
Vinyl chloride
Toluene-2,4- and 2,6-diisocyanate
(80/20 mix)
Dichlorodif luoromethane
p-Xylene
Phenol
Cyclohexane
Ethyl alcohol
Acetone
Vinyl acetate
Methanol
Trichlorof luoromethane
Phthalic anhydride
Polymethylene polyphenylisocyanate
Carbon tetrachloride
Caprolactam
Ispropyl alcohol
Cumene
Formaldehyde (37% by weight)
Acrylonitrile
1,1, 1-Trichloroethane
Production
Gg
346.3
3214
2710
1487
1163
2427
229.5
221.7
1055
1032
962.8
889.9
902.4
681.6
3204
151.4
463.8
128.0
475.1
297.7
832.3
1209
2194
614.2
248.7
Sales Volume
Gg
435.0
3065
1288
1283
594.9
1612
198.8
210.4
711.8
595.2
900.2
689.6
702.0
436.7
1743
149.2
290.8
101.4
448.8
133.3
408.1
635.4
1257
218.0
256.8
Market Value
$1000
518,667
228,103
199,141
193,317
165,875
147,518
126,261
110,812
110,635
100,508
89,680
84,015
67,928
67,095
64,306
61,352
61,326
59,536
59,531
57,944
52,533
52,510
51,578
50,878
49,534
*Exclusive of tetraethyl lead
Source: U.S. International Trade Commission.  Synthetic Organic Chemicals, United
        States Production and Sales, 1973.  ITC Publication 728.  Washington, GPO,
        1975.
                                       6-19

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producers shift to a higher percentage output of unleaded products in order




to service the increasing population of vehicles requiring such fuel.




     Dichlorodifluoromethane, trichlorofluorotnethane, and 1,1,1-trichloro-




ethane accounted for over 3 percent of total reported chemical sales in




1973.  Production and sales volume of these halocarbons can be expected to




diminish somewhat as a result of concern over the theoretically adverse




effect of halocarbons on atmospheric ozone.




     Four of the listed chemicals, toluene-2,4- and 2,6-diisocyanante, phthalic




anhydride, polymethylene polyphenylisocyanate and caprolactam, are used pri-





marily in the production of plastics and synthetic fibers and collectively




accounted for 4.25 percent of total chemical sales during 1973.  Seventeen




of the chemicals listed in Table 9 appear also in Table 8.  The chemicals




listed in Table 9, in aggregate, accounted for 39.4 percent of the total




market value of industrial organic chemical sales in 1973.  Appendix D lists




358 organic chemicals considered significant to the industry by reason of




production volume, economic impact, environmental impact or toxicity factors.






Companies




     The bulk of the output of industrial organic chemicals is contributed




by large multi-line chemical companies and by chemical divisions or subsi-




daries of the major oil companies.  Many of these are multi-national organi-




zations, some being headquartered outside the United States.  A list of the




leading chemical companies operating in the United  States  during  1973  is  pre-




sented in Table 10.  The companies listed are all producers  of industrial organic




chemicals.  However, the tabulated sales figures also  include sales  of basic




petrochemicals as well as downstream industrial products  including plastics
                                6-20

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           TABLE  10.    LEADING CHEMICAL  COMPANIES IN THE  U.S.  DURING 1973
CHEMICAL SALES
$ MILLIONS

Du Pont
Union Carbide
Monsanto
Dow Chemical
Exxon
Celanese
W. R. Grace3
Allied Chemical
Occidental Petroleum
Hercules
Eastman Kodak
Rohm and Haas
Shell Oil
rac
American Cyanamid
Phillips Petroleum
Borden
Stauffer Chemical
Mobil Oil
Standard Oildnd.)
Ethyl Corp.3
Akzona
Texaco
Gulf Oil
Diamond Shamrock
B. F. Goodrich
PPG Industries
Ashland Oil3
Standard Oil of California (Includes
Chevron Chemical Company)
U.S. Steel
Air Products3 ' b
Ciba-Geigy
01 in
Cities Service3
BASF Wyandotte
Mob ay (Formerly Baychem)
Goodyear Tire
William Cos.
El Paso Natural Gas
Tenneco
Kichhold Chemicals
Merck
Pfizer3
Lubrizol
Borg-Warner
Aircob
American Koechst
Chenetron
Pennwalt
1973
$4250
2400
2355
2250
1563
1508
1317
1114
1080
1000
792
750
748
745
708
697
690
621
570
510
499
485
480
455
454
452
440
427
422
394
388
380
370
367
356
333
325
312
301
299
294
280
279
274
264
262
260
249
246
1972
S3550
1960
1924
1800
1258
1279
1088
1001
831
795
694
588
645
657
644
490
515
543
470
410
458
391
400
363
404
363
405
352
304
310
342
350
329
424
299
263
250
205
254
277
217
235
222
217
201
240
220
224
199
1971
S2950
1884
1776
1550
1077
1131
974
892
705
678
612
482
556
646
600
408
450
493
420
341
416
351
350
300
368
286
359
327
277
298
297
380
281
391
254
209
236
50
271
254
194
210
204
198
165
192
200
224
183
TOTAL SALES
S MILLION
1973
3 5,276
3,939
2.648
3,068
25,724
1.609
2,808
1.665
3,456
1,155
4,036
789
4,884
1,719
1.472
2,990
2,554
621
11.390
5,416
699
704
11,407
8,417
651
1,661
1,513
2.053
7,762
6.952
399
550
1,239
2,035
378
333
4,675
744
983
3,910
294
1,115
1.284
274
1,547
584
339
353
504
1972
S i.366
3.261
2,225
2,404
20,310
1,385
2.315
1.501
2,721
932
3,478
619
4,076
1,498
1,359
2,513
2,193
543
9,166
4,503
632
572
8,693
6,243
617
1.507
1,396
1,780
5,829
5,429
351
500
1.098
1,862
316
263
4,072
578
1,097
3,275
217
958
1,093
217
1,283
492
260
314
441
1971
S 3.343
3,038
2,087
2,053
18,701
1,236
2,049
1.326
2,635
812
2,976
507
3,892
1,354
1,283
2,363
2,070
493
8,243
4,054
577
506
7,529
5,940
573
1,237
1,238
1,635
5,143
4,963
308
550
1,145
1,810
254
209
3,602
412
1,037
2,841
194
829
952
198
1.148
441
235
276
406
(a)Slgnificant nonchemlcal sales (welding and cryogenic  equipment, fabricated plastics products, coatings, metals, textiles
  and the like) Included with the clif.-iical sales.  (b)For fiscal year ended Sept.  30.  (na • not available).     '        '

Source:  Chemical and Engineering News, June 3,  1974.


                                                 6-21

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 and  resins,  dyes,  plasticizers  and  agricultural chemicals.  In addition, as

 noted  in the table,  the  sales figures may  include significant nonchemical

 sales.   Nevertheless,  the  relationship between tabulated data for chemical

 sales  and total  sales  during 1971 through  1973 is indicative of the degree

 of specialization  as chemical producers.

     In  addition to  the  companies listed,  there are hundreds of smaller

 companies specializing in  a limited line of intermediate or end-product

 chemicals.   In general,  sales and profits  are commensurate with the limited

 product  line.

     A number of factors account for the dominance of this industry by large

 multi-line and multi-national companies.   Among these are:

     1)   Substantial costs for  product and process research and
          development,

     2)   High plant investment  in order to affect reduced product
          prices  through  large scale production techniques,

     3)   Competition for world  supplies of raw materials,

     4)   Necessity of  an extensive  product line (horizontal inte-
          gration) in order to provide a broad economic base for
          the company,

     5)   Economic advantages realized by integration of basic
          operations common to the production of a number of
          different end products, and

     6)   Ability to compete in  the world market and to take
          advantage of world wide supply and demand fluctuation.


Traditionally, the industrial organic chemicals industry has relied heavily

upon horizontal integration to  assure some level of economic stability.  In

recent years, however,  the main influence  has been the need for vertical

integration.   Firms that until  recently were secure in the production of
                                 6-22

-------
intermediates or of end-products have been under pressure either to integrate




backward, by acquiring their own sources of raw materials, or to integrate




forward by gaining control of client industries.




     Thus, it may be expected that the more highly capitalized chemical com-




panies are better equipped for such vertical integration and can be expected




to maintain their present dominance of the industry.  Most have already en-




larged the scope of their activites, both by diverse acquisition and by




internal  expansion, and have advanced their position in the market at the




expense of companies which have maintained an original structure.




     A list of 260 companies involved in the production of industrial organic




chemicals at 544 sites is presented in Appendix E.






Environmental Impacts




     Hydrocarbons are major constituents of the gaseous emissions from indus-




trial organic chemical plants.  Hydrocarbons may be emitted to the atmosphere




in a number of ways.  Vent gases from various process operations may contain




hydrocarbons, and large quantities of hydrocarbon carrying gases may some-




times be vented as a result of upset conditions in a plant or by the passage




of gases through safety valves or relief vents.  Leaks in vessels, pump seals,




and pipe walls are also a source of fugitive hydrocarbom emissions.  Reaction




or process air required for a number of organic chemical manufacturing pro-




cesses can be a source of significant hydrocarbon emissions.  Some examples




of air requirements for processes are:  (1) for synthesis gas, every ton of




product requires 4 tons of the air; (2) the production of hydrogen cyanide




requires 10 tons of air per ton of product; and (3) acetic anhydride requires




5 tons of air per ton of product.  Feedstock shortages stemming from the
                                 6-23

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current energy crisis have caused the industry to expand efforts in develop-




ing technology for increased product recovery.  This, combined with more




effective recovery and recycling of reagent materials, should lead to a




significant decrease in atmospheric emissions from the chemical industry.




     While air pollution constitues a problem for manufacturers of organic




chemicals, its magnitude does not compare with that posed by industrial




water pollution.  The sources of liquid waste streams can be divided into




five general categories:  (1) waste containing a principal raw material




or product resulting from the stripping of the product from solution; (2)




by-products produced during reactions; (3) spills, slab wash-downs, vessel




cleanouts, sample overflows, etc; (4) cooling tower and boiler blowdown,




steam condensate, water treatment waste, and general wash water; and (5)




storm waters, for which the degree of contamination depends on the nature




of the drainage area.  The principal contaminants in the wastewaters in-




clude organics from residual products and by-products, oils from the bottom




of distillation and stripping columns, suspended solids, and catalysts.




Many of the compounds present in the effluents from typical processes are




indicated in Table 11.




     Numerous solvent processes are utilized in the purification of chemical




feedstocks, intermediates, and products used and manufactured by the organic




chemicals industry.  Since the solvents used are expensive, recovery and




recycle operations are usually employed.  Therefore, it is doubtful that




large quantities will be found in waste streams.  Nevertheless, even low




concentrations of many of the solvents used by the industry have possible




carcinogenic or other biological effects.
                                   6-24

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                   Table 11.  INDUSTRIAL ORGANIC CHEMICAL PROCESSES AS WASTE SOURCES
           Process
      Source
               Pollutants
ON
I
to
Ul
     Alkylation:
       Ethylbenzene

     Cyanide production   Water slops

     Dehydrogenation:
       Butadiene product  Quench waters
       from n-Butane and
       Butylene

       Ketone production  Distillation slops
       Styrene from
       ethylbenzene
     Extraction and
       purification:

       Isobutylene


       Butylene


       Styrene

       Butadiene
       Extractive
         distillation

     Halogenation
       (principally
        chlorination)

       Addition to
         olefins
Catalyst

Condensates from
  spray tower
Acid and caustic
  wastes

Solvent and caustic
  wash

Still bottoms

Solvent


Solvent
                       Tar,  hydrochloric acid,  caustic soda,  fuel oil

                       Hydrogen cyanide, unreacted soluble  hydrocarbons


                       Residue gas,  tars,  oils,  soluble hydrocarbons
Hydrocarbon polymers,  chlorinated hydrocarbons,
  glycerol, sodium chloride

Spent catlayst (Fe,  Mg,  K,  Cu,  Cr,  Zn)

Aromatic hydrocarbons,  including styrene,  ethyl
  benzene, and toluene,  tars
Sulfuric acid,  C^ hydrocarbon,  caustic soda


Acetone, oils,  Ci» hydrocarbon,  caustic soda,
  sulfuric acid

Heavy tars

Cuprous ammonium acetate,  C± hydrocarbons,
  oils

Furfural, Ck hydrocarbons
Separator
Spent caustic

-------
                Table  11.   INDUSTRIAL ORGANIC  CHEMICAL  PROCESSES AS WASTE SOURCES
            Process
                           Source
                                      Pollutants
ON
I
NJ
ON
      Halogenation:
         (continued)

         Substitution
  Hypochlorination

  Hydrochlorination

Hydrocarboxylation
  (0X0 Process)

Hydrocyanation  (for
  acrylonitrile,
  adipic acid,  etc.)

Isomerization in
  general

Nitration
  Paraffins


  Aromatics

Oxidation
  Ethylene oxide
  and glycol mfg

  Aldehydes,
  alcohols, and
  acids from
  hydrocarbons
                     HC1 absorber,
                       scrubber
Dehydrohalogenation

Hydrolysis
Surge tank


Still slops

Process effluents



Process wastes
                            Process  slops

                            Process  slops
Chlorine,  hydrogen chloride,  spent caustic,
  hydrocarbon isomers and chlorinated products,
  oils

Dilute salt solution

Calcium chloride,  soluble organics,  tars

Tars, spent catalyst, alkyl halides


Soluble hydrocarbons, aldehydes

Cyanides,  organic  and inorganic
                                                   Hydrocarbons; aliphatic, aromatic, and
                                                     derivative  tars
                       Byproduct aldehydes,  ketones,  acids,  alcohols
                         olefins,  carbon dioxide

                       Sulfuric acid,  nitric acid,  aromatics


                       Calcium chloride, spent lime,  hydrocarbon
                         polymers,  ethylene oxide,  glycols,  dichloride

                       Acetone, formaldehyde,  acetaldehyde,  methanol,
                         higher alcohols,  organic acids

-------
                      Table  11.   INDUSTRIAL ORGANIC  CHEMICAL PROCESSES AS WASTE  SOURCES
           Process
                           Source
                                      Pollutants
I
S3
-vl
     Oxidation  (Cont.)

       Acids, anhydrides   Condensates
       from aromatic       o_-ii   ->
       oxidation           Stl11  sl°Ps
       Phenol,  acetone
       from  aromatic
       oxidation

     Sulfation  of  olefins
Sulfonation of
  aromatics

Utilities
                     Decanter
                           Caustic  wash
Boiler blow-down
                           Cooling system blow-
                             down
                           Water  treatment
                       Anhydrides,  aromatics,  acids
                       Pitch

                       Formic acid,  hydrocarbons
                       Alcohols,  polymerized hydrocarbons,  sodium
                         sulfate,  ethers

                       Spent caustic
Phosphates,  lignins,  heat,  total dissolved
  solids,  tannins
Chromates,  phosphates,  algicides,  heat

Calcium and magnesium chlorides, sulfates,
  carbonates

-------
     Caustic washes utilizing aqueous sodium hydroxide solutions are frequently




used.  Sodium hydroxide solutions are used to extract from process streams




various acidic contaminants such as hydrogen sulfide, mercaptans, phenols,




biphenyls, and organic acids.  Most spent caustic streams can therefore be




expected to contain some or all of these compounds in the form of sodium




salts as well as some unreacted sodium hydroxide, small quantities of the




process product, and feed chemicals.  Caustic washes are also used to recover




unreacted acidic chemicals in such processes as chlorination, sulfation, sul-




fonation, polymerization, or oxidation.




     Organic chemical processing also involves the use of various acid washes




to remove basic materials from product streams.  Acidic washes are often used




also in removing contaminants from various phenolic product streams.  Acid




process effluents also are present in some operations, notably alkylation




processes.




     Caustic or acid washing is often followed by a clear water rinse to




remove traces of the washing compounds.  Off-gases from various units also




are scrubbed with water to remove contaminants.  Effluent waters usually will




contain pollutants similar in nature to those found in the preceding spent




caustic or acid washes, but at significantly lower concentration levels.




     Other possible processing operations which may contribute pollutants




include spillage of organic chemicals during transport or storage operations




and run-off from processing areas.  Spent catalyst material may be a com-




ponent of aqueous waste streams and often can be a serious pollutant in




terms of biological toxicity, even though it may be present only in small




quantities.
                                 6-28

-------
     The major solid waste from organic chemical processing is usually associated




with bottoms from process tanks, from distillation and stripping columns, and




in wastes from the cleaning of storage tanks.  This material is usually in the




form of a sludge which contains unreacted raw chemicals or products and spent




catalysts.  These sludges are usually disposed of either by incineration or




by landfill.




     Specific information relating to pollutants and abatement procedures, when




available, is included in the process descriptions.
                                6-29

-------
 Bibliography

 1.    Austin, George T.  The Industrially Significant Organic Chemicals",
       Part 1, Chem. Eng. .81 (2),  127 (1974);  and Part 9,  Chem. Eng.  81(16),
       96 (1974).

 2.    Federal Energy Administration,  Report  to Congress  on Petrochemicals.
       Washington, B.C., GPO, undated, circa  1974.

 3.    Frohning, C. D. and B. Cornils.  Chemical Feedstocks from Coal.
       Hydrocarbon Processing j>3(ll) ,  143 (1974) .

 4.    Garner, D. N. and P. S. Dzierlenga. Organic Chemical Producers'  Data
       Base Program, 2 vols., final report.   EPA Contract  No.  68-02-1319,
       Task 51.  Austin, Texas,  Radian Corporation, August 1976.

 5.    Gloyna, Earnest F. and Davis L. Ford.   Petrochemical Effluents
       Treatment Practices; detailed report.   Austin, Texas, Engineering-
       Science, Inc., 1970-

 6.    Hahn, Albert V.  The Petrochemical Industry.  N.Y., McGraw-Hill,  1970.

 7.    Hawley, Gessner G.  Condensed Chemical Dictionary.   8th Ed.   N.Y.,
       Van Nostrand-Reinhold, 1971.

 8.    Jewell, Wm. and Davis L.  Ford.   Preliminary Investigational  Requirements-
       Petrochemical and Refinery Waste Treatment Facilities.  Project  12020 BID.
       Engineering-Science, Inc., 1971.

 9.    Kent, James A., ed.  Reigel's Handbook of Industrial Chemistry.   7th  Ed.
       N.Y., Van Nostrand-Reinhold, 1974.

10.    Recession Clamped a Lid on Growth in Chemical Output Last Year,  With
       Production Down for Many Major Products. Chemical  and Engineering News  1975
       (2 June).

11.    Reuben, B. G. and M. L. Burstall.  The Chemical Economy.  London,
       Longman, 1973.

12.    Ross, J. F.  Which Raw Materials for Petrochemicals?  Hydrocarbon
       Processing 5^(11), 76-D (1975).

13.    Sax, N. Irving.  Dangerous Properties of Industrial Materials, 4th Ed.
       N.Y., Van Nostrand-Reinhold, 1975.

14.    Stanford Research Inst.,  Chemical Information Services.  Chemical
       Origins and Markets;  Product Flow Charts;  Tables of Major Organics
       and Inorganics.  Menlo Park, Ca., 1967.

15.    Stork, K., M. A. Abrahams and A. Rhoe.  More Petrochemicals from Crude.
       Hydrocarbon Processing .53(11) ,  157 (1974) .

16.    U.S. Department of Commerce, Bureau of Census, Social and Economic
       Statistics Administration.  1972 Census of Manufacturers, Industry
       Series, Industrial Organic Chemicals.   Washington, GPO,  1972.

                                    6-30

-------
17.    U.S. Environmental Protection Agency, Office of Water and Hazardous
       Materials, Effluent Guidelines Division.  Development Document for
       Effluent Limitations Guidelines and New Source Performance Standards
       for the Major Organic Products Segment of the Organic Chemicals Manu-
       facturing Point Source Category.  EPA 440/1-74-009-a.  Washington,
       D.C., 1974.

18.    U.S. International Trade Commission.  Synthetic Organic Chemicals,
       United States Production and Sales, 1973.  ITC Publication 728.
       Washington, GPO, 1975.

19.    U.S. International Trade Commission.  Synthetic Organic Chemicals,
       United States Production and Sales, 1974.  USITC Publication 776.

20.    U.S. Tariff Commission.  Synthetic Organic Chemicals, United States
       Production and Sales, 1965.  TC Publication 206.  Washington, GPO,
       1967.

21.    U.S. Tariff Commission.  Synthetic Organic Chemicals, United States
       Production and Sales, 1969.  TC Publication 412.   Washington, GPO,
       1971.
                                   6-31

-------
INDUSTRY ANALYSIS
     6-32

-------
INDUSTRY ANALYSIS




     The Industrial Organic Chemicals Industry is discussed in terms




of ten feedstock groups:  benzene, butylenes, sources of cresylic acids,




ethylene, methane, naphthalene, paraffins, propylene, toluene and xylenes.




In an effort to complete this study within the imposed time limitations




process descriptions vary from very detailed to somewhat general.  This




is an extremely complex industry and the prescribed brevity of process




descriptions has, no doubt, led to process oversimplifications in many cases.




     Each feedstock group is discussed in terms of a chemical tree—giving




an overview of the products and processing steps described; a process flow




sheet—giving a synopsis of the reaction steps involved in the generation




of a product and the more important input and output materials for each




reaction step; and a concise process description.  Examination of the




various feedstock chemical trees and process flow sheets will reveal




that many products could have come from more than one feedstock group and




that many more products could not have been generated without the use of




products of the other feedstock groups.




     Data are given in metric units according to the System Internationale




described in the ASTM Metric Practice Guide.




     For each process description an attempt was made to present data first




from a recognized authoritative source [e.g., Kirk-Othmer, "Encyclopedia of




Chemical Technology"; Lowenheim and Moran, "Industrial Chemicals," 4th Ed.




(1975)] and, if not available there then from various specialized publica-




tions.  The recognized deficiencies in the data prepared for this chapter




exist in the general lack of information on waste streams and to a some-




what lesser extent on utilities.  For those processes for which no waste
                               6-33

-------
stream information could be found in the literature best professional




judgement was used to indicate possible pollutants.  Another general




characteristic of the Industrial Organic Chemicals Industry is that




there appears to be a continuing change in processes for many of the




products generated.  Thus, this should be at least one of the industrial




segments that should require a periodic update.
                              6-34

-------
SECTION I
 BENZENE
6-35

-------
                                                  BENZENE
BENZENE
      Ethyl benzene —
                          »Acetophenone
                           Styrene
Chlorobenzene
                            5                        10                               11
                                   Dichlorobenzenes , - ^   Dichloronitrobenzenes  - » Dichloroani lines
                                                     28
                                                          o-Phenylenediamine
                                                         ,Trichlorobenzenes
                            2.	± Chloronltrobenzenes  	——^o-,p-Nitroanilines	^p-Phenylenediamine
                                 _i, Phenol
                            52
                           ^Diphenyl  oxide
                                     Aniline.
                                                              ) N-Methy1aniline
                                                          13
                                                               N,N-Oimethylaniline
                                                  14
                                                         N-Methyl aniline
                                                  15            .           16
                                                 	^Benzoquinone 	» Hydroquinone
                                                  17
                                                       -»Acetanilide	^  Chioroanilines
                                                  19
                                                          2'4.6-Trichloroaniline
                                                  20
                                                         Cyclohexylamine
                      Figure 1.   Benzene  Section Chemical Tree

                                          6-36

-------
BENZENE
     21                                 22                                  23
    	^ Benzenesulfonic acid	^  Benzenedisulfonic acids	—	^Resorcinol
     24
              -AFumaric acid
 25         .            	26
	^Nitrobenzene	
                                           Dinitrobenzenes	>  m-Phenylenediamine
                                            31
                                                    Aniline
                                                                    32    Diphenylthiourea
                                                                    33
                                                                         ->   Aniline Hydrochloride
                                                                    34
                                                                         -^ Oiphenylamine
                                                                    35
                                                                    49
                                                                            Sulfanilic Acid
                                                                        -}  Dicyclohexylamine
     36
                   Cumene
                             37
                                                > Phenol
                                                 Acetone
                                                 Acetophenone
      Figure  1.   Benzene  Section  Chemical Tree  (Cont.)
                                6-37

-------
BENZENE
 38                          39
        ->Maleic Anhydride	r^Succinic Acid
                                        40
                                               Tetrahydrophthalic Anhydride
            41                      42
                    Maleic Acid	Malic Acid
                                            43
                                                 -4 Fumaric Acid
  44                      45
 	^  Cyclohexane	—j^-Ad,ipic Acid
                                   46
                                                Cyclohexanol
, Cyclohexanone
                                                                 47
                                                                          Cyclohexene
                                                                48
                                                                        Cyclohexylamine
 50
           Bromobenzene
           Biphenyl
        Figure 1.   Benzene Section Chemical  Tree  (Cont.)
                               6-38

-------
u>
VO
1 Ethyl ene
! Steam
[Heat
!Coo1
lWa1
Sll
in
:er
9
r
V
fe
11'
Iftlkylatlonl
1.
Cl
Heat
ci2
1 A
4^
ilorination
                               CooUng!   | Ethyl benzene i    ICooHna
                                Haterj     \         /      iWater
                       Steam;1
                       I Heat
                      Refrlg.
                                      ..
                            ! Dehydrogenatlonj
            i Steam1

            I Heat!
lOxidationl
                                                     Acetophenone
                                                 Figure 2.   Benzene  Section  Process  Flow Sheet

-------
                         NaOH
                         Heat
 I

O
a
                               Hydrolysis    521

                               Condensation
                          ChloHnationl
                                                                   Si
Heat
1
^-— -^ ^-,
* A C12"l ^ A !.!•»» H|
28
Substitution
'b
Chlorlnation)
Nl
H2S04
10,
I Nitration!
                                                            D1-.
                                                        Chioronltro-
                                                         1 Benzenes  "
Fe°
t
HC1
|
Reduction!
                                                                     NO
                                                                                            n [Cooling-:—i
                                                                                           S   lUata^' "*~IT
                                                                                               I Water
Fe
1
HC1
1 A
i'Reductloh'l 30|
Substitution
                                                                                                        TPhenoT;
                                                                                                                      CH3OH

                                                                                                                      |CH3I
                                                                                                 lAniline
                                                                                            i ^ i
                                                                                            _S\      Cooling
                                                                                            |	fSjs
                                                                                                                     ISteamr-i          ti

                                                                                                                     |Heatllll       11
                                                                                                                                     Mater
                                                                                                      12.13,141
                                                                                                Alkylation  '
                                               Figure  2.   Benzene  Section Process Flow  Sheet  (Cont.)

-------
          MnO,
Cooling;'
 Water]
Oxidation!
                   15.
SO.!    'Coolingr   I  iAcetlc
 '    i wateiF£|__ji   i-~'••'
«20+Fe!
I '
Heat
1 4
Reduction | '
                      M
                                 Acetylatlonj
                           C1
                                   ^—^Aceti
-1
-
(rtL III
Steam |
i IP
iChlorlnationl8
'Hydrolysis
"•-<

IChlorination',
                                                                  19
                                                          2,4,6-

                                                          al^i H np°"
                                                          , am line
                                                          {Reduction'
                                 Figure 2.   Benzene  Section Process Flow  Sheet  (Cont.)

-------

Steam
H2S04i
HN03f
=n
I
/P
25
Nitration

HC1
1 '
Fe°
27
Reduction

Steam
H2s64
HN03f
=n i T A i IT ?•
Nitration! Z6
— — *•*
(Reduction; 1
o
JC ,
O "M.
CJ OS
r— iQJtrC
1 Aniline I —

1TH A "2-1 i
32
Condensation
— ^


f\ 1 • '
P Ether-. 11 O
/^ *f t >O
49
Hydrogenation
'33 v
Salt formation 1

|I|H2S04
I35
|Su1fonat1on<

                                         It
                                           ling I
                                          Water)
Figure 2.  Benzene Section Process Flow  Sheet (Cont.)

-------
 I
4N
U)
                    IPropylene
                        (Heat;
                             Oxidation and 37
                              cleavage
                                                                                                   ^Cooling
                                                                                                   } Water
=H
H,PO. Alri
V A I
36 1 -
Alkylatlon
1 Heat
II J ^.
38 1
!0x1dat1on ' I
J.
                                                                                                 Malelci
                                                                                               i anhydride
^1
id ii i
v^y

in A n
.39
Hydrogenatlon ,


E
A
141
Hydrolysis

lenzene
|H|ea* 11,3-Butadlene
ibiels-Alder40
! Reaction'

Heatl
I '
T A V \ 'T' A
42
Hydration

(Isomerizatlon

                                         Figure 2.   Benzene  Section Process Flow Sheet  (Cont.)

-------
Heat
                           Cooling
                            Water
Cooling] \ /
Water — .-^
ni
1 Steami « Isteami
'Oxidation I 4S

Heat
Oxidation 46
i

Dehydration 47
0

                                                I \
                                                 Reductive
                                                 ami nation
                         Figure  2.   Benzene Section Process Flow Sheet  (Cont.)

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 1
                Ethylbenzene (from benzene and ethylene)
                                                  CH2CH3
1.  Function - Over 90% of ethylbenzene Is produced synthetically and



    10% is recovered by careful fractionation of selected gasoline fractions,



    or of the C0 cut of aromatic naphtha.
               o


         Two synthetic processes are used, one of which involves a low-



    pressure liquid-phase reaction using aluminum chloride catalyst while



    the other operates in the vapor phase at high pressure with various solid



    catalysts.



         The liquid-phase process is carried out in a brick-lined steel



    tower or a glass-lined reactor operating at the boiling point of the



    reaction mixture (80-100°C) at atmospheric pressure.  The benzene used



    is known as "Styrene grade," which defines a benzene with a boiling



    range of 1°C and a minimum freezing point of 4.85°C (this ordinarily



    corresponds to a purity slightly above 99%).  In general, ethylene at



    least 90% pure is used.  Aluminum chloride is added to a reactor feed



    stream as a solid and forms the complex in the reactor.  Benzene, both



    feed and recycle, enters the process through a benzene drying column.



    Hydrogen chloride in the form of HC1 or ethyl chloride is also added



    to the reactor.



         The liquid products from the alkylator are cooled and pass  through



    a settler where the complex is removed and returned to the alkylator.



    The alkylate is then washed with water  (which breaks  any  residual  complex)
                                6-45

-------
    and scrubbed with 20% caustic soda for netralization, after which it




    is separated into components in a series of distillation columns.




         A prime example of a vapor-phase reaction is the Alkar process




    which offers the advantage of less corrosion than the aluminum chloride




    process and which can operate on refinery gas streams containing 8-10%




    ethylene.  The temperature and pressure in this process are typically




    290-310°C and 6.3 MPa, respectively.  Fresh benzene is mixed with recycle




    benzene and ethylene and, after heating, is introduced into the fixed-




    bed alkylator.  The high-pressure effluent is then flashed and fed




    into the benzene recycle column where the benzene is recovered as




    overhead product.  The bottoms become the feed to the following column




    where the product ethylbenzene is separated from the (polyalkyl)




    benzenes.  Most of the (polyalkyl) benzenes are recycled to a separate




    deaklylator along with the necessary benzene for conversion back to




    ethylbenzene.  The dealkylator effluent is then combined with the




    alkylator effluent for flashing.  The improved catalyst for the




    alkylation is apparently a boron trifluoride-modified anhydrous




    y-alumina, BF_ being added also in the alkylator feed.  The dealkylator




    presumably uses the identical catalyst and operates under less severe




    conditions (202°C and 3.45 MPa).




2.  Input Materials




    Benzene - 775 kg/Mg (lb/1000 Ib) product




    Ethylene - 270 kg/Mg lb/1000 Ib) product
                               6-46

-------
3.  Operating Parameters

    Temperature:  80-100°C (176-212°F) (liquid phase)
                 290-310°C (554-59Q°F) (vapor-phase alkylator)
                     202°C (396°F) (vapor-phase dealkylator)

    Pressure:  atmospheric (liquid-phase)
               6.3 MPa (62.2 atm) (vapor-phase alkylator)
               3.55 MPa (35.0 atm) (vapor-phase dealkylator)

    Catalysts:  Aluminum chloride - HCl complex (liquid-phase)
                BF» on modified y-alumina support (vapor-phase)

4.  Utilities

    Steam - 37.5 kg/Mg (lb/1000 Ib) product

    Cooling water - 300 kg/Mg (lb/1000 Ib) product

    Electricity - 76 MJ/Mg (9-6 kWh/1000 Ib) product

    Fuel - 5.0 GH/Mg (2.160 MM Btu/1000 Ib) product

5.  Waste Streams

    Liquid-phase process:

    Scrubber effluent (water) - benzene:   11 kg/Mg (lb/1000 Ib)
                                Hydrogen chloride:  3.9 kg/Mg (lb/1000 Ib)

    Separator effluent (water) - aluminum salts:  trace
                                 tarry material:  26.6 kg/Mg (lb/1000 Ib)

    Vapor process:  The major waste streams of this process are the spent

    caustic and washing streams from the crude alkylate washing step.

    These streams will contain significant amounts of tars, benzene,

    ethylbenzene, and other polymers.  The heavy aromatics fractions from the

    separation column are usually disposed of by incineration.

          Flow    -  3.15 x 10~4 m3/kg (37.7 gal/103 Ibs)

          COD     -  5,980 mg/1
                     1.88 g/kg

          BOD,.    -  433 mg/1
                     0.136 g/kg

          TOG     -  2,091 mg/1
                     0.66 g/kg

                               6-47

-------
6.  EPA Source Classification Code  - None




7.  References




    Yen, Y.  C. , "Styrene,"  Report No.  33,  Stanford  Research  Institute,




    Menlo Park, California, October 1967.





    Gloyna,  E. G.,  and Ford, D.  L., "The Characteristics  and Pollutional




    Problems Associated with Petrochemical Wastes," for FWPCA,  Contract No.




    14-12-461, February 1970.





    Sittig,  M., Pollution Control in the Organic  Chemical Industry, Noyes




    Data Corp., Park Ridge, N.Y., 1974, p. 132,133.





    Kirk-Othmer, Encyclopedia of Chemical  Technology,  2nd Edition, Interscience




    Publishers, New York, N.Y.,  Vol. 19   (1969),  p.  57-62.





    Lowenheim, F. A., and Moran, M. K., Industrial  Chemicals, 4th Edition,




    John Wiley and  Sons, New York,  N.Y., 1975,  p. 365-367.





    Austin,  G. T.,  "The Industrially Significant  Organic  Chemicals -  Part 5,"




    "Chemical Engineering," April 29,  1974, p.  145.







   "1975 Petrochemical Handbook,"  Hydrocarbon Processing," November,




   1975, p.  129-140.
                               6-48

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  2




                     Acetophenone (from ethylbenzene)
1.  Function - Acetophenone is produced by the oxidation of ethylbenzene.




    The reaction is carried out in two acid proof, brick-lined reactors in




    series.  Ethylbenzene and manganese acetate catalyst (15% aqueous solu-




    tion) are fed into the top of the first reactor and air is dispersed




    into the liquid at the bottom.  Liquid from the bottom of the first




    reactor is pumped to the top of the second reactor and more air is




    added at the bottom.  The temperature is maintained at 126°C and the




    pressure at 308 kPa in both reactors.  Total contact time between the




    air and ethylbenzene is 1.5 hours.




         About 16% of the ethylbenzene is oxidized in the first reactor




    and an additional 10% in the second.  Eighty-eight percent of the




    ethylbenzene that reacts forms acetophenone (2 parts) and a-phenylethyl




    alcohol (1 part).




         The remainder is oxidized to acids (including benzoic acid) and




    residue.  The product is treated with 10% aqueous sodium hydroxide to




    extract acids and precipitate the manganese catalyst.  Distillation of




    the organic layer yields ethylbenzene, which is recycled, and a mixture




    of acetophenone (68%) and a-phenylethyl alcohol (_32%).  a-Phenyl-




    ethyl alcohol is dehydrogenated at 200°C in the presence of a catalyst




    with a stream of nitrogen flowing through the reactor to remove hydrogen.




    A mixture containing 80% acetophenone, 6% a-phenylethyl alcohol,  and
                               6-49

-------
    14% ethylbenzene is produced.  Purified acetophenone is obtained by


    distillation.  Purity control is achieved by controlling the freezing


    point of the distillate which is bulked to give a product with a minimum


    freezing point of 18.3°C.

2.  Input Materials

    Ethylbenzene - 1.176 Mg/Mg (1,176.5 lb/1000 lb) product


    Air - 455 kg/Mg (lb/1000 lb) product

    Nitrogen - Not given

    Sodium hydroxide - Not given

    Manganese acetate catalyst (15% aqueous solution) - Not given

3.  Operating Parameters

    Oxidation temperature - 126°C (259°F)

    Oxidation pressure - 308 kPa (3.04 atm)

    Dehydrogenation temperature - 200°C (392°F)

    Product freezing point - 18.3°C (64.9°F) (minimum)

    Catalyst - Manganese acetate (15% aqueous solution)

    Contact time - 1.5 hrs.

4-  Utilities - Basis - 0.454 kg (1 lb) of product

    Electricity - 144 kJ (0.04 kWh)

    Fuel gas - 9.06 dm3 (0.32 cubic feet)
                          q
    Cooling water - 102 dm  (27 gallons)


    Steam - 3.2 kg (7.0 lb)

    Compressed air - 404 dm  (14.3 cubic feet )
                               6-50

-------
5.  Waste Streams




    Air:  Excess air from the oxidation reactors and nitrogen from the




    dehydrogenator may be vented to the atmosphere and would contain




    ethylbenzene, acetophenone, and a-phenylethyl alcohol in unknown




    quantities.  Emission from distillation should be minimal.




    Water:  Still bottom residues, excess and sodium salts of by-product




    acids would be the major wastewater pollutants with possibly small




    quantities of ethylbenzene, acetophenone and a-phenylethyl alcohol




    included.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 1 (1963), p.  168.





    "Synthetic Organic Chemicals," U. S. Tariff Commission, TC Publication




    681, 1972.
                               6-51

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  3

                  Styrene (dehydrogenation of ethylbenzene)
                                     cat.
1.  Function - The present commercial process for styrene production

    involves the catalytic dehydrogenation of ethylbenzene.   Dehydrogena-

    tion of ethylbenzene is effected at 600-700°C and atmospheric pressure

    in the presence of catalysts, e.g., SiO?-Al_0«,  solid phosphoric acid,

    zinc oxide promoted with alumina and chromates,  and cobalt oxides.

    Yields of 90% are commonly attained, with conversions of 30-40% per

    pass.

         The styrene recovery section consists of three columns.   The

    small amount of benzene and toluene produced by  cracking is removed

    in the first column and returned to the ethylbenzene system.   Ethyl-

    benzene for recycle is separated from styrene in the second column,

    and polymerization inhibitors such as sulfur, para-tertiary butylcatechol

    or 2-nitro-4,6-dichlorophenol are added.  In the third column, styrene

    monomer is separated from small amounts of tar and polymer formed during

    the operation.

2.  Input Materials - Ethylbenzene - 1.12 kg/kg styrene

3.  Operating Parameters

    Temperature - 600-700°C (1112-1292°F)

    Pressure - 101 kPa (1 atm)

    Catalyst - Si02 - Al^, solid phosphoric acid,  ZnO promoted with alumina
               and chromates, cobalt oxides.
                               6-52

-------
0.94
(248)
27.2
(30)
0.17
(6)
0.64
(169)
90.7
(100)

1.58
(417)
117.9
(130)
0.17
(6)
4.  Utilities - Basis:  2.87 kg/sec (6.3 Ib/sec) capacity
                                   Dehydro-         Separ-
                                   genation         ation       Total
    S team
    kg/sec                           27.2            13.1        40.3
    (Ib/sec)                         (60)           (28.9)      (88.9)

    Cooling
    Water
    m-Vsec
    (gals/sec)

    Refrigeration
    Mg
    (tons)

    Natural Gas
    sm3/sec
    (scf/sec)

    Electric Power
    (kW capacity)
      Process                         108             160         268
      Utilities                       466             270         736
5.  Waste Streams - Separator (water)
                               &
    Heavy ends and tarry matter  - 0.393 kg/Mg (lb/1000 Ib)  styrene

    Super heater (water) tarry matter  and heavy ends  - 5.9 kg/Mg (lb/1000 Ib)
                                                         styrene
                                      &
    Still bottom (solids) tarry matter  and heavy ends - 7.05 kg/Mg (lb/1000 Ib)
                                                         styrene

                             Plant 1                      Plant 2

     Flow            0.0235 m3/kg (2,810 gal/       0.00548 m3/kg (657 gal/
                             103 Ibs)                      103 Ibs)

     COD                     219 mg/1                     426 mg/1
                             5.13 g/kg                    2.34 g/kg

     BOD                      69 mg/1                      70 mg/1
        5                    1.62 g/kg                    0,381 g/kg

     TOC                      22 mg/1                      22 mg/1
                             0.53 g/kg                    0.12 g/kg
     Contains sytrene trimer, stilbene, biphenylnaphthalene, phenathrene,
    ethylphenanthrene, and other unidentifiable products.

                              6-53

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6.  EPA Saurce Classification Code -  None




7.  References




    Austin,  G. T.,  "The Industrially  Significant  Organic  Chemicals  -




    Part 8," "Chemical Engineering,"  July  22,  1974, p-  113,114.





    "1973 Petrochemical Handbook," "Hydrocarbon Processing," November,  1973,




    p.  179,180.





    Kirk-Othmer,  Encyclopedia of Chemical  Technology, 2nd Edition,




    Interscience  Publishers,  New York, N.Y., Vol. 19  (1969), p.  63-67.





    Sittig,  M., Pollution Control in  the Organic  Chemical Industry, Noyes




    Data Corp., Park Ridge, N.J., 1974, p.  191-195.





    Lowenheim, F. A., and Moran, M. K., Industrial Chemicals,  4th Edition,




    John Wiley and  Sons, New  York, N.Y., 1975, p. 779-782.





    "1975 Petrochemical Handbook," "Hydrocarbon Processing," November,  1975,




    p.  204,205.
                               6-54

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  4

                               Chlorobenzene

                                                  .Cl
                                                      + HC1


^•'  Function - Chlorobenzene is manufactured by passing dry chlorine

    into benzene in the presence of a catalyst.  The catalysts which may

    be used are molybdenum chloride, FeCl,, A1C1-, Fuller's earth, or simply

    iron turnings.  The reaction takes place in a boiling mixture of chloro-

    benzene and benzene at 101 kilopascals (1 atmosphere) pressure and 80-100°C

    (175-212°F).  HC1 released by the reaction is scrubbed with recycled

    benzene to remove hydrocarbons and then absorbed with water to form

    20°Be hydrochloric acid.  The bottoms are washed with sodium hydroxide

    to remove remaining HC1 and dichlorobenzenes.  The sodium hydroxide

    solution is decanted and the product fed to a stripping column where

    benzene is stripped off overhead and recycled to the HC1 scrubber.

    The bottoms are fed to a fractionating column where the pure mono-

    chlorobenzene is taken off overhead.

2.  Input Materials - Basis - 1 metric ton Chlorobenzene

    Chlorine - 875 kg (1929 Ibs)

    Benzene - 950 kg (2094 Ibs)

    Sodium hydroxide

    Catalyst (Fe turnings) - small

3.  Operating Parameters

    Temperature - 80-100°C (175-212°F)

    Pressure - 101 kPa (1 atm)

    Catalyst - molybdenum chloride FeCl-, A1C1_, fuller's earth,  iron  turnings
                               6-55

-------
4.  Utilities




    Electric power - Not given




    Water - Not given




5.  Waste Streams - Main pollutant by-products  are:   HC1,  dichlorobenzene,




    heavies and spent caustic sludge.   The HC1  and dichlorobenzenes  are




    absorbed.  Benzene is also a major air pollutant.   Two sources are




    the vent on the HC1 absorber and on the stripper.




6.  EPA Source Classification Code - None




7.  References




    Sittig, M., Pollution Control in the Organic Chemical  Industry,  Noyes Data




    Corp., Park Ridge, N.J.,  1974, p.  103-104.





    Austin, G. T., "The Industrially Significant Organic Chemicals - Part 2,"




    "Chemical Engineering,"  February 18, 1974,  p.  128.





    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd  Edition, Inter-




    science Publishers, New  York, N.Y., Vol. 3  (1964) , p.  373.





    Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th Edition,




    John Wiley and Sons, New York, N.Y., 1975,  p.  258-260.
                               6-56

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 5


                        Dichlorobenzenes

                                     Cl              Cl

                   Cl      FeC13_  I^Sr01         I^Sl



                                                    Cl
 •'••  Function - Dichlorobenzenes can be produced by chlorinating chloro-


     benzene in the presence of ferric chloride at 150-190°C.  This re-


     action produces basically a mixture of o- and p-dichlorobenzenes


     with the latter predominating.  The ortho isomer can be removed from


     the crystalline para isomer by washing the crystals of the para


     isomer with methanol.  The p-dichlorobenzene is finally freed from


     alcohol by heating at 100°C under vacuum.  The meta isomer of d±+


     chlorobenzene does not occur in high enough quantities in the above


     reaction process to make it a practicable source of that isomer.


     Usually, m-dichlorobenzene is obtained from the ortho and paua


     isomer by subjecting these to an isomerizing process.  This iso-


     merizing process is to heat the mixture to 120°C under approximately

             3
     4.5 x 10  kilopascals in the presence of aluminum chloride and


     hydrogen chloride; aluminum chloride in a small amount of water;


     or aluminum chloride alone at higher temperature.


 2.  Input Materials


     Chlorobenzene


     Ferric chloride


     Chlorine


 3.  Operating Parameters


     Temperature:  150-190°C (302-374°F)


     Pressure:  not given
                                6-57

-------
4.  Utilities




    Not given



5.  Waste Streams - No specific information was available, but one




    would expect some hydrogen chloride to be given off and possibly




    some benzene, trichlorobenzene, and ionic salts.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y.,  Vol.  5 (1964)»  p. 259-260.






    Chemical Technology,  Barnes and Noble Books, New York, N.Y., Vol. 4




     (1972), p.  213.
                          6-58

-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO.  6
                              Trichlorobenzenes
                    Cl
1.  Function - The 1,2,3- and 1,2,4-isomers of trichlorobenzene can




    be obtained by chlorinating o-dichlorobenzene at 25-30°C,  in the




    presence of ferric chloride, to a density of 1.4 (at 15°C), neutralizing




    the acid present, and fractionally distilling.   Similarly,  by chlori-




    nating m-dichlorobenzene, 1,3,5 trichlorobenzene can be obtained.




2.  Input Materials




    Dichlorobenzenes




    Ferric chloride




    Chlorine gas




3.  Operating Parameters




    Temperature - 25-30°C  (77-86°F)




    Pressure - not given




    Catalyst - ferric chloride




4.  Utilities - Not given
                               6-59

-------
5.  Waste Streams - Waste water from distillation bottoms may contain




    traces of dichlorobenzenes and trichlorobenzenes,  as well as poly-




    chlorinated benzenes.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience Publishers,  New York, N.Y., Vol.  5  (1964)  p.  260-262.
                               6-60

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  7
                 Chloronitrobenzenes (from chlorobenzene)


                                        Cl               Cl

                       HN03
1.  Function- Chloronitrobenzenes can be manufactured by the nitration of



    chlorobenzene using a mixed acid of nitric acid and sulfuric acid.



    Since the chlorine is ortho-para directing the substitution into the



    ring with the nitric group is on the ortho (34%) and para (65%)



    positions.  Thus the product from this reaction is a mixture of ortho



    and para Chloronitrobenzenes.  The para isomer is separated by recrystal-



    lization.  The o-chloronitrobenzene is purified by rectification.


2.  Input Materials



    Chlorobenzene-  4536  kg (10,000  Ibs)



    Nitric acid (30-35%)

                           19,570 kg (21,100  Ibs)

    Sulfuric acid (52-55%)



3.  Operating Parameters



    Temperature - 40-70°C  (104-158°F)



    Pressure - not given



    Reaction time - 12 hrs.



4-  Utilities - Not given



5.  Waste Streams - Possible aromatic emissions from the distillation process;



    possible NO  emissions during nitration process and acid wastes.
               X


6.  EPA Source Classification Code - None
                              6-61

-------
7.   References




    Hedley,  W. H.,  et al. ,  Potential Pollutants  From Petrochemical Processes.




    Technomic Publishing Co.,  Westport,  Conn., 1975.





    Austin,  G. T.,  "The Industrially Significant Organic Chemicals - Part 3,"




    "Chemical Engineering," March 18, 1974,  p. 90.





    Chemical Technology, Barnes  and Noble  Books,  New York,  N.Y.,  Vol.  4




    (1972),  p. 552.





    Sittig,  M., Pollution Control in the Organic  Chemical Industry,  Noyes




    Data Corp., Park Ridge, N.J.,  1974,  p. 172,173.
                              6-62

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  8




                      Phenol (from chlorobenzene)
                                 NaOH
1.   Function - Phenol is formed from chlorobenzene by reacting the




     chlorobenzene with sodium hydroxide at elevated temperature and




     pressure.  In this process, chlorobenzene and a 10 - 15% aqueous




     sodium hydroxide solution are introduced into a high pressure pump




     with approximately 10% by weight of diphenyl oxide.  Small quantities




     of anti-corrosion agents, emulsifiers, and a catalyst may also be




     added to the reactants.  This process stream is fed to a continuous-




     flow tubular reactor system in which the stream temperature is raised




     to 400°C (752°F) approximately 27.6 x 103 - 34.5 x 103 kilopascals




     (4000 - 5000 psi) and maintained at this temperature and pressure for




     10 - 30 minutes.  The heat exchanger in which this reaction is carried




     out is a steel pipe, nickel-lined exchanger using flue gas, and organic




     heat transfer agent, direct flame, or electrical heating coils as a




     heat transfer medium.  After leaving the exchanger the product stream




     is cooled.  The reaction products, consisting of sodium phenate, sodium




     chloride, water, and unchanged reactants, produce a two phase system.




     The first phase is an aqueous phase containing sodium phenate, and




     the second phase is an oil phase consisting principally of diphenyl



     oxidate and unreacted monochlorobenzene.  The oil phase is distilled




     to produce diphenyl oxide or is recycled to the reactor.  The aqueous




     phase is treated with hydrochloric acid to convert sodium phenate  to




     phenol which is decanted and distilled under vacuum.  The sodium





                              6-63

-------
     chloride that is formed is electrolized to form sodium hydroxide




     and chlorine which is recycled.




2.    Input Materials




     Chlorobenzene - 1.27 kg (lb)/kg  (Ib)  phenol produced




     Aqueous sodium hydroxide - 0.12  kg/Mg (0.24 Ib/ton) phenol produced




     Diphenoloxide - 0.13 kg (lb)/kg  (Ib)  phenol produced




3.    Operating Parameters




     Temperature:  400°C (752°F)




     Pressure:  27.6 x 103 - 34.5 x 103 kilopascals (4000 - 5000 psi)




     Catalyst:  not given




4.    Utilities




     Electric power - not given




     Cooling water - 3.85 kg (lb)/kg  (Ib)  phenol produced




5.    Waste Streams




     Acid stream dichlorobenzene column (water):




     Chlorobenzene




     Dichlorobenzene




     Other chlorinated compounds (assumed to be mainly chlorotoluene) -




       4.0 kg/Mg (7.9 Ib/ton) phenol




     Ortho-dichlorobenzene column waste (solid):




     Ortho-dichlorobenzene - 0.6 kg/Mg (1.2 Ib/ton) phenol




     Other chlorinated compounds (chlorotoluene) - 1.2 kg/Mg  (2.4 Ib/ton)




       phenol




     Extractor brine (water):




     Phenol - 0.75 kg/Mg (1.5 Ib/ton) phenol




     Sodium chloride - 1.559 kg/Mg (3,118 Ib/ton) phenol




     Benzene - 12.2 kg/Mg (24.4 Ib/ton) phenol





                              6-64

-------
     Diphenyl ether column wastes (solid):




     Diphenyl ether - 0.665 kg/Mg (1.33 Ib/ton) phenol




     Phenyl diphenyl ether - 19.4 kg/Mg (38.7 Ib/ton) phenol




6.   EPA Source Classification Code - None




7.   References




     Yen, Y. C., "Phenol," Report No. 22, Stanford Research Institute,




     Menlo Park, California, 1967.






     Sittig, M., Pollution Control in the Organic Chemical Industry,




     Noyes Data Corporation, Park Ridge, N.J., 1974, p. 181.






     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 8," "Chemical Engineering," July 22, 1974, p. 107, 108.






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 15  (1968), p. 153-155.
                              6-65

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  9



                               Aniline
1.  Function - Aniline is produced by combining chlorobenzene, and



    liquid ammonia at high temperatures and high pressures in the



    presence of a catalyst.  The catalyst used is the cuprous chloride



    made from the reaction of the cuprous oxide and ammonium chloride.



    The reaction takes place at 200°C and 6.2 megapascals (900 psi).



2.  Input Materials - Basis - 1 metric ton aniline



    Chlorobenzene - 1250 kg (2,756 Ibs)



    Cuprous oxide - 175 kg (386 Ibs)



    Liquid ammonia - (28% solution) 3725 kg (8,212 Ibs)



    NH_:  C,H._C1 ratio should be at least 5:1
      3    65






3.  Operating Parameters



    Temperature:  180-220°C  (356-428°F)



    Pressure - 6.2 MPa (61.2 atm)



4.  Utilities



    Electric power - not given



    Water - not given



5.  Waste Streams



    Ammonia



    Benzene



    Phenol
                             6-66

-------
6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd  Edition,




    Interscience Publishers,  New York,  N.Y.,  Vol.  2  (1963), p.  419-





    Austin, G. T., "The Industrially Significant Organic Chemicals  - Part 1",




    "Chemical Engineering," January 21, 1974,  p.  132.





    Astle, M. J., Industrial Organic Nitrogen Compounds, Reinhold Publishing




    Corp., New York, N.Y., 1961, p. 87.





    Lowenheim, F. A. and Moran,  M.  K.,  Industrial Chemicals,  4th  Edition




    John Wiley and Sons, New York,  N.Y.,  1975,  p.  111,112.
                             6-67

-------
 INDUSTRIAL ORGANIC CHEMICALS
                                        PROCESS NO. 10
            Dichloronitrobenzenes  (from dichlorobenzenes)
                                               JO,,
                              HNO,
Cl
Cl
              Cl
1.  Function - The dichloronitrobenzenes (3,4-dichloro- and 2,5-dichloro-

    1-nitrobenzenes) are prepared commercially by nitrating their corres-

    sponding dichlorobenzenes.  In many cases two immiscible layers are

    present in the nitrator.  For safety reasons and ease of operation,

    atmospheric pressures and temperatures from 0-120°C are used.  At

    the higher temperatures, competing oxidation reactions becomes

    important.

2.  Input Materials

    Dichlorobenzenes

    Nitric acid

    Sulfuric acid

3.  Operating Parameters

    Temperature - 0-120°C  (32-248°F)

    Pressure - 101 kPa (1 atm)

    Residence Time - 1-60 minutes

4.  Utilities - Not given

5.  Waste Streams - Some chlorinated benzenes, chloronitro-phenols, nitric,

    and sulfuric acid may be present in the waste streams.
                              6-68

-------
6.   EPA Source Classification Code - None




7.   References




    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience Publishers, New York, N.Y.,  Vol.  13 (1967),  p.  785-790,




    244.
                              6-69

-------
INDUSTRIAL ORGANIC CHEMICALS                                 PROCESS NO.  11



                  Dichloroanilines(from dichloronitrobenzene)




                        I*                         1?2            C1

                 Cl CLv^i^x            iron       ^Wci   c1'
                  or   n   ;|           urn  ^    K  71    or
                                                                N^^^SXN

        Cl  "^          ""'   ""2               ^   ^            ^""^ ^o

1-   Function - 2,5- and 3,4- Dichloroanilines are produced by reducing




     the corresponding dichloronitrobenzenes.   This can be achieved in




     two ways:  1) by employing iron and HC1;  and 2)  by using hydrogen




     and a catalyst with some heating.



2.   Input Materials




     Dichloronitrobenzene




     Iron




     HC1




     Hydrogen




     Catalyst




3.   Operating Parameters




     Temperature:  not given




     Pressure:  not given




     Catalyst:  not given




4.   Utilities - not given




5.   Waste Streams - Waste acid and some iron sludge  should be present




     in the aqueous waste streams.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y.,  Vol. 2(1963)  p. 424.
                                6-70

-------
INDUSTRIAL ORGANIC CHECMICALS                                PROCESS NO. 12
                 N-Methyl Aniline (from aniline and methanol)
                 ,NH_
1.   Function - N-Methyl aniline is most economically produced by the
     vapor - phase reaction of aniline and methanol at 285-325°C over
     a catalyst containing 86% alumina, 9% calcium oxide (or ZnO,
     CrO, MgO, FeO, MnD), and 5% (2-20%) copper.

     Tertiary amine formation is suppressed by the use of hydrogen at 207
     414 kPa (2.04 - 4.09 atm).  Yields of 96-98% are obtained.
2.   Input Materials - Basis:  1 kg N-Methyl aniline
     Aniline        0.90 kg
     Methanol       0.46 kg
     Hydrogen       4.8 g
3.   Operating Parameters
     Temperature:  285-325°C (545-617°F)
     Pressure:  101 kPa (1 atm)
     Catalyst:  86% alumina, 9% CaO, 5% copper
4.   Utilities - not given
5.   Waste Streams - Off-gases from the separator may contain methanol,
     aniline, methyl aniline, and by-products such as N,N-dimethyl
     aniline.
6.   EPA Source Classification Code - 3-01-034-01
7.   References
     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
     Interscience Publishers, New York, N.Y., Vol. 2  (1963)  p.  368,420.

     U.S. Patent No. 2,580,284 (Dec. 25, 1951)
                                6-71

-------
 INDUSTRIAL ORGANIC  CHEMICALS                            PROCESS NO.  13
        N,N-Dimethylaniline  (from aniline and methanol)



                            H SO

          C,H,.NH0 + 2 CH-OH  ——	*- C,HCN(CH,)0 +  2 H.O
           O  J   /        J              DJJi       /
 1.    Function  - Dimethylaniline is produced by heating  aniline  and methanol



      under  pressure  in an autoclave with an acid catalyst,  commonly hydro-



      chloric or sulfuric acid.  Sulfuric acid is used commercially since



      it  is  less corrosive than hydrochloric acid.  The  aniline, methanol,



      and sulfuric acid are mixed together, stirred (to  suspend  the aniline



      sulfate which precipitates out), and pumped into an unlined  steel



      autoclave.  The autoclave is heated (93.3-121.1°C  superheat  given



      to  steam  at 689.5 kPa) during the course of two hours  to around 200°C



      and kept  there  for five or six hours, during which time the  internal



      pressure  may rise to 3,620-3,792 kPa.  The autoclave may be  allowed



      to  cool or the  hot mixture may be discharged through a cooling con-



      denser into a vessel where the acid is neutralized with caustic soda.



      Vacuum distillation allows the recovery of excess  methanol and puri-



      fication  of the dimethylaniline produced.



2.    Input Materials - Basis - 1 metric ton product



     Aniline, kg                  1052.6



     Methanol,  kg                 1158.1



     Sulfuric acid (66° Be)  kg    105.5



3.   Operating Parameters



     Temperature,  °C               200         (392°F)



     Pressure,  kPa               3,620-3,792   (35.7-37.4 atm)


     Reaction time,  hrs              5-5



     Reaction Vessel:  unlined steel autoclave





                             6-72

-------
4.   Utilities




     Not given




5.   Waste Streams - Specific information was not available, but




     some aniline, monomethylaniline, and sulfate salts may be in the




     waste water.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 2 (1963), p. 420.






     Groggins, P. H., Unit Processes in Organic Synthesis, 5th Ed.,




     McGraw-Hill Book Co., New York, N.Y.,  1958  , p. 850, 851.






     Shreve, R.N., Chemical Process Industries, 3rd Ed., McGraw-Hill




     Book Co., New York, N.Y.,  1967 , p. 821, 822.






     Chemical Technology. Barnes and Noble Books, New York, N.Y., Vol. 4




      (1972), p.  275.
                              6-73

-------
INDUSTRIAL ORGANIC CHEMICALS                                 PROCESS NO.




               N-Methyl Aniline (from aniline and methyl iodide)




                   JSH,
                      2+
!•   Function - An alternate route to N-methyl aniline involves the




     reaction of aniline and methyl iodide at elevated temperatures.




     This results in a mixture of N-methyl aniline and N,N-dimethyl




     aniline, which may be separated by a series of distillations.




2.   Input Materials




     Aniline




     Methyl iodide




3.   Operating Parameters - Not given




4.   Utilities - Not given




5.   Waste Streams - The water effluent from the acid scrubber probably




     contains sodium iodide, caustic, methyl iodide, aniline, and




     traces of the secondary and tertiary amines.  Methyl iodide and




     hydrogen iodide may be present in the gas effluent.




6.   EPA Source Classification Code - 3-01-034-01




7.   References




     Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience  Publishers,  New York, N.Y., Vol. 2 (1963)  p. 420.
                                6-74

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INDUSTRIAL ORGANIC CHEMISTRY                          PROCESS NO.  15
                           p-Benzoquinone
                                  OX
                                          0
1.  Function - p-Benzoquinone is manufactured by the oxidation of
    aniline as the sulfate salt with sodium dichromate or manganese
    dioxide mixed with sulfuric acid.  Dilute sulfuric acid and
    approximately 25% of the total MnO_ is charged to the oxidizing
    tank.  This mix is cooled to 5-12°C, then a solution of the aniline
    and sulfuric acid is added to the tank.  The remainder of the Mn02
    is added so that there is always an excess of Mh02 in the tank.  Cooling
    is a critical factor since this reaction is very exothermic.   A
    variation of this process operates at 20-70°C and continuously at
    reduced pressure.  After completion of the reaction the acidity is
    reduced by addition of a hydrated lime slurry and the p-benzoquinone
    is distilled with steam.  The distillate is then chilled to form golden-
    yellow needles of a 99-100% purity product.
         The non-volatile mineral salts are used as a source of manganese
    in fertilizer and animal feed supplements.
         Often a marked increase in yield results if the substance contains
    an additional hydroxyl or amino group in the para position.
2.  Input Materials - Basis:    1 kg p-Benzoquinone produced
    Aniline - 0.85 kg
    Mn02 - 2.42 kg
    H2S04 - 4.19 kg
    Water - 14.65 kg

                             6-75

-------
3.  Operating Parameters




    Temperature:   5-12°C (41-54°?)  initial or 20-70°F (68-158°F) in modified case




    Pressure:  not given




    Catalyst:  none




4.  Utilities




    Not given




5.  Waste Streams - ammonia from distillation




6.  EPA Source Classification Code  - None




7.  References




    Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Ed., Interscience




    Publishers, New York,  N.Y.,  Vol.  2 (1963),  p.  415.





    Ibid, Vol. 16 (1967),  p.  907.





    Chemical Technology-. Barnes  and Noble, New York, N.Y., Vol. 4




    (1972),  p. 402,405.





    Carson,  J., Organic Reactions,  John Wiley & Sons, New York, N.Y.,



    Vol.  4 (1949), p.  306
                            6-76

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 16
                             Hydroquinone
                          0                   OH
                                  Fe
                          0                   OH
1.   Function - Hydroquinone is manufactured by reducing p-benzoquinone.
     This is done with the quinone in solution with iron dust and water
     at 60 - 76°C (140 - 149°F) and a slightly reduced pressure.  The
     reaction mixture is filtered to remove iron oxide, and excess iron
     and the filtrate passed to crystallizers.  In some processes the pure-
     white technical product obtained is purified by vacuum distillation.
     The distilled product is then dissolved in dilute sulfuric acid bath with
     the use of carbon, sodium bisulfite, or zinc dust as decolorizing
     agents.  The solution is then filtered and a small amount of sodium
     hydrosulfite is added to the filtrate from which the hydroquinone
     crystallizes.
2.   Input Materials - per kg (Ib) hydroquinone produced
     p-Benzoquinone - 1.25 kg (Ib)
     Iron dust - 12.5 kg (Ib)
     Water - 100 kg (Ib)
3.   Operating Parameters
     Temperature:  60 - 65°C (140 - 149°F)
     Pressure:  slightly reduced
     Catalyst:  none
4.   Utilities
     Electric power - not given
     Water - not given

                              6-77

-------
5.   Waste Streams - possible sludge handling problems, starting material,




     and phenolic resins.




6.   EPA Source Classification Code - Code




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers, New York,  N.Y.,  Vol.  11 (1966),  p. 485-487.
                             6-78

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INDUSTRIAL ORGANIC CREMICALS                          PROCESS NO.  17




                                Acetanilide
                         NH2 + CH3C02H  	»    ^£^,NHCCH,, + H^O
^'  Function - Acetanilide can be manufactured in two major ways.  The




    first uses a benzene solution of aniline and acetic acid and acetyl




    chloride.  This solution is refluxed in a jacketed, enameled still until




    no free aniline remains.  The reaction mixture is filtered and the




    crystals separating on cooling are recrystallized from hot water.




         The second process employs aniline and approximately 100% molar




    excess of acetic acid.  This solution is refluxed for 6 to 14 hours in




    a suitable still.  The product is dropped into hot water and allowed




    to crystallize.  If the acid is dilute the reaction is carried out




    under pressure at 150-160°C (302-320°F).




2.  Input Materials




    Process one




       Aniline - 0.69 kg (lb)/kg (Ib) acetanilide




       Acetic acid - 0.97 kg (Ib)/kg (Ib) acetanilide




       Benzene - as needed




    Process two




       Aniline - 0.69 kg (lb)/kg (Ib) acetanilide




       Acetic acid - 0.76 kg (lb)/kg (Ib) acetanilide
                               6-79

-------
3.  Operating Parameters




    Temperature - 150-160QC (302-320°F)




    Pressure - Not given




    Catalyst - None




    Reaction time - 6-14 hrs




4.  Utilities




    Electric power - Not given




    Water - Not given




5.  Waste Streams - Benzene from refluxing operations and some acetic acid.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-




    science Publishers,  New York,  N.Y.,  Vol.  1 (1963),  p. 151.





    Chemical Technology, Barnes  and Noble Books,  New York, N.Y.,  Vol. 4




    (1972), p. 526.





    Faith, W. L., et al., Industrial Chemicals,  3rd Edition, John Wiley




    and Sons, New York,  N.Y., 1965, p.  9,10.
                               6-80

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INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 18
               NHCOCH,
                      Chloroanilines (from acetanilide)
                            CL.
                                             NHCOCH
                          CH3COOH
                                             31                     "Cl




1.  Function - Acetanilide is mixed with acetic acid and chlorine gas to




    produce a mixture of o- and p-chloroacetanilides.  This mixture is then




    combined with water and acid to produce a mixture of o- and p-chloro-




    anilines.  The mixture can then be separated by steam distillation.




         The production of m-chloroaniline is by the reduction of m-nitro-




    chlorobenzene or by treating aniline in concentrated sulfuric acid




    with chlorine gas.




2.  Input Materials




    Acetanilide




    Acetic acid




    Chlorine




    Water




3.  Operating Parameters




    Temperature - not given




    Pressure - not given




    Catalyst - none




4.  Utilities - not given
                               6-81

-------
5.  Waste Streams - Possible chlorine gas from incomplete reaction in




    initial step and some acetic acid.




6.  EPA Source Classification Code - None




7.  References




    Astle, M. J., Industrial Organic Nitrogen Compounds,  Rheinhold




    Publishing Co., New York, N.Y., 1961, p.  109-





    Migradichian, V., Organic Synthesis,  Rheinhold Publishing Co.,




    New York, N.Y., Vol. 2 (1957), p. 1555.
                               6-82

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INDUSTRIAL ORGANIC CHEMICALS                                 PROCESS NO. 19



                         2,4,6-Trichloroaniline

                                            NH2

                                       n  .>O
                           HC1
                           solvent


                                             Cl
1.   Function - 2,4,6-Trichloroaniline can be manufactured by the



     direct chlorination of aniline according to the above reaction.



     In this reaction anhydrous hydrochloric acid in an anhydrous



     organic solvent is mixed with aniline to produce the 2,4,6-



     trichloroaniline, which is diluted with water, separated, and



     dried at 60°C/2.66 kPa.



2«   Input Materials



     Aniline                     400 parts



     Hydrochloric acid           157 parts



     Solvent



          CCl,                  4000 parts



          EtOH                    80 parts



     C12                        1060 parts



3.   Operating Parameters



     Temperature:  16°C (60.8°F)



     Pressure:  not given



     Catalyst:  none



     Reaction Time:  6 hours



4.   Utilities - Not given



5.   Waste Streams - Aniline, CCl,, EtOH, Cl , and HC1 traces should be



     present in the waste streams.



6.   EPA Source Classification Code - None
                                6-83

-------
7.    Reference




     Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers,  New York,  N.Y.,  Vol.  2 (1963),  p.  415.






     U.S.  Patent 2,675,409 (Apr.  12,  1954).
                                6-84

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  20
                      Cyclbhexylamirie (from aniline)
                      NH.
1.  Function - Cyclohexylamina is produced commercially by reducing
    aniline with hydrogen and a ruthenium or a Raney nickel catalyst.  The
    reduction employing the ruthenium catalyst takes place at approximately
    220°C and up to 3.45 - 6.90 MPa.  As of 1964, only one U. S. plant
    (Abbott) produced cyclohexylamine by this process, but it accounted
    for 28% of the total U. S. production.
2.  Input Materials
    Aniline
    Hydrogen
    Catalyst
3.  Operating Parameters
    Temperature - 220°C  (428°F)
    Pressure - 3.45-9.60 MPa  (34-94.7 atm)
    Catalyst - Raney nickel or ruthenium compound
4.  Utilities - Not given
5.  Waste Streams - Possibly excess hydrogen and some aromatics may be
    given off by the process.
6.  EPA Source Classification Code - None
                               6-85

-------
7.   References




    Astle,  M.  J.,  Industrial Organic Nitrogen Compounds, Rheinhold




    Publishing Co.,  New York, N.Y., 1961, p. 31.





    Chemical Technology,  Barnes and Noble,  New York,  N.Y.,  Vol.  4,  (1972),




    p. 514.





    Hahn, A.  V., The Petrochemical Industry;  Markets and Economics, McGraw-




    Hill Publishing  Co.,  New York, N.Y., 1970, p. 431, 432.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers,  New York, N.Y., Vol. 2 (1963), p. 125.
                              6-86

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  21
                        Benzenesulfonic Acid

                                                 H2°
1.  Function - Three basic methods have been used to produce benzene-




    sulfonic acid:  sulfuric acid, oleum, and sulfur trioxide.  Sulfur




    trioxide is considered to be the effective sulfonating agent regard-




    less of the sulfur reactant used.




    Sulfonation with sulfuric acid




    a) Batch process - Benzene and sulfuric acid monohydrate are added to




    a sulfonator with agitation over a one hour period at an initial




    temperature of 75°C.  The mixture is then heated to 105° for an hour




    and then held there for four hours.




    b) Continuous process - Sulfuric acid is fed continuously to the sulfo-




    nator concomitantly with benzene which has been previously fed through




    a vaporizer-superheater.  The reaction mass flows to the top of a




    plate column which acts as a second sulfonator.  This stream passes




    downward countercurrent to another stream of benzene vapor.  A seven-




    stage reactor operating at 180°C and a molar ratio of benzene to




    sulfuric acid of 10:1, has a residence time of 1.5 hr.  The benzene-




    sulfonic acid is discharge from the bottom of the tower while the




    benzene vapor and water are released at the top and collected in a




    condenser.  The benzene is separated, dried, and reused.




    Sulfonation with oleum




    Liquid benzene is charged to a presulfonator and 9.5% oleum is fed




    in over a period of time, the temperature being controlled by the rate of




                             6-87

-------
    addition of oleum.  The reaction mass is then pumped to the vapor-




    feed sulfonators and raised to reaction temperature, ~100°C.




    Benzene vapor is fed in until the desired residual-acid level is




    attained.  The reaction mass flows from the bottom of the reactor to




    storage.  The excess benzene and water of reaction is scrubbed with




    caustic to remove acids and is then condensed; the benzene is dried




    and returned to the process.




    Sulfonation with sulfur trioxide




    Benzene is allowed to react with sulfur trioxide in liquid sulfur




    dioxide at -90°C.  The liquid sulfur dioxide is evaporated until a




    temperature of 10-20°C is attained at which point benzene is added




    and the temperature is allowed to rise to 50-70°C.  The sulfur dioxide




    is removed by an air stream.




         In each process the benzenesulfonic acid can be crystallized




    from the sulfonation mass by cooling to -10°C (13°F) to give a low




    recovery of solid sulfonic acid.




2.  Input Materials




    Sulfonation with sulfuric acid




    a) Batch process:  benzene - 0.49 kg/kg product




                       H SO, - 1.24 kg/kg product




    b) Continuous process - benzene - 4.94 kg/kg product




                            sulfuric acid - 0.62 kg/kg product




    Sulfonation with oleum




    Benzene




    Oleum
                               6-88

-------
    Sulfonation with sulfur trioxide




    Benzene - 0.49 kg/kg product




    Sulfur trioxide - 0.62 kg/kg product




    Liquid sulfur dioxide




    Sulfur trioxide:  sulfur dioxide =1.8




3.  Operating Parameters




    Sulfonation with sulfuric acid




    a) Batch process - temperature - 65-105°C  (149-221°F)




                       pressure - not given




    b) Continuous process - temperature - 180°C  (356  F)




                            pressure - not given




    Sulfonation with oleum




                    temperature - ~100°C  (~212°F)   ,




                    pressure - not given




    Sulfonation with sulfur trioxide




    Temperature:  Stage 1 - 9°C  (48°F)




                  Stage 2 - 10-20°C  (50-68°F)




                  Stage 3 - 50-70°C (122-158°F)




    Pressure:  not  given




    Purification '




    Temperature - -10°C (14°F)




4.  Utilities




    Not given



5.  Waste  Streams - possible benzene vapors  from leaks  in  system;  diphenyl




    sulfone; HSO,.
                              6-89

-------
6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd  Edition,




    Interscience  Publishers,  New York, N.Y.,  Vol.  3  (1963),  p.  403,404.





    U.  S.  Patent  2,125,189 (July 26, 1938).





    U.  S.  Patent  2,798,089 (July 2,  1957).
                               6-90

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  22




                       Benzenedisulfonic Acids
                          +  oleum
1.  Function - The meta isomer of benzenedisulfonic acid is produced from




    the benzenesulfonic acid by direct sulfonation.  In this process the




    monosulfonic acid is reacted with 65% oleum at 30-85°C for 6.5-7.5 hr.




    The para isomer cannot be produced by direct sulfonation.  However,




    it is produced from the disodium salt of m-benzenedisulfonic acid by




    heating at 300°C under pressure, with a metal catalyst.




2.  Input Materials




    m-Benzenedisulfonic acid




    Benzenesulfonic acid




    65% oleum




    p-Benzenedisulfonic acid




    m-Benzenedisulfonic acid disodium salt




    Catalyst




3.  Operating Parameters




    Benzenedisulfonic acid:  temperature - 30-85°C  (86-185°F)




                             pressure - not given




    p-Benzenedisulfonic acid - temperature - 250-600°C  (482-1112°F)




                               pressure - 405 kPa (4 atm)




                               catalyst - heavy metal (Hg, Ca)




4.  Utilities




    Not given
                             6-91

-------
5.  Waste Streams - none identified but suspect  SO,,  S0?, benzene vapors.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers,  New York,  N.Y., Vol. 3 (1964), p. 406.





    Gilbert, E.  E., Sulfonation and Related Reactions,  Interscience Publishers,




    New York, N.Y., 1965,  p.  69-





    Groggins, P., Unit Processes in Organic Synthesis,  5th Ed., McGraw-Hill




    Book Co., Inc., New York, N.Y.,  1958,  p. 312.





    British Patent 834,251 (May 4, 1960).
                            6-92

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INDUSTRIAL ORGANIC CHEMICALS                                 PROCESS NO. 23


                                  Resorcinol

                  SO,Na                        OH

                                1. NaOH/A
                         SO-Na	
                           J    2. Acid



1.   Function - Resorcinol can be made from m-benzenedisulfonic acid.


     The final sulfonation mixture from the manufacture of m-benzenedisulfonic


     acid is treated with 0.9 equivalents of a solution of sodium sulfite


     under agitation.  The mixture is sent to another vessel containing


     a suspension of excess calcium carbonate in water, and the mixture


     is filtered.  The filtrate, containing sodium sulfonate and calcium


     sulfonate,  is treated with 0.1 equivalent of sodium carbonate.  After


     the calcium carbonate precipitate is removed on another filter, the


     sodium m-benzenedisulfonate is obtained as a 20% solution.  A steam


     heated drum dryer then concentrates the solution to 50%.






     This dry salt is mixed by stirring with flaked caustic soda and


     fused at 360°C (679°F) in a gas-heated, sealed, cast-iron vessel.


     After cooling the mass is taken up in water.  The solid sulfite is


     separated by filtration and the filtrate is acidified with hydro-


     chloric acid.  The free resorcinol is then extracted with diethyl


     ether in a continuous extractor.


2.   Input Materials


     m-Benzenedisulfonic acid - 2.17 kg (lb)/kg (Ib) product


     Sodium sulfite


     Calcium carbonate


     Water


     Sodium carbonate


     Caustic soda - 3.6 kg (lb)/kg (Ib) product


                               6-93

-------
     Hydrochloric acid



     Diethyl ether



3.    Operating Parameter



     Temperature:  360°C (679°F)



     Pressure:  not given



4-    Utilities - Not given



5.    Waste Streams - Various salts should be present in the sludge



     and SO  should be emitted to the air.
           x


6.    EPA Source Classification Code - None



7.    Reference



     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-



     science Publishers, New York, N.Y., Vol. 11 (1966)  p. 475.
                                6-94

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  24



                         Fumaric Acid (from benzene)
                                   CHCOOH       HOOCH

                                          	,11
                                    HCOOH         HCCOOH
1-  Function - Fumaric acid is manufactured from maleic acid and by direct



    oxidation of benzene without isolating the maleic acid formed.   Air



    and benzene are mixed and passed into a converter where oxidation takes



    place in the presence of V~0, + PO^S proprietary catalyst.   The temperature



    of the reaction is kept near 400-450°C by heat-transfer coolants.



         When fumaric acid is the desired product .the effluent  gases from



    the converter may be scrubbed with hydrochloric acid to effect  the



    isomerization.  Ammonium persulfate - ammonium bromide mixtures and



    10-20% HC1 may also be used to catalyze the isomerization of maleic



    acid to fumaric acid.



         The fumaric acid precipitates from the aqueous medium  and  may



    be purified by recrystallization or sublimation.



2.  Input Materials



    Benzene - 0.71 kg/kg product



    Air



3.  Operating Parameters - Converter:



    Temperature - 400-450°C (752-842°F)



    Pressure - 101-446 kPa (1.0-4.4 atm)



    Isomerization:



    Temperature - ~100°C (212°F)



    Pressure -  101 kPa (1 atm)



    Catalyst - HC1


                               6-95

-------
4.  Utilities - Not given




5.  Waste Streams - Waste water may contain unreacted maleic acid and




    dilute hydrochloric acid, and fumaric acid not recovered by crystallization.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 12 (1967), p. 819-829.





    A. L. Waddams, Chemicals From Petroleum, 3rd Ed., John Wiley & Sons, 1973,




    p. 224-225.
                                6-96

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INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO.  25



                          Nitrobenzene





                                                      2





1.   Function - The usual method for the commercial manufacture of



     nitrobenzene is the direct nitration of benzene using mixed



     sulfuric and nitric acids.  The reaction vessels are specially



     built cast-iron or steel kettles fitted with efficient agitators.



     The kettles are jacketed and generally contain internal cooling



     coils for proper temperature control of the strongly exothermic



     reaction.  The batch equipment is normally sized for 454-680 kg



     quantities of benzene and operates on a time cycle of 2-4 hr.

                                                       v

          In the typical batch process, the nitrator is charged with



     benzene and a heel of spent acid and the mixed acid (53-60%



     H SO,, 32-39% HNO  and 8% H,0) is added slowly below the surface
      £-  "t            J         £*


     of the benzene.  Although the ratio of reactants is expressed in



     different ways from plant to plant, using this concentration of



     mixed acid the weight ratio of mixed acid to benzene is usually



     2.5:1.  The temperature of the reaction is maintained at 50-55° C



     by adjusting the rate of feed of mixed acid, the rate of heat



     exchange, and the agitation of the mixture, and it is usually



     raised to 90° C toward the end of the nitration to promote comple-



     tion.  The reaction mixture is then run into a separator where



     the spend acid settles out and is drawn off from the bottom  of  the



     unit.  This spent acid is recovered or used as cycle acid  to start



     subsequent runs after steam stripping to remove starting material.



     The crude nitrobenzene is drawn off the top of the  separator and
                            6-97

-------
     can be used directly in the manufacture of aniline.   If pure nitro-




     benzene is required, the product is washed with water and dilute




     sodium carbonate and then distilled.




          Newer plants use a continuous process, as typified by the




     Biazzi process, for the production of nitrobenzene.   The sequence




     of operations is essentially the same as in the batch process




     but the main differences are the use of smaller reaction vessels,




     lower nitric acid concentrations, and higher reaction rates.  A




     typical 114 £ continuous nitrator has a production capacity




     equal to a 568 i batch nitrator.  Mixed acid of low nitric acid




     concentration and benzene sufficient to react with all of the




     nitric acid are mixed in the small stainless-steel nitrator




     fitted with a high-speed (600 rpm) agitator and a helical cool-




     ing coil.  The reaction time is 15-20 min due to the rapid, effi-




     cient agitation.  The reaction mixture is then drawn off from the




     side of the nitrator and allowed to separate for 10-20 min in a




     decanter.  The washings are carried out in small vessels similar




     to the nitrator using high-speed mechanical agitation and are




     normally complete in 10 min.




2.   Input Materials - Basis - 1 Mg Nitrobenzene




          Benzene - 650 kg




          Sulfuric Acid - 721 kg




          Nitric Acid - 530 kg




          Water - 109 kg




          Sodium Carbonate - 10 kg
                            6-98

-------
3.   Operating Parameters



     Temperature:        45 to 95° C  (113-203°F)



     Pressure:           101 kPa (1 atm)



     Reaction time:      2-4 hrs.



4.   Utilities



     Cooling Water - quantity not given



     Steam - quantitiy not given



     Electricity - quantity not given



5.   Waste Streams



     Reaction section - absorber vent (air)



          Benzene -8.2 g/kg nitrobenzene



          NO  - 0.09 g/kg nitrobenzene
            X


          Nitrobenzene - nil



     Acid concentration section - absorber vent (air)



          NO  - 0.16 g/kg nitrobenzene
            X


     Major wastewater streams would come from the nitrobenzene



     purification section for washing crude nitrobenzene and would



     contain benzene and nitrobenzene.



6.   EPA Source Classification Code - None



7.   References



     Anon., "Air Pollution From Nitration Processes," prepared for



     Office of Air Programs, Environmental Protection Agency,



     Contract No. CPA 70-1, March 1972.





     Austin,  G.  T,,  "The Industrially Significant Organic Chemicals -



     Part 7," "Chemical Engineering," June 24, 1974, p. 154,  155.




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd  Edition,



     Interscience Publishers, New York, N.Y., Vol.  13  (1967),  p.  836,  837,



     838.


                            6-99

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  26



                               Dinitrobenzene







                           HN03




i.  Function - Dinitrobenzene is produced by nitrating nitrobenzene



    with a hot mixture of sulfuric and nitric acids.   The process is



    essentially identical with the process for nitrobenzene (Process



    No.  25) except that the temperature is higher (140-180°C).   The



    product is purified by recrystallization.



2.  Input Materials



    Nitrobenzene - 830 kg/Mg dinitrobenzene



    Sulfuric acid - 720 kg/Mg dinitrobenzene



    Nitric acid - 530 kg/Mg dinitrobenzene



3.  Operating Parameters



    Temperature - 90-100°C (194-212°F)



    Pressure - 101 kPa (1 atm)



4.  Utilities



    Steam - quantities are not given



    Cooling water - quantities are not given



    Electricity - quantities are not given



5.  Waste Streams - Small quantities of NO  would be expected to be
              ^ J"r ~:                         X


    released to the air from reactor vents probably no more than 0.1



    kg/Mg dinitrobenzene.  Wastewater streams may be released from



    the purification step and may contain some spent acids, traces of



    mono-and dinitrobenzene, and some caustic soda used in the neutrali-



    zation step.
                               6-100

-------
6.   EPA Source Classification Code - None




7.   References




    Groggins, P., Unit Processes in Organic Synthesis,  5th Edition,




    McGraw-Hill Book Co., New York, N.Y., 1958,  p.  113-115.





    Chemical Technology, Barnes and Noble Books, New York, N.Y.,  Vol.  4




    (1972), p. 551.
                                6-101

-------
INDUSTRIAL ORGANIC CHEMICALS                                 PROCESS NO.  27




                              m-Phenylenediamine
                               cat.



1.   Function - m-Phenylanediamine is produced by the catalytic




     reduction of m-dinitrobenzene with iron and HC1 as in the case




     of p-phenylenediamine (Process No. 30).




2.   Input Materials




     m-Dinitrobenzene




     Iron




     HC1




3.   Operating Parameters - not given




4.   Utilities - not given




5.   Waste Streams - No specific information was available, but iron,




     iron sulfides, ammonia, and ammonium polysulfides should be




     present in the waste streams.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y. Vol. II (1963)  p. 90.






     Ibid,  Vol. 15 (1968)  p. 216, 217.
                                6-102

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INDUSTRIAL ORGANIC CHEMICALS                             PROCESS NO. 28
                             o-Phenylenediamine
1*   Function - o-Phenylenediamine is produced by the action of ammonia on




     o-dichlorobenzene.  The product is made in an agitated, induction heated,




     high pressure autoclave with 316 stainless steel lining and is




     purified by vacuum distillation.




2.   Input Materials





     o-Dichlorobenzene




     Ammonia




     Catalyst (Cu )





3.   Operating Parameters





     Temperature    1st Stage      180-190°C (356-374°F)




                    2nd Stage      200-210°C (392-410°F)




     Pressure:      Not given




     Reaction time:  24 hrs





4.   Utilities




     Not given




5.   Waste Streams - Ammonia, hydrochloric acid, and copper chlorides should




     be present in the waste streams.




6.   EPA Source Slassification Code




     None
                                6-103

-------
7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Ed.,  Inter-




     science Publishers,  New York, N.Y.,  Vol.  2 (1963), p. 361.
                                6-104

-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 29
     o- and p-Nitroanilines (from o- and p-chloronitrobenzenes)
                                NH,
1.   Function   o- and p-Nitroanilines are prepared commercially by
     ammonolysis of the appropriate chloronitrobenzene isomer.  The
     process may be either batch or continuous.
          The batch process will be described for the p-chloronitroben-
     zene but is identical for the o-isomer.  Mixed isomers may be used
     since the physical properties of the isomers are sufficiently
     different so as to make separation of the o- and p-nitroanilines
     by either vacuum distillation or fractional crystallization entirely
     feasible.
          In the batch method 1.892 m  (500 gal) jacketed autoclaves are
     used.  Molten p-chloronitrobenzene (227 kg; 500 Ibs) is added to
     1180.9 kg (2600 Ibs) of 26°B6 (28%) ammonia and heated over a 3 hr
     period to 175°C at a pressure of 3.65-4.00 MPa (530-580 psi).  These
     conditions are maintained for 16 hrs and then excess ammonia is vented
     to an absorption system until the autoclave pressure reaches 1.38 MPa
     (200 psi).  The charge is transferred to an ammonia still and then
     to wooden crystallizing tubs, where it cools and is then centrifuged.
     Operating yields of 95% are obtained and ammonia losses amount to
     only about 6%.
          In the continuous process, preheated aqueous ammonia is forced
     through an inlet pipe to the bottom of a vertical reaction  column
                              6-105

-------
     filled with p-chloronitrobenzene.  The ammonia passes upward through

     an annular space and overflows through a central outlet pipe leading

     to an ammonia still.  The product is drawn off and crystallized as in

     the batch process.

2.   Input Materials

                                       Batch                  Continuous
          Chloronitrobenzene:      227 kg (500 Ibs)         150-200 parts

          Ammonia (26° B6):        1180.4 kg (2600 Ibs)     900 parts

3.   Operating Parameters

                                       Batch                  Continuous
          Temperature:             175°C (347°F)            225°C (437°F)

          Pressure:                3.65-4.00 MPa            8.27 MPa (81.6 atm)

4.   Utilities - Not given

5.   Waste Streams - Chlorinated nitrobenzenes and nitrophenols may be

     present in the sludge and some ammonia is lost to the air.

6.   EPA Source Classification Code - None

7.   References

     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

     Interscience Publishers, New York, N.Y., Vol. 2 (1963), p. 352-353.
                              6-106

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  30
                         p-Phenylenediamine
1.   Function - p-Phenylenediamine is produced by the catalytic reduction




     of p-nitroaniline with iron/HCl, iron/ammonium polysulfide/hydrogen,




     or iron/ferrous chloride.




          A large wood vat is used in the process.  Sufficient water is




     introduced to cover the agitator paddles (which operate at 40 rpm)




     and 453.6 kg (1000 Ibs) iron borings are introduced.  Then 45.4 kg




     (100 Ibs) of 20° Be HC1 is added, agitated and heated until a good




     paste of FeCl2 is produced.  340.2 kg (750 Ibs) of p-nitroaniline is




     introduced and 226.8 kg (500 Ibs) fine iron is added.




          Just prior to filtration, the batch is made alkaline with soda




     ash, then sodium bisulfite/sodium sulfide are added to precipitate




     soluble iron salts and prevent subsequent oxidation.  The mixture is




     filtered on a large plate-and-frame filter.  The filtrate is concen-




     trated then dried in two-stage vertical evaporators and film evaporators.




     About 37.2 kg (82 Ibs) of crude product are obtained per 45.4 kh  (100 Ibs)




     p-nitroaniline reduced.




2.   Input Materials - Basis:  1 kg (Ib) product




     p-nitroaniline     1.28 kg  (Ib)




     Iron               1.60 kg  (Ib)




     HC1 (20° Be)       0.11 kg  (Ib)
                               6-107

-------
3.   Operating Parameters




     Temperature:  230-250°C (446-482°F)




     Pressure:  atmospheric




4.   Utilities - Not given




5.   Waste Streams - No specific information is given, but iron, iron




     sulfides, ammonia and ammonium polysulfides may be found in the waste




     s treams.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 2 (1963) p. 87-90.





     Ibid, Vol. 5 (1968) p. 217.
                               6-108

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 31

                                 Aniline
1.  Function - Aniline is produced commercially by the reduction of

    nitrobenzene is a continuous , vapor-phase process in which nitro-

    benzene is vaporized in a stream of hydrogen and fed to a fluidized

    bed reactor containing a hydrogenation catalyst.  The catalyst can

    be copper carbonate, cuprammonium nitrate, alumina, or sulfides of

    nickel, molybdenum, or tungsten.  The unreacted hydrogen is recycled

    to the reactor.  Reactor effluent goes to a separator, where two

    phases are formed.  The organic phase contains water, and is fractionated

    in a two- tower system to remove heavy residue water from the aniline

    product.

2.  Input Materials - Basis - 1 metric ton aniline

    Nitrobenzene - 1.35 Mg/Mg Aniline       1350 kg (2,976 Ibs)

    H_ - 65 kg/Mg Aniline                     81 m3 (2,860 ft3)

    Copper carbonate                         0.7 kg (1.54 Ibs)

3.  Operating Parameters

    Temperature - 250-300°C (482-572°F)

    Pressure - 238 kPa (2.35 atm)

    Reaction time - 0.5 to 100 seconds

    Catalyst - Cuprammonium nitrate or sulfide (nickel, molybdenum,
               tungsten) or alumina
                               6-109

-------
4.  Utilities

    Steam - quantity not given

5.  Waste Streams - The separator aqueous layer, formed by the water of

    reaction, contains some aniline and may be discharged to the sewer.

    Sometimes this aniline is recovered by solvent extraction using the

    nitrobenzene.

         Heavy residues and water from the fractionation tower may consti-

    tute an additional wastewater source.

                  Flow   -   1.58 I/kg (190 gal/1000 Ibs)
                  COD    -   13,400 mg/1
                             21.2 g/kg (lbs/1000 Ibs)
                  BOD    -   15 mg/1
                             0.02 g/kg (lbs/1000 Ibs)

                  TOC        12,150 mg/1
                             19.2 g/mg (lbs/1000 Ibs)

6.  EPA Source Classification Code - None

7.  References

    Hahn, A. V.,  The Petrochemical Industry:  Market and Economics,

    McGraw-Hill Book Company, New York, N.Y., 1970, p. 503.


    Austin, G. T., "The Industrially Significant Organic Chemicals -

    Part 1," "Chemical Engineering," January 21, 1974, p. 132.


    Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd Edition,

    Interscience Publishers, New York, N.Y., Vol. 2 (1963), p. 419-


    Waddams, A.  L., Chemicals From Petroleum, 3rd Ed., John Murray Ltd.,

    London, Eng., 1973, p. 223.
                               6-110

-------
Lowenheim, F. A. and Moran, M. K., Industrial Chemicals,  4th Edition




John Wiley and Sons, New York, N.Y., 1975, p. 113.





Sittig, M., Pollution Control in the Organic Chemical Industry,  Noyes




Data Corp., Park Ridge, N.J., 1974, p. 76.
                           6-111

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  32
                           Diphenylthiourea
1.   Function - Diphenylthiourea is produced by the reaction of aniline




     with carbon disulfide.  A mixture of aniline,  alcohol,  carbon disul-




     fide, and crystalline sulfur are heated to reflux for 5 to 6




     hours.  The mixture gradually solidifies.  Excess carbon disulfide




     is distilled off.  Excess aniline is removed with dilute hydrochloric




     acid.  The diphenylthiourea is recrystallized  from alcohol.




2.   Input Materials




     Aniline




     Alcohol




     Carbon disulfide




     Sulfur (catalyst)




3.   Operating Parameters




     Reflux 5 to 6 hours




4.   Utilities - Not given




5.   Waste Streams - Expect traces of carbon disulfide to be present




     in air due to this process.  Waste waters may contain dilute acids




     and salts from washings, as well as aniline, and oxidation products




     of aniline.




6.   EPA Source Classification Code - 3-01-034-01




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd  Edition,




     Interscience Publishers, New York, N.Y., Vol. 2  (1963),  p. 414.






                              6-112

-------
7.   References (continued)




     Houben Weyl, Methoden der Organischen Chemie, Vierte Auflage, Georg




     Thieme Verlag, Sttutgart, Bd. 9 (1955), p. 885.
                              6-113

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  33

                      Aniline Hydrochloride
                    NH,
                          + HC1
 1.  Function - Aniline hydrochloride is prepared by the direct reaction

     of aniline with hydrochloric acid.  This is usually accomplished by

     two methods:  a) by passing a stream of dry hydrogen chloride through

     an ethereal solution of aniline, or b) by neutralizing aniline at

     100°C with concentrated hydrochloric acid.  The product is purified

     by crystallization.

 2.  Input Materials

     Aniline - 0.704 kg/kg product

     HC1 - 0.276 kg/kg product

     Ethyl ether

 3.  Operating Parameters

     a)  Temperature - ambient

         Pressure - atmospheric

     b)  Temperature - 100°C  (212°C)

         Pressure - atmospheric

 4.  Utilities

     Not given

 5.  Waste Streams - No specific information available.  An air emission

     containing traces of HC1 and ether is possible from method (a).

     From method (b) aniline, HCl and traces of aniline hydrochloride

     are possible.
                           6-114

-------
6.  EPA Source Classification Code - 3-01-034-01




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience Publishers, New York, N.Y.,  Vol.  2 (1963),  p.  419-
                           6-115

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  34




                          Diphenylamine
 1.  Function - Diphenylamine is produced by heating aniline hydro-




     chloride in an autoclave at 210-240 °C and 730 kPa pressure.   If  a




     catalyst (0.5 weight % of amine) is used the aniline will condense




     with itself without the hydrochloride.




          The product is then boiled with dilute hydrochloric acid to




     remove the unreacted aniline as the hydrochloride, and is distilled.




 2.  Input Materials




     Aniline




     Aniline hydrochloride




 3.  Operating Parameters




     Temperature:  210-240°C (410-464 °F)




     Pressure:  730 kPa (7.2 atm)




 4.  Utilities




     Steam:  Quantities not given




 5.  Waste Streams - No information available but it is likely that a




     waste water stream would be generated containing distillation




     bottoms; small amount of hydrogen chloride or aniline may be given




     off.




 6.  EPA Source Classification Code - 3-01-034-01




 7.  References




     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 2  (1963)  p. 413,  420.
                            6-116

-------
Ibid, Vol. 7 (1967), p. 40.






Chemical Technology, Barnes and Noble Books,  New York,  N.Y.,  Vol.  4




(1972), p. 519.
                         6-117

-------
INDUSTRIAL ORGANIC CHEMICALS                                 PROCESS NO. 35




                               Sulfanilic Acid
                                                               Ho
                                                        SO,,H
1.   Function - Sulfanilic acid (p-aminobenzene sulfonic acid) is




     prepared by placing the sulfuric acid in an iron pan fitted with




     a stirrer and the aniline is run in over 3-4 hours.  The reaction




     mass is stirred for another 3-4 hours and then transferred to




     a heated cast iron oven fitted with a chimney.  The temperature




     is kept at 230 °C until no further sulfur dioxide is emitted.




     After cooling, the crude product can be dissolved in dilute




     caustic soda solution, filtered from the carbonaceous material,




     boiled to expell any free aniline, then acidified to yield the




     free acid (98% yield).




2.   Input Materials




     Aniline               1374 kg




     Sulfuric acid         1597 kg




3.   Operating Parameters




     Temperature:  230°C (446°F)




     Reaction Time:  6-8 hours (before baking)




4.   Utilities - Not given




5.   Waste Streams - Sulfur dioxide is emitted during the baking process




     and aniline vapors escape from the aniline recovery system.  Some




     caustic soda sludge also should appear in the wastewater.




6.   EPA Source Classification Code - None




7.   References




     Chemical Technology, Barnes and Noble Books, New York, N.Y.,




     1972, Vol. 4, p.  590.



                                6-118

-------
Groggins, P., Unit Processes in Organic Synthesis, McGraw-Hill




Book Co., New York, N.Y., 1958, p. 383.






Kirk-Othmer, Encyclopedia Of Chemical Technology, 2nd Ed., Inter-




science Publishers, New York, N.Y., Vol. 2 (1963)^ p. 424.
                           6-119

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  36
                       Cumene (alkylation)
                                              UGH

                                              CH
 1.  Function - Benzene is alkylated in the vapor phase with propylene


     in the presence of a phosphoric acid catalyst to yield cumene.


     An excess of benzene is maintained to suppress dialkylation,


     oligomerization and other side reactions.


 2.  Input Materials - Basis - 1 metric ton cumene


     Benzene:  800 kg (1,764 Ibs)


     Propylene:  430 kg (948 Ibs)


 3.  Operating Parameters


     Temperature:  250°C  (482°F)


     Pressure:  689 kPa (6.80 atm)


     Flow rates:  not given


     Equipment:  chamber type reactor


     Catalysts:  phosphoric acid on kieselguhr

                                   3
     Catalyst Consumption:  1.667 m  cumene formed/kg catalyst


 4.  Utilities


     Not given


 5.  Waste Streams - The principal waste water streams from the manufacture


     of cumene results from the recovery of cumene from the process stream.


     This stream contains some 1-4% of the product stream.  The quantity


     of water carrying the wastes depends largely upon the use of propane


     to control bed temperature.
                              6-120

-------
6.  EPA Source Classification Code - None




7.  References




    Brownstein, A. M.,  U.S. Petrochemicals - Technologies, Markets, and




    Economics,  The Petroleum Publishing Company, Tulsa, Oklahoma, 1972.






    "1969 Petrochemical Handbook," "Hydrocarbon Processing," Nov., 1969, p. 167,






    Gloyna, E. F., and Ford, D. L., "The Characteristics and Pollutional




    Problems Associated with Petrochemical Wastes," for FWPCA, Contract




    No. 14-12-451, Ada, Oklahoma, 1970.






    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 6  (1965), p. 544, 545.






    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 1  (1963), p. 892.






    Hedley, W. H., et al., Potential Pollutants from Petrochemical




    Processes, Technomic Publishing Co., 1975.






    Austin, G. T., "The Industrially Significant Organic Chemicals -




    Part 3,""Chemical Engineering,"March 18, 1974, p. 91.






    Lowenheim, F. A. and Moran, M. K., Industrial Chemicals,  4th  Edition,




    John Wiley and Sons, New York, N.Y., 1975, p. 294,  295.
                             6-121

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INDUSTRIAL ORGANIC CHEMICALS                 PROCESS NO.  37


  Phenol, Acetophenone, and Acetone  (from cumene via hydroperoxide)
          C,H,.C(CH,)9OOH               >    C,H,OH + (CH,)0CO
           OD-JZ                        OD        j 2

1.   Function - As of January 1, 1975, almost 91% of synthetic phenol

     capacity was based on the cumene peroxidation process.  Cumene is

     oxidized to cumene hydroperoxide as described in Process No.  294

     and fed to an acidifier containing 5-25% sulfuric acid.  The re-

     actants are agitated at 45-65°C until the cumene hydroperoxide is

     cleaved to phenol and acetone.

          After the reaction, the mixture is phase-separated to yield

     an oil layer containing cumene, phenol, acetone, a-methylstyrene

     (1.5%), acetophenone (0.8%), and tars.  These are separated from

     each other by distillation or by a combination of distillation and

     extraction.  The a-methylstryene can be hydrogenated to cumene and

     recycled or recovered as a by-product.  Acetophenone is recovered

     as a by-product.  Unconverted cumene can be removed after the

     oxidation step  or recovered in  the final distillation.



2.   Input Materials

     Cumene hydroperoxide (from cumene - 1.42 kg/kg phenol)
     Sulfuric acid

3.   Operating Parameters

     Temperature:   45 - 65°C (113-149°F)
     Pressure:   not given
                             6-122

-------
4.   Utilities  - Basis:  1.44 kg/sec capacity (100 M Ib/yr)

     Cooling water - 1.99 m /sec (1.89 M gph)
     Steam - 14.2 kg/sec (113,000 Ib/hr)
     Electricity - process - 1778.4 MJ (494 KW)
                   utilities - 626.4 MJ (174 KW)
     Nitrogen - 393 son /sec (50 scfh)
                  *
5.   Waste Streams

     Crude phenol surge vessel (water)

     Cumene - trace
     Acetone - 0.46 kg/Mg phenol
     Phenol - 0.08 kg/Mg phenol

     Single vessel mesityl oxide column (water)

     Mesityl oxide plus other contaminants - 19.9 kg/Mg phenol

     Hydrogenation column vent (air)

     Hydrogen - 15.0 g/Mg phenol
     Carbon monoxide - 20.0 g/Mg phenol

     Catalytic columns vent (air)

     Methylstyrene - trace
     Carbon monoxide - 0.22 kg/Mg phenol
     Phenol - 1.48 kg/Mg phenol

     Steaming column vent (air)

     No data given (assume phenol to be the major pollutant) - 0.5 -1.0
          kg/Mg product

     Evaporator residue (solid)

     Acetophenone - 1.9 kg/Mg phenol
     Phenol - 0.75 kg/Mg phenol
     Polymeric matter - 110 kg/Mg phenol
     Cumylphenol - 0.85 kg/Mg phenol

6.   EPA Source Classification Code 3-01-034-01

7.   References

     Austin, G. T., "The Industrially Significant Organic Chemicals -

     Part 1", "Chemical Engineering", January 21, 1974, p. 130.
     Ibid., Part 8, July 22, 1974

 Includes Process No. 36
                             6-123

-------
"1973 Petrochemical Handbook Issue", Hydrocarbon Processing,




November, 1973, p. 158.








Hedley, W. H., et al., Potential Pollutants from Petrochemical




Processes, Technomic Publishing Co., 1975.
                         6-124

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  38
                        Maleic Anhydride (from benzene)
                                 V 0      CHCO
                    4- 4 1/2  0,        >   ||   ;p + 2H 0 + 2CO,
                                          CHCO'              ^
1.  Function - A stream of benzene is vaporized in a mixer with an optimum

    amount of air.  The vapors from the mixer pass then through a converter

    containing vanadium pentoxide on an inert carrier.  Tubes that circulate

    mercury or fused salts serve to remove the heat of the reaction and thus

    control the temperature between 400 to 450°C.

         The reaction gases from the reaction pass through a vapor cooler

    and then to a condenser.  The bulk of the maleic anhydride is recovered

    in the condensers and contains some maleic acid.  This is converted to

    the anhydride by vacuum or azeotropic distillation (using hydrocarbons).

         As of 1973 all the maleic anhydride intentionally manufactured

    in the United States is produced via the oxidation of benzene.  It is

    also obtained as a by-product in the manufacture of phthalic anhydride.

    Use of C, hydrocarbons as feedstock is planned by different companies.

    One plant (Ashland) is designed to use benzene but can be adapted to

    butane feedstock.

2.  Input Materials - Basis - 1 metric ton maleic anhydride

    Air - 37.48 Mg/Mg (74,963 Ib/ton) product -  15,600-21,750 m3

    Benzene - 1.872 Mg/Mg (3,745 Ib/ton) product -  (550,909-768,094  ft3)

    Sodium perborate - 10.2 kg/Mg (20.2 Ib/ton) product - 1,340 kg  (2,954 Ibs)

    Demineralized water - 23.66 kg/Mg  (47.31 Ib/ton) product
                               6-125

-------
3.  Operating Parameters


    Temperature - 400-450°C  (752-842°F)


    Pressure -  101  kPa (1 atm)


    Contact time - -0.1 sec.


    Catalysts - V_0,. + MoO« (on aluminum turnings or diatomaceous earth)


4.  Utilities


    Basis - 13.6 (Jg/yr (30 M Ib/yr) capacity


    Water

                   3
    Coolant - 88 dm /s (1,400 gpm)

                           3
    Makeup cooling - 1.8 dm /s (28 gpm)

                          3
    Boiler makeup - <63 cm /s (<1 gpm)


    Steam


    Generated by reactor - 12.6 Mg/hr  (27,800 Ib/hr)


    Required - 1.3 Mg/hr  (2,800 Ib/hr)


    Net - 11 Mg/hr (25,000 Ib/hr)


    Electricity - 11 GJ (3,000 kWh/hr)

                    3
    Nitrogen - 6.2 m /hr  (200 scfh)


5.  Waste Streams


    Recovery section - scrubber (air)


    Benzene - 131 kg/Mg (262 Ib/ton product)


    Carbon monoxide - 780 kg/Mg (1,560 Ib/ton) product


    Maleic acid - trace


    Purification section - anhydride vacuum column-bottoms  (water)


    Maleic anhydride - 3.8 kg/Mg  (7.5 Ib/ton)


    High boilers (tar, fumaric acid, chromogenic compounds)  -  27 kg/Mg (53 Ib/ton)
                               6-126

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5.   Waste Streams (continued)




    Purification section - anhydride vacuum column-overhead (water)




    Maleic acid - 0.6 kg/Mg (1.2 Ib/ton)




6.   EPA Source Classification Code - None




7.   References




    Morse, Park L., "Maleic Anhydride", Report No. 46, Stanford Research




    Research Institute, Menlo Park, California, 1969.





    Gloyna, E. F., and Ford, D. L., "The Characteristics and Pollutional




    Problems Associated with Petrochemical Wastes", Report of FQPCA, 1970.





    Austin, G. T., "Industrially Significant Organic Chemicals - Part 7,"




    ''Chemical Engineering," June 24, 1974, p. 150, 151.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 12 (1967), p. 828, 829.





    Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th Edition,




    Interscience, New York, N.Y., 1975, p. 514-8.
    Chemical Week. May 9, 1973, p. 33.




    Chemical Week, February 5, 1975, p. 13.
                               6-127

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INDUSTRIAL ORGANIC CHEMICALS                                 PROCESS NO.  39



                     Succinic Acid (from maleic anhydride)





                   HC-c'°     H2
                                   >- HOOC(CH9)9COOH
1.   Function - Succinic acid is obtained from maleic anhydride by



     hydrogenation.  Molten maleic anyhydride is charged to a



     hydrogenator.  The vessel is purged and filled with hydrogen.



     A Raney-nickel catalyst is added as a slurry, agitation started,



     and the temperature is raised to 130 - 140°C (265 - 283°F).



     Hydrogen pressure of 17 megapascals (168 atm) is maintained for



     4-6 hours.  The product is then removed and distilled in two



     stages.  The first removes any unreacted maleic anhydride under



     a vacuum as overheads.  The second stage fed by the bottoms from



     the first removes the succinic acid under a vacuum as distillate



     overhead.  The product is condensed, dried and sold as a white



     flake.



2.   Input Materials



     Maleic anhydride



     Catalyst



     Hydrogen



3.   Operating Parameters



     Temperature:  130 - 140°C (265 - 283°F)



     Pressure:  17 MPa (167.8 atm)



     Reaction Time:  4-6 hours



4.   Utilities - Not given



5.   Waste Streams - The maleic anhydride and some catalyst may be



     present in the waste streams.
                                6-128

-------
6.    EPA Source Classification Code - None




7.    References




     Klrk-Othmer, Encyclopedia of Chemical Technology, Second Edition,




     Interscience Publishers, New York, N.Y., Vol. 19 (1969), p.  143.
                                 6-129

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INDUSTRIAL ORGANIC CHEMICALS                                 PROCESS NO.  40

                         Tetrahydrophthalic Anhydride
                                     ,0                 0
               H?C=CH-CH=CH2 +        0
1.   Function - cis-l,2,3,6-Tetrahydrophthalic anhydride is manufactured
     by the Diels-Alder reaction.  1,3-Butadiene reacts with maleic
     anhydride in benzene at room temperature (12 hours) and is then
     heated to 100° C for five hours in an autoclave.  The product is
     crystallized from benzene-ligroin.
2.   Input Materials - Basis - 1 kg (Ib) product
     1,3-Butadiene            0.458 kg (Ib)
     Maleic anhydride         0.715 kg (Ib)
     Benzene                  1.14 1 inside reaction vat
                              1.43 1 outside reaction vat
3.   Operating Parameters
     Temperature:  20 °C (67 °F)
     Pressure:  not given
4.   Utilities - not given
5.   Waste Streams - Possible benzene emissions from purification of
     product are the only wastes from this reaction since the yield
     is quantitative.
6.   EPA Source Classification Code - None
7.   References
     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,
     Interscience Publishers, New York, N.Y. Vol. 12  (1967)  p. 825.

     Adams, R. , Organic Reactions, John Wiley and Sons, New York, N.Y.,
     Vol. 4 (1948), p. 41.

                                6-130

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 41
                           Maleic Acid
n*            V90,-  ^COOH
             1+41/2 0,    5 >B     + H,0 + 2CO
         ^^                  S:OOH    z
 1.  Function - Maleic acid is produced in conjunction with the manu-

     facture of maleic anhydride (see Process 38).   If maleic acid is

     to be the sole product, the gases from the reactor are absorbed in

     water to give a 40% solution.  The solution is purified with acti-

     vated carbon, concentrated, and crystallized.

          A small amount of maleic acid is also obtained as a by-product

     in the manufacture of phthalic anhydride.

 2.  Input Materials

     Benzene

     Air

     Water

 3.  Operating Parameters

     Temperature:  400 - 500°C  (752-932°F)

     Pressure:  101 kPa (1 atm)

     Contact time:  ~0.1 sec

     Catalyst:  V2°5

 4.  Utilities

     Similar to those in Process

 5.  Waste Streams - Benzene vapors not recycled and maleic acid not

     recovered by crystallization; CO, C02 and hydrocarbons.

 6.  EPA Source Classification Code - None
                            6-131

-------
7.  References




    Lowenheim, F. A., Moran, M. K.,  Industrial Chemicals,  4th Edition,




    John Wiley and Sons, New York, N.Y., 1975, p. 514-518.






    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd  Edition,




    Interscience Publishers, New York, N.Y., Vol. 12 (1967), p.  829.
                           6-132

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  42
                     Malic Acid (from maleic acid)
                                        COOH
               HCCOOH       H20      HO-CH
               HCCOOH            "*     CH
                                        » 2
                                        COOH
1.   Function - R, S -Malic  acid can be produced from maleic acid by
     hydration at elevated temperatures and pressures in the presence
     of catalysts.  The reactors need to be corrosion-resistant.
          The vapors from the gas-phase oxidation of benzene are
     dissolved in water to give a solution of maleic acid.  The solution
     is treated 4 to 5 hr with oxygen at 70° C.  After preliminary
     purification the solution passes through three Ti reactors at
     185° C and 15 kg/cm  , with residence time of 2.5, 1.6, and .85
     hr.  The resulting solution is cooled to 40° C to remove fumaric
     acid.  The crude malic acid is purified further by recrystalli-
     zation.  Removal of  traces of fumaric acid and mineral ions
     (Fe, Cu, Ca, Mg, Al) may be accomplished by the use of ion-
     exchange resins.
2.   Input Materials
     Maleic acid
     Water
     Oxygen
     Catalyst - Co
3.   Operating Parameters
     Temperature - 185° C  (365°F)
     Pressure       15 kg/cm2  (1.47 MPa)
                            6-133

-------
4.   Utilities - Not given.




5.   Waste streams - Waste waters essentially free of traces of by-




     products and mineral ions with use of ion exchange resins.




6.   EPA Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Vol. 12, Interscience Publishers, New York, N.Y., 1967  p. 843-846.






     Allied Chemical Corp. Neth. Appl. 6,516, 753, July 1, 1966.




     (C.A. 65-P16867d)






     Ahlgreen, C. R. (to Allied Chemical Corp.) Belg. 670, 932,




     January 31, 1966 (C.A. 65-P13551C)






     Allied Chemical Corp. Neth. Appl. 6,600,665 (1966).  (C.A. 65-




     16867).
                            6-134

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  43


                    Fumaric Acid (from malelc acid)






                  VC°2H           VC°2H
                    II        	w     II
                    C                  C

                  W \02E        H02C/^ XH



1.   Function - Fumaric acid is manufactured by two main methods;  (1)


     directly from benzene or (2)  from maleic acid.   The process employing


     benzene is discussed under Process No.  38.   The  process using maleic


     acid feed uses amine bases, mercaptans, heavy metal salts, mineral


     acids, disulfides, and other materials  as catalysts.   In common use


     are ammonium persulfate-ammonium bromide mixtures  and  10 - 20% HC1.


     The conversion is carried out at atmospheric pressure  at 40 - 60°C


     (103 - 139°F).  Fumaric acid precipitates from the aqueous medium


     and after separation is dried and purified by recrystallization or


     sublimation.


2.   Input Materials


     Maleic acid


     Catalyst


3.   Operating Parameters


     Temperature:  40 - 60°C (103 - 139°F)


     Pressure:  101 kPa (1 atm)


4.   Utilities - Not given


5.   Waste Streams - Unreacted maleic acid,  HC1, and  catalyst  should be


     present in the waste streams.


6.   EPA Source Classification Code - None
                              6-135

-------
7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 6," "Chemical Engineering," May 27, 1974,  p.  102.






     Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 12  (1967),  p.  829.






     Sittig M., Chemicals from Aromatics, Noyes Development Corp.,




     Park Ridge, N.J., 1966, p. 28, 29.
                              6-136

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  44

                             Cyclohexane
                                    + H2 	'

1.  Function - Cyclohexane (35%) is produced from benzene by a liquid

    phase hydrogenation process.  The reaction occurs at 220°C (428°F)

    and 3.5 MPa (34.5 atm) using a platinum or Ni catalyst containing

    a small amount of lithium salt supported on alumina.  A typical plant

    incorporates several reactors for a stepwise operation.  The recycled

    cyclohexane, hydrogen and make-up hydrogen pass through the beds in

    series, while the benzene passes through in parallel.  This reduces

    the quantity of recycle cyclohexane and excess hydrogen required.

    The recycle cyclohexane absorbs the heat of hydrogenation, thus avoiding

    high bed temperatures and possible isomerization.

2.  Input Materials - Basis - 1 metric ton cyclohexane

    Benzene - 0.98 kg (lb)/kg (Ib) product  93.5 kg (2,061 Ibs)

    Hydrogen - 65 kg (143 Ibs)

    Catalyst - small

3.  Operating Parameters

    Temperature - 220°C (428°F)

    Pressure - 3.5 MPa (34.5 atm)

4.  Utilities - 45 M kg/yr (100 M Ibs/yr), 350 days/yr

    Electricity - 250 kW

    Steam - kg/hr (Ibs/hr) - consumed [4.2 MPa = 41.5 atm] - 4994  (11,000)
                             generated - (1.2 MPa 11.8 atm) 6350 (14,000)
                               6-137

-------
    Cooling water - (AT = 15°C)  0.039 m3/s  (618 gpm)

    HP steam required - 2.3 t/hr

    LP steam produced - 11.8  t/hr
                                                        —f\  *^
5.  Waste Streams - Outside of spent caustic wash  (2 x 10   m /kg =0.24
          o
    gal/10  Ibs), the only major source  of  wastewater is the cooling water
                                 o
    which amounts of 171-1717 g/m  (200-2,000  gal/ton) of cyclohexane and

    which may contain 50-200  mg/1 of COD.   In  the  aromatics extraction,

    there are two major sources of  wastewater:  the extract water washing

    which contains aromatic hydrocarbons and the wastes from solvent

    regeneration which contain appropriate  solvents.  Both wastes may be

    minimized by the use of stripping columns.

         Purge gas from the hydrogenation reactor  may contain benzene,

    hydrogen, sulfur, and carbon monoxide.

6.  EPA Source Classification Code  - None

7.  References

    Austin, G. T., "The Industrially Significant  Organic Chemicals -  Part  3,"

    "Chemical Engineering," March  18, 1974, p. 91,92.

    Kirk-Othmer, Encyclopedia of Chemical  Technology,  2nd  Edition,

    Interscience Publishers, New York,  N.Y.,  Vol. 6   (1965), p.  679.

    Sittig, M., Organic Chemical Process Encyclopedia  - 1969,  2nd Edition,

    Noyes Development Corp., Park  Ridge, N.J., 1969, p. 201.

    Hedley, W. H., et al., Potential Pollutants  from Petrochemical Processes^

    Technomic Publishing Company,  Westport, Conn.,  1975.
                              6-138

-------
7.   References (Continued)




    "1973 Petrochemical Handbook," "Hydrocarbon Processing," Novemberf




    1973, p. 116,117.





    Sittig, M.,  Pollution Control in the Organic Chemical Industry,




    Noyes Data Corp., Park Ridge, N.J.,  1974,  p. 116.




    Lowenheim, F. A., and Moran, M. K.,  Industrial Chemicals,  4th Edition,




    John Wiley and Sons, New York, N.Y., 1975, p.  299.





    Sittig, M.,  Chemicals from Aromatics, Noyes Development  Corp., Park




    Ridge, N.J., 1966, p. 4-9.





    U.S. Patent 3,254,134 (May 31, 1966).
                               6-139

-------
INDUSTRIAL ORGANIC CHECMICALS                                PROCESS NO. 45

                        Adipic acid (from cyclohexane)
      0/  V
ox.fc  /  g  \
                                               HOOC(CH2)4COOH
1.   Function - Adipic acid is obtained from cyclohexane in a two

     stage process.  First stage involves air oxidation of cyclohexane

     to an alcohol-ketone mixture.  The reaction carried out at 125-160°C

     and 404 kPa (4 atm.) uses a cobalt naphthenate or cobalt stearate

     catalyst.



     The second stage oxidizes the alcohol-ketone mixture to adipic acid

     using 40 to 50% nitric acid.  The reaction carried out at 50 - 150°C

     (122 - 302°F) and 345 - 1724 kPa (3.4 - 17.0 atm.) uses a catalyst

     made of ammonium meta-vanadate .and copper.



     The liquid product from the reactor is air stripped to remove

     nitrous oxides and steam distilled to remove nitric acid and low-

     boiling organics as overhead.  The still bottoms are cooled to

     40 - 50°C (104 - 122°F) and the adipic acid crystallizes.  The

     crystals are dried to produce the adipic acid.



     Adipic acid may also be made by air oxidation of cyclohexane.

2.   Input Materials

     Basis - 1kg (Ib) adipic acid

     1)   Cyclohexane - 1.65 kg (Ig)

          Air - variable

          Catalyst - 0.1 g (0.0001 Ib)

     2)   Nitric acid - 6.75 kg (Ib)

          Catalyst:  Copper - 15 g  (0.015  Ib)
                     Ammonium   meta-vanadate 5 g (0.005 Ib)
                                6-140

-------
3.   Operating Parameters




     1)   Temperature:  125 - 160°C (257 - 320°F)




          Pressure:  404 kPa (4atm)




     2)   Temperature:  50 - 150°C (122 - 302°F)




          Pressure:  345 - 1724 kPa (3.4 - 17.0 atm)




          Reaction time:  1 hour




*•   Utilities - Not given




5.   Waste streams - Air pollution - nitrous oxides and nitrogen




     dioxides from oxidizer; particulates from vent on product




     drying.









     Water pollution - metallic catalyst residues  and by-product




     organic acids.




6.   EPA Source Classification Code - None




7.   References




     Austin, G.T., "The Industrially Significant Organic Chemicals  -




     Part 1," "Chemical Engineering," January 21,  1974, p.  131.






     Hedley, William H., et. al., Potential Pollutants from Petrochemical




     Processes, Technomic Publishing Company, Westport, Conn., 1975.









     Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd  Edition,




     Interscience  Publishers, New York, N.Y., Vol. 1  (1963)   p.  411.






     Sittig,  M., "Pollution Control in the Organic Chemical Industry,"




     Noyes Data Corporation, Park Ridge, New Jersey.  1974.  p.  67,  68,




     69,  70,  71.
                               6-141

-------
Faith, W.L., et. al., Industrial Chemicals. 3rd Ed., John Wiley and




Sons, New York, N.Y., 1965, p. 46, 47.
                           6-142

-------
INDUSTRIAL ORGANIC CHEMICALS                        PROCESS NO. 46




                Cyclohexanol And Cyclohexanone (KA oil)
                                         Cr-CT
1.   Function - Cyclohexanol is produced by oxidizing cyclohexane with




    air in the presence of a catalyst.  The basic process takes place in




    the liquid phase by means of an oxygen- contain ing gas at  a temperature of




    120-250°C (248-482°F)  and a pressure high enough to keep  the cyclohexane




    from vaporizing, and in the presence of an oxidation catalyst such as




    cobalt naphthenate.  This reaction produces a mixture of  Cyclohexanol




    and cyclohexanone.  The two can be separated by conventional vacuum-




    fractionating  techniques.




        A second  technique which can be used if Cyclohexanol is the desired




    product is the oxidation of cyclohexane over a boric acid catalyst.  This




    process can result in alcohol-to-ketone yields as high as 10 to 1.




2.   Input Materials - Basis - 1 metric ton cyclohexanone




    Cyclohexane -  1010 kg (2227 Ibs)




    Air - variable




    Catalyst (Mn + Co acetates)




    Metaboric acid - 5 kg (11 Ibs)




    Zno - 0.75 kg  (1.65 Ibs)




3.   Operating Parameters




    Temperature -  120-250'C (248-482°F)




    Pressure - Not given
                            6-143

-------
4.  Utilities - Not giyen




5.  Waste Streams - Cyclohexane from separation process;  residual crude




    from distillation;  catalyst salts.




6.  EPA Source Classification Code - None




7.  References




    "1973 Petrochemical Handbook," "Hydrocarbon Processing," November, 1973




    p.  118.





    Austin,  G. T., "The Industrially Significant  Organic  Chemicals - Part 3,"




    "Chemical Engineering," March 18, 1974,  p. 92.






    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 6  (1965), p. 684-686.





    Lowenheim, F. A.,  and Moran, M. K. , Industrial Chemicals, 4th Edition,




    John Wiley and Sons, New York, N.Y., 1975, p. 304,305.
                              6-144

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  47




                              Cyclohexene
!•   Function - Cyclohexene can be manufactured by:




     a)  direct dehydration of cyclohexanol in presence of a catalyst;




     b)  dehydrohalogenation of the chlorocyclohexane or bromocyclo-




         hexane formed by halogenating cyclohexanol or cyclohexane.




2.   Input Materials




     Dehydration:




     Cyclohexanol




     Catalyst (Al^, H3P04>




     Dehydrohalogenation




     Chloro- or bromo-cyclohexane




       (from cyclohexanol or cyclohexane)




     Dehydrohalogenating agent




3.   Operating Parameters




     Dehydration




     (with H3P04)




     Initial temperature - 165-170°C




     Final temperature - 200°C




     Pressure - 101 kPa (1 atm)




     Dehydrohalogenation




     Catalyst - Zeolite impregnated with alkali oxide, or charcoal




                impregnated with
                              6-145

-------
3.   Operating Parameters   (continued)




     Temperature - 150-250°C




     Pressure - not given




     (nitrogen atmosphere)




     Catalyst-cyclic amidine in (CH.,)-80




     Temperature - 80-90°C




     Pressure - not given




4.   Utilities - not given




5.   Waste Streams - In some continuous processes the Br~ used to halo-




     genate cyclohexane is recovered by absorbing the HBr in magnesia and




     oxidizing the resulting mass at 300°C.




6.   EPA Source Classification Code - None




7.   References




     Houben Weyl - Methoden der Organischen Chemie, Vierte Auflage Bd. 5,




     T. Ib, George Thieme  Verlag Stuttgart, 1972, p. 71, 160, 176-179-






     French Patent  385,650 (January 15, 1965).






     Belgian Patent  632,808 (November 25, 1963).






     Organic Synthesis, John Wiley and Sons, New York, N.Y., Collective




     Vol. 2 (1943), p. 152.
                              6-146

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 48




              Cyclohexylamine (from cyclohexanone)
                 0
                                  Cat'>
 1.  Function - Cyclohexylamine is manufactured by the reductive amination




     of cyclohexanone.  This can be done in two ways both employing the




     same basic reaction with different operating parameters.




     Process #1




     Cyclohexanone is reduced with hydrogen in the presence of ammonia.




     A nickel catalyst supported on kieselguhr is activated by hydrogen




     at 427 °C and used to promote the reaction which proceeds at 200°C




     and 31,088  kPa.  One hundred percent conversion is achieved con-




     taining 81 wt.% Cyclohexylamine.




     Process #2




     In this process cyclohexanone is reduced with hydrogen in ammonia




     over nickel.  The operating parameters are at least 40°C and 769,359




     kPa.  Following the reaction the material is azeotroped with C.-H, then




     distilled to give a 99% pure product.




 3.  Input Materials




     Process #1^




     Cyclohexanone - 1.23 kg/kg product




     Ammonia - not given




     Hydrogen - not given




     Catalyst - not given
                               6-147

-------
    Process #2




    Cyclohexanone - 1 kg/kg product




    Ammonia - 0.65 kg/kg product




    Hydrogen - 0.04 kg/kg product




    Catalyst - 0.11 kg/kg product




    Benzene




3.  Operating Parameters




    Process #1




    Temperature:  200°C (392°F)




    Pressure:  31.088 MPa (306.8 atm)




    Catalyst:  nickel




    Process #2




    Temperature:  40°C  (104°F)




    Pressure:  769.359 MPa (7,593 atm)




    Catalyst:  nickel




4.  Utilities




    Not given




5.  Waste Streams - possible hydrocarbon emissions from leaks in system;




    some nickel compounds and benzene may leak out.




6.  EPA Source Classification Code - None




7.  References




    French Patent, 1,446,554  (July 22, 1966).






    British Patent, 1,050,589  (December 7, 1966).
                             6-148

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  49




                Dicyclohexylamine (from aniline)





                                                 NH
                                       / V "^w-<^

                                cat.
                                       (05.
1.   Function -  Dicyclohexylamine is best prepared by the vapor phase



     catalytic hydrogenation of aniline over a nickel catalyst.  The



     aniline (15 g/hr) is evaporated into a circulating hydrogen stream



     (425 1/hr)  and  the resulting mixture introduced into a reaction zone



     packed with a nickel-on-pumice (7 parts) catalyst.  The vapors leaving



     the reaction zone are cooled to about 45°C, liquifying the dicyclo-



     hexylamine  and  a small amount of cyclohexylamine.  The uncondensed



     vapors are  cycled to the reactor after removing part of the ammonia



     and adding  fresh aniline and hydrogen.




          Dicyclohexylamine may also be prepared from cyclohexanone (via



     the cyclohexylamine produced) as in Process No. 48  using a different




     set of operating parameters (101 kPa and  260°C).



2.   Input Materials - Basis - 1 kg dicyclohexylamine




     Aniline, g  1,250



     Catalyst:  7 parts nickel-on-pumice




3.   Operating Parameters




     Aniline feed, g/hr       15



     Hydrogen feed,  1/hr     425




     Temperature - not given




     Pressure -  not  given
                             6-149

-------
4.   Utilities




     Not given




5.   Waste Streams - Basis - 1 kg dicyclohexylamine




     There should be some aniline, hydrocarbons, and ammonia given off




     in addition to the 125 g cyclohexylamine and 11.4 g cyclohexanol.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 2  (1963), p. 416.






     German Pat. 805,518 (May 21, 1951).






     U.S. Pat. 3,551,486 (December 29, 1970).
                             6-150

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  50




                               Brbmobenzene
1.  Function - Bromobenzene can be manufactured from benzene by reacting dry




    bromine with benzene in the presence of a catalyst such as Fe.   This




    reaction takes place at 101 kPa (1 atm) and 80-100°C (175-212°F).




    Separation involves scrubbing to remove impurities and fractionating.




2-  Input Materials




    Bromine




    Benzene




    Catalyst




3.  Operating Parameters




    Temperature - 80-100°C (175-212°F)




    Pressure - 101 kPa (1 atm)




    Catalyst - Fe




4«  Utilities - Not given




5.  Waste Streams - Benzene from scrubbing and stripping operations,




    spent scrubbing sludge; unreacted iron and bromine.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,  Inter-




    science Publishers, New York, N.Y., Vol. 3 (1964), p. 775,776.
                               6-151

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS  NO.  51




                           Biphenyl (from benzene)
1.  Function - Biphenyl can be manufactured in 85-90% yield by the vapor




    phase non-catalytic reaction of benzene.   Benzene is placed in a stain-




    less steel, tubular coil reactor and heated to 600-800°C at 101 kPa.




2.  Input Materials




    Benzene




3.  Operating Parameters




    Temperature - 600-800 (1112-1472°F)




    Pressure - 101 kPa (1 atm)




    Reaction Time - 0.4-1.5 sec




4.  Utilities - Not given




5.  Waste Streams - Some benzene, hydrogen, polyphenyls and benzene




    degradation products should be present in the waste streams.




6.  EPA Source Classification Code - None




7.  References




    U. S. Pat. 3,227,525 (January 4, 1966).





    Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd Edition,




    Noyes Development Corp., Park Ridge, N.J., 1969, p. 275.
                               6-152

-------
INDUSTRIAL ORGANIC CHEMICALS                             PROCESS NO.  52









                             Diphenyl Oxide






                        Cl +  ^T^S-OH Na°?»  fl  IVo-ff  1>  + NaCl
1.   Function - Diphenyl oxide is produced in a continuous flow tubular




     reaction system.  Aqueous NaOH, chlorobenzene, and recycled products




     (containing phenol and sodium phenoxide) are pumped through a Ni-lined




     heat exchanger which raises the temperature to 275-300°C.  The tempera-




     ture is raised to 400°C  electrically and kept there for 10-30 min.




     during which time the reactants flow through the system.  Two phases




     are obtained:  1) aqueous phenoxide, and 2) an oily layer which consists




     mainly of diphenyl oxide and unreacted chlorobenzene.  This oily layer




     is distilled to produce the diphenyl oxide.  The reaction must be




     carried out under sufficient pressure (- 26.2 MPa) to prevent vapori-




     zation; otherwise, NaCl, NaOH, or phenoxide will deposit on the tube




     walls causing hot spots and excessive corrosion.




2.   Input Materials





     Chlorobenzene




     Phenol




     NaOH





3.   Operating Parameters





     Temperature:  1st Stage    275-300°C    (527-572°F)




                   2nd Stage      400°C      (752°F)




     Pressure:  ^26.2 MPa (258.6 atm)




     Reaction Time:  10-30 min.




4.   Utilities




     Not given                  6-153

-------
5.   Waste Streams - Sodium hydroxide, sodium chloride, and sodium phenoxide




     should be present in the aqueous waste streams; chlorobenzene and phenol




     should also be emitted.




6.   EPA Source Classification Code




     None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-




     science Publishers, New York, N.Y., Vol. 15 (1968)  p. 154.





     Chemical Technology, Barnes and Noble Books, New York, N.Y., 1972,




     p. 342.
                                6-154

-------
SECTION II
BUTYLENES
 6-155

-------
                                                                                        BUTYLENES
         n-BUTYLENES          63                           54
                         	)  Amy! alcohols             ) Amyl  acetates
Ul
ON
                            55
                           61
62
                                   sec-Butyl  alcohol
                           59                       60
                          	Butadiene
                                 -^Maleic anhydride
                                   Keptenes
                                                                                                                       56


57
V
7
58
\
                                                                                                                               Methyl  ethyl ketone
                                                                                                                              sec-Butyl  acetate
                                                                                                                               sec-Butyl amine
          ISOBUTYLENE      63
                          65
                          66
                          67
                           75
                          73
                                ->Methallyl chloride
                                -^Methacrylonitrile
                                -JMethacrylic  acid
                                    tert-Butyl alcohol
                                        Diisobutene
                                         Triisobutene
                                -} tert-Butyl  phenol
                                                             64
                                              •4   Methallyl alcohol
                                                                                                 68
                                                                                                  69
                                                                                                  71
                                                                                                 74
                                                                              ->•  tert-Butyl hydroperoxide
                                                                                                         -> tert-Butyl toluene
                                                                              > tert-Butylamine


                                                                              t tert-Butyl acetate


                                                                               Neopentancic acid
                                                                                                          70
                                                                                                                -^tert-Butylbenzole acid
                                                            Figure  3.    Butylenes  Section Chemical Tree

-------
                                                                      •n-Butylenes )
CO
Heat


^1
,
1 str -
Oxo Process
H2S04 Stean
, I O Refrlg
t S'^
V"^J r— • ••• 1 -j
° Hydration 55

•Tl
(
Cooling
Water Heat
If A I
!59
Dehydrogenation
^^j
? f
61
Oxidation

propylem
I
62
Addition
I
h-«

i2Acetic I


  'Heat
1. 1 ^"
^ ,
A
54 i
Esterificat1on|

71

tp JAcetlc-
/^d lacld^
56
Oxidation

Heat O I Heat
I 57
1 Etterifi cation

IHJNH-
1* i
58
lAminatlon
/>

I T2
T />,
! Addition & 60
IHydrogenation
V
                                                                                           [ Sulfolane!)
                                             Figure 4.  Butylenes Section Process Flow Sheet

-------
 I
I—1
l_n
OO
-*->
1
ciz|
\

A T3°l
63
Ch1or1nat1on|
V
Heat |£2,j!?!
P5
Ammoxidatior,


HN03 H SO i
* /4 ^
66 i
Oxidation.

H2° iHeatJ
f ^i
Hydration

Cooling
water
HH7SO.
Vf
75
3l1gomer1zat1on
^
                                   Figure 4.   Butylenes Section Process Flow  Sheet  (Cont.)

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 53
                             Amyl Alcohols
  CH_CH=CH-CH
  CH3-C=CH2
catalyst )     ™CELCHCH0OH
                      CO
                                                    CH3
1.  Function - The manufacture of oxo amyl alcohols entails the reaction of
    butylenes with carbon monoxide and hydrogen at high pressure and
    temperature in the presence of a catalyst, usually a cobalt carbonyl
    compound.  The reaction produces a mixture of primary C,. alcohols which
    are fractionated into 3 commercial grades:  primary amyl alcohol being
    approximately 60% 1-pentanol, 35% 2-methyl-l-butanol, and 5% 3-methyl-l-
    butanol; 1-pentanol being about 99% 1-pentanol; commercial 2-methyl-l-
    butanol consisting of 78% 2-methyl-l-butanol, 20% 3-methyl-l-butanol and
    2% 1-pentanol.
2.  Input Materials
    Mixed butylenes - 1-Butene
                      2-Butene
                      Methylpropene
    Synthesis gas   - CO
                      H2
3.  Operating Parameters
    Pressure - 20.65 MPa  (200 atm)
    Temperature - 125-145°C  (257-293°F)

4.  Utilities
    Not given
                                6-159

-------
5.  Waste Streams - Catalyst recovery section (air, water).  Air vent




    discharges some carbon monoxide, butylenes and alcohols.  Some catalyst




    recovery systems have a water waste stream which could contain small




    quantities of alcohols.




         Purification section (air).  Various by-products are formed in the




    oxo process, mainly dimeric alcohols and acetals.  In fractionation the




    heavy ends may be sent for incineration while some of the light ends may




    be flared to the atmosphere.




6.  EPA Classification Code - None




7.  References




    Denney, R. G., "Oxo Alcohols," Report no. 21, Stanford Research Institute,




    Menlo Park, California, 1966.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Interscience




    Publishers, New York, N.Y., Vol. 2  (1963), p. 377,378.





    Chemical Technology, Barnes and Noble, New York, N.Y., Vol. 4  (1972), p. 139,
                               6-160

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS  NO.  54
                     Amyl Acetates (from amyl alcohols)

                                   HSO
                C5H1;LOH + CH3COOH —-—^> CH COOC5H ± +  E^


1.  Function - Commercial amyl acetate, a mixture of isomers,  is  prepared

    by the esterification of mixed amyl alcohols with acetic acid.   Small

    amounts of sulfuric acid are used to catalyze the reaction.   The crude

    product is purified by rectification.  The principal isomers  are

    isoamyl, normal, and secondary amyl acetates.

2.  Input Materials

    Amyl alcohols - 0.8 kg/kg product

    Acetic acid - .505 kg/kg product

3.  Operating Parameters

    Temperature - 220-130°C (428-590°F)

    Pressure - 101 kPa (1 atm)

    Catalyst - H SO,

4-  Utilities - Not given

5.  Waste Streams - Air and wastewater emissions from separator and other

    purification equipment may contain acetic acid, amyl alcohol, amyl

    acetate, traces of sulfuric acid, and various reaction by-products.

6.  EPA Source Classification Code - None

7.  References



    Goldstein, R. F., The Petroleum  Chemicals Industry, 2nd Edition,

    John Wiley and Sons, New York, N.Y.,  1958,  p.  74,75.
                               6-161

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.   55



                              sec-Butyl Alcohol
                                     HO

                          oCH.CHCH, —	> CH.CH-CHCH,. + H0SO.
                          3  21   3          3  2[   3    2  4
CH3CH=CHCH3
CH3CH2CH=CH2
1.  Function - In this process sec-butyl alcohol is produced by absorbing



    n-butenes in 70-85% sulfuric acid to form butyl hydrogen sulfate which



    is then hydrolyzed to sec-butyl alcohol and dilute sulfuric acid.  The



    product is steam stripped from the dilute acid solution and purified



    by distillation.



2.  Input Materials



    n-Butenes - 900 kg/Mg alcohol



    Sulfuric acid



3.  Operating Parameters



    Sulfation:  temperature - 15-30°C (55-78°F)



                pressure - 698.8 kPa (100 psig) (7.8 atm)



    Hydrolysis: temperature - 30-40°C (78-94°F)



                pressure - 100 kPa



4.  Utilities - Not given



5.  Waste Streams -



    Distillation column (water) - Waste stream would contain some butyl



    alcohol.  If the process includes a caustic wash, there will be  some



    sodium hydroxide and sodium sulfate in the wastewater.
                               6-162

-------
    Acid recovery section (water)  -  Sulfuric  acid  is wasted as tars build




    up.




6.  EPA Source Classification Code - None




7.  References




    Faith,  W.  L.  et al.,  Industrial  Chemicals, 2nd Edition, John Wiley and




    Sons, New York, N. Y.,  1957.





    Astle,  M.J.,  The Chemistry of Petrochemicals,  Reinhold Publishing




    Corporation,  New York,  1956.





    Kirk-Othmer, Encyclopedia of  Chemical Technology,  2nd Edition,  Inter-




    science Publishers, New York, Vol. 3  (1964).





    Waddams,  A.L.,  Chemicals From Petroleum,  3rd  Ed., John Murray Ltd.,




    London,  1973  , p.  159.
                               6-163

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  56
                             Methyl Ethyl Ketone

                                               0
                                     Zn°
                         OH

1.  Function - Methyl ethyl ketone (2-butanone, or MEK) is made from sec-
    butanol by a process substantially the same as the acetone-from-iso-
    propanol process.  A catalyst of ZnO on pumice is used in a tubular
    reactor and the reactor temperature is maintained at 400-500 °C.
         Some MEK is obtained as byproduct from the oxidation of butane to
    acetic acid, some from the acetaldehyde process, and some from the
    ace taldehyde- to-acetic acid process.
2.  Input Materials
    sec-Butanol - 1175 kg/metric ton MEK
    ZnO
3.  Operating Parameters
    Temperature - 400-550°C  (752-1022°F)
    Pressure - 200-300 kPa (15-30 psi)  (1.97-2.96 atm)
    Catalyst - ZnO
4.  Utilities - Not given
5.  Waste Streams - Scrubber (water):  Wastewater stream would contain methyl
    ethyl ketone and reaction by-products.
6.  EPA Source Classification Code - None
7.  References
    Lowenheim, F. A. and Moran, M. K. ,  Industrial  Chemicals,   4th Edition,
    John Wiley and Sons, New York, N.Y.,  (1975) p.  539-542.
                                6-164

-------
7.   References (continued)




    Sittig,  M.,  Organic Chemical Process Encyclopedia 1969,  2nd  Edition,




    Noyes Development Corporation, Park Ridge, New Jersey,  (1969).
                                6-165

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  57

                              sec-Butyl Acetate
                                     H SO            9
                                         ^           -H
                    CH3                           CH3
1.  Function - The esterification of sec-butyl alcohol with acetic

    acid with concentrated sulfuric acid as a catalyst yields sec-butyl

    acetate.  This reaction is reversible and so the water of reaction

    and the ester product must be continuously withdrawn to increase the

    conversion going to the ester.  The overhead is usually a mixture of

    alcohol, ester, and water which is separated and the ester purified

    by rectification.

2.  Input Materials - Basis - 1 Mg ester

    sec-Butyl alcohol:  713 kg

    Acetic Acid:  550 kg

    H2S04:  1-4 kg

3.  Operating Parameters

    Temperature:  89°C (192°F)

    Pressure:  101 kPa (1 atm)

4.  Utilities - Not given

5.  Waste Streams - Separator

    (Water) - 1% ester
              3% alcohol
              96% E20

    (Air) - ester and alcohol vapors from air vent; some ^SO

6.  EPA Source Classification Code - None
                               6-166

-------
7.   References




    Faith, W.  L.,  et al.,  Industrial Chemicals,  3rd Edition,  John  Wiley




    and Sons,  New York, N.Y.,  1965, p.  176-178.





    Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience  Publishers,  New York,  N.Y.,  Vol.  8 (1966), p.  372.





    Groggins,  P.  H., Unit  Operations in Organic  Synthesis, 5th  Edition,




    McGraw-Hill Book Company,  New York, N.Y., 1958, p.  730.





    Lowenheim, F.  A., and  Moran, M. K., Industrial Chemicals, 4th  Edition,




    John Wiley and Sons, New York, N.Y., 1975, p.  173-176.
                               6-167

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  58
                          sec-Butyl Amine
                   OH                      NH2
 !•   Fuftction - Sec-butyl amine Is produced commercially by the cata-




     lytic addition of NH^ to the corresponding alcohol, with separa-




     tion of the mono-, di- and tri-substituted butyl amines.




 2.   Input Materials - Basis - 1 Mg mixed product




     Sec-butanol:  1.5 Mg (7.5 mole %)




     NH3:  425 kg (45 mole %)




     H2:  (43 mole %)




 3.   Operating Parameters




     Temperature:  350°C (662°F)




     Pressure:  1.48 MPa (14.6 atm)




     Flow rate:  1000/hr space velocity




     Catalyst:  Nickel




     These conditions yield:  50 mole percent monoamine




                              20 mole percent diamine




                              30 mole percent triamine




 4.   Utilities - Not given




 5.   Waste Stream - CO., and formaldehyde by-products; unreacted alcohols,




     H,,, and NH_ in vented gas streams.




 6.   EPA Source Classification Code - None




 7.   References




     Faith, W. L. et al., Industrial Chemicals, John Wiley and  Sons,




     New York, N. Y., 1950, p. 47, 48.




                              6-168

-------
Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd Edi-




tion, Noyes Development Corp., Park Ridge, N. J., 1969, p. 127.





U. S. Patent 2,182,807 (December 12, 1939).
                          6-169

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS  NO.  59
             Butadiene (catalytic dehydrogenation of n-butenes)
             „ r „   Shell Catalyst 205
             n"°4H8  621 - 677°C,  101 KPa
1.  Function - n-Butenes which have been treated for isobutylenes  and

    butanes removal are the exclusive feed for 15-20% of the butadiene

    manufactured in the U.S.  Two commercial processes compete:  one

    of which is based on the Dow Type B catalyst, the other on Shell

    Catalyst 205.

         Shell Catalyst 205 (ferric oxide, chromium oxide,  and potassium

    oxide)  effects dehydrogenation to butadiene at temperatures of 621-677°C

    and atmospheric pressure.  The preheated butene feedstock is mixed  with

    superheated steam in a mole ratio of 1:8 and passed over the 81-91  cm.

    deep catalyst bed at a space velocity of 500 volumes of butenes at

    standard condition per hour, per volume, of catalyst space.  Selectivity

    to butadiene is 73-75% with 26-28% conversion of n-butene per pass.

         The more recently developed Dow Type B catalyst (calcium nickel

    phosphate stabilized with 2% chromium oxide) effects dehydrogenation

    at slightly lower temperatures (593-677°C) and higher pressures

    (170-255 kPa) than Shell Catalyst 205.

         Selectivity to butadiene (90%) and butene conversion per pass

    (35-45%) are significantly higher with this catalyst, but larger

    quantities of diluent steam (1:20) and more frequent catalyst regenera-

    tion are required.  Whereas Shell Catalyst 205 is regenerated only
                               6-170

-------
    once a day for one hour, the Dow Type B Catalyst must be regenerated




    in fifteen minute cycles.




         This catalyst also has a greater tendency to produce ketones




    and acetylenic by-products than Shell Catalyst 205.  Although market-




    able quantities of acetone and methyl ethyl ketone may be obtained,




    their separation requires more extensive purification equipment.




         The resulting butane/butene/butadiene mixture is separated by




    extractive distillation with aqueous furfural or acetonitrile.  Butenes




    and butanes are collected overhead and recycled,  while butadiene and




    residual acetylenics remain in the solvent bottoms.  Since furfural




    cannot be used to separate butadiene from the 2-butenes, it is fre-




    quently advantageous to precede the extractive distillation with a




    feed splitter.  This column takes most of the butanes and 2-butenes as




    bottoms, and passes the 1-butene/butadiene overhead into the furfural




    unit.  Alternately, a final butadiene fractionator may be used on the




    2-butene/butadiene concentrate stripped from the furfural solvent.




         If acetonitrile is used as the extraction solvent, butanes and




    butenes separate almost quantitatively from butadiene and feed splitting




    is not required.  However, a final water wash is  necessary to remove




    the last traces of solvent from both the raffinate and product streams.




    Washing is not required to recover furfural due to the high boiling point




    of the solvent.




2.  Input Materials




    n-Butenes - (80-95%)




    Shell Catalyst 205 - 1.38-1.42 kg/kg product




    Dow Type B Catalyst - 1.14-1.18 kg/kg product
                              6-171

-------
    Hydrogen - (acetylenics removal)

    Furfural or acetonitrile

3.  Operating Parameters

    Shell Catalyst 205 - temperature:  621-677°C (1150-1251°F)
                         pressure:  101 kPa (1 atm)

    Dow Type Catalyst - temperature:  593-677°C (1099-1251°F)
                        pressure:  170-255 kPa (1.68-2.52 atm)

4.  Utilities - Basis:  1.43 kg/sec capacity (100 M Ib/yr)

    Water:  cooling - 272 m /sec (43,130 gpm)
            process and makeup - 118.0 dm /sec (1870 gpm)

    Power:  10.9 MW (14,600 hp)

    Refrigeration:  chilled water - 2.48 Gg (2735 tons)
                    ammonia - 1.65 Gg (1820 tons)

    Steam (at 4.24 MPa (41.8 atm), 399°C (750°F):  302 kg/sec (2400 Ib/hr)

    Natural gas:  2.41 m /sec (306,000 cfh)

5.  Waste Streams - Waste flows from butadiene production facilities

    were 417 m/Gg (100 gal/ton) of product with waste composition as

    follows (taken from one source only):

    pH:  8-9

    TOC:  100 to 200 g/m3

    Filtered COD:  250 to 375 g/m3
                                     3
    Suspended solids:  200 to 500 g/m
                              3
    Total solids:  3 to 4 kg/m

         The principal pollutant sources should be the quench waters

    containing tars, oils, and soluble hydrocarbons and  the solvent

    extract and wash waters (if acetonitrile is used) containing

    acetonitrile and C, hydrocarbons.  Some air emissions of furfural

    or acetonitrile may also occur.
                               6-172

-------
6.  EPA Source Classification Code - None




7.  References




    Hedley, W. H., et al.,  Potential Pollutants  from Petrochemical Processes,




    Technomic Publishing Co., 1975.





    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience Publishers,  New York,  N.Y.,  Vol.  3 (1964), p. 794-799.






    Sittig, M., Organic Chemical  Processes Encyclopedia -  1969,  2nd Edition




    Noyes Development Corp., Park Ridge,  N.J.,  1969,  p. 118.





    U. S. Pat.  3,200,166  (August  10, 1965).
                               6-173

-------
INDUSTRIAL ORGANIC CHEMICALS                                   PROCESS NO. 60
                                 Sulfolane

                                                0.  .0
                                  A            A
                                H2j ^H2        H2|  {H2
      CH2=CH-CH=CH2 + S02    »   HC=CH  	^ H2C—-CH2


1.   Function - Sulfolane is produced by the cyclic addition of sulfur

     diox , •>. to butadiene to form sulfolene.  The reactions is carried

     out in a Cr-steel tube (1300 x 100 mm) filled with catalyst.  The

     crude product is treated with a chloride of lime suspension (to

     remove any mercaptans found) and then distilled.  The sulfolene

     is then hydrogenated to Sulfolane.

          Steps must be taken to keep peroxides from entering the reac-

     tion with the reactants because undesirable polymeric by-products

     will result.

2.   Input Materials

     Catalyst  20% Cr20     3.70 kg       Butadiene  467    kg/Mg

             0.58% K20                    S02        553.4  kg/Mg

            79.42% A1203                  H2          17.3  kg/Mg

3.   Operating Parameters

     Temperature 500°C (932°F)

4.   Utilities

     Steam - quantities not given

5.   Waste Streams - Possible waste streams should  contain some  SO^,

     nickel, catalyst, and some polymeric byproducts.

6.   EPA Source Classification Code

     None
                               6-174

-------
7.   References




     Drake, L. R., et. al., J. Amer. Chem. Soc., 68, p. 2521 (1946).






     U.S. Patent 2,420,834 (May 20, 1947).






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed.




     Interscience Publishers, New York, N.Y., Vol. 19  (1969)  p. 250,
                                  6-175

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 61
                           Maleic Anhydride
                         n-C4H8
  0
0-
                                         0
1.   Function - Butenes are oxidized to maleic anhydride  at  a  temperature

     of 350°C and a pressure of 276-450 kPa (25-50  psig).  A catalyst is

     used for this oxidation which consists of the  oxides of molybdenum,

     vanadium, and phosphorous (in a ratio of 9:3:1),  supported on silica

     gel.  The maleic anhydride is solvent extracted from the  reaction

     gases and purified by vacuum distillation or sublimation.

2.   Input Materials

     Butenes

     Air

     Catalyst (oxides of Mo, V, P on silica gel)

3.   Operating Parameters

     Temperature:  350°C

     Pressure:  276-450 kPa (2.7 - 4.4 atm)

     Contact time:  1.5 sec.

4.   Utilities

     Cooling water - quantities not given

     Steam - quantities not given

5.   Waste Streams - Recovery section - air emissions containing  butenes,

     carbon oxides and traces of maleic acid

     Purification section - waste water stream from bottoms containing

     maleic anhydride and high boilers.  Another waste water stream from

     overhead containing maleic acid.


                              6-176

-------
6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 12 (1967),  p.  828,




     829.






     Morse, P. L., Maleic Anhydride, Report No. 46, Stanford Research




     Institute, Menlo Park, California, 1969.






     U.S. Patents 3,156-705 - 3,156,707 (1964).
                              6-177

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 62




                            Heptenes
                  CH=CHCH
                          3    4g -  ?14






1.   Function - Heptenes are a cut fractionated from the gasoline mixture




     that is produced by polymerizing CO~CA refinery gases .





          In general, the yield of heptenes is about 25% based on propylene




     and 33% based on n-butene and isobutene.  However, these figures vary




     considerably, depending on the reaction conditions and the feed




     composition.




2.   Input Materials




     C, Refinery gas




     Propylene:     1.7 kg/kg heptene




     C, Refinery Gas




     Butylenes:     1.71 kg/kg heptene




3.   Operating Parameters




     Temperature:  200-240°C (392-464°F)




     Pressure:  1.52-2.53 MPa (15-25 atm)




     Catalyst :  ELPO,




4.   Utilities




     Not given
                             6-178

-------
5.   Waste Streams - Since all the fractions  of  the  gasoline mixture




     product are utilized, there are no wastes from  this process.




     However, any number of olefins may be released  to  the atmosphere in




     small quantities by process leaks.




6.   EPA Source Classification Code - None




7.   References







     Goldstein, R. F., The Petroleum Chemicals  Industry,  2nd  Edition,




     John Wiley and  Sons, New York,  N.Y.,  1958 , p.  125.






     Waddams, A. L.,  Chemicals  from Petroleum,  3rd  Edition, John




     Murray Ltd., London, England,   1973,  p. 137, 144.
                             6-179

-------
INDUSTRIAL ORGANIC CHEMICALS                                   PROCESS NO. 63




                              Methallyl Chloride
                   CH0=C-CH«  + C10 - >-   CH,=C-CH0C1  + HC1
                     2-     j      Z.          Z  .    /
1.   Function - Isobiitylene and chlorine are mixed in a ratio of 2:1


     at 70-80°C to yield methallyl chloride.  The main mechanism of



     this reaction is an allylic substitution.



          The crude product is recovered by distillation with the over-



     head being approximately 95% methallyl chloride.



2.   Input Materials


     Isobutylene ")

                 >  2/1 molar ratio

     Chlorine   )



3.   Operating Parameters



     Temperature:   70-80°C (158-176°F)



4.   Utilities



     Steam:  quantity nat given



5.   Waste Streams - Distillation column:  heavy ends may be incinerated



     some Cl- and HC1 vapors may be present in the waste streams.



6.   EPA Source Classification Code



     None



7.   References



     Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,



     Interscience Publishers, New York, N.Y., Vol 3  (1964), p. 840, 841.




     Faith,  Clark, & Keyes,  Industrial Chemicals, 2nd Edition, J. Wiley



     & Sons, Inc., New York, 1950.
                               6-180

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 64
                        Methallyl Alcohol


       CH=C-CH2C1   +   NaOH  —*r    CH=C-CH2OH   +  NaCl

          CH0                           ™
1.   Function - Methallyl alcohol is produced from methallyl chloride by

     hydrolysis with caustic solution.

2.   Input Materials

     Methallyl chloride
     NaOH (10%)

3.   Operating Parameters

     Temperature: 145-155°C (293-311°F)
     Pressure: 1.5 MPa (19.8 atm)
     Reaction Time: <^ 15 minutes

4.   Utilities - Not given.

5.   Waste Streams - Wastewater streams would have some NaOH, NaCl,

     alcohol, and chloride.

6.   EPA Source Classification Code - None.

7.   References

     Goldstein, R. F., The Petroleum Chemicals Industry, 2nd Edition,

     John Wiley and Sons, New York, N. Y., 1958, p. 171.


     Astle, M. J., The Chemistry of Petrochemicals, Reinhold Publishing

     Corp., New York, N. Y., 1956, p. 69.
                             6-181

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  65
                         Methacrylonitrile




                                   o -| y

               CH.,-C=CH9  +  NHL       >  N5C-C=CH0
                 J t    i       j              ,    L


                   CH3                        CH3




 1.   Function - Methacrylonitrile is produced by the amminoxidation of



     isobutylene.   Isobutylene, ammonia, and air  are fed to a fluid-bed



     catalytic reactor operating at 800-900°C.   The reactor effluent is



     scrubbed and  the product recovered by distillation.



 2.   Input Material



     Isobutylene - 1  kg/kg product



     Ammonia - 0.5 kg/kg product



     Air - 20 kg/kg product



 3.   Operating Parameters



     Temperature:   800-900°C (1472-1652°F)



     Catalyst:  oxide of Co, Mn, or Mo



 4.   Utilities



     Cooling water:  470 kg/kg product



     Steam:   6.5 kg/kg product



     Refrigeration:  capacity not given



     Process water:  100 kg/Mg product



     Electricity:   capacity not given



 5.   'Waste Streams



     Reaction section - absorber off-gas to flare (air)



          Methacrylonitrile - 5 kg/Mg product



          Carbon monoxide - 200 kg/Mg product
                             6-182

-------
         Isobutylene - 100 kg/Mg product




         Ammonia - trace




    Purification section - off-gas from drying column to flare (air)




         Hydrogen cyanide - 1 kg/Mg product




    Reaction section - neutralizer (water)




         Wastewater contains ammonium sulfate




    Purification section - stripper (water)




         Wastewater may contain by-products such as acetonitrile




6.  EPA Source Classification Code - None




7.  References




    Kent, J. A., Editor, Riegel's Handbook of Industrial Chemistry,




    Van Nostrand Reinhold Company, New York, N.  Y., 1974, p.  810.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N. Y., Vol.  13 (1967), p. 333,




    342.
                            6-183

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  66
                       Methacrylic Acid


                             HNO

                 (CH  )  C=CH9  - =-*- CH9=C-COOH
                   j Z    Z          2.
1.   Function - Methacrylic acid is produced by the thermally activated



     reaction of isobutylene with nitric acid or mixtures of this acid



     with NO    The initial oxidation proceeds at low temperatures



     (0-5° C) , and in several intermediate stages the oxidation pro-



     ducts are converted to a-hydroxyisobutyric acid, which is then



     dehydrated to methacrylic acid.



          A plant was built in Pensacola, Florida, by Escambia Chemical



     Corporation to use this process.  There were some economic prob-



     lems with the process and its present status is unknown.



2.   Input Materials



     Isobutylene



     Nitric acid



3.   Operating Parameters



     Initial oxidation stage: temperature - 0-5°C (32-41°F)



     Subsequent oxidation stages:  temperature - higher but unknown



4.   Utilities - Chilling water - quantities not given



5.   Waste streams - No data available.  It is presumed that some



     isobutylene and oxidation products would be released  to the



     atmosphere through leaks and vents.



6.   EPA Source Classification Code - None



7.   References



     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,



     Interscience Publishers, New York, N.Y., Vol.  3  (1964), p.  842.
                            6-184

-------
Anon., Chemical Week. 9JK26), 17  (1962),






Fr. Pat. 1,335,166  (July 8, 1963).






U.S. Pat. 2,847,453  (Aug. 12, 1958).
                        6-185

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  67

                             tert-Butyl Alcohol
                                       OSO H           OH
                            H SO       |      H 0      |
                 CH,-C=CH_ —-—2+ CH_-C-CH0 —=-*• CH,-C-CH,
                   3 |   2           3 |   3         3 j   3
1.  Function - Isobutylene is absorbed in sulfuric acid to form t-butyl

    hydrogen sulfate which is subsequently hydrolyzed with water to t-butyl

    alcohol and dilute sulfuric acid.  The product is steam stripped from

    the acid solution and purified by distillation.

         The process is similar to that for sec-butyl alcohol except for

    the sulfuric acid being less concentrated (60-65% vs 75-80%) to minimize

    polymerization reactions.

2.  Input Materials

    Isobutylene - 850 kg/Mg alcohol

    Sulfuric acid - recycled

3.  Operating Parameters

    Sulfation:  Temperature - 30-45°C  (86-113°F)

                Pressure - not given

    Hydration:  Temperature 30-40°C  (86-104°F)

                Pressure - not given

4.  Utilities - Not given
                               6-186

-------
5.  Waste Streams -




    Distillation column (water)  - Some t-butyl alcohol will be present in




    the waste water.  If caustic washing is  included  the waste water stream




    will contain some sodium hydroxide and sodium sulfate.




    Acid recovery section (water) - As tars  build up  some  sulfuric  acid is




    wasted in the effluent stream.




6.  EPA Source Classification Code - none




7.  References



    Astle, M.J., The Chemistry of Petrochemicals, Reinhold Publishing




    Corporation, New York, 1956.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-




    science Publishers, New York, Vol. 3  (1964), p. 827.
                               6-187

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  68
                       tert-Butyl Hydroper oxide
                  |H3         H2so4      fa
              H3C-C-OH + H202 — — ^ H3C-C-OOH
1.   Function - The formation of t-butyl hydroperoxide can be achieved by


     three different methods.  First,  the alkylation of hydrogen peroxide


     by alkyl sulfates, chlorides or alcohols in the presence of sulfuric


     acid.  Second, the oxidation of an appropriate hydrocarbon, in this


     case isobutane, in the presence of a chain initiator (HBr) , and third,


     the oxidation of an appropriate Grignard reagent with oxygen


     saturated ether.  The method of choice is the alkylation of hydrogen


     peroxide with t-butyl alcohol in the presence of sulfuric acid.


          The t-butyl alcohol, 30-50% hydrogen peroxide, in equimolar


     quantities, and sulfuric acid are combined in a water-imiscible solvent


     (chloroform or methylene chloride) having a boiling point lower than


     that of t-butyl hydroperoxide.  The reaction is carried out at 60°C


     with very rapid stirring, necessary because of the dual phase system,


     for a short period of time (1/2 - 1 hour) .  The reaction mixture is


     rapidly cooled and the organic solvent evaporated under reduced pressure.


     The yields are 70-80% of a 97% pure product.  The t-butyl hydroperoxide


     may be purified by vacuum distillation provided the pressure is main-


     tained at 100 mm or less at which point the boiling point (53°C) is


     below the decomposition temperature (73°C) of the hydroperoxide.
                               6-188

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2.   Input Materials




     t-Butyl alcohol




     30% Hydrogen peroxide




     70% Sulfuric acid




     Methylene chloride or chloroform




3-   Operating Parameters




     Temperature - 60°C (140°F)




     Pressure - 100 kPa (1 atm)




     Catalyst - sulfuric acid




4.   Utilities - Not given




5.   Waste Streams - Vent streams from the reaction vessel and purification




     system contain organic solvent vapors.  Wash water, sulfuric acid,




     t-butyl alcohol and some t-butyl hydroperoxide.




6.   EPA Source Classification Code - None




7.   References




     "Encyclopedia of Polymer Science and Technology, Vol. 9, Interscience




     Publishers, New York, New York, 1968, p. 815.





     U. S. Patent 2,573,947 (1951 Shell Development Co.).
                               6-189

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  69




                       p-tert-Butyltoluene
                             CH2=C-CH3
 1.   Function - Toluene is alkylated with isobutylene or tert-butyl




     alcohol in the presence of sulfuric acid.   The alcohol dehydrates




     readily in the acidic conditions of this process.   The alkylation




     proceeds very cleanly if temperatures are controlled to no  more




     than 75 to 80°C.   The product is washed in a caustic scrub  to




     remove the last traces of acid catalyst.




 2.   Input Materials




     Isobutylene or tert-butyl alcohol




     Toluene




     Sulfuric acid




 3.   Operating Parameters




     Temperatures:  75 to 80°C (167-176°F)




     Pressure:  101 kPa (1 atm)




 4.   Utilities - Not given




 5.   Waste Streams - Wastewater stream from caustic scrubbing would  con-




     tain spent caustic and traces of product.




 6.   EPA Source Classification Code - None




 7.   References




     Schlatur, M.  J.  and Clark, R. D. , J. Amer. Chem. Soc. , Vol. 75




     (1953),  p.  361-369.
                              6-190

-------
Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




Interscience Publishers, New York, N. Y., Vol. 3 (1964), p. 873.
                         6-191

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 70




                      2-tert-Butylbenzoic Acid
1.   Function - The stable character of the tert-butyl side chain on




     tert-butyltoluene toward oxidation leads to the production of




     tert-butylbenzoic acid by air oxidation.  In this process, a co-




     balt catalyst is used and a temperature of 110-180°C with a pres-




     sure of about 450-625 kPa (4.4-6.2 atm).  Water is removed as soon




     as it is formed.  Generally, the tert-butylbenzoic acid is isolated




     by crystallization or by extraction and crystallization.




2.   Input Materials




     tert-Butyltoluene:  850 kg/Mg acid




     Air:  approximately 2 Mg/Mg acid




3.   Operating Parameters




     Temperature:  110-180°C (230-356°F)




     Pressure:  450-625 kPa (4.4-6.2 atm)




     Catalyst:  a cobalt compound




4.   Utilities




     Steam - quantities not given




5.   Waste Streams - The water of reaction removed  from  the  process




     would probably carry small quantities of both  product and reactant.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers, New York, N.Y., Vol.  3  (1964), p. 436.
                             6-192

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 71

                          tert-Butylamine
                      3          H2SO,
                CH3-C=CH2 + HCN  — — =*  CH3-C-CH3
                      3         Nl/H
                CH--C-OH + NH-  -
 1.  Function - Two routes are used to produce tert-butylamine:   (1)

     isobutylene or tert-butyl alcohol is reacted with HCN in the pre-

     sence of sulfuric acid at a temperature of 25°C;  the alcohol

     dehydrates readily in acid and reacts the same as isobutylene with

     the HCN; (2) tert-butyl alcohol is reacted with ammonia at  190°C

     in the presence of a nickel catalyst and hydrogen.

 2.  Input Materials

     (1)  Isobutylene or tert-butyl alcohol

          Hydrogen cyanide

          Sulfuric acid

     (2)  tert-Butyl alcohol

          Ammonia

          Hydrogen

 3.  Operating Parameters

     (1)  Temperature:  must be carefully controlled to around 25°C
                        (77 °F) to prevent polymerization

     (2)  Temperature:  190°C (374°F)

 4.  Utilities - Not given
                              6-193

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5.  Waste Streams - No specific information available but purification




    would give wastewater streams containing spent catalyst and prod-




    ucts in small amounts.   Vents in process 2 could allow some ammonia




    and hydrogen to escape to the atmosphere.




6.  EPA Source Classification Code - None




7.  References




    Faith, W. L. et al., Industrial Chemicals, 2nd Edition, John Wiley




    and Sons, New York, N.  Y.,  1957, p.  53, 54.
                             6-194

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INDUSTRIAL ORGANIC CHEMICALS                                   PROCESS NO. 72




                              tert-Butyl Acetate
                  H,C-C=CH0   + CH  COOH — *• H,C-C-OOCCH
                   -J   |    2.       J         -J         -
^-'   Function - Reacting isobutylene with glacial acetic acid in the


     liquid phase over a silica catalyst impregnated with V 0_ and K^SO,


     at 93.3°C (200°F) and 1.72 MPa (17.0 atm) yields tert-butyl acetate.


     Exxon Corporation is the only company which reported production of


     the acetate to the U.S. Tariff Commission.


2.   Input Materials


     Glacial acetic acid


3.   Operating Parameters


     Temperature 93.3°C (200°F)


     Pressure 1.72 MPa (17.0 atm)


4.   Utilities


     Not given


5.   Waste Streams - Purification would give a wastewater stream which


     could contain small amounts of acid, acetate, alcohol, and catalysts.


6.   EPA Source Classification Code


     None


7.   References




     Kirk-Othmer, Encyclopedia of  Chemical Technology, 2nd Edition,


     Interscience Publishers, New  York,  N.Y., Vol. 8 (1965), p. 342.
                               6-195

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 INDUSTRIAL ORGANIC CHEMICALS                                   PROCESS NO.  73




                              p-tert-Butylphenol


OH                               QH           OH
    - CH3-C=CH2
         *                        p fnis \                             r* fc*i3  \
         CH3                     LU/H3;3      C(CH3)3               L^h3;3


 1.   Function - Isobutylene reacts quite readily with phenol in the


      presence of any of a wide range of acidic and Friedel-Crafts


      catalysts to give, successively, the mono-, di-, and tri-tert-


      butylphenols.


           Under acidic condition, tert-butyl alcohol dehydrates readily


      and yields the same alkylated phenols as the isobutylene.   High


      temperatures favor dealkylation and trisubstituted tert-butyl-phe-


      nols.


 2.   Input Materials


      Isobutylene or tert-butyl alcohol


      Phenol


      Acidic (50% H SO ) or Friedel-Crafts catalysts


 3.   Operating Parameters


      Temperature:  controlled to 70°C (158°F), then taken to 150°C (302°F)


      Pressure:  atmospheric


      Reaction Time:  1 hr


 4.   Utilities


      Not given


 5.   Waste Streams  - No specific information available but it  is probable


      that  purification procedures would give wastewater streams contain-


      ing traces of  mixed isomeric butylphenols, isobutylene polymers,


      and H2SO^ or Friedel-Crafts catalysts.



                               6-196

-------
6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclop dia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 1 (1963)  p.  904.
                               6-197

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 74

                       Neopentanoic Acid (pivalic ac±d)


                     f 3          ECO H     f3
                  CH0COH + H0SO.   	=-> CH.C-COOH         (A)
                    3|      2  4           3,
                     CH3                    CH3
                           P3         H2so      fa
                     CH0 = C-CH0 + CO  ——-*-»• CH0C-C00H    (B)
                       23                3j    2
                                                 CH3
1.  Function - Neopentanoic acid is made by two different processes.   In

    one process (A) tert-butyl alcohol is reacted with sulfuric acid  and

    formic acid at a temperature of 20-25°C.   The product is purified

    by distillation.

         The other process (B) involves the carboxylation of isobutylene

    with carbon monoxide in aqueous sulfuric acid.  The isobutylene and

    acid catalyst are pumped to a pressurized reaction vessel where a CO

    rich gas is bubbled through the mixture to form a tertiary carbonium

    ion.  After degassing, the complex is hydrolyzed with water to spring

    the acid catalyst for recycle.  The crude acid is treated to remove

    the last traces of catalyst and then purified by distillation.

2.  Input Materials

    (A) tert-Butyl alcohol

        Formic acid

        Sulfuric acid

    (B) Isobutylene

        Carbon monoxide

        Dilute HS0            6~198

-------
3-  Operating Parameters

    (A) Temperature:  20-25°C (68-77°F)
        Pressure:  Not given

    (B) Temperature:  reaction - 20-60°C (68-140°F)
                      distillation - 163-165°C (325-329°F)
        Pressure:  reaction - 3.6 MPa (35.5 atm)
                   distillation - 101 kPa (1 atm)
        Reaction time:  5-180 minutes

4.  Utilities

    Steam - Not given

    Electrical power - Not given

5.  Waste Streams

    (A) Distillation bottom ends could give a wastewater stream containing

    small quantities of product and catalyst.

    (B) Reactor off-gas will contain CO and isobutylene vapors.   Water

    from springing of catalyst could give rise to a wastewater stream

    carrying some acid catalyst and crude product.

6.  EPA Source Classification Code - None

7.  References

    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,  Inter-

    science Publishers, New York, N.Y., Vol.  8  (1965), p. 853,854.


    Sittig, M., Chemicals  From C,  Hydrocarbons,  Noyes Development Corp.,

    Park Ridge, N.J.,  1966,  p.  88,89.
                              6-199

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  75

                       Pi- And Tri-Isobutenes

 1.  Function - The isobutene in a C,  stream (free of butadiene)  is

     absorbed in 50-65% sulfuric acid  at 10-20°C and then heated  to 80-

     100°C to coproduce diisobutylene  and triisobutylene in the ratio of

     80% to 20%.  The oligomers separate as an upper layer which  is

     separated, washed, and purified by distillation.

 2.  Input Materials

     Isobutene

     H2SO, (recycled)

 3.  Operating Parameters
     Temperature:   extraction - 10-20°C (50-68°F)
                   polymerication - 100°C (212°F)
                   time - 0.5 hour

 4.  Utilities - Not given

 5.  Waste Streams - Caustic washes (water)  - Waste stream contains

     sodium hydroxide, sodium sulfate, and organic by-products such as

     butyl alcohol.

          Distillation column produces heavy ends.

 6.  EPA Source Classification Code - None

 7.  References

     McKetta,  J. J., Editor, Advances in Petroleum Chemistry and Refining,

     Interscience Publishers, New York, N. Y., Vol. 7 (1963), p. 285-

     321.


     Goldstein, R. F., The Petroleum Industry Today, 2nd Edition, John

     Wiley and Sons, New York, N. Y., 1958,  p. 125.
                              6-200

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       SECTION  III
SOURCES OF CRESYLIC ACIDS
        6-201

-------
                                         SOURCES OF CRESYLIC ACIDS
CRUDE COAL TAR      76
PETROLEUM DISTILLATE
                              Carbolic Oil
                                                       27     Crude
                                                      	:—> Sodium
                                                              Carbolate
                                                                           78
                                   -> Phenol


                                   -» o-Cresol


                                   -» m,p-Cresols
                                  I—^Xylenols

                                      Phenolic  Pitch
                            79                                 80
                Toluene 	     )    Toluenesulfonic acids	
                p-Cymene
                                                                            p-Cresol
                 Phenol -
                              82
                                              .p-Cresol
                                              > tn-Cresol
o-Cresol
                                              ^Xylenols
                                               Higher methylated phenols
          Figure  5.   Sources of Cresylic  Acids Chemical  Tree
                                    6-202

-------
1

H.,0
Y I -
NaOH p
77
Extraction
r
M
O
              I  o-Cresol  I
Sulfonation
79

                                                           rp-Toluene
                                                             sulfonlc
                                                               acid

1
Steam
Heat j
2. 4
VA 1 I* <
Heat NaOH
T3ip Iv
1 Iry^. f *
H2° 1 0
\\fA
Fractionation78^ Substitution8" " j^SSlS^'

•*^ 	 —


L-^ ^~~^~^ ^^"^^N. ^f~^"^^. JX*"

"^""^. ^^^*
1 o *•
Cooling j =f |
waterjf f 4 4
Alkylation and 82
fractionation

^—•^ - — '



^-^ >-"

!
p-Cresol
I p-Cresol J
I  m-Cresol J
  Higher
I methylated)
  phenols
                                              Figure 6.   Sources of  Cresylic  Acids Process  Flow Sheet

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS  NO.  76




                                Carbolic Oil




1.  Function - As produced, crude coal tar is of value only as a fuel.




    Today, at least 85% of the tar produced is distilled.   The two main




    objectives in the primary distillation of crude tar are to obtain




    a pitch or refined-tar residue of the desired softening point  and to




    concentrate those components which are subsequently to be  recovered.




    In the case of continuous vertical-retort tar, the main aim is to




    concentrate the phenol, cresols,  and xylenols in the carbolic  oil




    fraction.  The amount of "phenolic bodies" in coal tar depends on the




    carbonization process used.   Coke-oven by-product tars contain between




    1 and 7% of "phenolic bodies", the average being close to  3%.   Gas-




    works tars derived from the carbonization of bituminous coal in




    continuous vertical retorts have  an average tar acid content of 15%




    and low-temperature tars may contain as much as 25%.




         Primary distillation of coal tar in the U. S. is done in "Recycle




    Continuous Stills".  Crude tar, after screening and doping with alkali,




    is pumped through a series of heat exchangers and a waste-heat coil




    and then injected into the lower  section of a dual flash chamber where




    it meets hot pitch overflowing from the upper section.  The water and




    light-oil vapors released in the  lower section pass up through a




    liquid seal into the upper part.   The mixture of dehydrated tar and




    pitch is pumped from the base of  the distillation column,  through the




    furnace coil and, at a temperature of 360°C enters the upper  chamber




    of the distillation column,  where the oil vapors  flash off assisted




    by the injection of superheated steam.  These vapors and  the  vapors
                              6-204

-------
    from the lower section  issue,  from  the  top of  the distillation column


    into the base of  the  side-stream fractionating column.  The pitch,


    which accumulates  at  the base of the upper section of the distillation


    column, is partly  withdrawn as product  and partly allowed to overflow


    into the lower section  where  it mixes with the crude tar before recycle

    through the  furnace coils.

2.  Input Materials

    Crude coal tar


    Steam

    Alkali

3.  Operating Parameters

    Temperature  - 360°C (680°F)

    Pressure - not given
         i
4.  Utilities

    Steam - quantities not  given

5.  Waste Streams - Small quantities of hydrocarbons would be expected to


    escape to the air  from  distillation columns.


       Waste Flow           3.38 I/kg (405.3 gal/103 Ib)       3.38 I/kg

       COD                  2,570 mg/lg

                            8.68 g/kg (lb/103 Ib)


       BOD5                 833 mg/1


                            2.81 g/kg (lb/103 Ib)


       TOC                  3,010 mg/1


                            10.16  g/kg  (lb/103 Ib)


6.   EPA Source Classification Code - None
                               6-205

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7.   References




     Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 6 (1965), p. 434.






     Ibid, Vol. 19 (1969), p. 653.






     Sittig, M., Pollution Control in the Organic Chemical Industry,




     Noyes Data Corp.,  Park Ridge, N. J., 1974, p. 108-113.
                             6-206

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 77




                           Crude Sodium Carbblate





!•  Fimction - Since only phenol, the cresols, and the lower-boiling




    xylenols are of commercial value, only those fractions obtained on




    the primary distillation of crude tar which distill between 185P




    and 240°C are treated for tar acid extraction.  These oils (carbolic




    oil) are contacted with a slight excess of 8-10% caustic soda solution




    at the minimum temperature which will prevent crystallization of the




    naphthalene which is also usually a major component.  Extraction may be




    carried out in stirred vessels, in packed or unpacked towers, in mixer-




    settler units, or simply by mixing the two streams by a gear pump.




         The other major source of cresols in the U. S. is from petroleum.




    The petroleum-based cresols are obtained from spent caustic liquor used




    to wash petroleum distillates.




2.  Input Materials




    Carbolic oil




    Petroleum distillates




    NaOH                                                    '




    H20




3.  Operating Parameters




    Temperature - not given




    Pressure - atmospheric




4,  Utilities - not given




5.  Waste Streams - Caustic soda may be released in wastewater streams; small




    quantities of non-acidic hydrocarbons released to the air or wastewater




    streams.
                               6-207

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6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,




    Interscience Publishers,  New York,  N.Y.,  Vol.  6 (1965),  p.  434.
                               6-208

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 78
          Phenol, o-Cresol, m,p-Cresol, Xylenols and Phenolic Pitch

1.  Function - Crude sodium carbolate is treated with live steam, some-
    times after extraction with a phenol and base-free coal-tar naphtha or
    light creosote oil.  The purified carbolate is then contacted counter-
    currently with a gas containing CO- in packed towers.  The springing
    medium may be flue gas containing 10-14% CO  or a richer gas containing
    30-35% C02>  Conditions in the springing towers are generally adjusted
    so  that  the aqueous phase leaving this stage contains 2-3% of the
    available alkali as bicarbonate.  After springing, the two layers are
    separated by decantation and the tar acid  layer, which contains about
    20% water, is retreated with the C02 - containing gas to convert any
    residual carbonate  to  bicarbonate.  Alternatively, the crude wet tar
    acids may be partially dehydrated by treating with concentrated sulfuric
    acid.  The partly  dried  tar acids are  first  distilled to yield water
    containing some phenol (this fraction  is recycled to the extraction stage),
    a main  fraction of "once-run tar acids", and a  residue of phenolic pitch.
    The main fraction  is  fractionated  in two or  three continuous  columns  to
    yield phenol, o-cresol,  m,p-cresol  mixture and  xylenols.
         The same procedure  may be used in treating the  crude  sodium carbolate
    from petroleum  sources or an  additional oxidation step may be introduced
    to  remove  any mercaptans.
 2.  Input Materials
    Crude  sodium carbolate
    co2

    V°4
     Steam
                                6-209

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3.  Operating Parameters




    Temperature - not given




    pressure - not given




4.  Utilities - not given




5.  Waste Streams - Caustic soda may be released in wastewater; small quantities




    of phenolic bodies released to the air from distillation columns.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd  Edition,  Inter-



    science Publishers,  New York,  N.Y.,  Vol.  6  (1965),  p. 434.
                               6-210

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INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 79




                         Toluenesulfonic Acids
1.   Function - The sulfonation of toluene produces all three isomers




     (o, m and p).  The para isomer is formed as the temperature of




     the reaction is increased.  Sulfonating with oleum at low temper-




     ature produces a mixture of ortho and para sulfonic acids, the




     ortho isomer predominating.  These isomers are separated either




     by converting to the sulfonyl chloride derivative (ortho-viscous




     oil; para-solid) or by crystallization.




         The pure meta isomer is produced by sulfonating p-toluidine




     and diazotization of the product.  The predominately para-isomer




     is made by raising the reaction temperature to 100°C.




2.   Input Materials - Basis:  1 kg of toluenesulfonic acid




     Toluene - 0.53 kg




     Oleum - >0.46 kg.




3.   Operating Parameters




     Temperature:        100°C  (212°F)




     Pressure:           100 KPa (1 atm)




     Catalyst:           None
                             6-211

-------
4.   Utilities - Not given




5.   Waste streams - No specific information was available.  The usual




     sulfonation process is enclosed to prevent the emission of acid




     mists.  Air pollution by mists can occur when storage vessels are




     loaded.  The distillation may result in toluene vapor emissions.




          There will be a wastewater stream containing neutralized




     acid, probably as sodium sulfate.  Some organic material will




     also be discharged into the waste stream (toluene and toluene




     sulfonic acid).  The wastewater will arise from three sources:




     (1) air pollution control devices (scrubber); (2) condensate




     from the distillation; (3) diluted acid from the reactor.




6.   EPA Source Classification Code - None




7.   References




     Medley, W. H., et al., Potential Pollutants from Petrochemical




     Processes, Monsanto Research Corporation, Dayton, Ohio, Technomic




     Publishing, Co., Inc., Westport, Conn., 1975, p. 330.






     Brooks, B. T., S. K. Kurtz and L. S. Schmerling, "The Chemistry




     of Petroleum Hydrocarbons," Vol. Ill, Reinhold Publishing Corp.,




     New York, N.Y., 1955.
                              6-212

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 80




                          p-Cresol (from toluene)




                                     CH,
1.  Function - Only a small tonnage of p-cresol is produced synthetically




    by sulfonation of toluene.  The sulfonation product is predominantly




    p-toluene sulfonic acid with a small amount of the o-isomer.   Fusion




    with caustic soda and caustic potash at 330-360°C yields the  alkali




    salts of the cresols from which they are recovered by neutralization




    and pure p-cresol is recovered by fractionation.




2.  Input Materials




    Toluene




    Sulfuric acid




    NaOH or Na^CO,




    Water




3.  Operating Parameters




    Not given




4.  Utilities




    Not given




5.  Waste Streams - Small quantities of sulfuric acid and cresol  would be
    expected to escape in waste waters and air.




         Flow         10.8 I/kg (




         COD          23,800 mg/1
Flow         10.8 I/kg (1291 gal/103 Ib)
                      256 g/kg  (lb/103 Ib)
                               6-213

-------
          BOD5           11,400 mg/1




                         123 g/kg (




          TOG            5,020 mg/1
123 g/kg (lb/103 Ib)
                         54 g/kg (lb/103 Ib)




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 6 (1965), p. 434.






     Ibid, Supplement Volume  (1971), p. 271






     U.S. Patent 2,225,564 (Dec. 17, 1940).






     Sittig, M., Pollution Control in the Organic Chemical Industry,




     Noyes Data Corp., Park Ridge, N.J., 1974, p. 113-116.
                             6-214

-------
INDUSTRIAL ORGANIC CHEMICALS

                         p-Cresol (from p-cymerie)
PROCESS NO. 81
                          ox.
                                                                    0
             *3    ^3            w"i
1.  Function - A small amount of p-cr%sol is also produced synthetically
    by oxidation of p-cymene.  The general tight supply of naval stores
    (from which p-cymene is isolated) and the recent high cost does not
    make this an economical starting material for the synthesis of
    p-cresol.  The Hercules Powder Co. has alkylated toluene with propylene
    in the presence of A1C1_ to give a mixture of cymenes rich in the m-
    and p- derivatives.  This mixture is treated with an oxygen-containing
    gas at 25-35°C in the presence of aqueous alkali and the resultant
    mixture of hydroperoxides is decomposed into cresols and acetone by
    treatment, in an alcohol solvent, with sulfuric acid at 65-85°C.
2.  Input Materials
    p-Cymene

    °2
    Alkali
    H20
    Methanol
3.  Operating Parameters
    Hydroperoxidation - 25-35°C  (77-95°F)
    Decomposition - 65-85°C  (149-185°F)
    Pressure - Atmospheric
                              6-215

-------
4.  Utilities - Not given




5.  Waste Streams - Waste water contains sodium hydroxide, p-cresol and




    acetone.  The air vents may emit p-cymene and acetone.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 6 (1965), p. 434.






    Ibid., Supplement Volume  (1971), p. 271.






    Brit. Patent, 754,872 (Aug. 15, 1956).
                               6-216

-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 82
                   p-Cfesol, m-Cresol, 6-Gresol, Xylenols



                        and Higher Methylated Phenols
          CH,OH
            -J     A
                            OH
                                                               '(CH3)2
                       '(CH3)>2
1.  Function - Vapor-phase methylation of phenol with methanol over an



    aluminum catalyst yields, according to the conditions, different



    methylated phenol products.  Careful control of the temperature and



    selection of different acidity silica - alumina catalysts permits some



    selectivity in methylation products.  The ratio of mono- to poly-



    methylated products can be controlled by the ratio of methanol to



    phenol.  The methyl group needed for the methylation of phenol may



    be derived from many different sources, e.g., methyl halides,  methyl



    ethers, methyl amine.  Co-catalysts may also be used to increase the



    selectivity in methylation.  In 1965 Koppers Company started the first



    synthetic cresol plant which was soon followed by Consolidated Coal



    Co.



         The pure cresols may be separated in a continuous fractional



    distillation.  The similarity in the b.p. of the m- and o- isomers



    precludes their separation by this means.  Azeotropic distillation



    with benzyl alcohol, selective solvent extraction or solid complex



    formation between the reagent and one of the cresol isomers are



  '  some of the techniques used in their separation.
                               6-217

-------
2.  Input Materials

    Phenol

    Methanol

3.  Operating Parameters

    Alkylation - Temperature from 175°C to 375°C depending upon the
                 products desired.

4.  Utilities

    Not given

5.  Waste Streams - Small quantities of phenol and methanol would be expected

    to escape in waste water as well as air.

6.  EPA Source Classification Code - None

7.  References

    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

    Interscience Publishers, New York, Vol. 6 (1965), p. 434.


    Ibid.. Supplement Volume  (1971)  p. 271.


    British Patent 602,257 (May 24, 1948).
                              6-218

-------
SECTION IV
 ETHYLENE
6-219

-------
   ETHYLENE
                                              ETHYLENE
  83
         Ethyl bromide
  95
          Vinyl acetate
  —	Acetaldehyde-,—'.	^Acetaldol •
114
                                                   86
1,3-Butylene glycol
                                          87                  88                      89
                                         —-xCrotonaldehyde__-_in-Butyraldehyde  —t—-—> n-Butyric acid
                         91
                                Glyoxal
                         92
                         93
                              yMethylpheny1carbi nol
                               Paraldehyde
                         94
                                      Formic acid
                        100
                               __^Pen ta ery thr i to 1
                                     Pyridine
                        101
        1 Ethylene dibromlde
                                    ,$-Picoline
                                    >Acetic  anhydride.
                                     Acetic acid.
                                                              96
                                                                   Sorbic acid
                    90
                        . 2-Ethylhexanol
                                                               97
                                                          102
n-Butanol
                                                                                 99
                      ^n-Butyl acetate
                                                                   iCrotonic acid
     Cellulose acetate
115
         Ethyl chloride
                            118
                                   116
                                   117
                                         i Tetraethyl  lead
                                         ,Tetraethyl  lead
                                    .Ethyl cellulose
               Figure  7.   Ethylene Section  Chemical  Tree


                                       6-220

-------
103
             >Ethyl acetate
                                  107
             ,Isopropyl acetate
Ethyl acetoacetate
                                                                                 128
                                                                                 129
                                                                                       Acetamide
                                                                                        Ethyl  sodium oxalacetate
104
      _iChloroacetic acid
                                               108
                                                  •^  Glycine
                                                109
                                                    -^Sodium chloroacetate-
                                                 110
                                                        Ethyl chloroacetate
                                                                                   112
                                                                                        -^Sodium carboxymethyl cellulose
                                                                                   	^ Cyanoacetic acid  	^ Ethyl cyanoacetate
 105
         Acetic anhydride
 106
        Sodium acetate
                                    Figure  7.    Ethylene  Section  Chemical Tree  (Cont.)

-------
   ETHYLENE
 119                  120
_	\ Ethanol -
                      121
  —> Ethyl amine
  —> Diethylamine
  	^Tri ethyl ami ne

•* Ethyl  oxalate
                      122  > Ethyl acrylate
                      I23  ) Acetal
                      124
                          -) Acetaldehyde
                      127
                          -»Di ethyl ether
 130
125
       -^Vinyl toluenes
          131
                  Ethylene dichloride
          132
               -jEthylene di chloride-
      -^Diethyl sulfate
                   133
                           Vinyl  chloride
                                          134
                                                 Ethylenediamine •
                                                                        135
                                                                              -^ Aminoethylethanolamine
                                            137                           139
                                           	^1,1,2-Trichloroethane	> Vinyl idine chloride
                                              138
                                                      ,1,2-Trichloroethane
                                         140
                           -£ Carbon tetrachloride
                           -4 Tri chloroethylene
                                                      -^Perchloroethylene .
                                                                            141
                                                       -^1,1,2-Trichloro-
                                                           1,2,2-Trifluoroethane
126
      -^Propanoic acid
          Figure  7.   Ethylene  Section  Chemical  Tree  (Cont.)
                                     6-222

-------
       ETHYLENE
      136
Ethylene chlorohydrin
                                                  >  Bis-(2-chloroethyl)  ether
      143                        144
     	>Ethylene oxide —|  •    |  >Ethylene  glycol
                                                                  145
 I
N>
KJ
                                    —>D1ethylene glycol
                                    —)Triethylene glycol
                                   149
                                                                146
                                                                       Dloxane
                                                                147
                                                         Dioxolane
                                                                1*8
                                                                     ->2-Methyl-l,3-dioxolane
                                                    Ethylene glycol  monobutyl ether.
                                                  , Ethylene glycol monoethyl ether
                                                  * Ethylene glycol monohexyl ether
                                                  >Ethylene giycol monomethyl  ether-
                                                  (Ethylene glycol monooctyl ether
                                                  yEthylene glycol iwnophenyl ether
                                                  ^Ethylene glycol monopropyl ether
                                                                                                               > Ethylene glycol monoacetate
                                                                                                               >Ethylene  glycol diacetate
                                                                                                    -)Diethylene glycol monobutyl ether-
                                                                                                    -)Diethylene glycol monoethyl ether.
                                                                                                    -^D1 ethyl ene glycol monohexyl ether
                                                                                                    -)D1ethylene glycol monomethyl ether-
                                                                                                    -^Trlethylene glycol monomethyl ether-
                                                          Figure 7.   Ethylene  Section  Chemical  Tree  (Cont.)

-------
ON

ts>
N3
•C-
         150
          151
                          ^Ethylene glycol dibutyl  ether
                         -^Ethylene  glycol diethyl ether
                     	^Ethylene glycol dimethyl  ether
                          (Ethylene  glycol monobutyl ether acetate
                         -^Ethylene glycol monoethyl ether acetate
                          iEthylene glycol monomethyl ether acetate
                                                                                         150
150
                                                                                          151
                ' Diethylene glycol dibutyl ether
                • Diethylene glycol diethyl ether
                i Diethylene glycol  dimethyl ether
                                                                                                  -) Triethylene glycol dimethyl  ether
               )Diethylene glycol monobutyl ether acetate
              -^Diethylene glycol monoethyl ether acetate
                                                                                                         kDiethylene glycol  monomethyl ether acetate
                                                Figure 7.   Ethylene  Section Chemical Tree  (Cont.)

-------
     152
CM
Kl
            —^Ethanolamine •
             -)Diethanolam1ne-
i—^Triethanolamine .
                                     153
                                            Morphollne
                                                                               154
                                                                                        Piperazine
      155
             Polyethylene glycol
      156,
           -> Ethylene carbonate
                                            Figure  7.   Ethylene Section  Chemical Tree  (Cent.)

-------
HBr
1
Steam ! 02
83
Hydrobromi nation
X|
Cooling H20 Acetic add 02
H J3 It
84
Oxidation
XI
Heat
* &
95
Oxyacetylation

                                                                      Acetaldehyde
                                                                                          I  Vinyl   \
                                                                                          I acetate  /
NJ
N3
Cooling:
water
It
Cooling
NaOH| n waterj
1 A It
85 1 "
Condensation, 1
Cooling
UNO, Steam water
i f> u
91
Oxidation1

*<3
Bromobenzene
Mg 1 Benzene H2S04
1 iifjo t
Grignard 92
reaction
i

XJ

HZ° Steam!
tl
^-* ¥
.93
i Polymerization

*D
	 »i
Base
[HCHOi _
1 1
94
Condensation
JL 1

r
          Heat]
ill
Reduction:
86
                                              Cooling
                                     Heat  ,H,| ' water i
                                       1  4   ti

                                       Hydrogenatlon
                                                                        iMethyl
                                                                       I phenyl-.
                                                                       carblnol:,
                                                                                 Air or 62
I ^ iCooUng
I"1 I water
                                                                                        ; Oxidation
                                                                                                 ; 89
                                                                                             •Cooling
                                                                                    i Steam  j H2|water
                                                                                       1   I   H
                                                                                       Condensation
                                                                                      Hydrogenation
                                               Figure 8.   Ethylene Section Process  Flow Sheet

-------
                                                                                                      D1ethyl oxalate

                                                                                                     Ethanol  I    "a  p

                                                                                                                I I A
                                                             Acetic acid
                        Cooling water    A1r|
                                       I VA
ho
                                                            Cooling waten»'Isopropanol
                              Chlchlbabln10.?
                               synthesis^
                                          Figure  8.   Ethylene  Section  Process  Flow  Sheet (Cont.)

-------
                        Cooling Mater
ON
 I
S3
N3
00
                                         Br2

                                          t  y^Vv
114


/ Ethyl ene\
*1 dlbromlde J

Cooling water


HC1
115
nation
     Acid
Steam  I   Ketene
                               am   I
                               *   I
                                                             Cooling watecTl
                                                              Steam    *|[ Acetic^acld

                                                                           99
                                                                 Esterlflcatlon
                                        Figure  8.   Ethylene  Section Process Flow  Sheet  (Cont.)

-------
  H20 —
Steam -.
 HeaJ-jJ
Steam
       Hydratlon
                119
Toluene
	L
                130 r
Cooling water
 Heat-ifl
    Alkylatlon &
    Dehydrogenatlon
                                                                                    EsterlfIcation

ULs
136
Carbonylatlon
»•*
                 Ammonolysls
                        Na2C03
                          109
               Neutralization
                       'Ethanol
                          no
               •Esterlflcatlon
                                                              Cellulose"
                                                                    OH
                                    Sodium;
                                    carboxy-
                                    roethyl
                                    cellulose
                                                                                               Heat
                                                                                                       Ethanol
                                                                                                         I  JO
                                                                                             Esterification
                                                                                                         113
                               Figure 8.    Ethylene  Section Process Flow Sheet  (Cont.)

-------
N3
U>
O
        •Cooling water;

              iHeat
                                                       Steam
          e-»







Diethylaminer"	
                                  Triethvlaralne
 Cooling
      „  iacld"
Steam.  II  !d1hydrate
31
mr<

NH3 Heat o
1 * /
120 VJ




121
JEsterlflcatlon
^< /
Cooling
watery Acrylic
*»it"f4Tj


122
Esterlflcatlon
=H
i - Ac1d ,'!Ket,
'Steam i aldehydeo
4 I I 7



123
ICnnHon^at inn

Steam. H2|°4
127

"XI ^
ft


                                       Figure 8.   Ethylene Section Process Flow Sheet (Cont.)

-------
     Cooling H20
Steam
   Refrlg.
  ON

  N>
  U)
            Cooling H20_,
        Steam.-
          Refrlg.
                iV
                       133
            Pyrolyslsi
                                        Heat  iuM  •
                                   Steam  I   >m*<
                                    Amnonolysls
 Heat |
  *
                                     Pyrolysls
                                   Cooling H20
                                   Steam
   y  z 1  r1
   -i  n   *
                                    ChloH nation
                                   Heat
       t

  •if   "I
Chlorinatfon .140
& Pyrolysls ;
                                                                                                  Cooling H20,-
                                                                      n    I   CaO
                                                                      rn-fo
                                                                                                                                               Bis-
                                                                                                                                             -chloroethyl)
                                                                                                                                              ether
                                            Figure 8.   Ethylene  Section Process  Flow  Sheet  (Cont.)

-------
           : Steam
Pooling
H20
t!

'
r
143
Oxidation
\G « i . 3 .
Steam
Mr
<* /
^
                                                                                           Ethylene
                                                                                            glycol
                                                                                          mono- &  dl
                                                                                           acetate
            145
 Ester1f1cat1on
                                                                               147
                                                                    Condensation
                                          Triethylene
                                            Glycol
                                                                                          2-Methyl-l,3
                                                                                           dloxolane
                                                                                            Ethylene
                                                                                             glycol
                                                                                            dlethers
                                           Ethylene.
                                            glyco
                                          mono'ethers
                                                                                            Ethylene
                                                                                            Glycol
                                                                                           Honoether
                                                                                            acetates
 Esterlflcatlon
                                                                                          '01 ethylene
                                                                                             glycol
                                                                                            dlethers
            ,1BO
  Alkoxylatiorr
                                          Dlethylene
                                             glycol
                                            noether
Steam Acetic add
                        .Diethylene
                        '  Glycol
                         Monoether
                          Acetates
                                                                    Esterlflcatlon
                                                             Alkyl chloride
                                                                    1
                           Tri-
                         ethylene
                           glycol
                         dimethyl
                            ther
                                           rl ethyl en
                                             glycol
                                             noether
Figure  8.    Ethylene Section  Process  Flow  Sheet  (Cont.)

-------
                                                  \   Heat
                                                  I    1

                                                   Ammonolysls
 HH3

J_
 152
                                                       NaOH
                                                  Steam  I    H20
OJ
CO
                                                     Hydratlon
                                                             15S
                                                   CO,
                                                  Condensation
                                                             156
                                                 Figure  8.  Ethylene Section  Process Flow Sheet  (Cont.)

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  83
                  Ethyl Bromide (from ethylene)







                  CH2=CH2 + HBr 	»• CELCH^Br






1.   Function - In recent years, ethyl bromide has been produced  by the




     vapor-phase reaction of high-purity ethylene and hydrogen bromide.




     The reaction is catalyzed by gamma radiation from cobalt-60.   It




     may also be prepared from ethanol and HBr.




2.   Input Materials




     Ethylene




     Hydrogen bromide




3.   Operating Parameters




     Temperature:  Not given




     Pressure:  Not given




     Catalyst:  Cobalt-60, as a source of gamma radiation




4.   Utilities




     Not given




5.   Waste Streams - Information on this process was too limited to




     evaluated its potential pollutant sources, but HBr and ethylene




     may leak out of the system.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers,  New York,  N.Y.,  Vol.  3 (1964),  p.  774.






     Shreve, R. N., Chemical Process Industries, 3rd Ed., McGraw-Hill




     Book Co., New York, N.Y.,  1967  ,  p.  793.





                              6-234

-------
References (continued)




Hahn A. V., The Petrochemical Industry;  Markets and Economics,




McGraw-Hill Book Co., New York, N.Y.,  1970   p. 316.
                         6-235

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS  NO.  84

                  Acetaldehyde (Wacker process)

         C2H4 + 1/2 02	1- CH3CHO + heat (244 kJ/mole)

 1.  Function - The Wacker process employs an aqueous catalyst solution

     of palladium chloride, promoted by copper chloride.

          The catalyst acts as the oxygen carrier and causes selective

     conversion of ethylene to acetaldehyde.  The reaction steps essentially

     are:
                                    PdCl?
     Reaction:  C2H4 + 2CuCl2 + H20 	=* CH3CHO + 2HC1  + 2CuCl

     Regeneration:  2CuCl + 2HC1 + 1/202 	* 2CuCl2 + H20


     There are two basic process variations, depending upon such factors

     as oxygen cost, utilities prices, and available ethylene purity.

     In the single-stage process, pure oxygen is employed as the oxidant.

     The reactor effluent is condensed and water-scrubbed.  Unreacted

     gas is recycled into the reactor.  By-products and water are separated

     from the acetaldehyde product by distillation.  Both the reaction

     and regeneration are effected at the same time.

          In the two-stage process, the oxidant is air.  The reaction is

     carried out with catalyst solution and ethylene in one reactor, and

     the regeneration is carried out with air in a separate reactor.  Lower

     purity ethylene can be used with this version of the process.  However,

     this process forms more by-products and requires high operating pres-

     sures .

        The production of acetaldehyde by vapor phase oxidation of propane-

     rich LPG is considered obsolete.

 2.  Input Materials  (per metric tonne  acetaldehyde)
                             6-236

-------
                                        Single-stage        Two-stage


     Ethylene 99.8 vol. %, kg               670               670*

               3
     Oxygen, Nm                             275


     Catalyst:  PdCl2, g                      0.9               0.9


       CuCl2 + 2H20, g                      150               150


     HC1 (100%) used as 30% aqueous
     solvent, kg                              4                15


 3.  Operating Parameters


     Temperature, °C(°F)                    130(266)


     Pressure, kPa (atm)                    294 (2.90)       784-883

                                                           (7.74-8.71)
 4.  Utilities


     Cooling water (25°C), m3               300               200


     Cooling water (12°C), m3                -                 12


     Process water, m                         6                 -

                       3
     Deionized water, m                       3                 -


     Steam, metric ton                        1.6               1.2


     Electric power, MJ  (kWh)               754 (210)         300**


     Credit for nitrogen (protection
     gas), Nm  (637 kPa)                      -               900


 5.  Waste Streams - Purification section - acetaldehyde scrubber vent


     to flare (air).


     Ethane:                  2.2 kg/Mg acetaldehyde


     Ethylene:                27.4 kg/Mg acetaldehyde


     Acetaldehyde:            trace


     Methane:                 trace


     Methyl chloride:         trace
   Ethylene of lower purity results in slightly higher consumption
**
   Including air compression
                             6-237

-------
    Purification section - acetaldehyde stripper vent  to flare (air)


    Methyl chloride:          8.65 kg/Mg acetaldehyde


    Acetaldehyde:            trace

                                                        3
         A typical Wacker process discharges about 4.4 m  (1,200 gallons)


    of waste per ton of product.   The chlorinated aldehydes are the


    principal contaminants in the waste streams which  have a COD of

                         3
    approximately 10 cg/m  (10,000 mg/1).


         The two-stage process yields relatively small amounts of a


    rather concentrated waste water which  must be pretreated before


    normal biodegradation.  The single-stage yields considerably more


    of a more dilute waste water suitable  for biodegradation.


6.  EPA source classification code - None


7.  References


    Morse, P. L., "Acetaldehyde," Report No. 24, Stanford Research


    Institute, Menlo Park, California, April 1967.



    Gloyna, E. F., and Ford, D. L., "The Characteristics and Pollutional


    Problems Associated with Petrochemical Wastes," for FWPCA, Contract


    No. 14-12-461, February 1970.



    Austin, G. T., "The Industrially Significant Organic Chemicals -


    Part 1," "Chemical Engineering," January 21, 1974, p. 127.



    "1975 Petrochemical Handbook," "Hydrocarbon Processing," 54, November


    1975, p. 100.



    Jira, R., et al., "Hydrocarbon Processing," 55, March  1976, p. 99.
                            6-238

-------
Sittig, M., Pollution Control in the Organic Chemical Industry, Noyes




Data Corporation, Park Ridge, N.J., 1974, p. 50,52.





Lowenheim, F. A., and Moran, M. K., Industrial Chemicals.  4th Edition,




John Wiley & Sons, New York, N.Y., 1975, p. 1,2.
                            6-239

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  85




                             Acetaldol






                   2 CH3CHO  	>  CH3CHOHCH2CHO






 1.   Function - Acetaldol is made from acetaldehyde via liquid-phase




     condensation at 10-25°C in the presence of dilute alkali.   This




     process results in a 95% yield with about a 60% conversion.




 2.   Input Material




     Acetaldehyde:  1.05 kg/kg acetaldol, 107 kg/hr




     H20: 20 kg/hr




     NaOH (20 g/A):  16 £/hr




 3.   Operating Parameters




     Temperature:   10-25°C (50-77°F)




     Pressure:   not given




     Catalyst:   10% NaOH




     pH:   4-5 (by HC02H)




 4.   Utilities - Not given




 5.   Waste Streams - Wastewater streams from acetaldehyde strippers may




     contain acetaldehyde, acetaldol,  and dilute sodium hydroxide.




 6.   EPA  Source Classification Code -  None




 7.   References




     Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N. Y., Vol. 1 (1963), p. 82.





     Ibid, Vol. 6  (1964), p. 446





     British Patent 630,904  (October 24,  1949).
                             6-240

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 86
           1,3-Butylene Glycol (reduction of acetaldol)






                                H2
          CH CHCH CHO       	=	*      CH_CHCH_CH0OH
            Ji   £             cat.           3,   2.  2.

             OH                                OH




1*   Function - 1,3-Butylene glycol is produced by the catalytic



     hydrogenation of acetaldol.  The hydrogenation can be effected with



     copper, platinum oxide, or several other catalysts, but preferably



     with Raney nickel.  Pressures and temperatures of 4.83 MPa and 65 -



     120°C are used.



          Low-boiling materials are stripped off under reduced pressure



     from the hydrogenation product.  The residue is then filtered to



     remove precipitated salts and catalyst, and is redistilled at low



     pressure to give pure 1,3-butylene glycol.



2.   Input Materials - Basis - 1.68 kg 1,3-butylene glycol



     Acetaldol (70%, 30% H20):  2.67 kg



     Hydrogen:  2.07 MPa (20.4 atm)



     Ni catalyst:  0.500 kg



3.   Operating Parameters



     Temperature:  65 - 120°C (149-248°F)



     Pressure:  4.83 MPa (47.7 atm)



     Catalyst:  Raney nickel, copper, platinum oxide



     Reaction Time:  0.5-2 hrs



4.   Utilities - not given



5.   Waste Streams - No specific information was available.  Waste gas



     from the strippers may contain quantities of ethanol, n-butanol,
                             6-241

-------
     and other by-products,  including 2,4-dimethyl-l,3-dioxane.   Waste-




     water streams from filtering operations probably contain various




     salts and traces of catalyst.  Heavy ends from distillation columns




     going to waste streams  are mainly dibutylene glycols and their




     butyl ethers.  Traces of acetaldehyde,  acetaldol, and 1,3-butylene




     glycol are probably present in all waste streams.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N. Y., Vol. 10 (1966), p. 664.






     Hancock, C. K., and Henson, D. D., "Industrial and Engineering




     Chemistry," Vol. 45 (1953), p. 629-632.
                             6-242

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 87




                              Crotonaldehyde
         2 CH3CHO  io-25°C    CH3CHOHCH2CHO d±gti£ CH3CH=CHCHO
1.  Function - Crotonaldehyde is most commonly made by the aldol conden-




    sation of acetaldehyde followed by dehydration.  After the initial




    condensation has proceeded to 60% of completion, the acetaldol is




    treated with acetic or phosphoric acid and passed through a dehy-




    dration column at 95°C.  Unreacted acetaldehyde is recovered and




    Crotonaldehyde is separated overhead in almost quantitative yield.




2.  Input Materials




    Acetaldol - 1.625 kg/kg Crotonaldehyde




3.  Operating Parameters




    Temperature - 10-25 °C (50-77 °F)




    Pressure - not given




    Catalyst - 10% NaOH




4.  Utilities - not given




5.  Waste Streams - There may be a wastewater stream.  The likely pollutants




    are acetaldehyde, acetaldol, Crotonaldehyde, and by-products.  Heavy




    ends from distillation columns are usually incinerated.




6.  EPA Source Classification Code - None




7.  References




    Austin, G. T.,  "The Industrially Significant Organic Chemicals -




    Part 2" /'Chemical Engineering',' February 18, 1974, p. 126.
                                6-243

-------
7.   References




    Hedley, W. H.,  et.  al.,  Potential Pollutants  from Petrochemical




    Processes, Technomic Publishing Co.,  1975.





    Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience Publishers,  New York, N.Y., Vol. 6  (1965), p. 446.





    Chemical Technology, Barnes and Noble Books,  New York,  N.Y.,  Vol.  4



    (1972), p. 365.





    Faith,  W. L., et.  al., Industrial Chemicals,  3rd Ed., John Wiley & Sons,




    New York, N.Y., 1965, p.  300, 301.





    Waddams, A. L., Chemicals From Petroleum,  3rd Ed., John Murray Ltd.,




    London, England, 1973, p. 79.
                               6-244

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  88
             n-B.utyraldeliyde (hydrpgenation of crotonaldehyde)
                     CH3CH=CHCHO
1.  Function - In the production of n-butyraldehyde, crotonaldehyde




    is vaporized and passed through a converter with hydrogen.  The




    converter tubes are packed with an activated nickel catalyst on an




    asbestos carrier.




         Steam on the outside of the tubes is used to bring them to the




    reaction temperature, and is later replaced by water to carry heat




    away from the exothermic reaction.




         The exit gases from the converter pass through condensers, and




    the hydrogen, which may be several times the theoretical amount, is




    recycled.  The crude butyraldehyde is purified by fractionation.




2.  Input Materials




    Crotonaldehyde




    Hydrogen




3.  Operating Parameters




    Temperature - 220-260°C (428-500°F)




    Pressure - 207 kPa (2,04 atm)




    Catalyst - Activated nickel supported on asbestos or copper chromite




    Space velocity - 400/hr




4.  Utilities - Not given




5.  Waste Streams - Some crotonaldehyde and n-butyraldehyde may escape




    to the atmosphere during processing and purification.  No specific




    information was available, however.
                               6-245

-------
6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience Publishers, New York, N.Y., Vol.  3 (1964),  p.  870,871.





    U. S. Patent 2,825,743 (March 4, 1958).





    Sittig, M., Organic Chemical Process Encyclopedia - 1969,  2nd Edition,




    Noyes Development Corp., Park Ridge, N.J., 1969, p. 132.
                               6-246

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  89




             n-Butyric Acid (oxidation of n-butyraldehyde)
                             1/2
•*••   Function - Some butyric acid is prepared commercially by the oxi-




     dation of n-butyraldehyde.  In this process, air or oxygen is passed




     into n-butyraldehyde in the presence of a catalyst such as manganese




     butyrate or a cobalt salt.




          Yields of about 90% are possible over a wide range of tempera-




     tures.




2.   Input Materials




     n-Butyraldehyde - 0.91 kg/kg butyric acid




     Air or oxygen




3.   Operating Parameters




     Temperature:  30-50°C (86-122°F)




     Pressure:  not given




     Catalyst:  0.5% manganese butyrate




                Cobalt salts




4*   Utilities - Not given




5.   Waste Streams - Although no information was available, some n-butyral-




     dehyde and butyric acid are probably present in the reactor off-gas.




     Process slops may also be a source of these pollutants, as well as




     reaction by-products.




6.   EPA Source Classification Code - None
                              6-247

-------
7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 3 (1964), p. 880.






     Chemical Technology, Barnes and Noble Books, New York, N.Y.,




     Vol. 4 (1972), p. 426.






     Goldstein, R. F., The Petroleum Chemicals Industry, 2nd Edition,




     John Wiley and Sons, New York, N.Y., 1958, p. 331.
                             6-248

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  90
                    2-Ethylhexanol (from n-butyraldehyde)
                 2CH3CH2CH2CHO 	+ CH3CH2CH2CH=CCHO + EJL

                                             H2
                                    CH3CH2CH2CH2
-------
4-  Utilities - 0.72 kg/sec capacity

                         o
    Cooling water - 32 dm /sec


    Steam - 0.45 kg/sec at 1.14 MPa


    Power - 447 KW capacity


5.  Waste Streams - Light hydrocarbons from hydrogenation - 113.5  kg/Mg.


    High boiling oxygenated compounds from the condensation of aldehydes  and


    alcohols.  Butyraldehyde 58.5 kg/Mg product.


6.  EPA Source Classification Code - None


7.  References


   Hedley, W. H.,  et  al., "Potential Pollutants from Petrochemical Processes,"


    Technomic Publishing Co., 1975.


    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-


    science Publishers, New York, N.Y., Vol. 14 (1963), p.  373-389.


    Waddams,  A.L.,   Chemicals From Petroleum   3rd Edition, John Wiley &  Sons,


    (1973)  p. 205.


    Lowenheim, F. A. -and Moran, M.  K., "Industrial Chemicals," 4th Edition,


    John Wiley & Sons, New York, N.Y., (1975), p. 413-417.
                              6-250

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO.  91
                Glyoxal (oxidation of acetaldehyde)
                    CH3CHO	>    CHOCHO
1*   Function - Recently, glyoxal has been produced by the nitric acid




     oxidation of acetaldehyde in an autoclave.  Previously the cataly-




     tic vapor-phase oxidation of ethylene glycol had been the standard




     commercial process.  The product is washed with NaHSO., and preci-




     pitated from EtOH/H20.




2.   Input Materials - Basis - 0.70 kg glyoxal




     Acetaldehyde:  0.783 kg




     Se02 (or HN03):  28 g




3.   Operating Parameters




     Temperature:  80°C  (176°F)




     Reaction Time:  2 hrs




4.   Utilities - not given




5.   Waste Streams - The information available on current production




     techniques was not sufficient to warrant a discussion of possible




     pollutant sources.  As in all oxidation processes, reactants, pro-




     ducts, and by-products may be emitted as a result of process slops.




6-   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N. Y., Vol. 1  (1963), p. 80.
                             6-251

-------
Ibid. Vol. 10 (1966), p. 646.





Riley, H. L., et al., J. Chem. Soc.. 1932, p. 1875-1883.
                         6-252

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.92
               Methyl Phenylcarbinol (from acetaldehyde)
                               Mg
                          CH3CHO
          C,H.-CH(CH0)OMgBr + H00 	»•  C,HCCH(CH0)OH + Mg
           653          2          653        ^





1.   Function - One method of synthesizing methylphenylcarbinol involves



     the addition of acetaldehyde to a Grignard reagent prepared from



     bromobenzene.



2.   Input Materials



     Acetaldehyde



     Bromobenz ene



     Ether (solvent)



     Magnesium



     Water



3.   Operating Parameters



     Temperature:  reflux temperature of solvent



     Pressure:  101 kPa  (1 atm)



4.   Utilities - Not given



5.   Waste Streams - Air - ether and bromobenzene vapors.



     Water - magnesium salts



     solid - unreacted Mg turnings and tarry materials.



6.   EPA Source Classification Code - None
                              6-253

-------
7.   References




     Horning, E. C., Organic Synthesis, John Wiley and Sons,  New York,




     N.Y., Collective Vol. Ill  (1955), p. 200-201.
                              6-254

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  93




                                 Paraldehyde
             3CH3CHO
1.  Function In the presence of sulfuric acid.acetaldehyde rapidly poly-




    merizes to paraldehyde, the trimer.  The crude trimer is washed with




    water to remove monomer and the acid catalyst, and dried.  Distillation




    separates the pure paraldehyde.  In the absence of acid catalyst the




    trimer suffers no depolymerization on distillation or storage.  Acetalde-




    hyde can be regenerated readily by heating gently and distilling the




    paraldehyde in presence of acid catalyst.




2.  Input Materials




    Acetaldehyde - 1.05 kg/kg paraldehyde




2.  Operating Parameters




    Temperature (distillation) - 124°C  (255°F)




    Pressure - 101 kPa  (1  atm)




    Catalyst - H2SO,




4.  Utilities - Not given




5.  Waste Streams - Waste water probably contains traces of acetaldehyde




    and sulfuric acid.




6.  EPA Source Classification Code - None
                               6-255

-------
7.   References




    Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd  Edition,




    Interscience Publishers,  New York,  N.Y.,  Vol.  1 (1963),  p.  81.





    K.  C.  Frisch, High Polymers, Vol.  XXVI,"Cyclic Monomers" John Wiley &




    Sons,  1972, p. 124.





    Brandrup, J.  and Goodman, M» Macromolecular Synthesis,  Vol.  3, John




    Wiley  & Sons, New York, N.Y., 1967, p. 74.
                               6-256

-------
 INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  94




                          Pentaerythritol
            CH3CHO + 2HCHO      >  CH2(CH2OH)CHO + HCHO







         CH2(CH2OH)CHO + 2HCHO  °   >  CH(CH2OH)2CHO + HCHO
         CH(CH2OH)2CHO + 2HCHO 	> C(CH2OH)3CHO + HCHO
        C(CH0OH)QCHO + HCHO + OlP'	»• C(CH0OH),  + HCOCQ
            2.   3                            LI*





1.     Function - Pentaerythritol is made by reacting formaldehyde and



      acetaldehyde in molar ratios ranging from 4:1 to 10:1.   The re-



      action is carried out in the presence of lime or caustic soda at




      near ambient temperatures and pressures.




           The reaction sequence involves three identical aldol conden-



      sations in which the alkali acts as a catalyst, followed by a



      cross-Canizzaro reaction in which the condensation takes place.




           Sodium carbonate is added to the reaction mixture to precipi-




      tate calcium ions in solution.  The reaction mixture, which contains




      pentaerythritol, polypentaerythritols, sodium formate,  and suspended




      calcium carbonate, is then filtered and passed through ion exchange




      and fractional distillation columns to obtain the final product.  The




      yield is high, with about 88% of the product occurring as pentaery-




      thritol, 10% as dipentaerythritol, and most of the remainder as tri-




      pentaerithritol.  The sodium formate is commonly treated with sul-




      furic acid to give formic acid as a by-product.
                              6-257

-------
2.   Input Materials - Basis - 1 metric ton pentaerythritol

     Acetaldehyde - 383 kg (844 Ibs)

     Formaldehyde - 3175 kg (7000 Ibs)

     Calcium hydroxide or sodium hydroxide
                                             1050 kg (2315 Ibs)
     Sodium carbonate

     Acid (formic) - 600 kg (1323 Ibs)

3.   Operating Parameters

     Temperature:  15-50°C  (59-122°F)

     Pressure:  101 kPa (1 atm)

     Catalyst:  Ca(OH)2 or NaOH

     Reaction Time:  3.5 hrs

4.   Utilities

     Not given

5.   Waste Streams

     Calcium carbonate precipitator (solid)

     Calcium carbonate

     Triple effect evaporator and vacuum crystallizer (air)

     Air streams may contain unreacted acetaldehyde and formaldehyde,

     as well as some organic, side products (methanol and ethanol).

     Vacuum crystallizer (water)

     Water streams contain sodium formate which is usually recovered as

     formic acid.  Inorganic sodium salts are then the final waste product.

6.   EPA Source Classification Code - None

7.   References

     Austin, G. T., "The Industrially Significant Organic Chemicals  -

     Part 7," "Chemical Engineering," June 24, 1974, p. 155, 156.
                             6-258

-------
7.   References (continued)




     Hedley, W.H., et a., Potential Pollutants from Petrochemical




     Processes, Technomie Publishing Co., 1975.






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 590,




     591.






     U.S. Patent 2,612,526 (September 30, 1952).






     Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd Edition,




     Noyes Development Corp., Park Ridge, N.J.,  1969 , p. 508.






     Lowenheim, F. A. and Moran, M.K., Industrial Chemicals, 4th Edition,




     John Wiley and Sons, New York, N.Y.,  1975 , p. 598, 599.
                             6-259

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 95
             Vinyl Acetate (vapor-phase reaction of ethylene)


             CH2=CH2 + 1/2 02 + CH COOH 	> CH COOCH=CH2 + H20


1.  Function - The most common route to vinyl acetate involves a vapor-

    phase oxyacetylation using ethylene, acetic acid, and oxygen.  The

    reaction takes place at 175-200°C and 485-965 kPa (70-140 psi) over

    a supported palladium catalyst.  The conversion per pass is about

    10% ethylene, 20% acetic acids, and 60% oxygen.

         The reaction mixture is partly condensed after leaving the reactor

    and separated into liquid and gas phase.  The gases are recycled via

    scrubbers in which vinyl acetate and carbon dioxide are removed.  The

    liquid condensate is fed to the distillation train where light ends,

    mainly acetaldehyde, water, and polymers are removed from the purified

    vinyl acetate.  Acetic acid is recycled to the reactor.

         The overall yield is 91% vinyl acetate, 8% carbon dioxide, and

    1% by-product, with better than 99% recovery of ethylene and acetic

    acid.  The liquid-phase route to vinyl acetate from ethylene has not

    been a success.

2.  Input Materials

    Ethylene - 0.36 kg/kg vinyl acetate

    Acetic acid -0-77 kg/kg vinyl acetate

    Oxygen - 0.20 kg/kg vinyl acetate

3.  Operating Parameters

    Temperature - 175-200°C (347-392°F)

    Pressure - 70-140 psi - 483-965 kPa (4.8-9.5 atm)

    Catalyst - supported palladium catalyst with small amount of potassium acetate
               (485-965 kPa)
                                6-260

-------
4.  Utilities - Not given




5.  Waste Streams - Waste gases from the scrubbers may contain traces of




    ethylene, acetic acid, vinyl acetate, acetaldehyde,  and other by-product




    gases.  Heavy ends from distillation columns include polymers and mixed




    aldehydes.




6.  EPA Source Classification Code - None




7.  References




    Austin, G. T., "The Industrially Significant Organic Chemicals -




    Part  9," "Chemical Engineering," August 5, 1974, p.  98.






    Lowenheim,  F.  A.  and  Moran, M. K.,   Industrial Chemicals,  4th  Edition,




    John Wiley and Sons,  New York, N.Y., 1975, p. 862-867.





    Waddams,  A.  L.,  Chemicals from Petroleum, 3rd Edition, John Wiley  and




    Sons, New York,  N.Y., 1973, p. 111.
                                6-261

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 96


                   Sorbic Acid (from crotonaldehyde)
   CH,CH=CHCHO + CH =C=0 	* H-[OCHCH,CO]-H   ^ > CH CH=CH-CH=CH-C02H
     j             ^                *   ^-   n  f\t-r^f     *^
                                    CH
                                    ii
                                    CH
1.   Function - Crotonaldehyde and ketene react in the presence of a


     catalyst to form a polyester of 3-hydroxy-4-hexenoic acid.


          The polymer intermediate may be isomerized to sorbic acid in


     acid or alkaline media.  The crude sorbic acid is purified by codis-


     tillation under vacuum with an organic solvent having the same general


     distillation range.


          Sorbic acid may also be manufactured by oxidation of 2,4-hexa-


     dienal.


2.   Input Materials


     Crotonaldehyde


     Ketene


3.   Operating Parameters


     Temperature:  not given


     Pressure:  not given


     Catalysts:  Reaction step - usually zinc carboxylic salts.   Isomeri-


                 zation step - acid or base.
                              6-262

-------
*•   Utilities - Not given




5.   Waste Streams - Waste water streams from the purification section




     may include acid or base catalysts, spent reaction catalysts, and




     distillation solvents in addition to traces of crotonaldehyde and




     sorbic acid.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 18 (1969), p. 590-




     591.
                              6-263

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS  NO.  97
                       n-Butanol (from crotonaldehyde)






                                   H2
                      CH3CH=CHCHO —=—»- CH3CH2CH2CH2OH




1*   Function - The reduction of crotonaldehyde to n-butanol accounts for



     approximately 20% of the n-butanol produced in the United States.



     The reduction is accomplished by the vapor phase hydrogenation over a



     reduced nickel-chromium catalyst at 180°C and 207 kPa.



          Precursor steps may include ethanol or ethylene to acetaldehyde,



     acetaldehyde to acetaldol, and acetaldol to crotonaldehyde.



2.   Input Materials



     Crotonaldehyde - 1.04 kg/kg n-butanol



     Hydrogen



3.   Operating Parameters



     Temperature - 180°C  (356°F)



     Pressure - 207 kPa (30 psi)  (2 atm)



     Catalyst - Nickel-Chromium



4.   Utilities - Not given



5.   Waste Streams - The wastewater stream from the stripper may contain



     some n-butanol and crotonaldehyde.  Heavy ends from distillation columns



     are usually incinerated.



6.   EPA Source Classification Code - None



7.   References



     Hedley, W. H., et al., Potential Pollutants  from Petrochemical  Processes,



     Technomic Publishing Co., 1975.
                            6-264

-------
7.   References (continued)




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 3 (1964), p. 826.






     Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th Edition,




     John Wiley and Sons, New York, N.Y.,  1975 , p. 658-660.
                             6-265

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 98
                           Crotonic Acid
               CH3CH=CHCHO -I- 1/202 	>  CH3CH=CHCOOH
1.   Function - Crotonic acid is prepared commercially by the catalytic




     oxidation of crotonaldehyde with air.  The catalyst is a copper




     acetate-cobalt acetate mixture, about 0.5 - 1.0% by weight of the




     total charge, and the temperature is held between 35 - 50°C.




          Percrotonic acid may be an immediate product of this process.




     In the continuous process, crotonaldehyde and catalyst solution are




     combined with an inert organic diluent such as benzene, methyl




     acetate, acetone, or methyl ethyl ketone in about equal volume and




     pumped into the oxidation kettle.  Air is bubbled in, while the




     crude product is drawn off continuously.  The diluent and unreacted




     crotonaldehyde are distilled off and returned to the process, while




     the crude crotonic acid is fractionated under reduced pressure.




2.   Input Materials - Basis - 157 parts crotonic acid




     Crotonaldehyde:  226 parts




     Air




     Organic diluent (MeOAc):  245 parts




     Catalyst [Cu(OAc)2]:  2.70 parts




              [Co(OAc)2]:  0.45 parts




3.   Operating Parameters




     Temperature:  35 - 50°C (95-122°F)




     Pressure:  not given




     Catalyst:  Copper acetate - cobalt acetate





                             6-266

-------
4.   Utilities - The principal pollutant source from this process




     should be the waste stream from the purification section, con-




     taining acetic acid, formic acid, other reaction by-products, and




     traces of crotonaldehyde, crotonic acid, organic diluent, and spent




     catalyst.




6.   EPA Source Classification Code - None




7.   References




     U.S. Patent 2,413,235 (December 24, 1946).





     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers, New York, N. Y., Vol. 6 (1965), p.  454, 455,





     British Patent 595,170 (November 27, 1947).
                            6-267

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 99
                        n-Butyl Acetate
                                H SO
               CH3COOH + C.HLOH — —
1.   Function - Butyl acetate's manufacture involves the classic reaction

     between butanol and dilute acetic acid, catalyzed by 0.1% ELSO, .

     Butyl acetate, which boils at 126. 5°C forms with butanol and water,

     a ternary azeotrope which boils (89.4°C) below a binary azeotrope

     that butyl acetate forms with butanol.  The ternary azeotrope

     separates into two layers on condensing - 81% ester, 13% butanol,

     and 6% water in the tops and 1% ester, 3% butanol, and 96% water

     in the bottoms.  These fortunate circumstances ease removal of the

     water -of -reaction, so that low concentrations of acetic acid in

     water work extremely well as feed to the process.

          A 10% excess of the stoichiometric requirement of butanol

     is fed to this reaction.

2.   Input Materials

     n-Butanol - 0.98 kg/kg (1,969 Ib/ton) n-butyl acetate

     Acetic acid - 0.81 kg/kg (1,620 Ib/ton) n-butyl acetate

3.   Operating Parameters

     Temperature:  90°C (194°F)

     Pressure:  not given

     Catalyst:  0.1% H2S04

4.   Utilities

     Not given
                             6-268

-------
5.   Waste Streams




     Separator (water)




          The separator may discharge a water stream containing n-butyl




     acetate, n-butanol, acetic acid, and sulfuric acid and may be




     treated to recover some of these materials.




     Separator (air)




          The separator air vent could emit n-butyl acetate and n-butanol




     vapors.




     Purification section




          No information was available on this section, but the same types




     of pollutants would be expected.




6.   EPA Source Classification Code - None




7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 2," "Chemical Engineering," February 18, 1974, p. 126.






     Hedley, W. H., et al., Potential Pollutants from Petrochemical




     Processes, Technomic Publishing Co., 1975.






     Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,




     John Wiley and Sons, New York, N.Y.,  1975 , p. 173, 174.
                             6-269

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 100




                    Pyridine and g-Picoline

1.   Function - Pyridine and beta-picoline are co-produced by the vapor




     phase reaction of acetaldehyde, ammonia, and formaldehyde.  The




     formaldehyde is usually added in excess to inhibit the formation of




     alpha- and gamma-picoline, but mixtures of formaldehyde and methanol




     are also used.




          In both process variations, the reactants are vaporized and




     passed through a fluid-catalyst-type reactor containing a fluidized




     catalytic bed of silica-alumina catalyst.  The reaction is carried




     out at 250 - 500°C and atmospheric pressure.




          The crude product is fractionated to obtain pyridine and 3-




     picoline.  Typical yields based on acetaldehyde feed are 35% for




     pyridine and 27% for beta-picoline.




2.   Input Materials - Basis - 47 parts pure mixed product




     acetaldehyde:  62 parts (6.37 kg/kg pyridine; 7.01 kg/kg 3-picoline)




     ammonia:  1 part




     formaldehyde:  67 parts




     methanol (in some process variations) :  32 parts




3.   Operating Parameters




     Temperature:  250 - 500°C (482-932°F)




     Pressure:  101 kPa (1 atm.)




     Catalyst:  Alumina-silica (13% Al^.,, 87% SiOj




4.   Utilities - not given



                             6-270

-------
5.   Waste Streams - Waste gases from the purification section may




     contain formaldehyde, ammonia, acetaldehyde,  various amine by-




     products, and methanol, if used.




6.   EPA Source Classification Code - None




7.   References




     U.S. Patent 2,807,618 (September 24, 1957).





     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N. Y., Vol. 16 (1968), p. 781,




     785.
                             6-271

-------
INDUSTRIAL ORGANIC CHEMICALS
                                 PROCESS NO.  101
                    Acetic Anhydride and Acetic Acid
CH3CHO
                                 (air)
CH3COOOH
                 CH3COOOH + CH3CHO
                     CH3COOOH + CH3CHO
                   (CH3CO)20
                       2CH COOH
1.  Function - Acetic acid and acetic anhydride are prepared primarily by

    the catalytic oxidation of acetaldehyde.   In this process, the peracetic

    acid formed by the initial oxidation is allowed to react with an excess

    of acetaldehyde to form the anhydride, as well as acetic acid.

         Copper, cobalt, or manganese acetate catalysts give selectivity

    to anhydride formation.  Entraining agents such as ethyl acetate further

    enhance this conversion by removing the water of reaction.

2.  Input Materials - Basis - 1 kg (ton) acetic acid   1 kg (ton) acetic anhydride
    Acetaldehyde, kg (Ibs)

    Catalyst, g (Ibs)

    Air, m3 (ft3)

    Diluent (less recovery),
      kg (Ibs)

3.   Operating Parameters

    Temperature, °C (°F)

    Pressure, kPa (atm)

    Reaction time, hrs
             1.10 (2,200)

             3.30 (6.6) (MnAc )

             0.251 (8,040)
                1.20 (2,400)

                 1.0 (2X^2)

                variable

                1.65 (3,300)
          55-80 (131-176)

          843-517 (4.77-5.10)

                  12
              50-70  (122-158)

              414  (4.09)
                                6-272

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4.  Utilities - Basis - 4,536 (100 M kg/yr)

    Water cooling, m3/min - 25.3 (6,690)
                   3
    Water makeup, m /min (gpm) - 1.25 (330)

    Power,kW - 1,665

    Steam, kg/hr (Ibs/hr) - 2.06 x 104 (45,420)

5.  Waste Streams

    Reaction section - off-gas scrubber vent

    Methane - 1.8 g/kg (3.6 Ibs/ton) acetic acid

    Carbon monoxide - 3.3 g/kg (6.5 Ibs/ton) acetic acid

    Higher acids

                             3       3
    Total waste flow - 4.17 m /kg (10  gallons/ton) product

    Organics - >15 g/1


                                   Plant 1             Plant 2

                 Flow            4.17 m3/kg          0.085 m3/kg

                 COD              186 mg/1         306,100 mg/1
                                 0.78  g/kg         26.18   g/kg

                 BOD               84 mg/1          64,000 mg/1
                    5            0.35  g/kg          5.44   g/kg

6.  EPA Source Classification Code - None

7.  References

    Austin, G. T., "The Industrially Significant Organic Chemicals - Part

    1," "Chemical Engineering," January 21,  1974, p. 128.


    Hedley, W. H., et al., Potential Pollutants from Petrochemical Processes,

    Technomic Publishing Co., 1975, p. 158,183.


    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

    Interscience Publishers, New York, N.Y., Vol. 8 (1965), p. 408.
                                6-273

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7.   References (continued)




    Faith,  W.  L.  et al.,  Industrial Chemicals,  3rd  Ed., Wiley  &  Sons




    New York,  N.Y., 1965, p.  18-19.





    Kent,  J. A.,  Riegel's Handbook of  Industrial  Chemistry,  7th  Ed., Van




    Nostrand Reinhold Co.,  New York, N.Y.,  1974,  p.  790.





    Sittig, M., Acetic Acid and Anhydride,  Noyes  Development Corporation,




    Pearl  River,  N.Y., 1965,  p.  29-31.





    Sittig, M., Pollution Control  in the  Organic  Chemical  Industry, Noyes




    Data Corp., Park Ridge,  N.J.,  1974, p.  54.





    Lowenheim, F. A.  and  Moran,  M.  K., Industrial Chemicals, 4th Edition,




    John Wiley &  Sons, New  York, N.Y., 1975,  p. 8,9,16,17.
                               6-274

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 102




                        Cellulose Acetate






[C,H 02(OH)_]  + 3n(CH3CO)20 	>- [C,H702(OOCCH3)3]n + 3nCH3COOH






1.   Function - Cellulose acetate is produced by the catalytic acetyla-




     tion of high-quality cellulose, usually 98-99% a - cellulose.  This




     rather complicated batch process may be explained in terms of several




     subprocedures.




     Pretreatment




          The cellulose is first dried to a fixed optimum moisture content.




     A pretreating reagent, acetic acid, is then added to swell the cellu-




     lose and permit the acetylation reagent to diffuse into the fiber




     more rapidly.  The time of pretreatment varies from 15 minutes to




     several hours.




     Acetylation




          The acetylation mixture consists of acetic anhydride, acetic




     acid (cellulose acetate solvent), and sulfuric acid catalyst.  The




     amount of acetic anhydride used is slightly in excess of that re-




     quired to react with the moisture in the cellulose and to form the




     triester.




          For many applications, the cellulose  acetate formed must  be




     deesterified to some extent.   This  is accomplished by adjusting  the




     water content to 5-10%  and allowing hydrolysis  to occur  in the




     presence of sulfuric acid catalyst.  When  the desired  ester con-




     tent is reached, hydrolysis is arrested  by neutralizing  the sul-




     furic acid, usually with sodium acetate.
                             6-275

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Precipitation and Purification




     The product is precipitated by dilution with water to some




point just short of precipitation followed by mixing with an excess




of aqueous acetic acid solution with vigorous agitation.  The freshly




precipitated product is purified by washing with water until all




traces of acid are removed.




Stablization




     For the most part, product instability is due to the presence




of sulfate ions in solution and trace amounts of sulfate esters.




These are removed by adding magnesium ion and boiling in slightly




acidified water.  The stable product is then centrifuged and dried.




Acetic Acid Recovery




     All wash liquors containing an appreciable amount of acetic




acid are combined to give an aqueous solution containing 18-20%




acetic acid.  Glacial acetic acid is obtained by concentrating this




liquor.




Input Materials - Basis - 1 metric ton cellulose acetate




Cellulose - 700 kg (1543 Ibs)




Acetic Acid - 3250 kg (7165 Ibs)




Acetic Anhydride - 2000 kg (4409 Ibs)




Sulfuric Acid (catalyst) - 100 kg (220 Ibs)




Water




Sodium acetate or sodium bicarbonate
                        6-276

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3.   Operating Parameters




     Temperature:  Pretreatment - 40-50°C (104-122?F)




                   Acetylation - 5-45°C (41-113°F)




                   Hydrolysis - 25°C (77°F)




                   Drying - 95°C (203°F)




     Pressure:  slightly above atm.




     Catalyst:  1% H^SO^




     Reaction Time:  15-30 min.




4.   Utilities




     Not given




5.   Waste Streams - The stills used to recover acetic acid and other




     solvents are major sources of waste water.  The wastes contain




     considerable amounts of degraded cellulose and sulfuric acid.




     About 12-15 cubic meters of waste waters are generated per Mg




     (12-15 gal/1000 Ib) of product with a solids loading of 200 g/m




     depending upon the relationship of flake to fiber production.




          Solvent handling operations are the principal potential




     sources of emissions to the air in the processing of cellulose




     acetate.  Various solvents may be involved.




6.   EPA Source Classification Code - None





7.   References





     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 2," "Chemical Engineering," February 18, 1974, p. 127, 128.






     Hedley, W. H., et al., Potential Pollutants from Petrochemical




     Processes, Technomic Publishing Co., 1975.
                             6-277

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Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




Interscience Publishers, New York, N.Y., Vol. 4 (1964) p. 633-635.






U.S. Patent 3,040,027 (June 19, 1962).






Sittig, M., Organic Chemicals Process Encyclopedia - 1969, 2nd




Edition, Noyes Development Corp., Park Ridge, N.J.,  1969 , p. 156.






Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,




John Wiley & Sons, New York, N.Y.,  1975  p. 239, 240.
                       6-278

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INDUSTRIAL ORGANIC CHEMICALS                 PROCESS NO.  103

                    Ethyl, Isopropyl Acetates
                  0                              0
               CH3COH   +   ROH  —^^—>•    CH COR   +   H20

1.   Function - Lower aliphatic acetates, such as ethyl and isopropyl
     acetate, are manufactured commercially by batch and continuous
     processes.  The continuous process is favored for large volume
     production.
     Batch Process - The esterification chamber (reactor) is a cylin-
     drical tank or pot, heated by closed coil steam pipe.   The acetic
     acid (8%), ethanol (95%), and catalyst (usually sulfuric acid) are
     charged in the ratio of 10:10:0.33.  The mixture is heated by
     steam, and the vapors are fed to the base of a fractionating tower.
     The temperature at the top of the column is maintained at the
     boiling point of the ternary azeotrope of ethyl acetate (83%),
     ethanol (9%), and water (8%).  The reflux from this tower is re-
     turned to the reactor.  The vapors from the top of the column are
     sent to a reflux condenser, part of the condensate is returned to
     the column as reflux, and the rest is sent to storage.

          The ultimate product of the batch process is the azeotrope
     ethyl acetate/ethanol/water.  The azeotrope is satisfactory  for
     many downstream commercial processes.  However, others require pure
     ethyl acetate which is separated from the ternary azeotrope  by the
     method used in the continuous process.
     Continuous Process - The sulfuric acid/excess ethanol/acetic acid
     mixture is brought to equilibrium with agitation and heating.  It
                             6-279

-------
is then pumped to a receiving tank.   The mixture is used in the




reflux condenser as a heat exchange  fluid.   The heated mixture is




then introduced near the tope of a reaction column.  The tempera-




ture at the top of the column is maintained at ethanol reflux




temperature.  Live steam is introduced at the base of the column.




An additional feed of recovered alcohol is  introduced simultaneously




near the bottom of the column.  Vapors from the reaction column




containing approximately 10% water,  are condensed and sent to a




recovery column.  The excess water and sulfuric acid are removed at




the bottom of the reaction column.  The acetic acid is consumed




completely because there is always an excess of ethanol due to the




constant removal of ethyl acetate and water.




     The recovery column removes the excess alcohol from the




ternary mixture and returns it to the reaction column.  The




ternary mixture, refluxing at the top of the recovery column,





is condensed and recycled (to the bottom) until it approaches the




composition of the constant-boiling ternary.  The constant boiling




ternary from the top of the recovery column is then sent to a




mixing coil where water is added to form two layers.  The layers




are sent to a separator.  The lower layer is sent back  to the




recovery column below the level of the feed plate, but  above  the




base of the column.




     The upper layer is sent  to a second recovery  column.  The




vapors are condensed and returned to the mixing  coils.   Ethyl




acetate of 95-100% purity is  taken from  the bottom of  the  second




recovery column.  This product is then fractionated to  obtain high-




purity ethyl acetate and a small amount  of  constant boiling  mixture




which is returned to the first recovery  column.




                        6-280

-------
          Ethyl acetate can be made by vapor phase esterification by

     reaction of ethylene with acetic acid,  or by dehydrogenation of

     ethyl alcohol.   These are not used commercially at present with the

     olefins below C,, insofar as is known.   Ethylacetate is also re-

     covered as a by-product in polyvinyl alcohol production.

2.   Input Material

     95% ethanol
     8% acetic acid/92% water
     50-66° Be sulfuric acid
     Water
     Steam

3.   Operating Parameters

     Batch process - top plate of fractionating tower - 70°C (158°F)

               '      est. reaction chamber temperature - 80°C  (176°F)

                     top plate of recovery column - 78°C (172°F)

                     catalyst - 50-66° Be sulfuric acid

                     equipment - cylindrical tank, steam coil,  perforated
                                 steam pipe, fractionating stills,  bellcap
                                 column,  pumps, condensers

     Continuous process  - top plate reaction column - 80°C  (176°F)

               bottom of recovery column -  100°C  (212°F)

               catalyst  - 50-66° Be sulfuric acid

               equipment - stirred reactors, steam-heated reaction
                           column, reflux condensers, total condensers,
                           mixing coils, separating tanks,  receivers,
                           cooling coils

4-   Utilities - Not  given.

5.   Waste Streams

     Batch Process -  Dilute  sulfuric  acid stream from separation column

     sent to sewer and liquid leaks from pump  seals.  Possible vapor

     leaks from reactors, separation  columns and condensers.   No solid

     wastes.
                             6-281

-------
     Continuous Process - Dilute sulfuric acid from recovery column sent




     to sewer.   Possible vapor leaks from reactors, reaction column,




     recovery columns,  condensers,  and fractionating columns.   Liquid




     leaks from pump seals.   No solid wastes.




6.   EPA Source Classification Code - None.




7.   References




     Keyes, D.  B., "Esterification Processes and Equipment", "Ind.  Eng.




     Chem.", Vol. 24 (1932), p. 1096-1103.






     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers, New York, N. Y., Vol. 8 (1965),  p.  313.







     Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd




     Edition, Noyes Development Corp., Park Ridge, N. J.,  1969, p.  299.






     U. S. Patent 2,787,636 (April 2, 1957).






     Lowenheim , F. A., and Moran,  M. K., Industrial Chemicals, 4th




     Edition, John Wiley and Sons,  New York, N. Y., 1975,  p. 350, 351.
                             6-282

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  104




                        Chloroacetic Acid





                  CH3COOH + C12 	•> C1CH2COOH + HC1





 1.  Function - In the U.S., virtually all chloroacetic acid is produced




     by the direct chlorination of acetic acid.  Catalysts such as  sulfur




     and red phosphorus are used at temperatures of 85-120°C.   The  yield




     is about 95% based on acetic acid.  Since HC1 is a reaction by-product,




     glass-lined or specially designed corrosion-resistant equipment  is




     used.




 2.  Input Materials




     Basis - 1 metric ton chloroacetic acid




     Acetic Acid - 688 kg (1517 Ibs)




     Chlorine - 813 kg (1792 Ibs)




     Red Phosphorus - 6.8 kg (15 Ibs)




 3.  Operating Parameters




     Temperature:  85-120°C (185-248°F)




     Pressure:  not given




     Catalyst:  Sulfur, red phosphorus




     Chlorine Flow:  9-27 kg




 4.  Utilities




     Not given




 5.  Waste Systems - Waste water streams from HC1 absorbers and scrubbers




     may contain chlorine,  hydrogen chloride, spent caustic, and chlori-




     nated by-products.  Vapors from reactors and the purification section




     may be expected to contain quantities of unreacted acetic acid,
                            6-283

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    chloroacetic acid,  and reaction by-products, as well as some chlorine




    and HC1.   However,  no specific  information was available.




6.  EPA Source Classification Code  - None




7.  References




    Kirk-Othmer, Encyclopedia of  Chemical  Technology,  2nd  Edition,




    Interscience Publishers, New York,  N.Y.  Vol.  8  (1965),




    p. 816,417.






    Faith, W. L., et al., Industrial Chemicals, John  Wiley & Sons,  Inc.




    New York, N.Y., 1965, p.  257,258.





    Lowenheim,  F. A. and Moran, M.  K.,  Industrial  Chemicals, 4th Edition,




    Jchn Wiley  & Sons, New York, N.Y.,  1975, p.  254,255.
                          6-284

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  105
             Acetic Anhydride (from acetic acid and ketene)


                         CH COOH 	> CH-CO + H.O


                     CH2CO + CH3COOH 	> (CH3CO)20


1.  Function - One method of producing acetic anhydride is the reaction of

    ketene and acetic acid.  Ketene is first prepared by the catalytic

    cracking of acetic acid at 700° - 750°C.  Triethyl phosphate is the

    usual catalyst.  As reaction gases leave the converter, ammonia gas

    (1 kg/4.2 kg TEP) is injected into the stream to prevent reversion if

    the ketene is the product.

         The reaction product passes from the pyrolysis tube to a cooling-

    separation system where the water from unreacted acetic acid are

    removed.  The ketene is then reacted with acetic acid in two absorption

    towers at 30 - 40°C to produce acetic anhydride in yields approaching

    90% based on acetic acid.

         About half of the acetic anhydride produced in the U.S. is made

    by the Celanese Process.  Acetic acid is cracked at somewhat lower

    temperatures (<700°C) to an equimolar mixture of ketene and acetic

    acid.  After water is removed by flashing with benzene, the two

    reaction products combine to yield acetic anhydride.

2.  Input Materials - Acetic acid - 1.25 kg/kg acetic anhydride 1350 mg/metric
                                    ton acetic anhydride

    Ammonia gas - 16.8 kg/kg acetic anhydride

    Benzene

    Triethyl Phosphate - 0.25 kg/kg acetic anhydride
                                6-285

-------
3.  Operating Parameters - Ketene production




    Temperature - 700°-750°C (1292-13829F)




    Pressure - 26.7 kPa (0.26 atm)




    Catalyst - Triethyl Phosphate




    Anhydride Production




    Temperature - 30-40°C (86-104°F)




    Pressure - Not given




4.  Utilities - Not given




5.  Waste Streams - Vent from gas scrubber  system (air:   This stream may




    contain methane, ethylene, and ketene,  and they are  normally fed to




    the burner to be used as fuel.  Acetic  anhydride column and acetic acid




    column:  Heavy ends from these columns  are generally incinerated.




    Gas scrubber system (water):   Water streams may contain sodium hydroxide




    and sodium acetate.  Some benzene expected in waste  streams from the




    Celanese process.




6.  EPA Source Classification Code - None




7.  References




    Austin, G. T., "The Industrially Significant Organic Chemicals Part 1,"




    "Chemical Engineering," January 21, 1974, p. 129.





    Hedley, W. H., et al., Potential Pollutants from Petrochemical Processes,




    Technomic Publishing Co., 1975.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-




    science Publishers, New York, N.Y., Vol. 8 (1965), p. 408.





    Lowenheim, F. A., and Moran,  M. K., Industrial Chemicals, 4th Edition,




    John Wiley and Sons, New York, N.Y., 1975, p. 17,18.
                                6-286

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 106
                Sodium Acetate (from acetic acid)






               CH3COOH + NaOH 	>- CH^COONa • 3H20






1.   Function - Sodium acetate is made on a commercial scale by reacting




     alkali with acetic acid.




2.   Input Materials




     Acetic acid




     Sodium hydroxide




3.   Operating Parameters




     Not given




4.   Utilities




     Not given




5.   Waste Streams - Separator waste streams are probably the main




     pollutant sources in this process.  Waste water streams may con-




     tain quantities of acetic acid and sodium hydroxide, and acetic




     acid may be present in the off-gas.




6.   EPA Source Classification Code - None




7.   References




     Chemical Technology, Barnes and Noble Books, New York, N.Y., Vol. 4




     (1972),p. 277.
                             6-287

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 107




             Ethyl Acetoacetate (from ethyl acetate)






                               I  + 2Na 	>
                CH3C(ONa)CHCOOC2H5
                2CH3C(ONa)CHCOOC2H5
1.   Function - Ethyl acetoacetate is most conveniently prepared by




     allowing high-purity ethyl acetate to react with metallic sodium




     or sodium ethoxide.




          The sodium derivative is then neutralized with sulfuric acid.




     The yield is better than 90% after separation and vacuum distilla-




     tion of the crude ester.




2.   Input Material




     Ethyl acetate - 1.50 kg/kg ethyl acetoacetate




     Sodium




     Sulfuric acid




3.   Operating Parameters




     Not given




4.   Utilities




     Not given




5.   Waste Streams - Waste water from the separators may contain varying




     amounts of organic and inorganic sodium salts (sodium ethoxide,




     sodium sulfate, ethyl sodioacetate, etc.), ethyl acetate, ethyl
                            6-288

-------
     acetoacetate,  and reaction by-products.   Scrubbers may be used to




     remove excess  sulfuric acid,  and should  also contribute to waste




     water pollution.   Emissions from reactor,  separation,  and scrubber




     vents may contain any of the volatile reactants,  products, and by-




     products.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd  Edition,




     Interscience Publishers, New York, N.Y., Vol. 1 (1963) p. 158.






     Chemical Technology, Barnes and Noble Books, New York, N.Y.,




     Vol. 4 (1972), p. 499.
                             6-289

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INDUSTRIAL ORGANIC CHEMICALS                 PROCESS NO.  108
          Glycine (ammonolysis of chloroacetic acid)
          C1CH2COOH   +


1.   Function - Glycine is prepared on a commercial scale by adding an

     excess of aqueous ammonia to chloroacetic acid.   Ammonium salts

     such as ammonium carbonate are often added to reduce the pH of the

     solution and inhibit conversion to the secondary and tertiary

     amine.  Yields are generally good.

2.   Input Materials - basic - 0.450 kg glycine

     Chloroacetic acid:  0.500 kg in 0.400 £ H-0
     Aqueous ammonia (30%): 1.00 £
     Ammonia salts (or hexamethylene tetramine) : 2.200 kg (NH,)7CO-
     H20: 0.500 I

3.   Operating Parameters

     Temperature: 40-90°C (104-194°F)
     Pressure: 101 kPa (1 atm)
     Reaction Time: 4-20 min.

4.   Utilities - Not given.

5.   Waste Streams - Wastewater from separators may contain ammonia,

     several ammonium salts, and traces of chloroacetic acid, glycine

     and other amine by-products.  In ammonia recovery, some air emis-

     sions may occur, but no specific information was available.

6.   EPA Source Classification Code - None.

7.   References

     Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,

     Interscience Publishers, New York, N. Y., Vol. 2 (1963), p. 350.


     Cheronis, N. D., and K. H. Spitzmueller, J. Org. Chem. , 6^, 349


                             6-290

-------
U. S. Patent 3,215,736 (November 2, 1965).




Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd Edition,




Noyes Development Corp., Park Ridge, N. J., 1969, p. 350.
                        6-291

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 INDUSTRIAL  ORGANIC  CHEMICALS                             PROCESS NO. 109
              Sodium Chloroacetate(from  Chloroacetic Acid)


                             +3             Na  CO
              CH3COOH + C12 	>•  C1CH2COOH —-—^-> ClCH2COONa


 1*    Function - Acetic acid  is chlorinated in the presence of  iron,

      H2S04,  or PC13 at 85-120°C  to yield monochloroacetic acid in  95%

      yield.   Even  though  the chlorine  in chloroacetic acid is  readily

      displaced from aqueous  solutions  of either itself or its  alcoholic

      salts,  the sodium chloroacetate is  prepared by heating  chloroacetic

      acid in Na2Ct>3 to 50°C, then  cooling to room temperature.



 2.    Input Materials


      Acetic  acid

      Chlorine

      Iron;H2S04 or PC13

      Sodium  carbonate


 3.    Operating Parameters


      Temperature:      1st Step       85-120°C (185-248°F)

                       2nd Step         50°C   (122°F)

      Pressure:  not  given

      Reaction  time:  not given


4.   Utilities

     Not given

5.   Waste Streams - Excess  chlorine,  ferric chloride, and HC1 should  be

      in the waste  streams from the first step and CO   and carbonic acid

      should be present from  the  second step.

                                6-292

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6.   EPA Source Classification Code




     None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 8 (1965), p. 415, 417.





     Organic Synthesis^, John Wiley and Sons, New York, N.Y., Coll. Vol. II




     (1943), p. 376.
                                6-293

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. J.1Q




                         Ethyl Chloroacetate
          C1CH2COOH  +  C2H5OH - »-  C1CH2COOC2H5  -I-  E^






1.  Function - Ethyl chloroacetate is produced by the direct esterification




    of chloroacetic acid with absolute ethanol.  Two moles of chloroacetic




    acid react with an excess of absolute ethanol (^ 3 moles) in the




    presence of 25g of concentrated sulfuric acid.  The mixture is refluxed




    for six hours.  The crude product is isolated and purified by conven-




    tional methods.




2.  Input Materials




    Chloroacetic acid




    Ethanol




3.  Operating Parameters




    Temperature:  Reflux




    Pressure:  101 kPa (1 atm)




    Catalyst:  H2SO,




4.  Utilities - Not given




5.  Waste Streams - Traces of volatile reactants and products may be detected




    in air.  Waste waters from washing crude product will contain sulfate




    salts, and traces of reactants and products.  By-products may be present




    in waste waters from the purification by distillation.




6.  EPA Source Classification Code - None
                              6-294

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7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology.  2nd Edition,




    Interscience Publishers, New York, N.Y.,  Vol.  8 (1965),  p.  372.





    Blatt, A. H., Organic Synthesis, Collective Vol.  II,  John Wiley  &




    Sons, New York, N.Y., 1943, p.  263.
                              6-295

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  Ill




                           Cyanoacetic Acid
     ClCH2C02Na + NaCN - > HCCH2COONa + NaCl - » NCCH2COOH




 1.  Function - Cyanoacetic acid is made by reacting the sodium salt of




     chloroacetic acid with sodium cyanide solution.  Neutralization of




     the resulting mixture yields Cyanoacetic acid.




 2.  Input Materials




     Chloroacetic acid - 1.24 kg/kg Cyanoacetic acid




     Sodium cyanide




 3.  Operating Parameters




     Not given




 4.  Utilities




     Not given




 5.  Waste Streams - Information available was insufficient to identify




     pollutant sources in this process.  However, waste water streams




     from various processing equipment may contain chloroacetic acid,




     sodium cyanide, Cyanoacetic acid, and reaction by-products.  Air




     vents may release any of the volatile reactants or products.




 6.  EPA Source Classification Code - None




 7.  References




     Kirk-Othmer , Encyclopedia of Chemical Technology, 2nd Edition,




     Inter science Publishers, New York, N.Y., Vol.  8  (1965), p. 417.






     Hahn, A. V., The Petrochemical Industry;  Market and Economics,




     McGraw-Hill Book Co., New York, N. Y.,  1970, p.  165.
                             6-296

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INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. .112
               Sodium Carboxymethyl Cellulose
          C,H-.00 (OH),   +   NaOH    —*    C,H700 (OH) 0ONa   +  H00
           o / z    j                       o / Z    Z          z
     C,H700(OH)0ONa   +   ClCH0COONa -^  C,H^00(OH)0OCH0COONa + NaCl
      D/ZZ              Z           o/ZZZ




1.   Function - Sodium carboxymethyl cellulose is produced by a two-step



     process, involving the addition of sodium hydroxide and sodium



     chloroacetate to cellulose.



          Only 13-50% of the available hydroxyl group react to yield



     alkali cellulose, the properties of the final product being quite



     dependent on this fraction.



          The alkali cellulose formed is then combined with sodium



     chloroacetate at 35-45°C to yield the final product.



          After drying, the crude product contains considerable amounts



     of sodium chloride and other diluents, such as sodium glycolate.



     If necessary, these impurities may be removed by washing with



     methanol or ethanol.



2.   Input Materials



     Cellulose 1 part

     Sodium hydroxide - 10 parts

     Sodium chloroacetate - 1.5 parts

     Methanol or ethanol




3.   Operating Parameters



     Temperature: 35-45°C  (95-113°F)

     Pressure:  101 kPa  (1  atm)



4.   Utilities - Not  given.
                             6-297

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5.    Waste Streams - Wastewater streams from washing operations may con-




     tain unreacted sodium hydroxide, alkali cellulose,  sodium chloro-




     acetate, or chloroacetic acid,  and reaction by-products,  such as




     sodium glycolate.   Methanol or  ethanol may also be  present.




6.    EPA Source Classification Code-None.




7.    References




     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 8", July 22,  1974, p. 112.






     U. S. Patent 3,322,798 (May 30, 1976).






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers,  New York,  N.Y., Vol.  4 (1964), p.  644,  645.






     Sittig, M., Organic Chemical Process  Encyclopedia - 1960, 2nd




     Edition, Noyes Development Corp.,  Park Ridge,  N.  J., 1969, p. 601.
                             6-298

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 113

                          Ethyl Cyanoacetate
           ClCH-COOH + Na?CO, 	>- ClCH^COONa + C0? + NaOH
                            J 10°C
                           ~QO°r                    i
        ClCH2COONa + NaCN -     ) NCCH2COONa + NaCl —	> NCCH2COOH
                                   H SO
                NCCH0COOH + CoH^OH   ., >  NCCH0COOC0H,.
                    2        25   reflux      2    25
1.   Function - Ethyl cyanoacetate is manufactured by esterification of

     cyanoacetic acid with ethyl alcohol.  The cyanoacetic acid is formed

     via the reaction of sodium chloroacetate with sodium cyanide.

          The crude ester (washed, dried) is purified by distillation

     under reduced pressure.

2.   Input Materials

     Chloroacetic acid

     Water

     Na?CO_ (neutralize chloroacetic acid)

     NaCN

     HC1 (to liberate cyanoacetic acid)

     C2H5OH

3.   Operating Parameters

     Temperature:  Neutralization C1CH2COOH - 10°C  (50°F)

                   Formation - sodium cyanoacetate - ~90°C  (194°F)

                   Esterification - reflux temperature
                              6-299

-------
4.   Utilities - Not given




5.   Waste Streams - Excess NaCN reacts with HC1 to give HCN,  which is




     vented to the air.   Waste waters may contain salts, dilute acids,




     traces of alcohol,  and of ethyl cyanoacetate.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 12 (1967),  p.  853-854.






     Oilman, H., Organic Synthesis, 2nd Edition, 5th Printing, John Wiley




     and Sons, New York, N.Y., Collective Vol. I, 1948, pp. 254-256.
                             6-300

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.




                       Ethylene Dibromide
                         + Br2 - >• BrCH2CH2Br






1.   Function - Ethylene dibromide is produced by the reaction of ethylene




     and bromine.  The reaction takes place in earthenware or glass vessels,




     the ethylene being passed into the bromine.  After any free acid is




     neutralized, the product is purified by fractionation.  The yield is




     approximately 90% of the theoretical.




2.   Input Materials - Per kg product (2.2 Ibs)




     Ethylene - 1.166 kg  (2.57 Ibs)




     Bromine - 0.933 kg  (2.06 Ibs)




3.   Operating Parameters




     Temperature    10-100 °C  (50-212 °F)




     Pressure       101  kPa  (1 atm)




     Reaction Time  16 hrs (batch)




                     2 hrs (continuous)




4.   Utilities




     Not given




5.   Waste Streams - No information was available, but waste streams from




     distillation columns and other processing equipment may contain traces




     of reactants, reaction products  (ethylene dibromide and by-products),




     and free acid neutralization products.




6.   EPA Source Classification Code - None




1 •   References



     Austin, G.  T.,  "The Industrially Significant Organic Chemicals -




     Part 5, ""Chemical Engineering," April 29, 1974, p. 146.





                             6-301

-------
7.   References (continued)




     Kirk-Othmer,  Encyclopedia of  Chemical  Technology, 2nd Edition,



     Interscience  Publishers,  New  York, U.Y., Vol.  3   (1964), p.  771.






     Sittig, M., Chemicals from Ethylene,  Noyes Development Corporation,




     Pearl River, N.Y.,  1965 , p.  36, 37.
                             6-302

-------
INDUSTRIAL ORGANIC CHEMICALS                             PROCESS NO.  115








                     Ethyl Chloride (from ethylene)




                                      AlCl-
                                  HC1
1.   Function - Eighty-eight percent of the ethyl chloride produced in the




     U.S. is made by the liquid-phase reaction of dilute ethylene and




     hydrogen chloride.





     The reaction is carried out at normal temperature and pressure in an




     0.2% solution of aluminum chloride in ethyl chloride.  The yield is




     approximately 90% of the theoretical.




2.   Input Materials




     Basis - 1 kg ethyl chloride





     Ethylene - 0.488 kg




     Hydrogen chloride - 0.625 kg




     Catalyst - 5 g




3.   Operating Parameters




     Temperature:    35-40°C (95-104°F)




     Pressure:       372 kPa (3.67 atm)




     Catalyst:       0.2% A1C1, solution




4.   Utilities




     Not given




5.   Waste Streams - Emissions from air vents and wastewater streams may




     include ethylene, hydrogen chloride gas, hydrochloric acid, CH, , C0_,




     ethyl chloride, and trace amounts of catalyst.




6.   EPA Source Classification Code - None
                                6-303

-------
7.    References




    Austin, G. T., "The Industrially Significant Organic Chemicals -




    Part 5,""Chemical Engineering," April 29,  1974,  p.  144,  145.





    Kirk-Othmer, Encyclopedia of Chemical Technology.  2nd Edition, Inter-




    science Publishers, New York, N. Y., Vol.  5  (1964),  p.  144.





    Sittig, M., Pollution Control in the Organic Chemical  Industry,




    Noyes Data Corp., Park Ridge, N.J., 1974, p. 133,  134.





    Sittig, M., Organic Chemical Processes, The Noyes  Press,  Inc., Pearl




    River, N.Y., 1962, p. 55.
                               6-304

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  116
                   Tetraethyl Lead (via lead amalgam)
                      4PbNa 	*  PbCCI^CH-),   +  3Pb  +  4NaCl
1.  Function - The major reaction for the production of tetraethyl lead
    involves the addition of lead amalgam to ethyl chloride at 65-75°C
    and 345-414 kPa (50-60 psig).  The lead amalgam used is about 90%
    lead and 10% sodium.
         The yield based on sodium feed exceeds 90%.  Some sodium is lost
    to side reactions, which form hydrocarbons.  The tetraethyl lead formed
    is steam distilled and purified.  The lead sludge is reprocessed.
2.  Input Materials
    Ethyl chloride
    Lead amalgam
         90% lead - 0.75 kg/kg tetraethyl lead
         10% sodium - 0.32 kg/kg tetraethyl lead
3.  Operating Parameters
    Temperature - 65-75°C (149-167PF)
    Pressure - 345-414 kPa (3.40-4.09 atm)
4.  Utilities - Not given
5.  Waste Streams - Hydrocarbons formed by combination and disproportionation
    of ethyl radicals are normally vented during reaction period.  The effluents
    from washings may contain small amounts of oxidizing agents, reaction
    products and sodium chloride from the washings of the lead sludge.
6.  EPA Source Classification Code - None
                               6-305

-------
7.   References




    Austin, G.  T.,  "The Industrially Significant  Organic  Chemicals  - Part




    8," "Chemical Engineering,"  July 22,  1974,  p.  114.





    Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience  Publishers, New York, N.Y., Vol.  12  (1967), p. 290-293.





    Lowenheim,  F. A.  and Moran,  M. K., Industrial .Chemicals, 4th Edition,




    John Wiley  &  Sons, New York, N.Y.,  1975 , p. 502-508.
                              6-306

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 117




                   Tetraethyl Lead (via electrolysis)






                     CH3CH2C1  +  Mg - * CH3CH2MgCl
      2CH3CH2MgCl  +  2CH3CH2C1  +  Pb -





1.  Function - The newer electrolysis process is used mainly to produce




    tetramethyl lead but is suitable for the manufacture of other lead




    alky Is.  The process consists of two major steps:  1) Synthesis of




    a Grignard reagent from magnesium and ethyl chloride in anhydrous




    mixed ethers such as THF and diethylene glycol; and 2) Electrolysis




    of the solution of the Grignard reagent where the ethyl radicals




    migrate to an anode of lead pellets and combine to form tetraethyl




    lead.  Magnesium migrates to the cathode (steel wall of the cell)




    and reacts with excess ethyl chloride to give magnesium chloride.




2.  Input Materials




    Ethyl chloride




    Magnesium




    Lead




    Tetrahydrof uran




    Diethylene glycol dibutyl ether




3.  Operating Parameters




    For Grignard reagent formation:  Temperature - 350°C  (662°F)




                                     Pressure - 69-138 kPa (0.68-1.36 atm)




4.  Utilities - Not given
                              6-307

-------
5.  Waste Streams - No Information available.   Possible emissions  from




    recycling and purification of solvents.




6.  EPA Source Classification Code - None




7.  References




    Austin, G. T., "The Industrially Significant Organic Chemicals - Part 8,'




    "Chemical Engineering," July 22, 1974,  p.  114,  115.





    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition, Inter-




    science Publishers, New York, N.Y.,  Vol.  12 (1967), p.  290-293.






    Lowenheim, F. A. and Moran, M. K.,  'Industrial Chemicals,   4th  Edition,




    John Wiley & Sons, New York, N.Y.,  1975',  p. 502-508.
                              6-308

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 118



                         Ethyl Cellulose
             R  ,, OH + NaOH 	>• R  - - OH •  NaOH
              cell                   cell
                 R  in OH • NaOH + C^H.Cl 	>•
                  cell              2 5
                    R  .. n OC0H,- + NaCl + H00
                     cell   25           2
1.   Function - On a commercial scale, ethyl cellulose is made by the



     liquid-phase reaction of alkali cellulose and ethyl chloride.  The



     alkali cellulose is prepared by mixing a 50% aqueous sodium hydroxide



     solution with cellulose.  Since high sodium hydroxide concentration



     favors the main reaction, the concentration is kept as high as pos-



     sible.



          After several hours, the alkali cellulose is added to a nickel-



     lined pressure vessel along with ethyl chloride and a diluent such



     as benzene or toluene.  The conversion to ethyl cellulose requires



     6-12 hours at 90-150°C.



          The exact substitution may be controlled by the sodium hydrox-



     ide  concentration, the ethyl chloride input, or the reaction



     temperature.



          A number of side reactions occur during this conversion, the



     principal ones being the hydrolysis of ethyl chloride to ethanol



     and the subsequent formation of ethyl ether.




                C2H5C1 + NaOH 	>- C^OH + NaCl





       C2H5OH + C2H5C1 + NaOH 	»- C^OC^ + NaCl + H20





                             6-309

-------
          The extent of these side reactions if reduced by increasing the




     sodium hydroxide concentration, decreasing the water content of the




     reaction mixture, and the presence of benzene or toluene.  However,




     the ethyl chloride efficiency is still rather low.




          At the end of the etherification, the pressure is released




     slowly, allowing the volatile ethyl chloride, ether, alcohol, and




     any diluent to distill off.  The spent sodium hydroxide is drained




     off for recovery, and the product is purified by washing in stain-




     less steel equipment.  The by-products, ethanol and ethyl ether




     may be reconverted to ethyl chloride by heating with HC1 in the pre-




     sence of ZnCl™ catalyst.




2.   Input Materials - Basis - 56 kg ethyl cellulose




     Cellulose - 45 kg (99.2 Ibs)




     50% NaOH solution - 628 kg (1384.5 Ibs)




     Ethyl chloride - 220 kg (485.0 Ibs)




     Benzene or toluene




     Hydrogen chloride




3.   Operating Parameters




     Temperature:  Alkali cellulose 35-40°C (95-104°F)




                   Ethylation 90-150°C (194-302°F)




     Pressure:  0.2-2.2 MPa (2-22 atm)




     Catalyst:  By-product conversion - ZnCl»




4.   Utilities




     Not given
                             6-310

-------
5«   Waste Streams




     Purification (air)




     Ethyl chloride, ethanol, ethyl ether, and benzene or toluene may




     be present in air emissions from distillation operations.




     Purification (water)




     Waste water from washing operations may be expected to contain




     quantities of caustic soda, ethyl cellulose, and all of the pollu-




     tants previously mentioned.  Degraded cellulose may also be present




     along with sodium chloride.




     By-product conversion




     Ethyl chloride, ether, alcohol, spent catalyst, and tars may be pre-




     sent in the waste streams from this process step.




     Benzene/Toluene recovery




     Benzene or toluene may be present in the extract water, and in air




     emissions along with purification solvents.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 4 (1964), p. 640, 641.
                             6-311

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  119

        Ethanol (hydration of ethylene)  and Diethyl Ether




        + H 0 (H3P°^   CH CH OH + CH CH  OCH CH  + 44 2 MJ k -mole

                                                  (19,000 Btu/lb-mole)



1.   Function - Synthetic ethanol has been manufactured from ethylene

     by two processes,  i.e., the direct  hydration process and the

     absorption process.   The last large absorption process plant shut

     down in late 1974, so that essentially all of the synthetic ethanol

     is now being manufactured by the direct hydration process.

          The hydration process involves catalytic addition of water

     to ethylene.  Phosphoric acid, impregnated on an inert support such

     as Celite diatomite is commonly used.   High pressures and tempera-

     tures are required for this exothermic process.

          Fresh ethylene feed (98+%) plus recycle ethylene are compressed

     and mixed with 0.5-1.0 mole water per mole of ethylene.  The gaseous

     mixture is preheated and then fed to a reactor.  The vapor leaving
                   I
     the reactor is slightly hotter than the feed because of the exothermic

     reaction.  The reactor effluent is  cooled and treated with a small

     amount of caustic  soda.  The condensed ethanol/water mixture is

     sent to a separator where the aqueous ethanol is separated from

     unreacted gases.   The gases are scrubbed with water to remove traces

     of ethanol, and  are returned to the reactor as recycle ethylene.

     A small purge stream is removed to  prevent buildup of impurities

     in the recycle ethylene.
                             5-312

-------
          The aqueous ethanol solution from the scrubbing step is com-




     bined with the liquid product from the separator.   The mixture is




     concentrated to 190° proof ethanol (95 vol %)  by conventional dis-




     tillation techniques.  For anhydrous ethanol (absolute ethanol;  200°




     proof ethanol), the 95 vol % ethanol is fed to a dehydrator where




     water is removed as an azeotrope.  Benzene is  commonly used.




          Relatively small amounts of by-products are produced in this




     reaction.  They are:  ether, aldehydes, higher hydrocarbons, higher




     alcohols, and ketones.  Ether is the principle by-product.




          The conversion of ethylene to ethanol is  limited to low values




     per pass by the thermodynamic equilibrium at practical operating




     conditions.  Therefore, a large recycle volume of unconverted




     ethylene is required.  The temperature, pressure,  water to ethylene




     ratio, and ethylene purity are important variables, and must be




     closely controlled for maximum efficiency.




          Ethanol is also produced by fermentation.  It can be synthesized




     by an oxo-related process which involves the reaction of methanol with




     carbon monoxide and hydrogen at high temperature and pressure over




     a cobalt catalyst.  Ethanol is also produced in minor quantities




     during the oxidation of n-butene.




2.   Input Materials




     Ethylene - 747 kg/metric ton (1495 Ib/short ton) product




     Water - 4,682 kg/metric ton (9,365 Ib/short ton) product




     Hydrogen - 0.035 kg/metric ton (0.07 Ib/short ton) product




     Sodium hydroxide - 2.5 kg/metric ton (5 Ib/short ton) product
                             6-313

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3.   Operating Parameters - The conditions recommended for highest


     efficiency are:


     Reactor temperature - 299°C (570°F)


     Reactor pressure - 6.7-7.0 MPa (661-69.1 atm)


     Reactor feed ethylene concentration, water free basis - 85%


     Ethylene makeup concentration -97+%


     Water to ethylene ratio in feed - 0.6


     Space velocity - 26.5-30 (volume of gas at 15.6°C (60°F) and


                      101 kPa (1 atm)/min - vol. of catalyst)


     Ethylene conversion per pass - 4.2-5%


     Water conversion - 7.0%


     Overall yield, ethylene to ethanol - >97%


4.   Utilities - Basis - 84,900 metric tons (93,600 short tons)/yr

                  3
     Water - 1.8 m /s (28,900 gpm)


     Steam - 97,800 kg (216,000 lb)/hr


     Fuel gas - 11 MW (38 MM Btu)/hr (excluding 1.2 dam (45,000 scf)/hr


                gas bleed)


     Electricity - 1.747 kW


     Nitrogen - 6.2 m3 (2,200 scf)/hr


5.   Waste Streams


     Water - The major source results from separation of product from


     process bottoms and may amount to 15-30 kg (33-66 Ib) of COD/metric


     ton of product.


     Air - 1.1 kg (2.5 Ib) ethanol/metric ton of product plus traces of


     acetaldehyde, ether, ethylene, and ethylene impurities  from the


     purification section.  Leaks in compressor seals, as well as  in
                             6-314

-------
     the gas handling system,  are also a possible source of air pollu-




     tion.   Also present  are olefin polymers, acetaldehyde, and diethyl




     ether.




6.   EPA Source Classification Code - None




7.   References







     Kirk-Othmer, Encyclopedia of  Chemical Technology, 2nd Edition,




     Interscience Publishers,  New  York,  N.Y., Vol.  8 (1965), p. 434,




     435, 436.






     Considine, D. M., Ed., Chemical  and Process Technology Encyclopedia,




     McGraw-Hill Book Co., New York,  N.Y., <1974 ,  p. 423-427.






     Gloyna, E. F., and Ford,  D. L.,  "The Characteristics and Pollutional




     Problems Associated with  Petrochemical Wastes," Prepared for FWPCA,




     Contract 14-12-461,  Robert S.  Kerr  Water Research Center, Ada,




     Oklahoma, February 1970.






     U.S. Patent 2,773,910 (December  11, 1956).






     Sittig, M., Organic Chemical  Process Encyclopedia - 1969, 2nd Edition,




     Noyes Development Corp.,  Park Ridge, N.J.,  1969 , p. 297.
                            6-315

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  120




            Mono-, di-, triethylamine (.from ethanol and ammonia')
                         OH
                                                        HO
1.  Function - Ethylamine,  diethylamine,  and triethylamine are all




    produced by the reaction of ethyl alcohol and ammonia under heat




    and pressure.   The reaction is run in the vapor phase.




         Although  mixtures  of amines are  always produced, the reaction




    products can be controlled to a certain extent.   A large excess  of




    ammonia favors ethylamine production.  If this product is recycled,




    more di- and triethylamines will be produced.  These amines used to




    be synthesized from ethyl chloride until they became large volume




    chemicals.  Then the starting material was switched to the cheaper




    ethyl alcohol.




         The alkylation of  ammonia by alcohols has been accomplished in




    the presence of hydrogen and a hydrogenation catalyst consisting of




    a mixture of nickel and copper deposited on alumina activated with




    boric acid.  Thus two moles of ethanol, one mole of ammonia, and




    three moles of hydrogen were passed over the catalyst at 220°C to




    yield a product consisting of ethyl-, diethyl-, and triethylamines




    in the ratio of 1:5:3.   The conversion of ethanol amounted to 52




    percent.
                              6-316

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2-  Input Materials - per metric ton  (2,205 Ibs) product
                                       MEA          PEA           TEA
    Ethyl alcohol, kg (Ibs)        1122 (2474)   1384 (3051)   1500 (3307)
    Ammonia - excess, kg (Ibs)      402 (886)     248 (547)     179 (395)
    Catalyst, kg  (Ibs)               12 (2.6)     1.2 (2.6)     1.2 (2.6)
    Hydrogen, m   (ft3)             14.2 (500)    14.2 (500)    14.2 (500)
3.  Operating Parameters
    Temperature - 400°C (752°F)
    Pressure - 10.13 MPa (100 atm)
    Reaction time - 2-3 hrs.
4.  Utilities - per 45.5 kg (100 Ibs) product
    Steam @ 1.04 MPa (10.3 atm) - 680.4 kg
    Cooling water (10°C rise) - 26.5 m3 (7,000 gal.)
    Electricity, MJ-28.8 (8 kWh)
5.  Waste Streams - Excess ammonia, ethyl alcohol, and all three amines may
    be present in the off-gas from the ammonia stripper.   Organic and inor-
    ganic ammonium salts, as well as the pollutants mentioned, should be
    expected in the wastewater stream.  If the liquid phase process is used,
    the alcoholic solvent may be present in both cases.   Volatiles may also
    be emitted from other processing steps.
6.  EPA Source Classification Code - None

7.  References
    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition
    Interscience Publishers, New York, N.Y.,  Vol.  8 (1963), p. 455.
                              6-317

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7.   References




    Astle,  M.  J.,  Industrial Organic Nitrogen  Compounds, Rheinhold Publishing




    Corp.,  New York, N.Y., 1961, p. 7, 8.





    Chemical Technology,  Barnes and Noble Books,  New York,  N.Y., Vol.  4




    (1972), p. 511,  512.





    "1973 Petrochemical Handbook"," Hydrocarbon Processing ."November, 1973,




    p.  115.
                              6-318

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INDUSTRIAL ORGANIC CHEMICALS                                   PROCESS NO. 121
                    Ethyl Oxalate (direct esterification)
                (COOH)2 •  2H20 	>• (COOH)2     2-* (COOEt).
1.   Function - Ethyl oxalate is manufactured by the conventional




     esterification of oxalic acid.  Oxalic acid is sufficiently acidic




     to serve as its own esterification catalyst, but mineral acids and




     ion exchange resins are sometimes used.




          Since commercial oxalic acid is generally the dihydrate, the




     process may be more economical if the acid is dehydrated and esteri-




     fied in a single operation.  If the dihydrate is reacted, it is




     necessary to remove twice the usual proportion of water to complete




     the reaction.




          Low-boiling solvents capable of forming azeotropes with water




     are preferred to remove the water of crystallization.  After dehy-




     dration, esterification is carried out in the same reactor using




     the same solvent to remove water produced during the reaction.  The




     last traces of water are most difficult to remove and this is accom-




     plished by a special step in the rectification.  Yields of 90 - 92%




     are achieved.




2.   Input Materials




     Oxalic acid dihydrate - 0.95 kg/kg ethyl oxalate




     Ethanol - 0.69 kg/kg ethyl oxalate




     Low-boiling solvent




3.   Operating Parameters




     Temperature:  not given






                               6-319

-------
     Pressure:  not given




     Catalyst:  Mineral acids




                Ion exchange resins




4.   Utilities




     Not given




5.   Waste Streams - Although no information was available, wastewater




     streams from the separator may be expected to contain quantities




     of solvent, unreacted ethanol and oxalic acid, ethyl oxalate, and




     reaction intermediates and by-products.   Some solvent and ethanol




     are probably released through air vents in the separator and other




     processing equipment.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York,  N.Y.,  Vol.  14 (1967), p.  370.
                               6-320

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  122
                 Ethyl Acrylate (direct esterification)
             CH2=CHCOOH + C£H5OH  - >   CH



1.  Function - Ethyl aery late is usually made in a modification of an

    acrylic acid process by adding ethanol to the reactant mix.  The

    processes based on propylene for acrylic acid appear to be growing

    fastest because of propylene's low cost; acetylene and ethylene are

    being phased out as raw materials.   The esterification of acrylic

    acid is accomplished in the presence of sulfuric acid, Dowex*^ 50 ion

    exchange resin, or silica gel catalyst.

         Hydroquinone or other polymerization inhibitors are added during

    distillation.

2.  Input Materials

    Acrylic acid - 737.5 kg/Mg product

    Ethanol - 476.5 kg/Mg product

3.  Operating parameters

    Temperature - not given

    Pressure - not given

    Catalyst - H-SO,, Dowex^SO ion exchange resin or silica gel.

4.  Utilities - basis:  0.430 kg/sec (0.95 Ib/sec) capacity

    Steam - 364 kg/sec (8 Ib/sec)

    Power - 169 kW capacity
                          o
    Cooling water - 151 dm /sec (40 gal/sec)
                          o
    Makeup water - 5.11 dm /sec (1.35 gal/sec)


    Refrigeration - 15.4 Mg


    * Data from plant using Dowers-'SO ion exchange resin.

                              6-321

-------
                 *
5.  Waste Streams


    Heavy ends from the ester purification column:


    Polymers - 11.9 kg/Mg (lb/1000 Ib)  product


    Hydroquinone - 13.75 kg/Mg (lb/1000 Ib) product


    Overhead from the ester purification section (air):


    Ethanol - 2.65 kg/Mg (lb/1000 Ib) product


    Ethyl acrylate - 1.6 kg/Mg (lb/1000 Ib) product


    Ethyl acetate - 5.25 kg/Mg (lb/1000 Ib) product


    Sodium carbonate - 0.26 kg/Mg (lb/1000 Ib) product


6.  EPA source classification code - None


7.  References


    Austin, G. T., "The Industrially Significant Organic Chemicals -


    Part 4,""Chemical Engineering," April 15, 1974, p.  90.



    Hedley, W. H., et al.,  Potential Pollutants from Petrochemical Processes,


    Technomic Publishing Co., 1975.



    Kirk-Othmer, Encyclopedia of Chemical Technology4 2nd Edition,


    Interscience Publishers, New York,  N.Y., Vol. 1 (1963), p. 297, 298.
      Data from plant using Dowex^SO ion exchange
resin.
                               6-322

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INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 123


          Acetal (from acetaldehyde and ethanol)


          CH3CHO  +   CH3CH2OH     Cat>       CH3CH(OCH2CH3)2


1.   Function - Acetal (specifically, diethyl acetal) is formed by the

     condensation reaction of acetaldehyde and ethanol.  Catalysts used

     in this process may be acids (hydrochloric, p-toluenesulfonic) or

     salts (calcium chloride, ammonium chloride).  In some cases,  azeo-

     tropic distillation is employed to remove the water of reaction and

     improve the yield.

2.   Input Materaisl

     Acetaldehyde
     Ethanol

3.   Operating Parameters

     Temperature:  Not given

     Pressure:  Not given
     Catalyst:  acids or salts

4.   Utilities - Not given.

5.   Waste Streams  - Wastewater streams from the purification section

     may contain acetaldehyde, ethanol, acetal, and either acid or salt

     catalyst.  Volatile reactants and products may be emitted through

     air vents in the reactor, separator, and other process equipment.

6.   EPA Source Classification Code - None.

7.   References

     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

     Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 81, 108.
                             6-323

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INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO.  124




                   Acetaldehyde (from ethanol)
               CH3CH2OH + 1/2 02   -> CH3CHO + H20




 1.  Function - As of 1974, only 15% of the United States acetaldehyde




     capacity was based on ethanol.  There are two processes for conversion




     of ethanol to acetaldehyde, i.e., oxidative dehydrogenation and




     catalytic dehydrogenation.




     Oxidative dehydrogenation




          The vapor phase reaction is carried out over solid silver gauze




     catalyst at 538°C (1000°F) .  Aqueous ethanol, steam, and air are




     fed to the oxidizer (reactor) .  The reactor effluent is condensed




     and is passed to a phase separator which also serves as a scrubber




     (refrigerated water) .   The  off gases are vented from the system and




     the wash is combined with the liquid stream.  The combined liquid




     stream is sent to a flash column where it is separated into acetal-




     dehyde product, alcohol for recycle, and waste water.  The acetaldehyde




     product from the flash column is sent to an ethanol recovery still




     where acetaldehyde product  is taken from the top and the bottoms




     (primarily ethanol) are recycled to the reactor.




     Catalytic dehydrogenation




          The primary reaction is:




                    CH3CH2OH -^ CH3CHO + HZ




          The vapor phase reaction is carried out over a solid copper




     catalyst promoted by cobalt or chromium on an asbestos support at




     260°C (500°F) .  The recovery and isolation systems are almost identical




     to those in oxidative dehydrogenation.  The yields in both processes




     range from 85  to 95%.






                             6-324

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2.  Input Materials

         Oxidative dehydrogenation:  air

                                     ethanol

                                     steam

                                     water

         Catalytic dehydrogenation:  ethanol - 1150 kg/metric ton (2,535 Ibs/ton)
                                               acetaldehyde
3.  Operating Parameters

         Oxidative dehydrogenation:  temperature - 538°C (1000°F)

                                     pressure - 410 kPa (4.05 atm)

                                     flow rate - not given

                                     equipment - multitubular reactor,

                                                 phase separator, flash

                                                 column, still

                                     catalyst - solid silver gauze

         Catalytic dehydrogenation:  temperature - 260°C (500°F)

                                     pressure - not given

                                     flow rate - not given

                                     equipment - see oxidative

                                                 dehydrogenation

                                     catalyst - solid copper catalyst

                                                promoted by cobalt or

                                                chromium on an  asbestos

                                                support

4.  Utilities - The water usages of  two plants are:

                             Process water            Cooling water

    Plant 1               5.9 kg/kg  product         47.2 kg/kg  product

    Plant 2               0.45 kg/kg product        45.4 kg/kg  product


                            6-325

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5.  Waste Streams

    Air - Off gases from the phase separator; it has been estimated that

    12.2 Mg (27 MM Ib) of CO is emitted annually from this industry.

    Water - The only wastewater stream generated is either from the

    acetaldehyde flash column or ethanol recovery still.  It contains

    liquid products such as acetaldehyde, ethanol, and ethyl acetate.

    Data on two plants (one using each of the two processes) was as

    follows:

                             Plant 1                  Plant 2

    Flow                6.0 m3/                    529 dm3/
                        454 kg                     454 kg
                        product                    product

    COD                 0.186 kg/m3 (186              	
                        mg/1) 1.1 kg/454
                        kg

    BOD                 0.084 kg/m3 (84 mg/           	
                        1) 0.50 kg/454 kg


    TOC                      	                   14.4 kg/m3 (14,400
                                                   mg/1) 7.6 kg/454
                                                   kg


6.  EPA Source Classification Code - None

7.  References
    Austin, G. T., "Industrially  Significant  Organic Chemicals -

    Part 1," "Chemical Engineering," January  21,  1974, p. 128.
                            6-326

-------
Waddams, A. L., Chemicals from Petroleum, 3rd Ed., John Murray Ltd.,




London, Eng., 1973, p. 75, 76.




Sittig, M., Pollution Control in the Organic Chemical Industry,




Noyes Data Corporation, Park Ridge, N.J., 1974,  p. 47-50.





Lowenheim, F. A. and Moran, M. K.,  Industrial Chemicals, 4th Edition,




John Wiley & Sons, New York, N.Y.,  1975, p.  3.
                        6-327

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  .125




                         Diethyl Sulfate (from ethylene)
                                 H SO
1.  Function - The most economical route to diethyl sulfate involves




    the action of 96% sulfuric acid on ethylene at 60°C.   The resulting




    mixture of 43% diethyl sulfate, 45% ethyl hydrogen sulfate, and 12%




    sulfuric acid is heated with anhydrous sodium sulfate under vacuum




    and diethyl sulfate is obtained in 86% yield.




2.  Input Materials




    Ethylene




    Sulfuric acid




    Sodium sulfate




3.  Operating Parameters




    Temperature - 60°C  (140°F)




4.  Utilities - not given




5.  Waste Streams - No process information was available.  If excess acid




    and the water of reaction are separated prior to distillation, waste-




    water streams may contain sulfuric acid, diethyl sulfate, and mono-




    ethyl sulfate, a reaction intermediate.  Miscellaneous air emissions




    may contain the same pollutants.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 19 (1969), p. 492.
                                6-328

-------
7.   References (continued)




     Chemical Technology, Barnes and Noble Books, New York, N.Y.,  Vol.  4




     (1972), p. 278, 504.
                             6-329

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  126




                    Propanoic Acid (from ethylene)





                  H2C=CH2 + H20 + CO 	>• CH3CH2COOH





1.   Function - One competitive process for the production of propionic




     acid  involves the reaction of ethylene, carbon monoxide, and water




     in the presence of a NiCCo/H-BO., catalyst.  The liquid phase reaction




     is run in a stainless steel autoclave.  The product (40% propionic




     acid in water) may be purified by rectification.  The autoclave is




     charged with 300 g of 17.2 weight percent propionic acid, 0.823 g




     Ni as NiC03, 3.15 g H3B03, 100 g C^, and 50 g CO.  The temperature




     is raised to 153°C at 13.88 MPa (137 atm) at which time the tempera-




     ture and pressure jump to 288°C and 23.3 MPa (230 atm).  The reaction




     is cooled after 30 min and filtered to yield a 40% solution of pro-




     pionic acid which also contains 0.70 g Ni.  In a continuous process,




     the normal rate of 292 g acid/g Ni goes to 1320 g acid/g Ni by using




     a stoichiometric excess of H-BO- with respect to the nickel ion con-




     centration.




          Propionic acid has also been prepared from ethanol and carbon




     monoxide.




2.   Input Materials




     Ethylene - 100 g (0.22 Ibs)




     Carbon monoxide - 50 g (0.11 Ibs)




     Propionic acid (17.2 wgt %) - 300 g (0.66 Ibs)




     H3B03 - 3.15 g (0.0069 Ibs)




     Ni (as NiCOj  - 0.823 g (0.0018 Ibs)
                             6-330

-------
3.   Operating Parameters




     Temperature:   1st stage      153°C (307° F)




                    2nd stage      288°C (550° F)




     Pressure:      1st stage      13.88 MPa (137 atm)




                    2nd stage      23.3 MPa (230 atm)




     Catalyst:      NiCC^/H-BO




4<   Utilities - None given.




5.   Waste Streams - Propionic acid will be in the aqueous waste




     streams along with nickel salts and boric acid.  Excess CO and




     ethylene may be present in air emissions.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 16 (1968), p. 555.







     Sittig, M., Oxo Process and Products,  Noyes Development Corp.,




     Park Ridge, N.J., 1966, p. 105,  106.






     U.S. Patent 3,151,155  (September 29,  1964).
                            6-331

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO. 127
                  Diethyl Ether (from ethanol)
 1.   Function - There have been several processes for the manufacture of
     ethyl ether, i.e.,  dehydration of ethanol with sulfuric acid;
     the addition of sulfuric acid to ethylene (indirect  hydration or
     absorption process) ;
                   0
            CH3CH2OS=0  + CH2=CH2  +  ^0 - *•
                   OH

     the direct hydration of ethylene.
            2 CH2=CH2  +  H20  - >  (CH3CH2)20

     The dehydration process was designed primarily for the production
     of ethyl ether, whereas ethyl ether is  the principal by-product in
     the direct or indirect hydration process.  At present, most of the
     ethyl  ether produced is manufactured by the vapor phase catalytic
     dehydration of ethanol.
 2.   Input  Materials
     Ethanol
     Catalyst (tungsten oxide /A120 )
                              6-332

-------
3.  Operating Parameters




    Temperature:  120-375°C (248-707°F)




    Pressure:  0.103-10.3 MPa (1.02-102.1 atm)




    Contact Time:  30 min




4.  Utilities - Not given




5.  Waste Streams - Unreacted ethanol and some catalyst should be pre-




    sent in the waste streams.




6.  EPA Source Classification Code - None




7.  References




    Faith, W. L., et^ al^., Industrial Chemicals, 3rd Edition, John Wiley




    and Sons, New York, N. Y., 1965, p. 335-338.






    U. S. Patent 2,805,260 (September 3, 1957).






    Chemical Technology, Barnes and Noble Books, New York, N. Y., Vol.




    4 (1972), p. 333.





    Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd Edition,




    Noyes Development Corp., Park Ridge, N. J., 1969, p. 326.
                             6-333

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS  NO. 128




            Acetamide (ammonolysis of ethyl acetate)
1.   Function - Acetamide is currently produced by the interaction of




     ethyl acetate and aqueous ammonia.  Ethanol is a by-product of




     this reaction.  The crude product is purified by crystallization.




          In the past, acetamide has been made from the acid chloride,




     acetic anhydride, ammonium acetate,  acetic acid, and ketene, among




     other materials.  Recently, the ethyl acetate route has proven




     most economical.




2.   Input Materials




     Ethyl acetate




     Aqueous ammonia




3.   Operating Parameters




     Not given




4.   Utilities




     Not given




5.   Waste Streams - Waste water and air emissions from the ammonia




     stripper may contain any of the reactants or products.  Some addi-




     tional air emissions may result from recycling operations.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 1  (1963), p.  144.
                             6-334

-------
INDUSTRIAL ORGANIC CHEMICALS

                      Ethyl Sodium Oxalacetate
                                                 PROCESS NO.  129
COOC H
I           +
COOC2H
                         ONa
                O
                           C2H5OOC(ONa)CHCOOC2H5
1.  Function - Ethyl sodium oxalacetate is made by the reaction of pure

    ethyl acetate with the adduct formed by the reaction of diethyl

    oxalate and sodium alcoholate.

2.  Input Materials

    Ethyl acetate

    Ethyl oxalate

    Sodium

    Absolute alcohol ether

3.  Operating Parameters

    Addition of reagents - Ice-water bath

4.  Utilities - Not given

5.  Waste Streams - Wastewater streams may contain organic sodium salts

    and any of the reactants or products.
                              6-335

-------
6.  EPA Source Classification Code - None




7.  References




    Houben-Weyl,  Methoden Per Organischen Chemie,  Vierte Auflage,  Georg




    Thieme Verlag,  Sttutgart, Bd.  8 (1952),  p.  582.
                            6-336

-------
INDUSTRIAL ORGANIC CHEMICALS
           PROCESS NO.  130
                              Vinyltoluenes
GIL
        CH,
uciA   +
                                    CH,
                                  d
cut..
  CH,
6
                                                    CH=CH,
                                                                     CH=CH,
1.  Function - Vinyltoluenes are produced commercially by alkylation of

    toluene with ethylene  followed by dehydrogenation of the m-, and

    p-ethyltoluenes.  Toluene is alkylated with ethylene in a reactor

    similar to that used for ethylbenzene manufacture.  Reaction

    temperature is kept below 100°C.

         The crude alkylation product consists of a mixture of o-, m-, and

    p-ethyltoluene, polyethyltoluenes, benzene, ethylbenzene, xylenes,

    "lights", and tars.

         The crude product is cooled, washed with alkali, and purified by

    a series of fractional distillations.  Toluene, polyethyltoluenes,

    and the unusable o-ethyl toluene are recycled to the alkylator while

    other by-products are  reclaimed by other means.  The m- and p-ethyl-

    toluene mixture is then heated to 450-500°C, mixed with two to three

    times its weight of super-heated steam, and passed over a dehydrogena-


    tion catalyst.

         The separation of the m- and p- Vinyltoluenes from the crude hydro-


    genation mixture is accomplished by a series of vacuum distillations.


2.  Input Materials


    Ethylene

    Toluene

    A1C13


                                6-337

-------
3.  Operating Parameters




    Ethylation




    Temperature:  < 100°C (212°F)




    Pressure:  Not given




    Dehydrogenation




    Temperature:  450-500°C  (842-932°F)




    Pressure:  Not given




    Catalyst:  various dehydrogenation catalysts




4.  Utilities - Not given




5.  Waste Streams - Ethylation:  Effluents likely contain solutions of aluminum




    salts, HC1, sodium hydroxide, sodium chloride, and traces of the various




    aromatic reactants and by-products.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 19 (1969), p. 77-80.
                                6-338

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  131

    Ethylane-Bichloride (1,2-dichloroethane)  (direct chlorination)

                              FeCl
                H2C=CH2 + C12 	^ C1CH2CH2C1


 !•  Function - There are two commercial processes for making ethylene di-

     chloride (EC) from ethylene: the oxychlorination process and the

     direct addition process.  Over 95% of the EC produced in the United

     States in 1974 was made by the "balanced process," which is a

     balanced combination of the two processes.  Approximately 2.4% of

     the EC was made exclusively by oxychlorination, while 2.6% was made

     exclusively by the direct addition of chlorine to ethylene.  The

     oxychlorination process is described in Process No. 131.

          As of 1975 EC accounts for close to half of the chlorine

     used to make chlorinated organics.  Most of the EC is produced

     captively in the synthesis of vinyl chloride monomer.


          The direct chlorination of ethylene may be carried out in the

     liquid phase in the presence of ferric chloride catalyst.

          Approximately equimolar proportions of acetylene-free ethylene

     and chlorine are fed to a tower-type reactor through distributors.

     The reaction is fast, complete, and exothermic.  The tower-type re-

     actor is unique in that the top is a fractionator, complete with

     vented reflux condenser.

          The gas stream from the reactor is passed  through  a  caustic

     scrubber, where the unreacted gases and traces  of  HC1 are removed.

     The uncondensed gases  (primarily unreacted  ethylene  and chlorine)

     are then totally recycled to the reactor.
                            6-339

-------
         The liquid stream from the reactor is sent to a distillation



    column to remove heavy ends and then to a wash tower, where a caustic



    solution is used to remove some impurities.  The crude product is



    sent to a distillation column for purification.  Liquid EC, 99% pure



    (95% yields), is taken from the top of the fractionation column.



2.  Input Materials



    Acetylene-free ethylene - 297 kg/metric ton product



    Chlorine - 730 kg/metric ton product



    Ferric chloride - amount not given



3.  Operating Parameters



    Temperature of reactor - 90°C (194°F)



    Pressure in reactor - 150 kPa (1.48 atm)



4.  Utilities



    Basis:  72.5 Gg/yr capacity (reactor section)



            243 Gg/yr capacity (purification section)


                            3                                   3
    Water:  cooling - 21.3 m /minute process and makeup - 450 dm /minute



    Steam - 19.5 Mg/hr



    Refrigeration - 21.9 MJ (8.09 kWh)



5.  Waste Streams



    Total hydrocarbon emissions (est.) from the direct process industry -



    13.1 Gg (29 MM lb)/yr (all volatile organics except methane)



    Air:  vent on reflux condenser



    Ethane - 3.0 kg/metric ton EC



    Ethylene - 7.5 kg/metric ton EC



    Methane - 3.0 kg/metric ton EC



    Chlorine - 500 g/metric ton EC



    HC1 - 500 g/metric ton EC





                           6-340

-------
Water:  HC1 absorber  (scrubber)




Chlorine - 874 g/metric ton EC




EC - 2.45 kg/metric ton EC




HC1 - 3.8 kg/metric ton EC




Vinyl chloride (VCM)  - 600 g/metric ton EC




Methyl chloride - 50  g/metric ton EC




Ethyl chloride - 50 g/metric ton EC




Purification section  - caustic storage




EC - 150 g/metric ton EC




Sodium hydroxide - 600 g/metric ton EC




Sodium chloride - 200 g/metric ton EC




Purification section  - filter effluent




EC - 300 g/metric ton EC




Sodium hydroxide - trace




The waste water streams of one plant were surveyed  (combined liquid




effluents from the reactor offgases scrubber and from the wash tower)




Flow - 3.63 dam3/454  kg EC




COD - 6.050 kg/m3; 2.9 kg/454 kg EC




BOD_ - not given




TOG - 1.106 kg/m3; 0.40 kg/454 kg EC




Solid:  purification  section - filter effluent




Mercuric hydroxide -  3.5 g/metric ton EC




Tars - trace




Solids (as carbon) -  50 g/metric ton EC




Purification section  - distillation column bottoms
                        6-341

-------
    EC - 1.5 kg/metric ton EC




    1,1,2-trichloroethane - 2.45 kg/metric ton EC




    Tetrachloroethane - 2.45 kg/metric ton EC




    Tars - trace




6.  EPA Source Classification Code - None




7.  References




    Sittig, M., Pollution Control in the Organic Chemical Industry,




    Noyes Data Corp., Park Ridge, N.J.,  1974, p. 146.





    Considine, E.  M., Ed.-in-Chief,  Chemical and Process  Technology




    Encyclopedia,  McGraw-Hill Book Company, New York,  N.Y.,  1974,




    p. 1135-1136.





    Hedley, W. H., et al., Potential Pollutants from Petrochemical




    Processes, Prepared for EPA, Final Report MRC-DA-406, Contract No.




    68-02-0226, December 1973,  p.  194-195.





    "Chemical Week,"  March 12, 1975, p.  35, High Polymers, Leonard,  E.  C.,




    Editor, Vol. 24,  Part 3, p.  1220-1221.





    Lowenheim, F.  A.  and Moran,  M.  K.,  Industrial  Chemicals, 4th Edition,




    John Wiley and Sons, New York,  N.Y., 1975, p.  392.
                               6-342

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 132
             Ethylene Bichloride (oxychlorination)

                                 CuCl
         CH2=CH2 + 1/2 02 + 2HC1


  -  Function - As of late 1974, one plant of the 12 plants producing EC,

     used oxychlorination exclusively.  The other 11 plants used the oxy-

     chlorination of ethylene as part of the "balanced process."  The

     balanced process is a combination of direct addition of chlorine to

     ethylene and oxychlorination of ethylene.  The balanced process

     acquired its name from the fact that the overall process is balanced

     to yield only vinyl chloride, (VCM).  There is no net production of

     HC1.

          The manufacture of EC exclusively by the oxychlorination process

     accounted for only 2.4% of the total production in 1974 (108 Mg

     (240 MM Ib) out of 46 Gg (10.045 billion lb)).

          Either a fluid bed catalyst or fixed bed catalyst can be used.

     Approximately stoichiometric proportions of ethylene, anhydrous

     hydrogen chloride, and air are fed to the "oxy" (catalytic) reactor

     at low pressure and moderate temperatures.  The reactor effluent is

     cooled generally either by direct water quench or indirect heat ex-

     change.  The partially condensed effluent is sent to a phase separator.

     The gases are contacted with water in a quench column (absorber) for

     removal of HC1.  The resulting hydrochloric acid stream is treated

     offsite to recuperate the anhydrous hydrogen chloride.  The gases are

     then sent to the EC stripper for recovery of entrained EC which is

     combined with the EC effluent from the phase separator.  Noncondensi-

     ble gases (mainly nitrogen) are vented to the atmosphere.


                            6-343

-------
         The aqueous phase from the decanter is collected in the effluent


    separator and discharged to waste.   The organic phase is usually


    treated with aqueous caustic soda to remove traces of HCl.   It is


    then sent to product distillation to remove water and chlorinated


    hydrocarbon impurities which are sent to offsite disposal.   The crude


    EC (96 - 98% purity) is usually combined with the crude EC  from the


    direct chlorination.  The combined stream is purified by distilla-


    tion in an EC finishing column prior to being sent to the cracking


    furnace for product of VCM (Process No. 133).


2.  Input Materials - Basis:  Production of 317.5 Mg/yr EC


    Ethylene (99-9% purity) - 12.3 Mg/hr;


                               0.288 metric tons/metric ton EC


    Anhydrous hydrogen chloride - 30.5 Mg/hr;


                                   0.711 metric tons/metric ton EC


    Air - 42 Mg/hr; 0.961 metric tons/metric ton EC


    Dilute caustic soda - 313 kg/hr; 0.007 metric tons/metric ton EC


    Catalyst - cupric chloride impregnated on a fluid or fixed bed support


    Waste disposal system (direct fired boiler plus scrubber emission con-


    trol system):

                                      3
    Process vent gas - 36 Mg/hr; 493 m  ;


                       (17,420 scf)/minute @38°C  (100°F)


    Caustic feed - 367 kg/hr


    Waste disposal system (thermal incinerator and scrubber system):


    Combustion air - 14 Mg/hr (§27 °C (80°F)

                                      3
    Process vent gas - 36 Mg/hr; 493 m  ;


                       (17,420 scf)/minute @38°C  (100°F)


    Caustic feed - 367 kg/hr



                           6-344

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3.  Operating Parameters




    Reactor outlet temperature - 302°C (575°F)




    Reactor temperature - 232 - 315°C (450 - 600°F)




    Preheated feed temperature - 149°C (300°F)




    Reactor pressure - 239 - 618 kPa  (2.36-6.10  atm)




    Waste disposal system (direct fired boiler plus scrubber emission




    control system):




    Boiler temperature - 982°C (1800°F)




    Flue temperature - 288°C (550°F)




    Flue gas temperature from packed scrubbing tower - 60°C (140°F)




    Waste disposal system (thermal incinerator and scrubber system):




    Incinerator temperature - 982°C (1800°F)




    Combustion air and process gas preheat - 149°C (300°F)




    Incinerator flue temperature - 871°C  (1600°F)




    Flue gas temperature from packed scrubbing tower -11°  (170°F)




4-  Utilities - not given for overall oxychlorination process; data




    available on some parts of process based on  reactor outlet tempera-




    ture 302°C.




    Heat out




    Steam generation - 2.82 MG/kg EC




    Reactor heat loss - 13.9 kJ/kg EC




    Quench plus effluent cooling (302°C to 38°C)  - 1.4 MJ/kg EC




    Heat in




    Exothermic heat of reaction




    EC formation - 3.21 MJ/kg EC




    Effluent neutralization - 4.6 kJ/kg EC
                            6-345

-------
    Feed vaporization and preheat (149°C) - 372 kJ/kg EC




    Waste disposal system (direct fired boiler plus scrubber emission




    control system):




    Feed water - 21.2 Mg/hr 
-------
Component
Carbon
dioxide
Carbon
monoxide
Nitrogen
Oxygen
Methane
Ethylene
Ethane
EC
Ethyl
chloride
Aromatic
solvent
Composition,
mol. %
0.6-3.5
0.6-1.3
82-95
0.5-7.5
0 -5.0
0.2-0.8
0 -3.8
0.07-0.75
0 -0.75
0 -0.75
Flow rate,
kg/hr
957
264
31.6
1.8
78
191
260
272
231
42.6
Water:




Combined waste water - 0.1908 metric tons/metric ton EC




Waste disposal system - scrubber reject (from thermal incinerator




and scrubber system) - 11.9 Mg/hr




Scrubber effluent  (from thermal incinerator and scrubber system) -




80 Mg/hr; 1.29 dam3/min




Waste disposal system - scrubber reject (from direct fired boiler




plus scrubber emission control) - 11.9 Mg/hr




Scrubber effluent  (from direct fired boiler plus scrubber emission




control) - 62.1 Mg/hr; 906 m /min.




Solids emissions (est.):




Particulates - 181 Mg/yr
                       6-347

-------
6.  EPA Source Classification Code - None




7.  References




    Considine,  D.  M.,  Ed.-in-Chief,  Chemical  and Process Technology




    Encyclopedia,  McGraw-Hill Book Comapny, New York, N.Y.,  1974,




    p.  1137-1138.






    Anon., "Engineering and Cost Study Industry, Vol.  3, Ethylene




    Bichloride Manufacture by Oxychlorination," PB 240,  492, prepared




    for EPA, Contract 68-02-0255, Air Products  and Chemicals Inc.,




    November 1974.
                           6-348

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  133




               Vinyl Chloride ("Balanced Process")






                 CH2C1CH2C1 —£-*• CH2=CHC1 + HC1






 •"-•  Function - The synthesis of vinyl chloride monomer (VCM) uses an




     ethylene and chlorine feedstock first to produce ethylene dichloride




     (EC) which is then pyrolyzed to yield VCM.  In the "balanced pro-




     cess" the HC1 formed in the cracking of EC, is made to react with




     more ethylene in the presence of oxygen (oxychlorination reaction)




     to form more EC.




          As of 1975, approximately 94% of the commercial vinyl chloride




     monomer (VCM) was manufactured by the thermal dehydrochlorination




     of EC.  The other 6% was produced by addition of HC1 to acetylene.




          If low pressure cracking is used, the VCM and EC are generally




     removed from the quench vapor stream by condensation or absorption




     before the remaining HC1 is compressed and fed to an oxychlorinating




     unit.  If high pressure cracking is used, the quench vapor stream




     is- fed directly to the distillation unit which consists of two columns,




     i.e., the anhydrous HC1 recovery column, and the VCM recovery column.




          In the HC1 recovery column, anhydrous HC1 is recovered overhead




     by distillation with refrigerated reflux.  The HC1 is purified to




     remove acetylene and vinyl chloride which would yield higher chlori-




     nated by-products in the oxychlorination unit.  In the VCM recovery




     column, EC and other high boiling impurities are separated by frac-




     tionation to produce high purity VCM.  The EC and higher boiling




     impurities, as well as the EC and heavy bottoms from the quench
                             6-349

-------
    column, are reprocessed in the EC purification unit.  Purified




    EC is recycled to the cracking furnace, and the heavy bottoms




    (higher chlorinated organics) are sent to waste disposal.




2.  Input Materials




    Ethylene dichloride - 2700 kg/metric ton VCM




3.  Operating Parameters




    Temperature of cracking furnace effluent:  500 - 515°C (932-959°F)




    Pressure:  2.53 MPa (24 atm)




4-  Utilities - Basis:  91 Mg/yr capacity




    Total process water usage - 1.27 kg/kg VCM




    Total cooling water usage - 1571 kg/kg VCM




    Steam:  317 kg/hr




    Power:  361 kW (484 hp)




    Natural gas:  1.34 dam (47,500 scf)/hr




    Refrigeration:  46 kW (130 tons)/hr




5.  Waste Streams




    Tail gas absorber (air)




    Hydrogen chloride - 0.1 kg/metric ton product




    Vinyl chloride - 5.0 kg/metric ton product




    1,2-Dichloroethylene - 0.15 kg/metric ton product




    1,1-Dichloroethylene - 0.4 kg/metric ton product




    Acetylene - 1.5 kg/metric ton product




    Water - The major waste water sources are the effluents from




    scrubbing systems required for HC1 removal, recycle purification




    of EC  and effluent from associated by-product production units.




    Some typical data are:
                           6-350

-------
    Flow      1.27 m /454 kg product




    COD       2.733 kg/m3




              3.475 kg/454 kg product




    TOC       0.120 kg/m3




              0.150 kg/454 kg product




    Solids (filter solids)




    EC - 0.8 kg/metric ton product




    Tars as (C-HC1) - 0.05 kg/metric ton product




    Solids (as c) - 0.2 kg/metric ton product




6.  EPA Source Classification Code - None




7.  References
    Sittig, M., Pollution Control in the Organic  Chemical  Industry, Noyes




    Data Corporation, Park Ridge, N.J.,  1974,  p.  214-215.





    Considine,  D.  M., Ed.-in-Chief,  Chemical and  Process Technology




    Encyclopedia,  McGraw-Hill Book Co.,  New York, N.Y., 1974, p.  1136-1137.





    Hedley, W.  H., et al., Potential Pollutants from Petrochemical Processes,




    Final Report MRC-DA-406,  prepared for EPA, Contract 68-02-0226, Task No.




    9, December 1973, p.  198-199.





    Anon., Engineering and Cost Study of Air Pollution Control  for the




    Petrochemical  Industry.   Ethylene Bichloride  Manufacture by Oxychlori-




    nation, PB-240 492, prepared for EPA, Contract No. 68-02-0255,




    Air Products and  Chemicals, Inc., November 1974.





    Leonard, E.  C., Editor, High Polymers, Vol. XXIV, Part 3, p.  1214-1245.
                               6-351

-------
7.   References (continued)




    Lowenheim, F.  A.  and Moran,  M.  K.,  Industrial Chemicals,  4th Edition




    John Wiley & Sons, New York, N.Y.,  1975,  p.  868.





    "1975 Petrochemical Handbook,"  Hydrocarbon Processing," November




    1975, p.  213-217.
                               6-352

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. -134


                       Ethylene Diamine
           C1CH2CH2C1 + 2NH3 - >-  NH2CH2CH2NH2 •  2HC1


1.   Function - Both aqueous and anhydrous ammonia react readily with

     ethylene dichloride, in both the liquid and vapor phases to form

     ethylene diamine.

          In the vapor-phase reaction ethylene dichloride and an excess

     of anhydrous ammonia are reacted at 150°C and 9.0 MPa (88.8 atm) .

     Anhydrous ethylene diamine hydrochloride is formed, which, on treat-

     ment with caustic soda at 100°C, yields the free amine.  The diamine

     vapors, steam, and unreacted ammonia are led to a dehydrating column

     where the diamine is dried and condensed.

          In the liquid phase process, ethylene dichloride is treated with

     excess aqueous ammonia at 100°C and 1.0 MPa (9.87 atm).  The aqueous

     product solution containing ethylene diamine hydrochloride, ammonium

     chloride, and ammonia is heated with caustic soda and fractionated.

     The ethylene diamine is drawn off and the ammonium chloride is re-

     turned to the reaction vessel.

          Both processes result in low yields, on the order of 70%.  By-

    - products of this reaction include diethylenetriamine , triethylene-

     tetramine, tetraethylenepentamine, pentaethylenehexamine, and higher

     polymers .

2.   Input Materials

     Ethylene dichloride - 2.4 kg/kg product

     Ammonia

     Water (liquid-phase process)

     Sodium hydroxide
                             6-353

-------
3.   Operating Parameters




     Vapor-phase reaction




     Temperature:  150°C (302°F)




     Pressure:  9.0 MPa (88.8 atm)




     Dehydrochlorination temperature:   100°C




     Liquid-phase reaction




     Temperature:  100°C (212°F)




     Pressure:  1.0 MPa (9.87 atm)




4.   Utilities




     Not given




5.   Waste Streams - Reactor pressure vents, dehydration columns, and




     distillation columns are probably sources of ammonia, diamine,




     higher amine, and unreacted ethylene dichloride emissions.




          Waste water streams from dehydrochlorination and drying




     operations undoubtedly contain quantities of caustic soda, and




     possibly smaller amounts of ammonium chloride, as well as the




     pollutants previously mentioned.








6.   EPA Source Classification Code - None




7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 5," "Chemical Engineering," April 29, 1974, p. 145, 146.






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 7  (1965), p.  31.
                             6-354

-------
U.S. Patent 2,805,254 (September 3, 1957).






Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd Edition,




Noyes Development Corp., Park Ridge, N.J.,  1969 , p. 313.






Chemical Technology, Barnes and Noble Books, New York, N.Y.,




Vol. 4 (1972), p. 513.
                        6-355

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  135




                       Aminoe thylethano lamine





a)  NHCHCHNH  + C1CHCHOH — - >-  NHCHCHNHCHCHOH + HC1
b)  NH2CH2CH2NH2 + CH2C
1.  Function - Aminoe thylethano lamine may be prepared by the reaction




    of ethylenediamine with ethylene chlorohydrin or ethylene




    oxide.




2.  Input Materials




    a)  Ethylenediamine




        Ethylene chlorohydrin




    b)  Ethylenediamine




        Ethylene oxide




3.  Operating Parameters - Not given




4.  Utilities - Not given




5.  Waste Streams - Waste water may contain traces of acids, products of




    decomposition, and polymeric products.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y. , Vol. 5 (1964), p. 307.





    Ibid. , Vol. 1 (1963), p. 815.





    Houben-Weyl, Methoden Per Organischen Chemie, Vierte Auflage, Georg




    Thieme Verlag Sttutgart, Bd. 11, Tl (1957), p. 312.
                             6-356

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.136
              Ethylene Chlorohydrin (from ethylene)





                     CaO + C12 	>• CaClOCl






             CaClOCl + C12 + H20 	>- CaCl2 + 2 HOC1






                 CH2=CH2 4- HOC1 	»• HOCH2CH2C1






1.   Function - Ethylene chlorohydrin is most economically produced by




     the reaction of ethylene gas and dilute hypochlorous acid in aqueous




     media.  In this process ethylene and chlorine are simultaneously




     introduced into an aqueous solution of hydrated lime at 20°C and




     20.3 MPa so that the ethylene concentration is about 28 g/1 alkali.




     The calcium oxychloride immediately decomposes to calcium chloride




     and hypochlorous acid which reacts with the ethylene.  To avoid excess




     formation of ethylene dichloride and g,8'-dichloroethylene ether,




     the process is interrupted when a 6-8% solution of ethylene chloro-




     hydrin has been formed, which is quite satisfactory for industrial




     applications.




          Anhydrous ethylene chlorohydrin can be obtained by concentrating




     the reaction product to 25-30% chlorohydrin, causing an oily layer




     to separate.  This layer is fractionated and the water removed




     azeotropically with benzene.





2.   Input Materials




     Ethylene




     Chlorine




     Water




     Lime




                             6-357

-------
3.   Operating Parameters




     Temperature    20°C  (68°F)




     Pressure       20.3 MPa  (200 atm)




4.   Utilities




     Not given




5.   Waste Streams - Spent catalysts,  solvents,  various salts,  or HC1




     itself may be present in the waste streams  from this operation.




     The resulting waste water may contain hypochlorous acid,  chlorine,




     spent caustic, HC1, some ethylene chlorohydrin, ethylene  dichloride,




     and B,$'-dichloroethyl ether.




          Waste products from purification, principally hypochlorous  acid




     and its degradation products (HC1 and oxygen),  are rejected, and




     should be present in other waste streams.




6.   EPA Source Classification Code - None




7.   References




     Chemical Technology, Barnes and Noble Books,  New York, N.Y., Vol.  4




     (1974), p. 281.






     Faith, W. L. et al., Industrial Chemicals  3rd Ed., John Wiley & Sons,




     Inc., New York, N.Y.,  1965 , p.  373.






     Astle, M. J., The Chemistry of Petrochemicals,  Reinhold Publishing




     Corp., New York, N.Y.,  1956 , p. 75, 76.






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers,  New York,  N.Y., Vol. 5 (1964), p.  308.
                             6-358

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 137

                  1,1,2-Trichloroethane (liquid-phase
                  chlorinatioii of ethylene dichloride)
               C1CH2CH2C1 + C12 	> C12CHCH2C1 + HC1
•*••   Function - Most 1,1,2-trichloroethane is made by chlorinating

     ethylene dichloride in the liquid phase at 120°C and 345 kPa

     (3.40 atm).

          Many variations of this process are in commercial use.

2.   Input Materials

     Ethylene dichloride - 0.62 kg/kg product

     Chlorine - 0.77 kg/kg product

3.   Operating Parameters

     Temperature:  120°C  (248°F)

     Pressure:  345 kPa (3.40 atm)

4.   Utilities

     Basis:  0.59 kg/sec capacity (41 M Ib/yr)

     Cooling water - 51.2 dm3/sec 948.700 gph)

     Makeup water - 2.9 dm /sec (2,800 gph)

     Steam - 1.36 kg/sec (10,800 Ib/hr)

     Power - 48 kW

5.   Waste Streams - The primary sources of emissions from this process

     are probably the waste streams from the HC1 scrubber.  Waste water

     streams may contain chlorine, HC1, spent caustic, and various chloro-

     hydrocarbons, including ethylenedichloride, trlchloroethane and

     reaction by-products.  Hydrogen chloride and a number of organic

     chlorides are probably present in the waste gas.

                             6-359

-------
6.   EPA Source Classification Code - None




7.   References




     Hedley, W. H., et al., Potential Pollutants from Petrochemical




     Processes, Technomic Publishing Co., 1975.






     Kirk-Othmer, Encyclopedia of Chemical Technology 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 5 (1964),  p.  158.






     Elkin, L.M., "Chlorinated Solvents," Report No. 48, Stanford




     Research Institute, Menlo Park, Calif., 1969.
                             6-360

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  138

                1,1,2-Trichlordethane (oxychlorination
                      of ethylene dichloride)
           C1CH2CH2C1 + HC1 + 1/2
1.   Function - Some 1,1,2-trichloroethane is produced by the oxychlori-

     nation of ethylene dichloride with HC1.  Reaction conditions vary

     from one process to another.

2.   Input Materials

     Ethylene dichloride

     Hydrogen chloride

     Oxygen

3.   Operating Parameters - Not given

4'   Utilities - Not given

5.   Waste Streams - Waste water and vent gases from the separator con-

     tain a number of chlorohydrocarbons, including ethylene dichloride,

     trichloroethane, and by-products.

          The crude product is probably scrubbed to remove unreacted

     acid.  Waste water from this operation would contain some HC1.

6.   EPA Source Classification Code - None

7.   References

     Hedley, W. H., et al., Potential Pollutants from Petrochemical

     Processes, Technomic Publishing Co., 1975.


     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

     Interscience Publishers, New York, N.Y., Vol. 5  (1964), p. 159-
                              6-361

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 139
              Vinylidene Chloride (from 1,1,2-trichloroethane)
               CH2C1CHC12 + NaOH - >• CH2=CC12 + NaCl + H20



1.  Function - Vinylidene chloride is made by dehydrochlorinating


    1,1,2-trichloroethane with lime or aqueous sodium hydroxide at


    ~70°C.  A long cylindrical reaction vessel is used.   Crude product


    is separated and purified by distillation under a nitrogen atmosphere


    and washing with ferrous sulfate and caustic soda solutions.


         Purified Vinylidene chloride is generally polymerized within 48


    hours of its production.  If it is to be stored, small amounts of


    polymerization inhibitors (hydroquinone , alkylamines or organic sulfur


    derivatives) are added.  Peroxide formation has to be monitored.


    Vinylidene chloride may also be manufactured by continuous chlorination


    of ethane.


2.  Input Materials


    1,1,2-trichloroethane - 1.38 kg/kg product


    Sodium hydroxide - 0.46 kg/kg product


3.  Operating Parameters


    Temperature - 70°C  (158 °F)


    Pressure - 101 kPa  (1 atm)


4.  Utilities - Basis:  0.427 kg/sec capacity (2.97 M Ib/yr)


    Cooling water - 5.15 dm3/sec (4900 gph)

                           3
    Process water - 1.60 dm /sec (1520 gph)


    Power - 305 kW
                              6-362

-------
5.  Waste Streams


    Vinylidene chloride separation column (water)

                         3
    Water stream (1.69 dm /sec or 1604 gph)  contains


    Sodium hydroxide - 45.5 kg/Mg product


    Sodium chloride - 605.5 kg/Mg product


    Ferrous sulfate and sodium hydroxide may also  be  present  in  the wastewater


    from washing operations.


6.  EPA Source Classification Code - None


7.  References


    Hedley, W. H., et al. , Potential Pollutants  From  Petrochemical Processes,


    Technomic Publishing Co., 1975.


    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,


    Interscience Publishers,  New York, N.Y., Vol.  5   (1964),  p.  129.



    Lowenheim, F. A., and Moran, M. K.,  Industrial Chemicals, 4th Edition,


    John Wiley and Sons, New York, N.Y.,  (1975),  p.  838-840.
                               6-363

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS  NO.  140




             Perchloroethylene,  Trichloroethylene,  and Carbon




         Tetrachloride (oxychlorination of ethylene dichloride)








                     HC1 + 1/2 00 	>•  C10 + H00
  2CH2C1CH2C1 +1.5 C12 + 1.75 02 	>- C2C14 + C2HC13 + CC14 +3.5
1.  Funct ion - Perchloroethylene, trichloroethylene,  and carbon tetra-




    chloride are co-produced by the oxychlorination of ethylene dichloride.




    The chlorine is produced from hydrochloric acid by the Deacon process




    and combined with ethylene dichloride and additional air in the




    presence of fluid catalysts.




         The actual reaction is highly complex with substitutive chlori-




    nation, cracking, Deacon reaction, and carbon burning all occurring




    simultaneously.  Ethylene dichloride, chlorine, oxygen, and recycled




    chlorinated organics are fed to a fluid bed reactor.  An inexpensive




    oxychlorination catalyst (PPG) is used in the main reaction and the




    Deacon process catalyst contains copper chloride. The catalysts are




    contained in a vertical, tubular reactor which operates at moderate




    pressure and around 425°C (or 600-900°F).  Reaction heat generates




    a large portion of the process steam requirements.




         After vent scrubbing, the condensed crude and weak acid are




    phase separated and the crude dried by azeotropic distillation.  The




    crude is fed to a distillation train where it is split into a perchlor-




    rich and trichlor-rich stream.  The products are separated in stills,




    neutralized, washed, and dried.
                              6-364

-------
         Carbon tetrrchloride is recovered as a by-product of this




    vigorous chlorination.




2.  Input Materials - Basis - 1 metric ton CJCl, (and 793 kg C HC1 )




    Ethylene dichloride - 1195 kg (2,632 Ibs)




    Chlorine - 692 kg (1,414 Ibs)




    Oxygen - 388 kg (855 Ibs)




    Catalysts - Small




3.  Operating Parameters




    Temperature - ~425°C (or 600-900°F)




    Pressure - moderate




4.  Utilities - Not given




5.  Waste Streams - Although no information was available, mixed chloro-




    hydrocarbons, chlorine, and hydrogen chloride may be present in the




    waste gases of various production components.  Heavy ends from the




    various stills are usually incinerated.




6.  EPA Source Classification Code - None




7.  References




    Lowenheim, F. A., and Moran, M.  K., Industrial Chemicals, 4th Edition,




    John Wiley and Sons, New York, N.Y., 1975, p. 604, 605, 845.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 162.





    "1973 Petrochemical Handbook," "Hydrocarbon Processing," November,




    1973, p. 157.
                             6-365

-------
7.   References (continued)




    "1975 Petrochemical Handbook," "Hydrocarbon Processing,"  November,




    1975, p.  169.





    Belgian Patent 602,840  (April 20,  1961).





    Austin, G. T., "The Industrially Significant Organic Chemicals-




    Part 7,"  "Chemical Engineering," June 24,  1974,  p.  156.
    Ibid.,  Part 8,  July 22,  1974,  p.  115.
                             6-366

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INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 141

              1.1,2-Trichloro-1,2,2-Trifluoroethane
                    (from perchloroethylene)
          CC12CC12 + 3HF + C12 	* CC12FCC1F2 + 3HC1


-1-'   Function - 1,1,2-Tr ichloro-1,2,2-trifluoroethane (fluorocarbon 113)

     is produced by reacting a mixture of hydrogen fluoride and chlorine

     with perchloroethylene at 225-400°C in the presence of partially-

     fluorinated antimony pentachloride or zirconium chloride catalyst.

     The by-product of this reaction is an extremely pure grade of

     anhydrous HCl which is important in several industrial operations.

          The product is purified by distillation and by scrubbing through

     water and slightly alkaline solution.  It is then dried by passage

     in the liquid phase through beds of silica gel, alumina gel, or

     synthetic zeolite.

2.   Input Materials

     Perchloroethylene

     Hydrogen fluoride

     Chloride

3.   Operating Parameters

     Temperature:  225-400°C  (437-752°F)

     Pressure:  Not given

     Catalyst:  Partially fluorinated antimony pentachloride zirconium

                chloride

4.   Utilities

     Not given
                             6-367

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5.   Waste Streams - The main pollutant source in this process is probably




     the scrubber effluent.   Waste water streams should contain quantities




     of caustic soda or other alkali,  and perhaps some hydrochloric acid.




     Various chlorofluorocarbons may be present in low concentrations in




     both the waste water and vent gas.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 198.
                             6-368

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  142
                    Bis(2-Chloroethyl)  Ether


                         H.SO,
             2C1CH2CH2OH -^—5	>• (C1CH2CH2)20 + H20


!•   Function - In the past, bis(2-chloroethyl)  ether has been produced in 75%

     yield by heating ethylene chlorohydrin with sulfuric acid at 90-100°C.

          It has also been prepared by saturating an aqueous solution of

     ethylene chlorohydrin with chlorine and ethylene.  Bis(2-chloroethyl)

     ether has also been produced by chlorinating ethyl ether in the pre-

     sence of a catalyst.


           (CH3CH2)20 + 2C12 	>• (C1CH2CH2)20 + 2HC1


2.   Input Materials

     Ethylene chlorohydrin

     Ethyl ether - chlorine

3.   Operating Parameters

     Not given

4.   Utilities

     Not given

5.   Waste Streams - Although no process description was available, the

     HC1 scrubbers probably contribute to waste water and air emissions.

     Ethyl ether, chlorine, hydrogen chloride, and some dichloroethyl

     ether may be present in these emissions.

6.   EPA Source Classification Code - None

7.   References

     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

     Interscience Publishers, New York, N.Y., Vol. 8  (1965), p.  487.

                             6-369

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  143
             Ethylene Oxide (oxidation of ethylene)
                                          0
1.   Function - Presently, ethylene oxide is manufactured by direct vapor-
     phase oxidation of ethylene over silver oxide catalyst.  Approximately
     75% of the processes use air as the oxidant, and the remainder use
     oxygen.
          Silver is the only effective high selectivity catalyst.   Selec-
     tivity is highly sensitive to temperature, dropping as the tempera-
     ture rises.  Therefore, careful temperature control within a  narrow
     range is an absolute necessity.  The selection of the carrier is also
     of considerable importance because of the critical problem of heat
     removal .
          Methods have been sought for retarding the combustion of ethylene
     to carbon dioxide.  Numerous compounds have been proposed, but only
     ethylene dichloride and polychloroaromatics have been effective on a
     commercial scale.
          A mixture of ethylene, air, and recycle gas (3-5 vol. % ethylene)
     is pressured and sent to a tubular reactor with a fixed bed,  silver
     catalyst.  A heat transfer agent is used to hold the temperature within
     a narrow range which is adjusted to the temperature/activity relation-
     ship of the particular catalyst bed.  The reactor effluent gas is
     cooled by a circulating gas in a heat exchanger.  The  cooled gas  is
     sent to a scrubbing tower in which the ethylene oxide  is  scrubbed
     with water.
                             6-370

-------
          The gas that is not absorbed is primarily unreacted ethylene
     and oxygen.  Part of this mixture is returned to the reactor as re-
     cycle gas (3-5 mol. % ethylene).  The other part is sent forward, re-
     heated in a heat exchanger and sent to a second reactor where oxida-
     tion is completed.  The effluent is sent to a scrubbing tower where
     the ethylene oxide is absorbed.  The noncondensable gases are purged.
          The dilute aqueous ethylene oxide solutions from both scrubbing
     towers are combined and sent to a stripper (desorber) where ethylene
     oxide is removed by heating.
          The crude ethylene oxide is fractionated on distillation columns.
     The water from the stripper (desorber) can be returned to the scrubbing
     towers, or in some cases it is sent to an ethylene glycol plant be-
     cause this water contains ~2% ethylene glycol.
          In the oxygen process, ethylene, oxygen, and recycle gas are fed
     to the reactor under pressure.  The reactor effluent is sent through
     a carbon dioxide removal system, and is recycled to the reactor to
     reduce the partial pressure of ethylene.  The gases are ultimately
     sent to a scrubber, thence to the stripper (desorber).
2.   Input Materials     Per kg ethylene oxide
     Ag                  4.37 x 10~4 g
     Air                 13,100 g
     Ethylene             1,100 g
     Steam                  100 g
     Water               0.208 m
3.   Operating Parameters
     Reactor temperature  - 104-149°C (219-300°F)
     Reactor pressure - 0.929-2.2 MPa (9.2-21.7 atm)

     Catalyst - silver oxide supported on inert carriers
                             6-371

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4.   Utilities
     Electricity 6.74 x 106 J (1.87 kWh)/kg prod.
5-   Waste Streams
     Air:  Purge gases from air oxidation may contain small amounts of
     ethylene oxide and ethylene.  Ethylene oxide escape from oxide com-
     pressor seals.  Reactor gas leaks from cycle compressor seals.
     Water:  The main waste stream is the draw-off from the ethylene oxide
     separator (stripper; desorber) bottoms.  The flow from two plants is
     given:
                   Plant 1                      Plant 2
     Flow      67.3 dm                     496 dm
               454 kg                      454 kg

     COD       52 kg/m (52,000 mg/1)       4.8 kg/m (4,800 mg/1)
               3.49 kg                     2.4 kg
               454 kg                      454 kg

     BOD       4.8 kg/m (4,800 mg/1)       0.65 kg/m (650 mg/1)
               0.32 kg                     0.32 kg
               454 kg                      454 kg

     TOC       19 kg/m (19,650 mg/1)       2.699 kg/m (2,699 mg/1)
               1.32 kg                     1.34 kg
               454 kg                      454 kg

     Process water usage (including steam) - 0.113 kg/0.45 kg of product
     Cooling water - 0.043 kg/0.45 kg of product
6.   EPA Source Classification Code - None
7.   References
     Considine, D. W., Ed.-in-Chief, Chemical and Process Technology
     Encyclopedia, McGraw-Hill Book Company, New York, N.Y., 1974,
     pp. 443-446.
                             6-372

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References (continued)




Kent, J. A., Ed., Riegel's Handbook of Industrial Chemistry,  Seventh




Ed., Van Nostrand Reinhold Company, New York, N.Y.,  1974,  pp. 779-780.






Sittig, M., "Ethylene Oxide from Ethylene," Pollution Control in the




Organic Chemical Industry, Noyes Data Corp., Park Ridge, N.J.,




1974, pp. 150-152.






Faith, W. L., et al., Industrial  Chemicals, 3rd Ed., John Wiley &




Sons, New York, N.Y.,  1965 , p. 382.
                         6-373

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  144
Mono-, Pi-, and Triethylene Glycols (from hydration of ethylene oxide)
1.   Function - Ninety percent of the ethylene glycols produced in the U.S.




     are made by the direct catalytic oxidation of ethylene to ethylene




     oxide followed by hydration.  Process No. 143 discusses the ethylene




     to ethylene oxide conversion, so only the hydration step will be con-




     sidered here.




          Ethylene oxide can be converted to glycol by catalytic or non-




     catalytic hydration.  The catalytic process employs a large excess




     of dilute aqueous acid, usually sulfuric acid and the noncatalytic




     process employs a large excess of water.  The reaction is carried




     out at 180°C and 2.17 MPa in the liquid phase.




          Di- and triethylene glycols are reaction by-products which




     normally account for 9% and 1%, respectively, of the total product.




          However, yields of these ether glycols may be increased by




     modest alternations (higher temperature and slightly lower pressure)




     in the reaction conditions.  Polyethylene glycols are also formed




     (in minute quantities only under normal reaction conditions) but




     their yields may be increased by using a NaOH catalyst  (see Process




     No. 155).
                             6-374

-------
          Following reaction, the respective glycols are separated and




     purified by dehydration of the reaction effluent and vacuum distil-



     lation.




2.   Input Materials^




     Ethylene oxide




     For ethylene glycol - 0.75 kg/kg




     For diethylene glycol - 0.84 kg/kg




     For triethylene glycol - 0.90 kg/kg




     Water - 2.0 kg/kg product




3.   Operating Parameters




                         Catalytic           Noncatalytic




     Temperature         165-180°C (329-356°F    95°C      (203°F)




     Pressure            2.17 MPa (21.4 atm)   1.5-2.0 MPa  (14.8-19.7 atm)




     Catalyst            0.15-1.0% H2S04         	




     Reaction time       30 min                  	




4.   Utilities




     Not given




5.   Waste Streams - Dehydration (water)




     Water flow - 4.873 m /Mg (2575 gal/ton) product




     COD - 8.66 kg/Mg (lb/1000 Ib) product




     BOD - 0.34 kg/Mg (lb/1000 Ib) product




     TOG - 4.53 kg/Mg (lb/1000 Ib) product




     The chief organic pollutants are ethylene glycol ethylene oxide,




     acetaldehyde, crotonaldehyde, and some sulfuric acid.




6.   EPA Source Classification Code - None
                             6-375

-------
7.   References




     Austin,  G. T.,  "The Industrially  Significant Organic Chemicals, -




     Part 4,""Chemical Engineering1,1  April  15,  1974, p. 88.






     ibid., Part 5,  April 29,  1974,  p.  146,  147, 148






     ibid., Part 9,  August 5,  1974,  p.  96, 97.






     "1973 Petrochemical Handbook Issue,""Hydrocarbon Processing,"




     November 1973,  p. 130.






     Hedley,  W. H.,  et al., Potential  Pollutants from Petrochemical




     Processes, Technomic Publishing Co.,  1975.






     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd  Edition,




     Interscience Publishers,  New York, N.Y.,  Vol.  10  (1966),  p.  642,




     646, 648.





     Faith, W.L. et al.,  Industrial Chemicals,  3rd Ed., John Wiley




     and Sons, New York,  N.Y.,   1965  , p. 375.






     Sittig, M., Organic  Chemical Processes,  Noyes Press,  Inc., Pearl




     River,  New York, N.Y., 1962 ,  p. 59.






     Chemical  Technology,  Barnes &  Noble Books, New York, N.Y., Vol. 4




      (1972),  p.  293,  337, 339.
                             6-376

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 145




                Ethylene Glycol Mono- And Diacetates






        HOCH2CH2OH  +  CH3COOH  <*=*  C




        HOCH2CH2OH  +  2CH3COOH  ^=*




 ^'  Function - Ethylene glycol mono- and diacetates are coproduced by




     any of the standard methods of esterificatiion of hydroxyl groups




     such as esterification with acid halides,  acid anhydride, and




     acids.




          The ester and diester are separated by distillation.




 2.  Input Materials




     Ethylene glycol




     Acetic acid (glacial)




 3.  Operating Parameters - Not given




 4.  Utilities - Not given




 5.  Waste Streams - Air and wastewater emissions may contain ethylene




     glycol, acetic acid, and ethylene glycol mono- or diacetate.




 6.  EPA Source Classification Code - None




 7.  References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N. Y.,  Vol. 10 (1966), p.  645.





     Curme, George 0., Johnston, F.,  Glycols,   ACS Monograph 114,




     Reinhold Publishing Corp., 1952, p. 128.
                              6-377

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO. 146

                 Dioxane (from ethylene glycol)
                       H2SO,
          2HOCH2CH2OH  ——-^  I    I  4- 2H20
0
                                  0"
 1.  Function - 1,4-Dioxane is produced on a commercial scale by heating

     ethylene glycol in the presence of a dehydration catalyst such as

     sulfuric acid.

 2.  Input Material

     Ethylene glycol

 3.  Operating Parameters

     Temperature:  160°C (320°F)

     Pressure:  Not given

     Catalyst:  H2SO, (4% by weight of ethylene glycol)

 4.  Utilities

     Not given

 5.  Waste Streams - The separator water effluent may contain quantities

     of sulfuric acid, ethylene glycol, and dioxane.

 6.  EPA Source Classification Code - None

 7.  References

     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

     Interscience Publishers,  New York, N.Y., Vol. 10 (1966), p. 643.


     Chemical Technology, Barnes  and Noble Books, New York, N.Y., Vol.  4,

     (1972),  p.  352.
                           6-378

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 147
                                1, 3-Dioxolane
                     CH2CH2 + CH20 - * J   I     + H20
                     OH OH              \  /
1.  Function - Ethylene glycol derivatives react with aliphatic and
    aromatic aldehydes or ketones to give 1,3 dioxolanes.
2.  Input Materials
    Ethylene glycol
    Formaldehyde
3.  Operating Parameters - Not given
4.  Utilities - Not given
5.  Waste Streams - Wastewater from the separator may contain unreacted
    formaldehyde and ethylene glycol, and possibly, dioxolane.  Some
    air emissions may also result from this operation.
6.  EPA Source Classification Code - None
7.  References
    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
    Interscience Publishers, New York, N.Y., Vol. 10 (1966), p. 639.

    Van der Plas, H. C., Ring Transformations of Heterocycles , Academic
    Press, 1973 p. 17.

    UvS. Patent 3,324,145 (June 6, 1967).
                               6-379

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  148
                           2-Methy1-1,3-Dioxolane
                   CH -CH            ft"  CH -CH
                   OH  OH+  CH3CH°      'I    +H2°

                                          Y
                                           CH3

1.  Function 2-Methy1-1,3-dioxolane is derived from the reaction of

    ethylene glycol and acetaldehyde.

2.  Input Materials

    Ethyl glycol

    Acetaldehyde

3.  Operating Parameters - Not given

4.  Utilities - Not given

5.  Waste Streams - The separator may release a waste stream containing

    acetaldehyde, ethylene glycol, and some methyldioxolane.

6.  EPA Source Classification Code - None

7.  References

    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

    Interscience Publishers, New York, N.Y., Vol. 10 (1966), p. 639-646.

    Van der Plas, H. C., Ring Transformations of Heterocycles, Academic

    Press, Vol. 1 (1973), p. 17.
                               6-380

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  149
           Ethylene Glycol  and Diethylene Glycol Monothers

                      A
                         H)  + ROH - >•
1.  Function - Ethylene glycol monoethers are made by reacting ethylene
    oxide and anhydrous alcohol under a variety of reaction conditions.
    The reaction proceeds spontaneously at 180° C - 200° C and 3.0 - 4.0
    MPa (435-580 psig) , but can be carried out at 100 - 150°C in the
    presence of an  acid or base catalyst  (caustic soda or boron tri-
    fluoride).  Alcohols commonly used to produce glycol monoethers
    include methanol,  ethanol, propanol, butanol, hexanol, octanol, and
    phenol.
         Diethylene glycol monoethers are by-products of ethylene glycol
    monoether production, normally accounting  for 10 - 15% of the total
    product.  Higher polyglycol monoethers  (2-3%) are also formed.  The yield
    of di-  and  polyglycol monoethers may  be  increased by lowering the
    ratio of  alcohol to  ethylene  oxide.
         Of the 230 million  Ibs.  of  glycol  ethers produced in 1965,  78% were
    ethylene glycol monomethyl ethers,  19%  were  diethylene glycol ethers,  and
     3% were triethylene  glycol ethers.
 2.  Input Materials - Ethylene oxide
    For ethylene glycol monomethyl ether       -  0.58 kg/kg
    For ethylene glycol monoethyl ether        -  0.54 kg/kg
    For ethylene glycol monobutyl ether        -  0.41 kg/kg
    For diethylene glycol monomethyl ether     -  0.74 kg/kg
     For diethylene glycol monoethyl ether      -  0.69 kg/kg
     For diethylene glycol monobutyl ether      -  0.59 kg/kg
     Other ethylene glycol monoethers           -  0.39 kg/kg
                                6-381

-------
    Alcohol




    For ethylene glycol monoethers -




    Methanol, ethanol, propanol, hexanol, octanol,  phenol




    For diethylene glycol monomers -




    Methanol, ethanol, butanol, hexanol




3.  Operating Parameters - Noncatalytic Process




    Temperature - 180-200°C  (356-392°F)




    Pressure - 3-4 MPa  (29.6-39.5 atm)




    Catalytic process




    Temperature - 100-150°C (212-302°F)




    Pressure - not given




    Catalyst - acid or base




4.  Utilities - not given




5.  Waste Streams - No information was available,  but waste streams may




    contain ethylene oxide, ethylene and higher polyglycols, alcohols,




    glycol monoethers, reaction by-products, and traces of acid or base




    catalyst.




6.  EPA Source Classification Code - None




7.  References




    Austin, G.  T.,  "The Industrially Significant Organic Chemicals - Part 5,"




   "Chemical Engineering" April 29, 1974, p. 150.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol.  10 (1966), p. 643.
                               6-382

-------
7.  References (continued)




    Chemical Technology, Barnes and Noble, New York, N.Y.,  Vol.  4,




    (1972). p. 336.





    Hahn, A. V., The Petrochemical Industry;   Markets and Economics,  McGraw-




    Hill Book Co., New York, N.Y.,  1970,  p. 282.






    Lowenheim,  F.  A.  and Moran, M.  K.,  Industrial Chemicals, 4th Edition,




    John Wiley and Sons, New York,  N.Y.,  1975,  p. 403, 404.
                               6-383

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  No.  150



            Mono-, Pi-,  and Triethylene Glycol Diethers
        RO(CH0CH00) Na  +  RC1  —>  RO(CH0CH00)  R  +  NaCl
             2.  2.  n                      Z  2. n
        n = 1,  2,  3

        R = methyl, ethyl,  butyl
 1.  Function - Glycol diethers may be prepared by the general methods of



     ether preparation, but the preferred method is by reacting an alkyl



     chloride with the sodium salt of the corresponding glycol mono-



     ether.



 2.  Input Materials



     Mono, di- or triethylene monoether sodium glycolate



     Alkyl chloride



 3.  Operating Parameters - Not given



 4.  Utilities - Not given



 5.  Waste Streams - Wastewaters contain sodium chloride,  alkyl chloride,



     and possibly other reactants and products.



 6.  EPA Source Classification Code - None



 7.  References



     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,



     Interscience Publishers, New York, N. Y., Vol. 10 (1966), p. 643.




     Curme,  George 0., Johnston, F.,  Glycols  in ACS Monograph 114,



     Reinhold Publishing Corp., 1952, p. 118.
                             6-384

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  151



            Mono- and Diethylene Glycol Monoether Acetates
        R(OCH0CH0) OH + CH0COOH 	>•  R(OCH0CH0) OOCCH, + H00
             /  / n       j                 
-------
 INDUSTRIAL ORGANIC  CHEMICALS                             PROCESS NO.  152








                  Ethanolamines  (from ethylene  oxide)





  CH -CH + NH. 	»• H0NCH0CH0OH + HN(CH0CHOH)0 + N(CH0CH0OH)Q
    \l /      3          2.   2.  2.          2.     2.       2.  2.   J





 1.   Function - Monoethanolamine is produced together with di- and



     triethanolamines by a reaction between ethylene oxide and an excess



     of aqueous ammonia at 50-100°C.  The yield is about 95% based on



     ethylene oxide.




     Excess ammonia is stripped from the reaction effluent.  The over-



     head from the  ammonia stripper, together with fresh ammonia makeup,



     enters an ammonia absorber where the aqueous ammonia solution is



     prepared for reaction.  The bottoms from the ammonia stripper are



     first evaporated to produce a recycle water stream and are then



     dried in a separate column.  A product distillation train of three



     columns produces the three products, recycle amine streams, and



     rejected heavies.




     The product mixture can be partially controlled by temperature,



     the ratio of ammonia to ethylene oxide, and recirculation of products.



     A large excess of ammonia favors monoethanolamine production.  Recircu-



     lation of this product shifts the reaction equilibrium in favor of di-



     and triethanolamines.



2.   Input Materials



     Ethylene oxide





     For monoethanolamine 	.75 kg/kg



     For diethanolamine - 0.88 kg/kg



     For triethanolamine - 0.93 kg/kg



     Aqueous  NH~


                               6-386

-------
3.   Operating Parameters




     Temperature:  50-100°C (122-212°F)




     Pressure:  Not given 1.03-2.07 MPa (10.2-20.4 atm)




4.   Utilities




     Not given




5.   Waste Streams - Some atmospheric emissions probably result from strip-




     ping, evaporating, drying, and fractionating operations.   Ammonia and




     traces of the various ethanolamines may be present  in these waste




     gases.  Rejected heavies from still bottoms are primarily higher




     amine ethers.




6.   EPA Source  Classification Code




     None




7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 4," "Chemical Engineering," April 15, 1974, p. 87,88.





     "1973 Petrochemical Handbook," "Hydrocarbon Processing," November




     1973, p. 120.





     "1975 Petrochemical Handbook," "Hydrocarbon Processing," November,




     1973, p. 136, 137.






     Kirk-Othmer, Encyclopedia of  Chemical Technology.  2nd Edition,




     Interscience Publishers, New  York,  N.Y.,  Vol. 1 (1963)  p. 814.
                                6-387

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  153




                   Morpholine (from diethanolamine)
                           /          I   Z  /    Z I  H.    L








1.   Function - Morpholine is almost exclusively made by dehydration of




     diethanolamine with sulfuric acid.




          The reaction mixture is neutralized to give an aqueous solution




     of morpholine.  Morpholine is extracted with organic solvents and




     purified by distillation.




2.   Input Materials




     Diethanolamine



     Qc
-------
7.   References (continued)




     Waddams, A. L., Industrial Organic Chemicals, 3rd Edition, John




     Wiley and Sons, New York, N.Y., 1973, p. 89.
                              6-389

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.154
                  Piperazine  (from ethanolamines)

                                  H
                                          2H20

                                        H
                                  H
o  *.*
         NX.
         .>
                                               H

 1.   Function -  Piperazine is produced by treating mono-,  di- or tri-



     ethanolamines with excess ammonia over a Ni/Cu/Cr catalyst.
 2.   Input Material



     Ethanolamines



     Ammonia  (excess)



     Catalyst  (Ni/Cu/Cr)



 3.   Operating Parameters



     Temperature:  200-260°C  (392-500°F)



     Pressure:  10.3-41.4 MPa  (102.1-408.3 atm)



 4-   Utilities - Not given



 5.   Waste Streams - The only wastes should be some unreacted ethanol-



     amines, ammonia, and catalysts.



 6.   EPA  Source Classification Code - None



 7.   References



     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,



     Interscience Publishers, New York, N. Y., Vol. 15 (1968), p. 640,



     641.




     U. S. Patent 3,151,115  (September 29, 1964).
                             6-390

-------
Sittig, M.,  Organic Chemical Process Encyclopedia - 1969, 2nd Edi-




tion, Noyes  Development Corp., Park Ridge, N. J., 1961,  p.  531.
                         6-391

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 155




        Polyethylene Glycol (hydration of ethylene oxide)
                        (CH2)
                                                         H






1.   Function - Like di- and triethylene glycols, polyethylene glycol is




     a by-product of ethylene glycol production.  For significant conver-




     sion to the polyglycol, however, ethylene oxide and water must be




     combined in the presence of sodium hydroxide catalyst.








2.   Input Materials




     Ethylene oxide - 1.10 kg/kg




     Water




3.   Operating Parameters




     Temperature:  120-150°C  (248-302°F)




     Pressure:     294 kPa  (2.9 atm)




     Catalyst :     NaOH




4.   Utilities




     Not given




5.   Waste Streams - Process  slops may  carry  ethylene  glycol  and sodium




     hydroxide .
                             6-392

-------
6.   EPA Source Classification Code - None




7.   Reference




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 10 (1966), p. 655.
                              6-393

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.156




                Ethylene Carbonate (from ethylene oxide)
A,
CHCH  4-
                        ,
                    CH9CH, 4- CO, — — *-
                      22     2 cat.   CH_
1.   Function - Ethylene oxide reacts with carbon dioxide under pressure



     and in the presence of a catalyst to give ethylene carbonate.



          The product is centrifuged to remove the catalyst and the crude



     product distilled in vacuum to give pure ethylene carbonate.



2.   Input Materials



     Ethylene oxide



     Carbon dioxide



3.   Operating Parameters



     Temperature - 190-220°C



     Pressure - 13.2 MPa (130 atm)




     Catalyst - Lil



4.   Utilities - Not given




5.   Waste Streams - Waste water may contain traces of ethylene carbonate,




     ethylene glycol, ethylene oxide, and carbon monoxide.



6.   EPA Source Classification Code - None




7.   References




     U.S. Patent 3,025,305 (1962).






     German Patent 1,135,490.
                              6-394

-------
 SECTION V
  METHANE
6-395

-------
                                              METHANE
   METHANE
  157
       , Methyl chloride
  158  \ Methylene chloride
 159i  ) Chi orof orm ••	;	> Chi orodi f 1 uoromethane
 160
      , Carbon tetrachloride .
                                     163
                                                    >Dichlorodifluoromethane
                                                   -4 Trichlorof1uoromethane
                                     162
                                             Carbon  tetrabromide
 164,                       165
	—>Carbon disulfide	^ Perchloromethyl mercaptan
  166
       t Hydrogen cyanide'
                                   167
         -}£thyl ortho-formate
                                   168
                              1fi9
         -^Cyanogen chloride—i	^Cyanuric chloride



                                       -iZi.—^Methacrylic acid
                                   170,
                                        >Acetone cyanohydrin •
                                                                      17?
                                                                              Methacrylic esters
Acetylene
                         175
>Difluoroethane
                        174
                                Vinyl acetate
                         177
                             -^Methyl butynol
                         178
                                                         >Chl orodi fluoroethane
                               -^Methyl pentynol
                        179                          180

                                ) Tetrachloroetnane	
                                                                       Perchloroethylene
                                                                    -^ Tri chloroethylene
                 Figure  9.   Methane Section  Chemical Tree
                                        6-396

-------
METHANE
           -^Synthesis  gas
                                                              185
                                    184
       181
            >Synthesis gas-
                                           Urea
          -^•Guanidine
                                                              186
           -^Cyanuric acid
                                    183
                                           Urea
                             387                    188
                            —•	)0xo aldehydes	^Oxo alcohols
                             189
                                    Phosgene
                             190
                                 -^Sodium formate
                             191
                                     Methanol
192
     -^Methyl amines
                                                      193
                                                         j	^Methyl chloride
                                                      194

                                                      198
                                                           ^Methyl  acetate	.	^Methyl acetoacetate




                                                                            197'
                                                           ^Dimethyl ether	) Dimethyl sulfate
                                                          -^Methyl  formate-
                                                                             200
                         _^.N,N-Dimethylformamide
                                                                               199
                                                                                     Formamide
                                                      2"dl
                                                            Acetic acid
                                                     202                     203
                                                     —	^Formaldehyde—^	—	^Ethylene glycols
                                                                            204
                                                                           	^Methylene dlanlllne
                                                                            206
                                                                                -^Hexamethylenetetramine
                                                     206                      207
                                                    —-—^Dimethyl sulfide	—) Dimethyl  sulfoxide
            Figure  9.   Methane  Section Chemical  Tree  (Cont.)
                                   6-397

-------
CO
>«
oo
Cooling
Heat
water 1
111

ClV Moat-
l O Refrig. nef'- .
\ /£. A 1 '
1571
Chlorlnatlon 1

C12 Heat
.158]
Chlorlnatlon 1

C12 Steam Heat
\ 4y7\ I
,160
Chlorlnatlon

ijjj * i Heat psteam
/w ic * T * '
159F
Chlorlnatlon I
164
Substitution


                                                                T7
                                                          Cooling water
                                           Steam
                                       Dlchloro-
                                       d1f luoro-
                                        methane
I
tut
fo e\
SJ\. *
163
.ion

pA18r3
«fj
/?>
162
Broml nation

„_      Cooling water

T  A     Jl
                        165
               Chlorlnatlon'
              fPerch!oro-^
                 methyll
               imercaptany
                                             Figure  10.   Methane Section Process  Flow Sheet

-------
                                                                  Refrig.
                                                                               NH3';Air

                                                                                I t
                                                                         Andrussow
                                                                         Process
                                                                                  166
V
                                Ethanol
                                                                                       Acetone
                                                                                           Coo ling
 I
OJ
VD
Refrig. f HCI
• t t d-
.167
Condensation
s> cf2' 1 jo Acid *

168
Chlorlnatlon
XJ
1 water
170
Addition
                                                   Cooling water

^
169
Polymerization
X|
                                                                              Ste
uy water
Til
»2° ^0 Steam RJH ,
171
Hydrolysis
XI
1
172
Hydrolysis
                                                                               H2SO,
                                                                                                                     water
                                                                                   JMethacrylicl
                                                                                      add
                                             Figure 10.   Methane  Section  Process Flow  Sheet (Cont.)

-------
-p-
o
o
                 Steam f~
                                                         ( Methane  j

                                                      "iirl
1 Cooling H20

IL&
                                                           Pyrolysls
                                                                  173

1 HF n Refrig. 1 NH3' Acetone steam
175
ori nation
^g
Ethynylatloti
XJ

Butanone _, Cooling water 1 ya
^ ^*J 1 Ir 1 t
1 78
Ethynylation
XJ
179
Chlorination
_ Acetic acid 1
[Cd

Condens
                                    Cooling
                                     water
                                                                 Dimethyl acetal
                                                                   formaldehyde
                                                          \     ./  Cooling water
                                                                                      180
                                                                           iehydrochlor1natioi
                                                                         Perchloro-w Trichloro-
                                                                          ethylene II ethylene
)  LOO 111
  watei
	n_
                                                                                                          174
                                  Figure 10.   Methane Section Process  Flow Sheet  (Cont.)

-------
I
-p-
o
T3 1
1 t ^> '
185
Ammonolysis

Heat
186
Condensation
steam
I
Heat p
1 /A
Steam 181.182|
Reforming 1
1,00 n n
"71 fT"?*3 >> Olel1ns ' HAat ^oco°11ny|ter| 51* ^ Hef
1 84*1 83
Ammonolysis ana
dehydration
•s
187
Oxo process
JL JL

189
Catalytic
Chlorination
^JL^ Heat
^-
-------
ON

-P-
O
1
Cooling
water
Heat 1 1
1 II

HC1
•
(193 XJ
Substitution
Steam
Acetic acid
1 J*
194 XJ
Esterification
Cooling water
sTlt
H2S04
1
196
Condensation
4 T
Est

CO 0
1 p>
erification 1
                                        Cooling water
                                           "*°nit I5tri
                                                       H2S04
                                                        195
                                               Condensation
oonng
water
n
so3
1 ^
197
Addition
XJ
                                                                                                  199
Ammonolysis
                      Dimethyl amine
                     	1 ISteam
Ami da t ion
200
                                          Figure  10.  Methane  Section  Process Flow  Sheet  (Cont.)

-------
Cooll
St
ng water
Ttl


Cooling water
tO - steay [ (
201
Carbonylatlon

Water fr>o
^^i 202 ^^
Oxidation

CS2 Heat
1 \ >c
206 XI
Condensation
o
LJ
                                  Water
                                    rr
IROH ^" Cooling water
itlon 203
Ion
XJ
Aniline 1
204
Condensation
^
Condens
NH3


 205
                                                                               Hexa-
                                                                             [ methylene-J
                                                                             itetramlne;
Heat
N02
\
207
Oxidation
•<
                                      Figure  10.   Methane Section Process Flow Sheet (Cont.)

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO.  157




                         Methyl Chloride




                   CH4 + C12 	* CH3C1 + HC1





 !•  Function - As of 1970, chloromethane was made either b'y the chlori-




     nation of methane (70%) or the hydrochlorination of methanol (22%).




          The chlorination of methane process sequence requires four main




     steps; reaction, HC1 recovery, chlorides recovery and chlorides re-




     fining.  High purity methane,  chlorine and recycle methane are pre-




     mixed and fed to the reactor.   The reactor effluent,  containing




     organic chlorides, HC1, excess methane, and only traces of chlorine,




     is cooled and fed to the HC1 recovery system.




          The first column in this  system is an absorber designed for




     efficient HC1 removal.  The bulk of the absorbing liquor  is HC1 azeo-




     trope (about 20 percent by weight HC1).  The rich acid is thus above




     the azeotrope and allows stripping of anhydrous  HC1.   The second




     column distills off anhydrous  HC1 and produces the required azeotrope




     in the bottoms.  For high yields of methyl chloride,  the  amount of




     recirculating methane is increased.




          The HCl-free gases from the absorber are washed with caustic




     soda to remove final traces of HC1 and are then  ready for chlorides




     recovery by compression, cooling, and drying with sulfuric acid.




 2.   Input Materials - Basis - 1 metric ton methyl chloride




     Methane - 179 kg/Mg (358 Ib/ton)  product           1445 m3 (15,713 ft3/ton)




     Chlorine - 1587 kg/Mg (3,174 Ib/ton) product       1405 kg (3,097  Ibs/ton)




     Sulfuric Acid




     Caustic Soda
                            6-404

-------
3.  Operating Parameters

    Temperature - 400 - 500°C  (752-932°F)

    Pressure - 200 kPa  (2 atm)

    Flow Rate - not given

    Catalyst - None

4.  Utilities

    Electric Power - not given

    Cooling Water - not given

5.  Waste Streams

    Dehydrator (air)

         Purge on recycled methane to remove inerts

         CH4 - 1 kg/Mg (2 Ib/ton) product

         CH3C1 - 13 kg/Mg (26 Ib/ton) product

         CH2C12 - 2 kg/Mg (4 Ib/ton) product

         CHC13 - 1 kg/Mg (2 Ib/ton) product
              - 1 kg/Mg (2 Ib/ton) product

    Waste acid solution is discharged from the dehydrator.

    Waste caustic solution is discharged from the washer. where traces

    of HC1 are removed from the product gases .

6.  EPA Source Classification - None

7.  References
    Sittig, M. , Pollution Control in the Organic Chemical Industry,

    Noyes Data Corporation, Park Ridge, N.J., 1974, p. 105-

    Austin, G. T., "Industrially Significant Organic Chemicals - Part 3,"

    "Chemical Engineering," March 18, 1974, p. 89,90.

    Lowenheim, F. A. and Moran, M. K. , Industrial Chemicals , 4th Edition,

    John Wiley & Sons, New York, N.Y. , 1975, p. 531,532.
                           6-405

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 158




            Methylene Chloride (chlorination of methane)






             CH^ + 2C12	> CH2C12 + 2HC1 + co-products






1.   Function - Processes for CHLC1- manufacture are based on chlorination




     of methane, although the other chloromethanes are probable co-products




     of this route, their relative proportions are determined by process




     operating conditions.




          A typical methane chlorination synthesis of methylene chloride




     and co-products is as follows.   A preheated mixture of methane and




     chlorine passes into a vessel where reaction is promoted by a control




     of feed-gas flow rate and the reactor temperature.  In addition to




     chloromethanes, the exit gas contains unreacted methane and hydrogen




     chloride.  Initial separation of the product group from CH, and HC1 is




     generally affected by scrubbing the effluent gas with a refrigerated




     mixture of higher chloromethanes, in which the methane and hydrogen




     chloride are only slightly soluble.  The methane, freed from acid by




     water scrubbing, is recycled to the chlorinator and the chloromethanes,




     containing the desired CH_C1~,  after washing, alkali scrubbing, and




     drying, pass to a sequence of fractionating columns.




2.   Input Materials




     Methane - 0.179 kg/kg product




     Chlorine - 1.587 kg/kg product




3.   Operating Parameters




     Temperature:  360 - 500°C (680 - 932°F)
                               6-406

-------
     Pressure:  205 kPa  (2 atm)




     Catalyst:  UV light from mercury vapor lamps




4.   Utilities




     Not given




5.   Waste Streams - Scrubbing water effluent with chloromethanes to




     remove methane and hydrogen chloride from the desired products




     results in the following emissions.




     CH  - 1 g/kg product




     CH Ci - 13 g/kg product
     CH
2C12 - 2 g/kg product
     CHCl  - 1 g/kg product




     CC1, - 1 g/kg product




     Water scrubbing to free HCl from methane stream should lead to




     emissions of CLand a waste acid solution.  Alkali used in neutra-




     lizing the latter and in scrubbing the CH_C12 - containing stream




     yield spent caustic as a further pollutant.




     Note that methylene chloride forms toxic products, such as phosgene,




     when exposed to hot surfaces or open flames.




6.   EPA Source Classification Code - None




7.   References




     Hedley, W. H., et. al., Potential Pollutants from Petrochemical




     Processes, Technomic Publishing Co., 1975.






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 115.
                                 6-407

-------
Austin, G. T., "The Industrially Significant Organic Chemicals -




Part 7," Chemical Engineering, June 29, 1974, p. 154.






"Air Pollution from Chlorination Processes," prepared for Office




of Air Program, Environmental Protection Agency, Contract No.




CPA 70-1, Task Order No. 23, March, 1972.
                            6-408

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 159




              Chloroform (chlorination of methane)





          CH,  + C12 	>• mixed products including CHC13




 1.  Function - Chloroform was formerly made by reaction of chlorinated




     lime (bleaching powder) and acetone, acetaldehyde, or ethanol, but




     this appears to be uneconomical in most cases.   Currently, chlorination




     of methane is the principal route to chloroform, with other chloro-




     methanes usually co-produced.  Control of the chlorine/methane feed




     ratio and other operating conditions influence the yield of CHCl.,.




     A two-stage chlorination provides the maximum yield.   Purification




     of chloroform is accomplished by extraction with concentrated sul-




     furic acid followed by repeated distillation.




          Chloroform may also be made by substituting methanol for methane.




 2.  Input Materials - Basis - 1 metric  ton chloroform




     Methane- 187 m3  (6,604 ft3)




     Chlorine- 1780 kg  (3924 Ibs)




 3.  Operating Parameters




     Temperature:  elevated (250 - 800°C ?) (482-1472°F)




     Pressure:   not given




     Catalyst:   ultraviolet light (optional)




 4.  Utilities




     Not given




 5.  Waste Streams - Various chloromethanes might be emitted from the




     methane chlorinator.  Neutralization of sulfuric acid used in puri-




     fication and by-product hydrochloric acid may lead to spent caustic




     and traces of acid in the waste water flow.
                            6-409

-------
    Note that chloroform slowly oxidizes to phosgene on exposure to




    sunlight.




6.  EPA Source Classification Code - None




7.  References




    Austin,  G.  T., "The  Industrially Significant Organic Chemicals -"




    Part 3," "Chemical Engineering," March 18, 1974, p.  89.






   "1975 Petrochemical  Handbook," "Hydrocarbon Processing," November




   1975, p.  127.





   Lowenheim,  F. A. and Moran, M. K.,  Industrial Chemicals, 4th Edition,




   John Wiley  & Sons, New York, N.Y.,  1975,  p.  266.
                          6-410

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 160
                Carbon Tetrachloride (chlorination of methane)





                 CH. + C10	>• CC1, + CHC1, + CH0C10 + CH,C1
                   42          4       3223




1.  Function - Since the 1950's chlorination of hydrocarbons, particularly



    methane, has been a more important production route to carbon tetra-



    chloride in the United States than chlorination of carbon disulfide.



    The chemical process is referred to as chlorinalysis, which involves



    the simultaneous breakdown of hydrocarbons and chlorination of molecular



    fragments.  As methane and chlorine react in this manner, some carbon



    tetrachloride is produced,  along with varying amounts of other chloro-



    methanes.  The relative quantities depend on the composition of the



    hydrocarbon starting material and the conditions of chlorination.   With



    a C12/CH, molar ratio of 0.6, and a reaction temperature of 340-370°C,



    the following yields are obtained:   CCl,-2%, CHC13~10%,  CH-Cl2-29%,



    CfLCl-58%.  Recycling partially chlorinated materials and using light



    as a catalyst permits essentially complete conversion to carbon tetra-



    chloride.  The gas flow must be rapid to keep the likelihood of an



    explosion to a minimum.  This process requires corrosion resistant



    metals (Ni) and exacting controls since the reaction is  quite exothermic.



         In Hlils process, a 5:1 ratio of C19 to CH, by volume is reacted at



    650°C, the temperature being controlled by regulating the gas flow rate.



    A heat exchanger cools the exit gas to 450°C before it is passed to a



    second reactor for the addition of more methane.  Perchloroethylene  is



    the principal co-product in this case.
                              6-411

-------
         Crude carbon tetrachloride is generally purified by neutralization




    and drying, followed by distillation.  Additional purification can be




    obtained at the distillation stage by maintaining the carbon tetrachloride




    for a prolonged period under total reflux before actually starting the




    distillation itself.  Decomposition of carbon tetrachloride upon contact




    with water or on heating in air make it practical to add a small quantity




    of stabilizer to the commercial product.




         Carbon tetrachloride may also be prepared from carbon disulfide:






                        CS2 + 3C12  2pfc ) CC14 + S2C12
                                          >. CC14 + 6S
                         4S + 2C12 	»• 2S2C12






    Carbon tetrachloride is also a by-product of the vigorous chlorination




    and dehydrochlorination of ethylene dichloride and the Deacon process.




2.  Input Materials - Basis -  1 metric  ton product




    Methane -  110  kg  (242.5  Ibs)




    Chlorine -  2.210  kg  (4872  Ibs)




3.  Operating Parameters




    Temperature - 250-650°C  (482-1202°F)




    Pressure - atmospheric




    Catalyst - light (optional)




    Reaction time - very short
                              6-412

-------
4.  Utilities - Basis - 1,000 kg CC14




    Electricity, GJ - 0.486  (135 kWh)




    Steam (1.2 MPa, 12 bar), kg-135 (298 Ibs)




    Steam (0.95 MPa, 4.5 bar), kg-135 (298 Ibs)



    Cooling water,  m3 - 85 (22,457 gal)




    Fuel, GJ-0.837 (2 x 105 kcal)




5.  Waste Streams - Various chloromethanes emitted from the  process  during




    the early repeated-chlorination stage (8 Ibs./lOO Ibs. product).   An




    alkali of some sort is used to neutralize hydrochloric acid (118 Ibs./




    100 Ibs. product)  which is formed by the chlorination reaction and




    traces of the spent liquid might appear in wastewater flow.




6.  EPA Source Classification Code - None




7.  References




    Austin,  G. T., "The Industrially Significant Organic Chemicals -




    Part  2," "Chemical Engineering," February 18, 1974, p.  127.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers,  New York,  N.Y., Vol. 5  (1964),  p. 132,133.






    Faith, W. L., et. al., Industrial  Chemicals. 3rd Ed., John Wiley & Sons,




    Inc., New York, N.Y.,  1965,  p.  229-231.





    Sittig,  M., Organic Chemical Processes, Noyes Press, Inc., Pearl River,




    N.Y., 1972, p. 39,40.
                              6-413

-------
7.  References (continued)




    "1973 Petrochemical Handbook,"  "Hydrocarbon  Processing," November 1973,




    p.  156-157.





    "1975 Petrochemical Handbook,"  "Hydrocarbon  Processing," November 1975,




    p.  126.





    Lowenheim, F.  A.  and Moran, M.  K.,  Industrial  Chemicals, 4th  Edition,




    John Wiley & Sons,  New  York, N.Y.,  1975, p.  232.
                              6-414

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 161

    Chlorodifluoromethane (chloroform and hydrogen fluoride)


                           (SKI,)
               CHC1, + 2HF 	—*• CHC1F2 + 2HC1


1.   Function - Chlorodifluoromethane is derived by reaction of chloro-

     form with anhydrous hydrogen fluoride, catalyzed by antimony tri-

     chloride.

2.   Input Materials

     Chloroform

     Anhydrous hydrogen fluoride

3.   Operating Parameters

     Temperature:  not given

     Pressure:  not given

     Catalyst:  SbCl,

4.   Utilities - not given

5.   Waste Streams - Various chlorofluoromethanes are potential gaseous

     emittants.  By-product hydrochloric acid and caustic solution used

     in neutralization may appear in waste water streams.

6.   EPA Source Classification Code - None

7.   References

     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

     Interscience Publishers, New York, N.Y., Vol. 9 (1966), p. 743,

     746.
                            6-415

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 162



              Carbon Tetrabromide (from carbon tetrachloride)





                                AlBr

                          CC1.  	-->  CBr.
                             4             4




1.  Function - Carbon tetrachloride reacts with aluminum tribromide



    at high temperature to yield carbon tetrabromide.



2.  Input Materials



    Carbon tetrachloride



    Aluminum tribromide



3.  Operating Parameters



    Temperature - 100°C (212°F)



    Pressure - Not given



4.  Utilities - Not given



5.  Waste Streams - The various bromethanes are possible emissions from



    this process.  Carbon tetrachloride, aluminum hydroxide, and possibly



    some HBr or Br_ may be present in the waste streams.

        >.

6.  EPA Source Classification Code - None



7.  References



    Kirk-Othmer, Encyclopedia of Chemical Technology.  2nd Edition,



    Interscience Publishers, New York, N.Y.,  Vol. 5 (1964), p. 131.
                             6-416

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 163

       Dichlorodifluoromethaiie and Trichlorofluoromethane
         (catalytic fluorination of carbon tetrachloride)


                       SbCl,- catalyst
         3CC14 + 2SbF3	
                 6HF + 2SbCl3 	>- 2SbF  + 6HC1


                        SbCl5
            2CC14 + 3HF 	>• CClgF + CCl^ + 3HC1


1.   Function - Preparation of these two chlorofluoromethanesis not by

     direct fluorination but rather by the replacement of chlorine atom

     of carbon tetrachloride with fluorine due to the action of SbF, con-

     taining antimony pentahalide, either SbCl,-  or SbF,., as catalyst.

     The industrial process uses liquid hydrogen fluoride as an inex-

     pensive source of fluorine arid involves  continuous  regeneration

     of a small initial batch of SbF .

          The process is usually conducted at about 100°C and from 0 to 3.45

     MPa (0-34.0 atm) with gaseous HF.   Dichlorodifluoromethane and

     hydrochloric acid, which is insoluble in liquid HF, are taken off

     to a column which readily separates the partially fluorinated sub-
                                                                           \

     stance CC1-F.

2.   Input Materials - Basis - 1 metric ton dichlorodifluoromethane

     Carbon tetrachloride CC14 - 1600 kg (3527 Ibs)

     Antimony (III) fluoride SbF- - small

     Hydrogen fluoride - 413 kg (911 Ibs)
                           6-417

-------
3.   Operating Parameters




     Temperature:   0-100°C (0-212°F)




     Pressure:  0-3.45 MPa (0-34.0 atm)




     Catalyst:  SbCl5 (or  SbF5)




4-   Utilities - Not given



5.   Waste Streams - Hydrogen chloride produced, which is insoluble in




     liquid HF, must be removed  and neutralized before ultimate disposal,




     leading to possible pollution of waste liquid  flow by HCl, spent




     caustic, and perhaps  traces of dissolved HF.   Any gas-phase  reaction




     is a potential source of chlorofluorohydrocarbons to be  emitted to




     the air.




6.   EPA Source Classification Code - None




7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 4," "Chemical Engineering," April 15, 1974, p. 86,  87.






     U.S.  Patent 3,381,044 (April 30,  1968).






     Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd Edition,




     Noyes Development Corp., Park Ridge, N.J.,1969, p. 232.






     Lowenheim, F. A. and Moran, M. K., Industrial Chemicals,  4th Edition,




     John Wiley and Sons,  New York, N.Y., 1975, p. 325, 326.
                            6-418

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.164
        Carbon Bisulfide (catalytic methane-sulfur reaction)
                   CH.  +  4S 	> CS0  +  2H0S
                     4                 22
1.  Function - The basic production of CS? in the United States is



    currently limited to the catalytic reaction of methane (or natural



    gas) and sulfur vapor; this Thacker process having almost com-



    pletely (70%) replaced the older charcoal-sulfur retort method.



    This system provides yields of over 90 mole percent carbon disulfide



    per pass with the use of active catalysts such as silica gel.   The



    process usually operates in the temperature range 500-700°C,  and the



    pressure may be about 170 kPa (25 psi).   Space velocities,  based on



    hydrocarbon gas charge,  in this case methane,  are on the order of 100-



    400 volumes of gas per hour per unit volume of catalyst.   Sulfur is



    usually charged in slightly higher than stoichiometric amounts.



         The hydrogen sulfide formed may be used as an end product or it



    may be reconverted to elemental sulfur,  for recycle to the  reaction



    system, in a separate partial oxidation unit using the Glaus  process.



    This involves burning H2S with air to form sulfur dioxide,  which then



    reacts with the remaining H2S,  at about 300°C  in the presence of catalyst,



    to form sulfur.   The Glaus process permits about 95% conversion to



    sulfur based on the hydrogen sulfide charge.



         The process flow for the carbon disulfide formation reaction is



    as follows.   Molten sulfur,  maintained at about 130°C, is transferred



    to a sulfur boiler where it is  vaporized and further heated to 575-650°C



    to convert the sulfur vapor to the diatomic form.   Methane, or natural
                             6-419

-------
gas from which higher molecular weight paraffins are substantially




removed, is preheated to 550-650°C and mixed with the sulfur vapor.




The mixed stream, with or without additional heating, is passed down-




ward through a fixed-bed catalytic reactor for the formation of CS_.




The reason for avoiding higher molecular weight hydrocarbons in the




feed is that under specified conditions, these are more reactive than




CH, and will combine with sulfur to produce polymerization and conden-




sation products, leading to catalyst contamination.




     The reactor effluent is cooled to about 130°C and the unreacted sul-




fur is separated in a gas-sulfur separator and recycled to the process.




Simultaneously, small amounts of sulfur dust in the product stream are




removed by scrubbing with liquid sulfur.  The carbon disulfide is




separated from H-S by preferential absorption in a suitable mineral oil




solvent from which it is subsequently stripped and sent to a distilla-




tion section.




     The stripped carbon disulfide is separated from small amounts of




impurities in two successive distillations with low-boiling impurities




removed overhead in the first column.  The bottoms material from this




section is distilled in a second column where the final high-purity CS0




is recovered as the distillate.  The off-gas from the carbon disulfide




absorber contains 90-95% H_S and passes to the sulfur recovery unit.




     Due to the corrosive nature of sulfur and hydrogen sulfide at




high temperatures, stainless-steel alloys are employed in the preheaters




and reactor units.  High-chromium (25% Cr) and stabilized nickel-




chromium alloys are satisfactory.
                         6-420

-------
2.  Input Materials - Basis - 1 metric  ton CS_

    Methane:(or natural gas stripped of higher molecular weight paraffins)
    345 m3  (12,184 ft3)

    Sulfur:(vapor) 925.kg (2,039 Ibs)

3.  Operating Parameters

    Temperature:  500-700°C  (932-1292°F)

    Pressure:  130-300 kPa (1.28-2.96 atm)

    Catalyst:  activated Al_0  + Cr-O-

    (others - alumina, silica-alumina, bauxite, silica-zirconia)

    Hourly space velocity:  600 per hr.

4.  Utilities

    Not given

5.  Waste Streams -  Carbon disulfide manufacture contains a large number

    of potential emission sources and hence pollutants.   The sulfur boiler

    and the introduction of recycle sulfur at the start  of the process flow

    may lead to sulfur vapor escaping.  Heating the methane or natural gas

    feed stream could be a source of gaseous hydrocarbons.  Light mercaptans

    and heavy di-acid polysulfides are formed.  The Glaus sulfur recovery

    unit and the purification of carbon disulfide by staged distillation

    should give off undetermined amounts of sulfur compounds, including

    H2S and S0_.

6.  EPA Source Classification Code - None

7.  References

    Austin, G.  T., "The Industrially Significant Organic Chemicals -

    Part 2," ''Chemical Engineering," February 18, 1974,  p. 127.
                              6-421

-------
7.   References   (continued)




    Kirk-Othmer,  Encyclopedia of Chemical Technology, Interscience




    Publishers, New York, N.Y., Vol. 4 (1964), p. 376-378.





   Hahn, A. V., The Petrochemical Industry;  Markets and Economics,  McGraw-




   Hill Book Co., New York, N.Y., 1970, p. 168,169.





   Lowenheim, F.  A.  and Moran,  M.  K.,  Industrial Chemicals, 4th Edition,




   John Wiley and Sons, New York,  N.Y.,  1975, p. 224,225.
                             6-422

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 165
      Perchloromethyl Mercaptan  (chlorination of carbon disulfide)







                   CS2  +  6C12	> SC12  +  Closer






1.  Function - Perchloromethyl mercaptan is prepared by the chlorination




    of carbon disulfide at 20°C  in the presence of iodine as a catalyst.




    The reaction is carried out  in glass-lined jacketed vessels.  Chlori-




    nation is continued until 3-5% excess chlorine is present.  (The




    excess chlorine converts any S-Cl- to SCI-).




         The reaction mixture is then fractionally distilled under a




    20 in. vacuum to remove the  SC1_, excess chlorine, unreacted CS» and




    CCl^, .  An 85% yield of 97-98% purity product is obtained.  Perchloro-




    methyl mercaptan is an intermediate for the fungicide Captan.




2.  Input Materials




    Carbon disulfide




    Chlorine




3.  Operating Parameters




    Temperature - 20°C  (68°F)




    Pressure (for distillation) --2.66 kPa (0.026 atm)




    Catalyst - Iodine




4-  Utilities - Not given




5.  Waste Streams - Emission probably contains traces of reactants, hydrolysis




    products of chlorinated compounds, and sulfur from decomposition of





    S2CV
                                6-423

-------
6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd  Edition,  Inter-




    science Publishers,  New York, N.Y., Vol.  19  (1969),  p.  374.





    Senning,  A., Editor,  Sulfur  in Organic and Inorganic Chemistry,




    Marcel Dekker,  Inc.,  New York,  N. Y., Vol. 1,   1971  ,  p.  244.





    Kharasch,  N. and Meyers,  C.Y., The Chemistry  of  Organic Sulfur Compounds,




    Vol. 1,  1961 , p. 362-364.
                              6-424

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 166




        Hydrogen Cyanide (reaction of methane, ammonia, and air)







                2CH4  +  2NH3  +  302	>• 2HCN  +  6H20






1.  Function - As of January 1971, 70% of the hydrogen cyanide produced




    in the United States was manufactured via the Andrussow process.  In




    the process a mixture of air, CH,, and NH_ in a volume ratio of 6:1:0.9




    is passed over the catalytic surface at a pressure of about 250 kPa




    (22 psig) and gas velocity of .53 m/sec.  A typical catalyst consists




    of a number of layers of woven, 80-mesh 90% platinum - 10% rhodium




    gauze made of 3-mil wire.  The hot gases from the reactor are quenched




    (to prevent polymerization of HCN),  and unreacted ammonia is removed




    (as (NH,)_SO,)  or recycled.  The off-gas, with ammonia removed goes




    to a cold water acidic absorber to remove HCN which is then stripped




    and fractionated by conventional means.  Assuming recycle of unreacted




    NH_, the ultimate yield of HCN can be 87% of the theoretical value.




    The DEGUSSA and Fluohmic processes are variations of the Andrussow




    process.




2.  Input Material - Basis - 1 metric ton HCN (99.5%)




    Methane - 115m3




    Air - 7500 m3




    Ammonia - 830 kg (assuming 75% yield)




    Phosphoric acid, 85% (stabilizer)




    Sulfuric acid, sp.gn.1.7 - 725 kg
                               6-425

-------
3.  Operating Parameters




    Temperature - 1000-1200°C (1832-2192°F)




    Pressure - ~250 kPa (2.47 atm)




    Gas feed velocity - .53 m/sec.




    Catalyst:  Pt/Rh mesh




4.  Utilities - Not given




5.  Waste Streams - Possible air emissions - NH3, CH^, HZ, HCN,  CO.   Waste




    water - solutions of sulfuric acid, and ammonium sulfate.




6.  EPA Source Classification Code  - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology? 2nd Edition,  Inter-



    science Publishers,  New York, N.Y., Vol. 6  (1965), p. 576-580.






    Lowenheim,  F.  A.  and Moran, M.  M.,  Industrial Chemicals.   4th Edition,




    John Wiley & Sons, New York, N. Y., 1975, p. 482-486.
                              6-426

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 167



               Ethyl Orthoformate(from HCN/HCl/EtOH)




                                NH

                        TTpi     "             T?t~OH

         HCN  +  EtOH       > H-C-OEt •  HC1     r,» HC(OEt).,
                                              cold          J




 •'••  Function - Ethyl orthoformate is prepared in a two-step process by



     reacting hydrogen cyanide, ethanol, and hydrochloric acid at room



     temperature followed by reaction with ethanol in the cold.



 2.  Input Material



     Hydrogen cyanide



     Ethanol



     Hydrochloric acid



 3.  Operating Parameters



     Temperature:  1st Step - room temperature



                   2nd Step - reduced temperature



 4.  Utilities - Not given



 5.  Waste Streams - Unreacted HCN, EtOH, and HC1 should be present along



     with ammonia and/or ammonium salts.



 6.  EPA Source Classification Code - None



 7.  References



     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,



     Interscience Publishers, New York,  N. Y., Vol. 6 (1965), p. 574.
                              6-427

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 168




            Cyanogen Chloride (chlorinatlbri of hydrogen cyanide)




                    NaCN (aq) + C±2	>• NCC1+ NaCl




                      HCN + C12	> NCC1H- HC1






1.  Function - Cyanogen chloride is readily formed by the reaction of




    hydrogen cyanide and chlorine in the liquid phase.  A possible pre-




    liminary stage in cyanogen chloride manufacture is the reaction of




    hydrogen cyanide with sodium hydroxide in aqueous solution to form




    NaCN.  Sodium cyanide may then be chlorinated in aqueous solution




    (pH <8.5) to give NCC1.




2.  Input Materials




    Hydrogen cyanide




    Chlorine




3.  Operating Parameters




    Not given




4.  Utilities




    Not given




5.  Waste Streams - chlorine gas, HCN,  and NCC1 are all possible air-




    borne emissions.   Wastewater will probably contain trace of




    hydrogen cyanide as well as spent caustic and sodium chloride




    from scrubbing operations used to nuetralize the hydrochloric




    acid by-product.




6.  EPA Source Classification Code - None
                               6-428

-------
7.   References




    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,



    Interscience Publishers,  New York,  N.Y.,  Vol.  5  (1964), p.  3.





    Hahn, A. V., The Petrochemical Industry;   Markets  and Economics,




    McGraw-Hill Book Co.,  New York, N.Y.,  1970,  p. 160.
                               6-429

-------
INDUSTRIAL ORGANIC CHEMICALS                 PROCESS NO. 169





     Cyanuric Chloride (polymerization of cyanogen chloride)




                                   Cl
               3C1-C=N
                                           C
                                           i

                                           Cl
1.   Function - Cyanuric chloride is prepared by the vapor phase



     polymerization of cyanogen chloride.



2.   Input Materials



     Cyanogen chloride

     Charcoal carrier impregnated with 3.75% CaCl2, BaCl2, or S^l-



3.   Operating Parameters



     Temperature:  250-480°C (482-896°F) .



4.   Utilities - Not given.



5.   Waste Streams - Spent polymerization catalysts may be present in



     process wastes.  Possible atmospheric emissions include cyanogen



     chloride and by-products.



6.   EPA Source Classification Code - None.



7.   References



     British Patent 602,816 (June 3, 1948).





     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,



     Interscience Publishers, New York, N.Y., Vol. 20  (1969), p.  667.
                             6-430

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INDUSTRIAL ORGANIC CHEMICALS                                PROCESS NO. 170




                         Acetone Cyanohydrin






                  (CH3)2CO  +  HCN  ->•   (CH3)2COHCN






1.  Function - Acetone cyanohydrin is manufactured on an industrial




    scale by the base-catalyzed condensation of acetone and hydrogen




    cyanide.  The reaction temperature is normally kept under 40°C.




    The product must be acidified to prevent decomposition.




2.  Input Materials




    Acetone - 0.6 kg/kg product




    Hydrogen cyanide




    Unspecified acid  •




3.  Operating Parameters




    Temperature:  < 40°C  (104°F)




    Pressure:  atmospheric pressure




    Catalyst:  caustic soda




4.  Utilities




    Not given




5.  Waste Streams - Information available on this process was too limited




    to identify specific pollutant sources.   However, reactants are probably




    present in air emissions from reactor vents and purification procedures.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers,  New York,  N.Y.,  Vol.  6 (1965), p.  672.
                               6-431

-------
7.   References  Ccontinued)



    Waddams, A. L., Chemicals from Petroleum, 3rd Ed., John Murray Ltd.,




    London, Eng., 1973, p. 127.
                                6-432

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO.  171
           Methacrylic  Acid  (from acetone cyanohydrin)
      (CH3)2COHCN
                                  P
CH2=C(CH3)CONH2  •  H2S04  + H20 ™   )CH2=C(CH3)COOH
 -•   Function - In the preparation of methacrylic acid,  acetone cyano-


     hydrin and concentrated sulfuric acid are pumped to a hydrolysis


     kettle where they react to form methacrylamide sulfate.   This


     conversion is usually carried out at 130 - 150° C.


          After cooling, the crude intermediate is taken to a second


     reactor where is combines with water to form methacrylic acid


     and ammonium bisulfate.


          The product stream is then pumped to the acid-stripping


     column where methacrylic acid and some water distill.   The resi-


     due,  made up of sulfuric acid,  ammonium bisulfate,  and water, is


     sent  to the ammonium sulfate plant.


          The overhead from the acid-stripping column enters a recti-


     fier  column where methacrylic acid comes over the  top, is condensed,


     and is sent to the wash column.   Crude methacrylic  acid comes off


     on the top of the wash column,  and is shipped to other plants for


     further distillation.   The water solution from the  bottom of the


     column is recycled to  the rectified  column to complete methacrylic


     acid  recovery.


          Polymerization inhibitors  are added at the acid-stripping


     column and the rectified columns.
                            6-433

-------
2.   Input Materials




     Acetone cyanohydrin - 1.18 kg/kg product




     Sulfuric acid




     Water




     Polymerization inhibitors




3.   Operating Parameters




     Temperature:   first reactor - 130-160° C (266-320°F)




                     second reactor - 90° C (194°F)




     Pressure:      Not given




4.   Utilities - Not given




5.   Waste streams - The waste water stream from the rectifier column




     probably contains small quantities of methacrylic acid and poly-




     merization inhibitors.  Traces of methacrylic acid and other




     organics may be discharged to the air by various processing




     equipment.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd  Edition,




     Interscience Publishers, New York, N.Y., Vol. 13 (1967), p. 333.
                            6-434

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  172


                 Methacrylic Esters (from acetone cyanohydrin)
            (CH3)2COHCN
                            H2S04 + ROM       CH2


1.  Function - Methacrylic esters are prepared from acetone cyanohydrin


    in the same manner as methacrylic acid (see Process No. 171).  In


    this process variation, the methacrylamide sulfate intermediate is


    reacted with ethyl, n-butyl, isobutyl, n-hexyl, or n-lauryl alcohol

                                                       *
    rather than water to yield the corresponding ester.


         Ester recovery operations are essentially the same as those used


    in methacrylic acid purification.  An alcohol recovery section is


    necessary, however, to strip excess alcohol from the rectifier bottoms


    for recycle.


2.  Input Materials


    Acetone cyanohydrin


    Sulfuric acid


    Water


    Alcohol


    Polymerization inhibitors


3.  Operating Parameters - see Process No. 171


4.  Utilities


    Cooling water - 166 kg/kg product


    Steam -0.25 kg/kg product
     Many other alcohols are also used.
                              6-435

-------
5.  Waste Streams - Waste water from the alcohol-recovery column




    probably contains some methacrylic acid,  alcohol,  and polymeri-




    zation inhibitors.  Traces of alcohol and methacrylic acid may also




    be discharged through reactor and various distillation column vents.




    Sulfuric acid is discharged in waste water streams.




               COD   -  1.78 x 105 mg/1




               BOD5  -  2.07 x 104 mg/1




               TOC   -  6.99 x 104 mg/1




6.  EPA Source Classification Code - None




7.  References




    Sittig, M., Pollution Control in the Organic Chemical Industry, Noyes




    Data Corporation, Park Ridge, N.J., 1974, p.  164-166.
                               6-436

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INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 173



                       Acetylene (BASF process)





                        2CH, 	>•  CHECH + 3H0
                           4                  t-




1.   Function - In the United States,  the initial commercial pro-



     duction of acetylene from hydrocarbon sources began in 1951.  Today,



     most of the manufacture of acetylene for chemical synthesis is based



     on the process researched by Badische Anilin-und Soda-Fabrik (BASF)



     in the 1920's.



          In this so-called partial oxidation, or one-stage combustion



     method, the necessary energy for  cracking the feedstock is derived



     by partial combustion of the hydrocarbon feed.  Natural gas or other



     methane-rich feedstock is mixed with a limited amount of oxygen



     sufficient for complete combustion, and fed through a specially de-



     signed distributor or burner to a single reaction zone in which



     ignition occurs.  Improved results are claimed for variations which



     involve preheating of the separate gas streams (Societe Beige de



     1'Azote, SBA) or preheating the premixed composite feed (Hydrocarbon



     Research, Inc.).  The Montecatini process,  in addition employs pres-



     sure operations of up to six atmospheres and effects partial cooling



     of the burner gas by injecting higher hydrocarbons after the flame,



     resulting in production of ethylene and additional acetylene.



          Design of the burner is of considerable importance and is a



     common point of process variation.  Preignition, stability, and blow-



     off of the flame, the possibility of backfiring through the burner



     head ports,and deposition of carbon on the  burner walls all depend
                            6-437

-------
on the burner design and the gas and flame velocities.   The com-




bustion of the gas mixture must be as uniform as possible across the




reaction chamber so that the residence time of the reactant hydro-




carbon is as short as possible, usually on the order of 1 to 10




milliseconds.




     Yields of acetylene based on carbon in the natural gas feed




vary from 30 - 36% by weight for the various processes.  The com-




position of the cracked gas produced from a natural gas feedstock




by the BASF one-stage combustion process is given in the following




table:




               Composition of BASF Process Gas




Component                                    % by Volume




acetylene                                        8.5




hydrogen                                        57.0




carbon monoxide                                 25.3




carbon dioxide                                   3.0




methane                                          4.0




higher acetylenes                                1.0




inert material                                   1.0




     The actual operation of the BASF converter begins with separate




preheating of methane and oxygen (95 - 98% pure) to about 650°C.




The feed streams are then mixed in a venturi-type chamber in a molar




ratio of about 0.6:1.0, oxygen to methane.  The mixed gas is passed




to the flame space through a number of tubular channels in a burner




block.   About one third of the methane entering the burner is cracked




to acetylene, the remainder is burned with 0~.  The pyrolysis products








                        6-438

-------
     are immediately quenched to about 280°C by one or more water sprays




     located in the lower part of the reactor, and the effluent gases pass




     through scrubbers for the removal of water and soot.  Higher acetylenes




     present in the pyrolysis gas must be removed because of this tendency




     to polymerize.  Electrostatic units, combined with water scrubbers,




     moving coke beds, and bag filters, are being used for soot removal.





          The unstable, explosive nature of acetylene imposes certain




     limitations on the use of customary separation techniques.   Studies




     indicate that operating conditions where acetylene partial pressure




     exceeds 100 to 200 kPa or where temperatures exceed 95 - 105°C




     should be avoided.  All commercial processes for the recovery of




     hydrocarbon-derived acetylene are based on absorption/desorption




     techniques using one or more selective solvents (i.e., dimethy-



     formamide).




2.   Input Materials




     Methane - 4.11 kg/kg acetylene produced




     Oxygen - 4.75 kg/kg acetylene produced




3.   Operating Parameters




     Temperature: .1480 - 1540°C (2,696-2,804°F)




     Pressure:  reduced




4.   Utilities - Not given




5.   Waste Streams - Hydrocarbons from the feedstock may be emitted




     to the air.   Water spray used to quench the reaction mixture may




     pick up traces of dissolved gases, such as carbon oxides, hydrogen,
                             6-439

-------
5.   Waste Streams (continued)




     or hydrocarbons, which would eventually find their  way to  waste




     water streams.  Carbon black may give rise to particulates suspended




     in air or water.





     Flow - 0.0047 m3/kg (561 gal/103 Ibs)




     COD - 1,274 mg/1




           5.95 g/kg




     BOD5 - 410 mg/1




            1.92 g/kg




     TOC - 393 mg/1




           1.80 g/kg




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 178-180.







     Lowenheim,  F.  A. and Moran, M. K., Industrial Chemicals,  4th Edition,




     John Wiley & Sons, New York, N.Y., 1975,  p.  30-33.
                             6-440

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.   174
                      Vinyl Acetate  (from acetylene)

                                                  0
                   HC^CH + CH3COOH       >  CH2=CHOCCH

1.  Function - Until 1967 vinyl acetate was produced in the United  States
    predominantly from acetylene.  By 1973 about 75% of the vinyl acetate
    was manufactured by the vapor-phase oxyacetylation of ethylene.
         In the acetylene process, the acetylene is specially purified
    to remove H~S and phosphorus compounds.  It is then mixed with  gaseous
    acetic acid and fed into a fixed-bed reactor with zinc acetate  on
    carbon as catalyst.  Reactor temperature is maintained at 175-200°C.
    The reactor effluent is condensed, light ends removed, and vinyl acetate
    distilled.
2.  Input Materials
    Acetylene - 325 kg/metric ton vinyl acetate
    Acetic acid - 710 kg/metric ton vinyl acetate
3.  Operating Parameters
    Temperature - 175-200°C  (347-392°F)
    Pressure - not given
    Catalyst - Zinc acetate on carbon
4.  Utilities - not given
5.  Waste Streams - Waste gases may contain traces of light ends  (methyl
    acetylene, allene, acetylene).  Waste waters may contain traces of  acetic
    acid.
6.  EPA Source Classification Code - None
                               6-441

-------
7.   References




     Lowenheim, F.  A.  and Moran,  M.  K.,   Industrial Chemicals.   4th




     Edition,  John Wiley & Sons,  New York,  N.Y.,  1975,  p.  862-867.






     Waddam,  A. L., Chemicals from Petroleum,  3rd Edition,  John Wiley




     & Sons,  New York, N. Y., 1973,  p. 42.
                            6-442

-------
INDUSTRIAL ORGANIC CHEMICALS                 PROCESS NO. 175

      1,1-Difluoroethane (hydrofluoric acid and acetylene)



     H-C=C-H     +       2HF    	>    CH CHF2


1.   Function - 1,1-Difluoroethane is derived by passing acetylene and a

     selected catalyst into the bottom of a stainless steel column of

     liquid hydrogen fluoride.  The gaseous reaction products are

     washed with soda lime, distilled and condensed.

2.   Input Materials - Basis - 0.93 part.

     Acetylene: 1 part
     Hydrogen fluoride: 1.6 parts
     BF3 (10%): 0.52 parts

3.   Operating Parameters

     Temperature:  0-20°C (0.68°F)
     Pressure:  68.9-517 kPa (0.58-5.10 atm)
     Catalyst:  Anhydrous stannic-chloride
     Contact Time:  20 sec.

4.   Utilities - Not given.

5.   Waste Streams - Acetylene, difluorethane, and HF "may be emitted

     to the atmosphere.  Soda lime sludge should be present.



6.   EPA Source Classification Code - None.

7.   References

     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

     Interscience Publishers,  New York,  N.Y.,  Vol.  9 (1966), p.  835.


     U.  S.  Patent 2,830,099 (April 8, 1958).
                             6-443

-------
U. S. Patent 2,425,991 (1947).
Sittig, M., Organic Chemical Process Encyclopedia - 1969, 2nd




Edition, Noyes Development Corp.,  Park Ridge,  N.  J., 1969, p. 246.
                       6-444

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INDUSTRIAL ORGANIC CHEMICALS                 PROCESS NO. 176


   1,1,1-Chlorodifluoroethane (chlorination of dif luoroethane)


                            AIBN
                                                        HC1
1.   Function - 1,1,1-Chlorodifluoroethane is prepared by chlorinating

     1,1-dif luoroethane in the presence of azobis-isobutyronitrile  (AIBN)

2.   Input Materials

     Dif luoroethane
     Chlorine

3.   Operating Parameters

     Temperature: 70-100°C (158-212 °F)
     Pressure:  2.59 - 3.79 MPa (25.5-37.9 atm)
     Catalyst:  AIBN
     Reaction Time:  2-8 seconds.

4.   Utilities - Not given.

5.   Waste Streams - Spent caustic and salt are pollutants from the

     scrubber used to remove hydrochloric acid by-product.  Some

     chlorine may be emitted to the air as well as chlorinated com-

     pounds, acetylene and vinyl chloride.

6.   EPA Source Classification Code - None.

7.   References

     Sittig, M., Organic Chemical Process Encyclopedia - 1969,

     2nd Edition, Noyes Development Corp., Park Ridge, N. J., 1969,

     p. 169.
                            6-445

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  177



             Methyl Butynol (ethynylation of acetone)
                 Cflf \E,
                   J     ,:
                                              OH


                              HC=CH	^ HC=C-C-CH^
-'-•   Function - 2-Methyl-3-butyn-2-ol is produced by ethynylation of



     acetone with excess acetylene in liquid ammonia in the presence of



     sodamide (NaNH9) or some other basic catalyst.  The reaction is



     carried out at a temperature of 10-40°C and high pressure (1.97 MPa).



          The process is terminated by adding a material to decompose the



     catalyst.  The pressure is then dropped to atmospheric in a suitable



     flash tank.  Ammonia and excess acetylene are recycled to the reactor,



     and unreacted acetone is removed from the product in a distillation



     column.  A second distillation step takes the methyl butynol overhead



     as an azeotrope containing 28.4% water, leaving behind deactivated



     catalyst salts and heavy by-products.



2.   Input Materials



     Acetylene



     Acetone



     Ammonia



3.   Operating Parameters



     Temperature:  10-40°C (50-104°F)



     Pressure:  1.97 MPa (19.4 atm)



     Catalyst:  NaNH2 (alkali or alkaline earth oxides also acceptable)
                               6-446

-------
4.   Utilities - Not given




5.   Waste Streams - Recycling of ammonia and excess acetylene to the




     reactor is a potential source of leaks to the atmosphere.  Distil-




     lation to remove remaining reactants may cause atmospheric emission




     of solvents.  The second distillation bottoms include deactivated




     catalyst salts and heavy by-products, which will eventually appear




     in waste water flow.




6-   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 208.






     Ibid., Vol. 12 (1967), p. 120.







     Chemical Technology, Barnes and Noble Books,  New York, N.Y.,  Vol. 4




     (1972), p. 291.
                             6-447

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 178


           Methyl Pentynol (acetylatlon of 2-butanone)



         «                 CH.OH         ™2CH3

     CH-^CHCH   +HCECHCS7-*  CV^0-"
     LH3     2° 3                        OH


1.   Function - 3-Methyl-l-pentyn-3-ol is manufactured by the reaction


     of acetylene and 2-butanone in dimethylacetal of formaldehyde as


     the solvent.  Sodamide, sodium or potassium hydroxide, potassium


     t-butoxide, or other alkali or alkaline earth oxides are used as


     condensing agents.


          A typical yield for this process is 50% based on 2-butanone.


2.   Input Materials


     2-Butanone - 1.47 kg/kg product


     Acetylene


     Dimethylacetal of formaldehyde (solvent purposes only)


3.   Operating Parameters


     Temperature:  not given


     Pressure:  not given


     Catalyst:  NaNH2, NaOH or KOH, KOC(CH3>3, or other alkali or alkaline


                earth oxides.


4.   Utilities - Not given


5.   Waste Streams - See description under Process No. 177.


6.   EPA Source Classification Code - None


7.   References


     Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,


     Interscience Publishers, New York, N.Y., Vol. 1  (1963), p. 208.
                             6-448

-------
7.   References (continued)




     Ibid., Vol. 12 (1967), p. 120.
                             6-449

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 179





         1,1,2,2-Tetrachloroethane  (chlorinatlon  of  acetylene)
                      HC^CH + 2C12     - >   HCC12CHC12






1.  Function - Chlorine and acetylene are  mixed independently with portions




    of a mixture of tetrachloroethane and  antimony trichloride.  These two




    mixtures, one containing chlorine (60-80°C) and the other acetylene




    (80-100°C) are then brought in contact under controlled conditions.  The




    product 1,1,2,2-tetrachloroethane is distilled from the reaction mixture




    and mostly used for production of trichloroethylene.   Less than 10% of




    trichloroethylene is derived directly  from acetylene.




2.  Input Materials




    Acetylene




    Chlorine




3.  Operating Parameters




    Temperature - 70-80°C  (158-176°F)




    Pressure - Not given




4-  Utilities - Not given




5.  Waste Streams - The following air emissions arise from the reflux condenser




    vent of the chlorination reactor.




    Ethane - 1.25 g/kg product




    Methane - 1.25 g/kg product




    Tetrachloroethane - 0.50 g/kg product




    Waste water flow may contain traces of tetrachloroethane and alkali metal




    compounds from washing operations as well as suspended particles of  iron




    or other inorganic catalyst species used.






                               6-450

-------
6.   EPA Source Classification Code - None




7.   References




     Lowenheim, F. A., and Moran, M. K.,  Industrial Chemicals,  4th




     Edition, John Wiley and Sons, New York, N.Y., 1975, p. 607, 608,




     845-848.






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 5  (1964), p. 161-163,






     Hedley, W. H., et al., "Potential Pollutants from Petrochemical




     Processes," Technomic Publishing Co., Westport, Conn., 1975.
                             6-451

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  180




           Trichloroethylene (from tetrachloroethane)





                 CHC12CHC12 -£-»• CHC1=CC12  + HC1




 ^•'   Function - The cracking of tetrachloroethane  in the presence of a




     catalyst of BaCl~  on carbon is the currently  preferred method of




     production.  The reaction takes place  at 250-300°C and produces a




     mixture of trichloroethylene and 10 percent perchloroethylene, which




     may be separated by distillation.   After distillation from heavy




     ends,  a small amount (20 ppm by weight)  of  trimethylamine or pyrrole-




     based  compounds may be added to stabilize the product.




         A small amount of trichloroethylene can  be made by pyrolyzing




     1,1,2-trichloroethane in the presence  of air  or 0~:





             2CH2C1CHC12 + 02 -£-*• 2 CC12=CHC1 + H20





 2.   Input  Materials




     Tetrachloroethane




 3.   Operating Parameters




     Temperature,. ._. ,^^_. _250-30Q°C (482-572.°F)




     Catalyst                  30 percent BaCl2/C




 4.   Utilities




     Not  given




 5*   Waste  Streams  - No  specific information  was available, but one would




     expect  some HC1 and various chlorohydrocarbons to  be present in the




     gaseous and  aqueous waste streams.




 6.   EPA  Source  Classification Code - None
                            6-452

-------
7.  References




    Austin, G. T., "The Industrially Significant Organic Chemicals




    Part 8," "Chemical Engineering," July 22,  1974,  p.  115.






    Faith, W. L. et al., Industrial Chemicals, 3rd Ed., John Wiley




    & Sons, Inc., New York, N. Y., 1965,  p.  784.






    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed.,




    Interscience Publishers,  New York,  N.Y., Vol.  5  (1964),  p.  190.
                            6-453

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  181




            Synthesis Gas (catalytic steam-hydrocarbon reforming)




                         CH  + H0 - > CO + 3H
                             2H20
                         CO
1.  Function - Synthesis gas is any mixture  of  carbon monoxide and




    hydrogen, in variable proportions,  usually  intended for conversion




    to ammonia, purified hydrogen,  hydrocarbons,  alcohols,  or other




    organic compounds.   By 1965, catalytic steam-hydrocarbon reforming




    used to recover hydrogen from hydrocarbon feedstocks up to and




    including light gasoline fractions, and  producing more  hydrogen,




    and synthesis gas mixture than  any  other method.   In this process,




    gaseous hydrocarbons, such as methane are reacted with  steam at




    650°C to 1050°C in  the presence of  a suitable nickel catalyst to




    produce carbon oxides and hydrogen  at about the same temperatures.




        Important factors to be considered in the design of a steam-




    hydrocarbon reforming plant are:




        1)   Process Hydrocarbon. Basic requirements for a  satisfactory




            hydrocarbon feed to a steam-reforming operation are:




            a)  Freedom from sulfur compounds.   The total sulfur




                content should be less  than  1-5 parts per million,




                since sulfur acts as a  catalyst poison.




            b)  Absence of unsaturated  hydrocarbons.  These compounds




                tend to deposit carbon  on the reforming catalyst,




                causing both loss of activity and physical deteriora-




                tion.




                              6-454

-------
    c)  The hydrocarbon feed should be in the vapor phase




        when it contacts the catalyst.




2)  Operating Pressure.  Ammonia and methanol synthesis, petroleum




    hydrogenation, hydrogen liquefaction, and the pressure storage




    of hydrogen gas all require hydrogen at elevated pressures




    ranging up to 100 MPa  (1000 atm).  Since natural gas is often




    available at pipeline pressures of 4 MPa (40 atm) or more,




    and steam may be generated efficiently at this pressure,




    carrying out the steam hydrocarbon reforming process at




    higher pressures, 1.8-3.2 MPa (18-32 atm), may result in




    substantial economics.   Increased pressure operation also




    permits heat recovery from the reaction product stream at




    higher temperature levels, due to the higher partial pressure




    of the excess steam in the gas mixture.




3)  Catalyst selection.  Several commercial catalyst are available.




    These catalysts contain 20-35% nickel oxide mixed with refrac-




    tory cement.  Coimpregnation of a small amount of magnesium




    oxide with the nickel oxide has been found to improve the




    activity and stability of alumina-supported catalyst.




4)  Tube surface temperature.   The low strength of 25-20 chrome-




    nickel steel tubes imposes an external surface temperature




    limit of 930-980°C for operation at pressure greater than




    1 MPa (10 atm).




5)  Steam-hydrocarbon ratio.  At atmospheric pressure, hydrocarbons




    may be reacted to produce hydrogen with less than 0.1%




    residual CH,  by using two molecules of steam per atom of
                      6-455

-------
             carbon in the hydrocarbon, and carrying out the




             reaction at temperatures above 870°C.  As the




             operating pressure is increased, the ratio is generally




             increased to between 3 and 4 molecules of steam per carbon




             atom in the feed material.




         6)  Product gas temperature at furnace outlet.   This parameter




             is important in determining the amount of unreacted methane




             remaining in the product stream and is influenced by the




             maximum allowable tube surface temperature, the tube diameter,




             and the type of furnace.




         7)  Flue gas temperature.  The flue gas temperature will probably




             be between 900°C and 1050°C, and the flue gas will be raised




             to preheat the furnace feed streams and to generate steam.




         8)  Carbon monoxide removal.  Substantially complete removal of




             CO from the product stream is required when synthesis  gas




             is used as a source of hydrogen in the synthesis of ammonia.




             This processing step is accomplished by causing the raw gas




             mixture to react with steam via the water gas shift.  The carbon




             dioxide formed is scrubbed with appropriate solvents.




2.  Input Materials




    Natural gas (methane) or other hydrocarbon feed




    Steam - 2 to 6 kg/kg synthesis gas produced




3.  Operating Parameters




    Temperature:  650-1050°C (1202-1922°F)
                              6-456

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3.   Operating Parameters (continued)




    Pressure:  1.8-3.2 MPa (17.8-31.6 atm)




    Catalyst:  20-35% nickel oxide on alumina support




    Residence time:  0.2-10 seconds




4.   Utilities - Not given




5.   Waste Streams - Condensates from catalytic reforming generally contain




    spent catalyst particles, hydrogen sulfide formed from residual sulfur




    in the feed, and ammonia formed by reaction of  air with the  hydrocarbons




    at elevated temperatures.




         Regeneration of the activated carbon used  for sulfur  removal may




    lead to gaseous emissions of hydrogen sulfide and/or sulfur  dioxide,




    if this operation is performed on site.




         It is unlikely that hydrocarbons from the  feed  stream or  carbon




    monoxide from the product stream would be emitted to the air.




6.   EPA Source Classification Code - None




7.   References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y.,  Vol. 2 (1963), p. 275,276.





    Ibid., Vol. 10 (1966), p. 415-419.






    U.S. Patent 3,367,882  (February  6,  1968).





    Sittig, M., Organic  Chemical Process Encyclopedia - 1969, 2nd Edition




    Noyes Development Corp., Park Ridge, N.J., 1969, p. 623.
                             6-457

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  182
      Synthesis Gas (continuous,  non-catalytic  partial  oxidation)
                             C02  - *• 2CO
                                      CO + 3H2
                        CO
     Function - Synthesis gas is a mixture of  carbon monoxide and hydrogen
     with minor amounts of carbon dioxide and  nitrogen.   There are two
     general processes used - the steam reforming process (using a nickel
     catalyst) and the process described here, the non-catalytic partial
     oxidation process.
          The partial oxidation process involves the burning of hydrocarbons
     in air or oxygen to produce a gas containing hydrogen and carbon monox-
     ide  with small quantities of methane, CO- and water vapor.  The use
     of oxygen yields a product gas of lower nitrogen  content often
     necessary for subsequent uses of synthesis gas.
          The mixture of hydrocarbon and oxygen is pre-heated to 235-650°C
     (455-1202°F)  depending on the composition of the  gas stream.  It
     then passes to a reactor which operates at 1100-1600°C (2012-2912°F)
     and pressures up to 4 MPa (40 atm) .  The  hot effluent gases are cooled
     in a heat exchanger, compressed and C02 removed by absorption in water
     or ethanolamine solution.

          The non-catalytic partial oxidation  process  can operate on any
     hydrocarbon feedstock that can be compressed or pumped.  No desulfuri-
     zation process is necessary since there is no catalyst involved that
     can be poisoned.
                             6-458

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2-   Input Materials
                                       o
     Natural gas (methane) - 0.27 kg/Nm  of crude dry gas produced

                                o
                             (Nm  = normal cubic meters, 0°C, 760 mm Hg.


     Steam - 13.40 kg/1000 Nm  of crude dry gas or 0.05 kg/kg natural gas


             feed (steam saturated at 246°C (470°)).

                     3   3
     Oxygen - 0.26 Nm /Nm  of crude dry gas


3.   Operating Parameters


     Temperature:  1100-1600°C (2012-2912°F)


     Pressure:  1.48-4.24 MPa (14.6-41.8 atm)


     Residence time:  <10 seconds


4.   Utilities

                                   3
     Boiler feed water - 0.83 kg/Nm  crude dry gas

                               3
     Cooling water - 0.32 kg/Nm  crude dry gas

                                  3
     Fresh water - 67.0 kg/1000 Nm  crude dry gas

                              3
     Electricity - 16.2  kJ/Nm  crude dry gas


5.   Waste Streams - The partial oxidation process produces 0.12 kg of

                      3
     condensate per Nm  of crude dry product gas.  Again as in catalytic


     reforming, it is doubtful that reactants, natural gas or oxygen,


     are emitted to the atmosphere during feed to the reactor.  For


     natural gas, no soot will appear in the waste water flow.  Carbon


     dioxide from stripping of the gas absorption system may be vented


     to the air.


6.   EPA Source Classification Code - None


7.   References


     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,


     Interscience Publishers, New York, N.Y., Vol. 10 (1966), p. 419-422.
                            6-459

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INDUSTRIAL ORGANIC CHEMICALS                            PROCESS NO.  183



                      Urea (once-through process)







                      2NH- + CO,	>-  H?NCOONH,
                         ,j     £t *  ~    &•       "
1.   Function - All commercial production of  urea is  based  on the reaction



     of ammonia and carbon dioxide to form ammonium carbamate which in



     turn decomposes to urea and water.



          The reaction is run at 175-190°C and a pressure of 16-25 MPa



     (160-250 atm).  Under these conditions,  the equilibrium urea con-



     versions of only 40-70% can be expected.  The effluent contains



     ammonium carbamate, urea and excess ammonia.  The unreacted carbamate



     is decomposed to ammonia and carbon dioxide gas  by heating the effluent



     at low pressure.  The gaseous mixture is separated from the urea solu-



     tion and used to produce ammonium salts  by absorbing NH_, either in



     sulfuric or nitric acid.  C0~ is vented  to the air.



          Urea is recovered from the stripped effluent solution either by



     evaporation or crystallization.  Biuret, a condensation product of



     urea forms under conditions of high temperature  and reduced pressure,



     and must be minimized for certain industrial uses of urea.  Urea,



     produced by crystallization, contains only 0.2-0.3% of biuret.



     Product produced by evaporation contains a much higher biuret con-



     tent.



          Urea is marketed in the form of small spherical particles called



     prills.  These are formed by spraying molten urea, at the  top of a



     50M cylinderical column into a counter current stream of air.


                             6-460

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     The molten urea freezes into spheres which are collected at the




     column bottom.  The biuret content in this material is 0.6-1.5%.




2.   Input Material




     Ammonia - 1.87-1.77 kg/kg urea produced




     Carbon dioxide (from synthesis gas) - 0.91-1.47 kg/kg urea produced




3.   Operating Parameters




     Temperature:  175-190°C (347-374°F)




     Pressure:  16-25 Mpa (160-250 atm)




4.   Utilities - Not given




5.   Waste Streams - The high vapor pressure of ammonium carbamate at




     elevated temperatures,  may result in atmospheric emissions of that




     species from the urea synthesis reactor.  Some ammonia may be emitted




     during solidification of urea by evaporation as a by-product of




     biuret formation.  The prilling tower may be a source of particulates




     as well.




6.   EPA Source Classification Code - None




7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 9," "Chemical Engineering," August 5, 1974, p. 97.





     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 21 (1970), p. 43-45.





     U.S. Patent 3,072,721 (January 8, 1963).





     Sittig, M., Organic Chemical Process Encyclopedia - 1969,




     2nd Edition, Noyes Development Corp., Park Ridge, N.J., 1969, p. 690.





     Lowenheim, F. A.  and Moran, M. K., Industrial Chemicals, 4th Edition,




     John Wiley and Sons, New York, N.Y., 1975, p. 857.





                               6-461

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 184




                       Urea (recycle processes)
1.   Function - The urea synthetic processes can be divided into two general




     classes, the "once through process," described as a separate process,




     and the "recycle process."  The recycle process is one in which




     unreacted carbon dioxide and ammonia either in the free form or




     combined as ammonium carbamate, are returned to the system for




     further conversion to urea.




          There are many versions of the recycle process which differ




     basically in the manner in which the CCL and NH, are recovered and




     returned to the reactor.  There may be two or three stages of car-




     bamate decomposition each succeeding stage operated at a lower pres-




     sure and temperature.




          Ammonia and carbon dioxide gases are liquified (compressed)




     and charged to a steam-heated, silver lined autoclave which




     is maintained at 175 - 200°C and 170 - 408 atm.  The




     ammonia and carbon dioxide are converted to ammonium carbamate




     which decomposes to urea.  The product mix consists of 35% urea, 15%




     ammonia, 21% ammonium carbamate and 14% water.  The product is fed




     to a carbamate decomposer at a pressure reduced from that of the
                            6-462

-------
     reactor.  Here carbamate decomposes into NH~ and CO^, the gas


     is recovered, cooled, and recycled to be again converted to ammonium


     carbamate.  The effluent solution is passed to a second carbamate


     decomposer which is operated at a lower temperature and pressure.


     Additional carbamate decomposition occurs here, the gases being


     collected, cooled and recycled as before and the effluent passing


     to a third carbamate decomposer which again operates at a lower


     temperature and pressure.  Effluent from the third stage passes to


     a crystallizer where urea crystals are recovered.


2.   Input Materials - Basis - 1 metric ton urea


     Ammonia - 2000 kg


     Carbon dioxide - 900 kg


3.   Operating Parameters


     Temperature:  Reactor - 175-200°C (347-392°F)


                   1st Decomposition stage - 150°C (302°F)


                   2nd Decomposition stage - 130°C (266°F>


                   3rd Decomposition stage - 120°C (248°C)


     Pressure:  Reactor - 17.2-41.4 MPa (170-408 atm)


                1st Decomposition stage - 1.8 MPa (18 atm)


                2nd Decomposition stage - 0.4 MPa (4 atm)


                3rd Decomposition stage - 100 kPa (1 atm)


4.   Utilities -  Data for Stamicarbon recycle urea plant producing


     fertilizer grade plus, biuret content = 0.2-0.25%


     Basis - 1000 kg urea


     Steam  - (2.6 MPa) - 1100 kg

                         3
     Cooling water - 65 m


     Power - 504 MJ (140 kw)



                             6-463

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5.   Waste Streams - Loss of NH,  to  the  atmosphere  during  staged  decom-




     position and absorption are  possible  emissions.   CO™  may  also be




     emitted in the various  stripping  operations.




6.   EPA Source Classification Code  -  None




7.   References




     Kirk-Othaier, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers,  New York,  N.Y., Vol.  21,  (1970), p. 45-51.







     "1975 Petrochemical Handbook," "Hydrocarbon Processing," November,




     1975, p. 210-11.






     Lowenheim, F. A. and Moran,  M.  K.,  Industrial Chemicals, 4th Edition,




     John Wiley and Sons, New York,  N.Y., (1975), p. 854-857.
                             6-464

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 185
                        Guanidine (from urea)
                                 SO
^•*  Function - Guanidine may be manufactured by the reaction of urea
    with ammonia and sulfur dioxide.  Urea, liquid sulfur dioxide, and
    ammonia (in molar ratio 1:3:7) are heated to 275°C under pressure
    for approximately 30 minutes.  Guanidine (as the sulfate) is obtained
    in 80% yield.  The reaction product is dissolved in water and filtered
    to remove sulfur.  The solution is concentrated and treated with nitric
    acid to form guanidine nitrate.  Guanidine is usually marketed as the
    nitrate or the chloride.
2.  Input Materials
    Urea

    S02
    NH3
3.  Operating Parameters
    Temperature:  245-2 75 °C
    Pressure:  20.2 MPa (200 atm)
    Time:  30 minutes
4-  Utilities - Not given
5.  Waste Streams
    Air - NH3 and S02
    Water - Traces of reactants and products
    Solid waste - Sulfur
                               6-465

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6.  EPA Source Classification Code - None




7.  References




    Astle, M.  J.,  Industrial Organic Nitrogen Compounds,  Reinhold Publishing




    Corp., New York,  N.Y., 1961, p. 301.





    Boivin, J. L., "Canadian J.  Chem," _34, 827 (1966).
                              6-466

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 186
          Cyanuric Acid (thermal decomposition of urea)
                                                  OH
                   0                              i
                   "                             4?  ^
                  yCv                          IT   N
          3   H/ V2  	  ™3 +      IJ
               2        2                   HO*»XSlI
 1.  Function - Heating urea for several hours at 200-300°C results
     in deamination and the formation of cyanuric acid.
          For temperatures much above 300°C, the yield of product de-
     creases due to depolymerization.
          Conversion to cyanuric acid occurs in stages.  Initially, urea
     melts at 133°C to form a free-flowing liquid.  As heating continues,
     the reaction mass thickens and finally solidifies, although at this
     point significant amounts of urea, biuret, H~NCONHCONH_, and triuret,
     H-NCONHCONHCONH-, are present.  Additional heating converts these to
     cyanuric acid.  The product of pyrolysis strongly adheres to the walls
     of the reactor and is removed with great difficulty.  Several methods
     have been patented to overcome such problems.
     (1)  conducting pyrolysis on a molten tin or lead bath
     (2)  conducting pyrolysis in a fluidized bed
     (3)  recycling 60-90% of crude cyanuric acid into a rotating kiln
          to mix with urea prior to pyrolysis
     (4)  running the reaction in certain high-boiling organic solvents
     (5)  heating urea at 165°C for about two hours to get a liquid mix-
          ture consisting of urea, biuret, triuret, and cyanuric acid,
          followed by further pyrolysis for ten minutes at 240-270°C
          on a rotating heated drum.
                             6-467

-------
         Crude cyanuric acid produced by pyrolysis may be contaminated




    with as much as 20-30% impurities consisting mostly of ammelide and




    ammeline with minor amounts of melamine,  biuret,  urea, and triuret.




    Two general purification techniques will  be described.




         Cyanuric acid may be dissolved in ammonium hydroxide solution or




    hot dimethylformamide solution.  Filtering the mixture will remove




    most of the impurities.  The product may  be precipitated from the




    ammonium solution by acidification with mineral acid or from the




    DMF solution by cooling and adding carbon tetrachloride.




         Crude cyanuric acid may also be purified by heating it in




    10-20% sulfuric, nitric, or hydrochloric  acid for several hours.




    This process hydrolyzes most of the ammelide, ammeline, and melamine




    to cyanuric acid.  The slurry is then filtered or centrifuged and




    the solids collected are washed with water to remove residual traces




    of the acid used earlier.  Cyanuric acid  can be dried in any con-




    ventional dryer, up to a maximum temperature of 200°C, to give a




    product of at least 98% purity.




2.  Input Materials - urea




3.  Operating Parameters




    Temperature:  200-300°C  (392-572°F)




    Pressure:  101 kPa (1 atm)




4.  Utilities




    Not given




5.  Waste Streams - Ammonia produced during decomposition of urea is




    probably emitted to the atmosphere.  All other compounds  (cyanuric




    acid, biuret, triuret, ammeline, ammelide, melamine) are  solids at




    ordinary temperatures, and although they occur in the liquid phase





                           6-468

-------
    during reaction,  the vapor pressures are probably too low to lead




    to any pollution problems.




         Purification is a source of additional emissions.   The precipi-




    tation method will lead to the presence of the various  solvents or




    acid in wastewater.  The acid-digestion process waste is probably




    neutralized, leading to spent caustic in wastewater.   Drying operations




    should not pose any significant pollution problems.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 20 (1969), p. 667, 668.
                            6-469

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  187
                         Oxo Aldehydes (oxo process)
              RCH=CH0 + CO + H-  cobalt   ;  RCH CH CHO + R-CHCHO
                    2         2  carbonyl      2  2         j
1.  Function - The oxo process consists of the hydroformylation of


    olefins to give aldehydes (and ultimately alcohols) of the next


    higher homologue.  The olefin feed is usually mixed with a slurry


    of the cobalt catalyst (usually in the form of cobalt naphthenate)


    and introduced to the converter together with the synthesis gas.


    The reaction takes place in the liquid phase at 130-175°C and 200-


    300 atm.


         The liquid reaction products go to a phase separator then to


    a cobalt removal system (decobalter).  The cobalt catalyst is re-


    generated and recycled.  The crude aldehydes are refined by distillation.


2.  Input Materials


    Olefin - (90%)


    Synthesis gas - [CO (98-99%) + H2 (98-99%)]


    Co catalyst


    Steam


    co2


3.  Operating Parameters


    Temperature - 130-175°C


    Pressure - 200-300 atm. (20.2-30.4 MPa)
                               6-470

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4.  Utilities - Not given




5.  Waste Streams -




    Air - Emissions stemming from the formation of by-products such as




    paraffins from hydrogenation of starting olefin;  olefin feed and syn-




    thesis gas leaks.




    Water or solid wastes - Wastes resulting from the high-boiling oxygenated




    compounds formed from condensation of aldehydes and alcohols.




6.  EPA Source Classification Code - None




7.  References




    Sittig,  M. ,"0xo Products From Olefins,"  in  Pollution Control in the




    Organic Chemical Industry,  Noyes Data Corporation,  Park Ridge,  New




    Jersey, 1974, p. 175.





     US Petrochemicals,  Technologies, Markets,  and Economics,   Brownstein,




    A.  M., Ed., The Petroleum Publishing Company,  Tulsa,  Oklahoma,  1972,




    pp. 92-93.





    Hahn, A.V.,  The Petrochemical Industry;   Markets and Economics.




    McGraw-Hill Book Company,  New York,  1970,  pp.  104-105.





    "Oxo Process" in  Chemical and Process Technology Encyclopedia.




    Considine, D. M.,  Ed-in-Chief,  McGraw-Hill Book Company,  New York,




    1974, pp.  793-794.





    Haberstroh, W.  H»  and  Collins,  E.M.,"Oxo Chemicals,"  in  Riegels'




    Handbook of Industrial Chemistry,  7th edition, Kent, J.  A., Ed.,




    Van Nostrand Reinhold Company,  New York,  1974,  pp.  774-775.
                               6-471

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  188




                                Oxo Alcohols
                        RCH2CHO
                             OlP            H2
                   2RCH.CHO     >   R-C-CHO —^> R-CHCH OH

                       2             II            I    2
                                    HCCH2R        CH2CH2R






1.  Function - Alcohols are usually the ultimate product of the oxo-process



    (Process No. 187).   The alcohols are obtained by:   (a)  direct reduction



    of the aldehyde; (b) dimerization of the aldehyde  by aldol condensation



    followed by reduction to the alcohol; or (c) single stage low pressure



    oxo process.  In (a), the aldehyde from the decobalter is hydrogenated at




    elevated temperature and pressure to give the alcohol.   In (b) the



    aldehyde from the decobalter is fed into a condensation reactor where




    the aldolization is carried out in the presence  of caustic.  Water is



    continually removed from the consendation reaction to drive it to




    completion.  The resulting aldehyde is then hydrogenated to the alcohol.



         An alternate route was recently introduced.  Olefin feed and




    recycled catalyst are charged to the first of a  series of packed reactors




    at controlled  rates.  Synthesis gas (H2:CO = 2.5:1) is fed separately to



    each reactor.  The overhead stream from the final reactor is sent




    directly to the recovery column.  The bottoms from the recovery column




    contain catalyst complex in a mixture of alcohols and heavy ends.  This




    stream is recycled to the first reactor with periodical purging to




    remove built-up heavy ends.
                               6-472

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         This reaction is carried out in alkaline medium with a specially


    promoted cobalt carbonyl catalyst.   The dimer and monomer alcohols


    are obtained directly from the reaction mixture.


2.  Input Materials

    Aldehyde

    Hydrogen


    Phosphine-promoted cobalt carbonyl


    Nickel catalyst


    Zinc compound

    Olefin

    Synthesis gas

    Caustic

3.  Operating Parameters

    a.  Temperature - 150-200°C (302-392°?)


        Pressure - (1500-3000 psi) 10.3-20.6 MPa (102-204 atm)

    b.  Temperature - 90-230°C  (194-446°F)


        Pressure - < than (a)


    c.  Temperature - Not given

        Pressure - < 30 atm. 3.04 KPa (30 atm)


4.  Utilities - Not given

5.  Waste Stream - Air - hydrocarbons from leaks.  Water - High boiling


    oxygenated intermediates, byproducts, and heavy ends.  A typical plant

                                 o                        q
    survey showed:  Flow - 1.59 m /454 kg, COD - 1.21 kg/m  and 1.93 kg/


    454 kg, BOD5 - 0.9 kg/m3, 1.43 kg/454 kg, and TOC - 0.549 kg/m3,


    .87 kg/454 kg.

6.  EPA Source Classification Code - None
                                6-473

-------
7.   References




    Sittig,  M.,"0xo Products  from Olefins,"  in  "Pollution Control in  the




    Organic  Chemical Industry," Noyes Data Corporation,  Park Ridge,




    New Jersey,  1974, pp.  175-177.





    Long,  F.W.,  "Technology and Markets  of Petrochemicals Derived from




    Synthesis Gas," in "US Petrochemicals:   Technologies, Markets, and




    Economics,"  Brownstein, A. M., Ed.,  The  Petroleum Publishing  Company,




    Tulsa, Oklahoma, 1972, pp. 92-94.





    Waddams,  A.L.,  Chemicals  From Petroleum,  3rd Edition, John Murray Ltd.,



    London (1973),  p.  204-206.
                              6-474

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 189
              Phosgene (catalytic reaction of carbon monoxide

                               and chlorine)




                         Co  +  ci2catalyst> coci2



1.  Function - Phosgene is manufactured by reacting chlorine gas and carbon


    monoxide in the presence of activated carbon. Dry carbon monoxide of


    the highest possible purity is metered and mixed in a reactor with dry


    and pure chlorine at a temperature of 200°C and 2 to 4 psig over gas-


    mask grade activated charcoal.


         The hot effluent gases leaving the reactor are led to a condenser,


    where liquid phosgene is removed.  The non-condensable gases are scrubbed


    with a hydrocarbon solvent to remove entrained phosgene.  Nearly


    all phosgene is used at the point of manufacture, mostly in the manu-


    facture of isocyanates for polyurethane resins.


2.  Input Materials

                           3
    Carbon monoxide - 230 m /metric ton product


    Chlorine - 720 kg/metric ton product


3.  Operating Parameters


    Temperature - 200°C (392°F)


    Pressure-  13.8-27.6  kPa  (0.14-0.27  atm)


    Catalyst - activated charcoal 15 kg/metric ton product


4.  Utilities - Not given
                               6-475

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5.  Waste Streams - Any phosgene waste (not feasible to recycle) is




    scrubbed with sodium hydroxide.




6.  EPA Source Classification Code - None




7.  References




    Lowenheim,  F.  A.  and Moran,  M. K.,  Industrial Chemicals,   4th  Edition,




    John  Wiley &  Sons,  New York,  N.  Y., 1975, p. 624-627.





    Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,  Inter-




    science  Publishers, New York,  N.Y., Supplemental  Volume  (1971)  p.  677-681.





    Austin,  G.  T.,  "The Industrially Significant Organic  Chemicals  - Part




    8," "Chemical  Engineering,"  July 22,  1974, p. 108-109.
                                6-476

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 190
            Sodium Formate (carbon monoxide and sodium hydroxide)


                                       HO
                          NaOH  +  CO —=-> HCOONa

1.  Function - Clean and compressed synthesis gas (source of carbon monoxide)

    is introduced countercurrently into a 25-30% sodium hydroxide solution

    at 160-200°C to give sodium formate.  Sodium formate crystals are

    obtained by drying the reaction product.

2.  Input Materials

    Synthesis gas (source of carbon monoxide)

    Sodium hydroxide

3.  Operating Parameters

    Temperature - 160-200°C  (320-392°F)

    Pressure - 140-170 kPa  (1.38-1.68  atm)

4.  Utilities - Not given

5.  Waste Streams - Waste water is likely to contain sodium hydroxide.

    Atmospheric emissions of carbon monoxide and hydrogen are possible.

6.  EPA Source Classification Code - None

7.  References

    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-

    science Publishers, New York, N.Y., Vol. 10  (1966), p. 101.

    Gmelins Handbuck der Anorganische Chemie, System-Nummer 21, 8 Auflage

    Erganzungsband, Lieferung 4, Verlag Chemie,  1967, p. 1398.
                                 6-477

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS  NO. 191





            Methanol (high-pressure  catalytic  synthesis)
            CO  +  2H2  +   CH3OH   AH°9g  =  -90.79 kJ
1.  Function - Methanol synthesis  from CO  and H?  is  favored by  high pres-




    sures and low temperatures.  The  temperature  and pressure applied  in




    commercial processes is  dependent on:   composition  of  synthesis gas




    utilized, and rate of reaction at a given temperature  and pressure in




    the presence of a given  catalyst.




         The main source of  synthesis gas  at present is the steam reforming




    of natural gas.   Very exact process control is needed  to maintain  a




    desired carbon monoxide  - hydrogen ratio.




         The reforming of natural  gas by steam may be represented by the




    following equation





                 3CH4  +  C02  +   2H20  -»•   AGO  + 8H2





         The synthesis gas is compressed to remove water and entrained




    oil.   The compressed mixture of gases  is passed  through a catalytic




    converter.   Commercial processes  usually operate at temperatures




    ranging from 350°C to 400°C and at pressures  in  the 19.6-29.4 MPa  range.




    Catalyst used in  the high-pressure synthesis  consists mainly  of mixtures




    of  chromium oxide and zinc oxide.   Close control of operating parameters




    to  suppress side  reactions is  of  utmost importance.  The mixture of




    gases  from  the converter pass  through  a condenser and  then  through a




    separator.   The crude methanol condensate is  subsequently purified




    in  a two-step distillation.  By-products are  mixed  alcohols  (19.3  g/kg




   methanol) and dimethyl ether (20.4  g/kg methanol).




                              6-478

-------
         Methanol plant equipment must be resistant to carbon monoxide




    at high temperatures and pressures.




         Copper-based catalyst have been known to increase the rate of




    the reaction for the formation of methanol from synthesis gas,  but




    were readily inactivated by sulfur impurities present in synthesis




    gas.  Improved methods of removing sulfur from synthesis gas and




    newly-perfected copper-zinc catalyst has led to a new low-pressure




    process for the manufacture of methanol from synthesis gas.   The new




    low-pressure process developed by Imperial Chemical Industries  Limited




    of United Kingdom operates at pressures nearly half of those utilized




    in usual processes.  Some methanol was also produced in the liquid phase




    oxidation of butane—rich hydrocarbon gas (Process No. 227) . However,




    this process has not been in commercial use since 1973.




2.  Input Materials




    1)  Synthesis gas - produced by steam reforming of 0.829 kg natural




        gas per kg CH^OH.




        a)  5.8-7.3 kg CO/kg CH^H (based on 12-15% conversion of CO)




        b)  .87-1.31 kg H2/kg CH3OH (based on H2:CO molar ratio of  2.1-2.5)




    2)  Carbon dioxide - recovered from reformer flue gases.




3.  Operating Parameters




    Temperature:  350-400°C (662-752°F)




    Pressure:   20-30 MPa (200-300 atm.)




    Catalyst:  Cr_03  +  ZnO
                                6-479

-------
4.  Utilities - Basis - 10.5  kg/sec  (1000  tons/day)  capacity

                           o
    Cooling water - 2.089 m /sec  (33,110 gal/min)

                          o
    Makeup water - 70.0 dm /sec (1,100  gal/min)


    Power - 11.0 GJ (3.06 Mw)


    Natural gas - 13.49 Nm3/sec (1.715  M scfh)

5.  Waste Streams - Major waste water streams are  from slab and vessel


    washdowns together with bottoms  from the methanol  purification  process.

                             o
    This amounts to 0.4-2.1 m /kg of product  (100-500  gal/ton) and  contains
                                           i

    some oils, methanol, and higher-boiling organic  compounds  to  the  extent
    of about 0.2-0.5 kg/1000 m3.
                                   Plant  1               Plant  2
             Flow                 0.492  m3/kg           0.352 m3/kg

             COD                    320  mg/1            4,930 mg/1
                                  0.16    g/kg           1.74    g/kg

             BOD-                   119  mg/1            2,620 mg/1
                                  0.059   g/kg           0.92    g/kg

             TOC                    107  mg/1              583 mg/1
                                  0.053   g/kg           0.21    g/kg

6.   EPA Source Classification Code - None

7.   References

    Chemistry In The Economy - American  Chemical Society Study,p.  31, 1973.


    Hedley, William H.,  et al., Potential Pollutants From Petrochemical

    Processes, Technomic Publishing Co., Westport,  Conn., 1975.


    Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,  Inter-

    science Publishers,  New York, N.Y.,  Vol.  13 (1967), p. 375-378.


    Sittig, M., Pollution Control in the Organic Chemical Industry, Noyes

    Data Corp., Park Ridge, N.J., 1974,  p. 158-159.
                                6-480

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INDUSTRIAL ORGANIC CHECMICALS                                PROCESS NO. 192
                                 Methylamines
                     (vapor-phase aimnonolysis of methanol)
1.   Function - The manufacture of methylamines is a classic example of

     vapor phase ammonolysis of alcohols.  Methylamine, with smaller

     quanties of both dimethylamine and trimethylamine, is produced

     by passing methanol and ammonia, in a 1:5 volume ratio and pre-

     heated to 350°C, over a dehydrating catalyst at space velocities

     of 0.75 - 1.5 and a catalyst temperature of 450°C.  The process

     is usually carried out under atmospheric pressure, but it can be

     performed under pressures in excess of 690 kPa (6.8 atm) with

     direct fractionation of the products at these conditions.  Catalysts

     commonly used are alumina (A^Os) , aluminum silicate, aluminum

     phosphate, and diammonium phosphate.  Conversion of the ammonia

     is 13.5% to primary, 7.5% to secondary, and 10.5% to tertiary amine.



     Part of the exothermic heat of reaction may be used in the feed

     preheater.



     Since exclusive production of one of the amines is difficult and

     frequently uneconomical, much of the process development con-

     cerning methanol ammonolysis has dealt  with the problem of

     satisfactory separation of the three co-products.  Recycling of

     the less desirable amines to increase the yield of the desired

     product is generally effective even if the secondary or tertiary

                                6-481

-------
amine is preferred.  If dimethylamine is desired, the other two
amines may be recycled without separation from each other.
Separation or fractionation of the product stream is rather
difficult because the boiling points of the methylamines all
lie in a temperature range of only about 10°C.


The crude product can be separated by a series of four column
distillations.  The first column is maintained at a suitable
temperature and pressure so that the trimethylamine—ammonia
azeotrope to be recycled is recovered overhead, the recyclable
ammonia from the upper middle of the column, and a mixture of mono-,
di-, and some tri-methylamine as bottoms.  The mixture goes to
the trimethylamine (TMA) column where water is added for ex-
tractive distillation and pure TMA is collected overhead and sent
to storage or recycle.  The bottoms from this operation are sent
to the mono-methylamine  (MMA) column where pure MMA is removed overhead.
Finally, the MMA column bottoms are sent to a fourth column where
pure dimethylamine goes  overhead with water drained from  the
bottom to waste.


Procedures have also been devised for separating  the methylamines
from mixtures by extractive distillation.  Mono-methylamine  is
separated from the other two by absorbing the vapors in a liquid
in which it has the lowest «olubility of the three, such  as di-
methylaniline, 1,2,3,4-tetrahydronaphthalene,  or  diraethylcyclohexyl-
amine.   Fractional distillation of this solution  yields MMA over-
head.   Dimethylamine is separated from MMA and TMA by subjecting
the mixture to extractive distillation using aniline, morpholine,
                           6-482

-------
     dimethylformamide, or diethanolamine, in which DMA is the most




     soluble.  The diemthylamine is recovered by flashing from the




     solvent.  By using solvents in which TMA is the least soluble,




     the member of the series may be distilled from mixture.




2.   Input Materials - kg/kg of desired methylamine produced




     Methanol (industry average factor/highest value)




     a)   MMA;  1.05/1.2




     b)   DMA:  1.45/1.6




     c)   TMA:  1.65/1.8




     Ammonia (assuming 97% yield)




     a)   MMA;  0.565




     b)   OMA:  0.389




     c)   TMA:  0.297




3.   Operating Parameters




     Temperature:  450°C  (842°F)




     Pressure:  690 kPa (6.8 atm)




     Catalyst:  A^OS




4.   Utilities - basis:  45.4 kg (100 Ib) of anhydrous product




     Steam - 590 kg (1300 Ibs)




     Water - 13.2 m3 .(3500 gallons)




     Electricity - 32.4 MJ (9 kWh)




5.   Waste Streams - The staged distillation process is the source of




     most of the pollutants in methylamine manufacture.  The bottoms




     from the DMA column, the last in the series of four, are drained




     to wastewater and will contain some of all three methylamines in




     solution.
                                 6-483

-------
     Two examples of the wastewater are:
Flow
COD
BOD5
TOG
#1
3.58 I/kg
22.56 g/kg
6.303 g/1
0.35 g/kg
99 rng/1
41.65 g/kg
11.634 g/1
#2
3.57/1/kg
4.21 g/kg
1.178 g/1
0.62 g/kg
1.74 mg/1
13.63 g/kg
3.808 g/1
     Atmospheric emissions of hydrogen and cqrbon monoxide and of




     methylamines will arrise from crude product storage and final




     storage, respectively.




6.    EPA Source Classification Code - None




7.    References




     "1973 Petrochemical Handbook," "Hydrocarbon Processing,"




     November,  1973,  p.  150.






     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition, Inter-




     science Publishers,  New York,  N.Y.,  Vol.  2 (1963),  p. 122.
                                6-484

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INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 193



                         Methyl Chloride








 1.  Function



          Methyl chloride is produced by the action of hydrogen chloride



     on methanol, with the aid of a catalyst, in the vapor phase.  Vapors



     of methanol and hydrogen chloride are continuously mixed in approxi-



     mately equimolecular ratios and passed through a preheater maintained



     at about 180°C.



          The gas mixture is then passed at substantially atmospheric



     pressure through a converter at a temperature of 340°C to 350°C.  The



     converter is packed with previously ignited alumina gel of 8 to 12



     mesh size or a similar catalyst, such as zinc chloride on pumice,



     cuprous chloride, or activated carbon.  Space velocities of about


           3                                    3
     7.79 m  (275 cubic feet) per hour per 28 dm  (cubic foot) of gross



     catalyst volume are generally used (based on gas volumes at STP).



          The effluent gases from the reactor are scrubbed with water



     to remove excess HC1, followed by an alkali wash, and a sulfuric



     acid wash (to dry the product).  Crude methyl chloride is distilled



     under pressure at -24°C to yield pure methyl chloride.



 2.  Input Materials - Basis - 1 metric ton methyl chloride




     Methanol - 360 kg/Mg (720 Ib/ton) of product        700 kg  (1,543 Ibs)



     HC1 - 1587 kg/Mg (3,174 Ib/ton) of product          800 kg  (1,769 Ibs)




     Sulfuric Acid



     Caustic Soda
                             6-485

-------
3.  Operating Parameters

    Preheater temperatures:   180  - 200°C  (356  -  392°F)

    Converter temperatures:   350PC (662°F)

    Pressure:  atmospheric
                          3
    Space velocity:  275 m /hr

    Catalyst:  Alumina gel.   Cuprous  chloride  on activated carbon or

    pumice.   Zinc chloride on activated carbon or pumice.  Phosphoric

    acid on activated  carbon.

4.  Utilities

    Not given

5.  Waste Streams -  Waste  water from  scrubbers contains  traces of HC1,

    some alkali and  sulfuric  acid.

6.  EPA Source Classification Code -  None

7.  References



    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,


    Interscience Publishers,  New York, N.Y.,  Vol. 5  (1967),  p.  106,107.


    Lowenheim, F. A. and Moran,  M. K., Industrial Chemicals, 4th  Edition,


    John Wiley and Sons, New York, N.Y., 1975,  p. 533.
                            6-486

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 194




                  Methyl Acetate (by esterification)
                        + CELOH 	>•  CHgCOOCHg +
1.   Function - In a general procedure for manufacturing methyl esters




     the aliphatic carboxylic acid (in this case acetic acid) is reacted




     with an excess of methanol in ethylene dichloride as solvent.  Sul-




     furic acid is used as catalyst for the reaction.  The mixture is




     heated to reflux from 6 to 15 hours.  After cooling the reaction




     product is washed with water, sodium bicarbonate, water and dried




     by conventional methods.  The ethylene dichloride is removed by




     distillation.  The crude ester is then distilled.




2.   Input Materials




     Methanol




     Acetic acid




     H2S04




     Ethylene dichloride




3.   Operating Parameters




     Temperature:  Reflux




     Pressure:  101 kPa (1 atm)




     Catalyst:  H-SO,




     Time:  6-15 hrs




4.   Utilities - Not given




5.   Waste Streams - Waste water may contain dilute solutions of  salts




     of acids, traces of methanol, methyl acetate, and other organic by-




     products.





                              6-487

-------
6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York,  N.Y.,  Vol. 8 (1965), p. 350,






     U.S. Patent 2,787,636 (April 2, 1957).
                             6-488

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  195
      Methyl Acetoacetate (action of metallic sodium on methyl acetate)
                                            £> Na®
                    2CH C-OCH  + 2Na 	> CH^C = CH-COOCH,
                                             NaOCH3
               [CH3COCHCOOCH3P'Nas' +  E^SO^	* CH3
1.  Function - Methyl acetoacetate is prepared by the reaction of high-purity

    methyl acetate with metallic sodium in absolute methanol.  The sodium

    derivative is then neutralized with sulfuric acid to give the product.

         The crude ester is separated and purified by vacuum distillation.

2.  Input Materials

    Methyl Acetate

    Metallic sodium

    Absolute Methanol

    Sulfuric acid

3.  Operating Parameters - Not given

4.  Utilities - Not given

5.  Waste Streams - Hydrogen, a by-product; may be released into the atmos-

    phere.  Wastewaters may contain sodium hydroxide and sodium bisulfate

    as well as traces of methanol and sulfuric acid.

6.  EPA Source Classification Code - None
                               6-489

-------
7.   References




    Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd  Edition,




    Interscience  Publishers,  New York,  N.Y., Vol.  1  (1963),  p.  154-155.
                              6-490

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 196




                          Dimethyl Ether
 1.  Function - Dimethyl ether is produced from methanol using sulfuric




     acid as the dehydration catalyst or by passage over catalyst   such




     as alumina.




          A mixture of methyl alcohol and concentrated sulfuric acid is




     slowly heated to 110-140°C.   In this temperature range the reaction




     is initiated.  An azeotrope of ether-water-alcohol distills from




     the reactor at 110 °C and passes to a scrubber.   The vapors pass




     count ercurrently to a slow moving stream of dilute sodium hydroxide.




     The vapors from the top of the scrubber run to a continuous frac-




     tionation column where separation takes place.   Alcohol and sulfuric




     acid are recycled.




 2.  Input Material




     Methanol




     Sulfuric Acid




 3.  Operating Parameters




     Temperature:   140°C (284°F)




     Pressure:  101 kPa (1 atm)




     Catalyst:  I^SO^




 4.  Utilities - Not given




 5.  Waste Streams - Waste water may contain traces of ether, aldehydes,




     and peroxides as well as sodium sulfate from neutralization.
                             6-491

-------
         Some reduction of sulfuric acid occurs with evolution of sul-




    fur dioxide.  Tarry materials are disposed as solid waste.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience Publishers,  New York, N. Y.,  Vol.  8 (1965), p.  474-




    476.





    Houben-Weyl, Methoden der Organischen Chemie, Vierte Auflage,




    George Thieme Verlag, Stuttgart, Bd.  6,  T.  3, (1965), p. 13.





    Faith, W.  L., et^ al^., Industrial Chemicals,  3rd Edition, John Wiley




    and Sons,  New York,  N.  Y.,   1965 , p. 335-336.
                            6-492

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 197





                          Dimethyl Sulfate








         .  „  ,   „„   45-47°C,
1.  Function - Dimethyl sulfate is obtained in a continuous process




    utilizing dimethyl ether and liquid sulfur trioxide as the input




    materials.  Gaseous dimethyl ether is bubbled into the bottom of




    an aluminum tower filled with dimethyl sulfate.   Liquid sulfur tri-




    oxide is introduced at the top of the tower.  The mildly exothermic




    reaction is controlled at 45-47°C.  The reaction product (96-97%




    dimethyl sulfate) is continuously withdrawn and purified by vacuum




    distillation over sodium sulfate.




2.  Input Materials




    Dimethyl ether (74.3 kg/hr)




    Sulfur trioxide (129.1 kg/hr)




3.  Operating Parameters




    Temperature 45-47°C  (113-117°F)




4.  Utilities




    Not given




5.  Waste Streams - Possible gaseous emissions of SO .  The bottoms from
    - •--'•"    	                                        X



    distillation contain sulfuric acid and methyl hydrogen sulfate.




6.  EPA Source Classification Code - None




7.  Reference




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-




    science Publishers, New York, N.Y., Vol. 19 (1969), p. 492.






                               6-493

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  198


                             Methyl Formate
                       CH,OH  +  CO 	->  HCOOCH
                         J          /*iTT f\Tfin
1.  Function - Methyl formate may be prepared industrially by the reaction

    of methanol with carbon monoxide (from synthesis gas)  in the presence

    of metal alkoxides.   Hydrogen reacts with excess carbon monoxide to

    form methanol which is re-cycled.

2.  Input Materials

    Methanol

    Synthesis gas (CO + H~)

    CH3ONa (CH OH + Na)

3.  Operating Parameters

    Temperature - 80°C (176°F)

    Pressure - 2.96 kPa  (300 atm)

    Residence time - 350 sec.

4.  Utilities - Not given

5.  Waste Streams - By product of the reaction, e.g., dimethyl ether.  Also

    some high-boiling tars are formed.

6.  EPA Source Classification Code - None

7.  References

    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

    Interscience Publishers, New York, N.Y.,  Vol.  4 (1965), p. 434-435.


    Waddams,  A.  L.,  Chemicals from Petroleum, 3rd  Edition, John Wiley

    and  Sons,  New York,  N.Y.,  1973 ,  p. 204.
                               6-494

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 199




                                  Formamlde






                     HCOCH   4-  NH  	*  HCNH2  +  CB^OH





1.  Function - Formamlde can be manufactured by the reaction of ammonia




    with methyl formate.  Formamide was used as a source of HCN.  This HCN




    process is considered obsolete now.




2.  Input Materials




    Methyl formate




    Ammonia




3.  Operating Parameters




    Temperature - 40°C (104°F)




    Pressure - 140 kPa (200 psi) (1.38 atm)




4.  Utilities - Not given




5.  Waste Streams - Gaseous emission of methanol, ammonia and methyl formate




    are possible.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-




    science Publishers, New York, N.Y., Vol. 6 (1965), p. 576.





    Ibid., Vol. 10 (1966) p. 105.





    Lowenheim, F. A.  and Moran, M. K.,  Industrial Chemicals,  4th Edition,




    John Wiley and Sons, New York, N.Y., 1975, p. 484.
                               6-495

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  200




                           N , N-Dime thy 1 f o rmami de
                                          CH3OH
1.  Function - N , N-Dimethylf ormamide (DMF)  is derived from the reaction of




    methyl formate with dime thy lamine.   The reaction product is separated




    from methanol and unconverted reactants by distillation.




2.  Input Materials




    Methyl formate




    D ime thy lamine




3.  Operating Parameters




    Not given




4.  Utilities - Not given




5.  Waste Streams - Possible atmospheric emissions are - methanol, methyl




    formate and dime thy lamine.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-




    science Publishers, New York, N.Y., Vol. 10 (1966), p. 109.





    Astle,  M.J., Industrial Organic Nitrogen Compounds - ACS Monograph No. 150,




    Reinhold  Publishing Corp., 1961 p. 74.
                               6-496

-------
INDUSTRIAL ORGANIC CHEMICALS                 PROCESS NO. 201
          Acetic Acid (from methanol by carbonylation)
                  CH3OH + CO         > CH3COOH

 1.  Function - Methanol is carbonylated with carbon monoxide to produce

     acetic acid.  Various types of catalysts have been proposed for the

     carbonylation of methanol.  The catalyst most widely employed consists

     of two main components:   1) a carbonyl-forming metal from the iron

     sub-group  (iron,  cobalt,  or nickel), and 2) either BF  or

     H3P04.

 2.  Input Materials  - Basis - 1 metric ton acetic acid

     Methanol - 610 kg/Mg  acetic acid          553  kg (1,175 Ibs/ton)

     Carbon monoxide - 787 kg/Mg acetic  acid   467  kg (1,030 Ibs/ton)

 3.  Operating Parameters

     Temperature:  200 - 300°C (392-572°F)

     Pressure:  20 to  70 MPa  (197-691 atm)

     Flow rates:  not  given - > reaction time 1-3 minutes; vapor or

     liquid phase

     Size of Equipment :  not given - tubular reactor type

     Types of catalysts:   Fe,  Co, or Ni  acetate +  BF_ or HJ?0, .  Monsanto

     has a new catalyst  ( a  soluble rhodium-metal -carbonyl  complex acti-

     vated with an iodide  promoter)  which  permits this reaction to pro-

     ceed at pressures as  low  as 210 kPa (~ 2  atm) and allows  use of


     synthesis gas as  a CO source.

 4.  Utilities - Basis:  45.5  Gg/yr  (100 M  Ib/yr)  capacity:


     Water
                     o
     Cooling - 287 dm  /s  (4,560  gpm)
                             6-497

-------
    Makeup - 6.1 dm /s (97 gpm)




    Power - 6.98 GJ (1940 kWh)




    Steam - 15.8 Mg/hr (34,800  Ib/hr)




5.  Waste Streams - Reaction section - off-gas scrubber vent (air)




    Hydrogen - 5.5 kg/Mg acetic acid




    Carbon monoxide - 204 kg/Mg acetic acid




    Methane - 12.7 kg/Mg acetic acid




    Methanol - 14.9 kg/Mg acetic acid




    Light ends - 2.2 kg/Mg acetic acid




    About 40 kg (-88 pounds) of organics (50% propionic acid and 50%




    higher organics) are produced in the liquid waste stream per Mg




    (tonne) of acetic acid produced.  The waste stream amounts to about




    200 dm /Mg (50 gallons per  ton) of product including drains.




6.  EPA Source Classification Code - None




7.  References




    Yakaoka, S., "Acetic Acid," Report No. 37, Stanford Research Institute,




    Menlo Park, California, March, 1968.






    Gloyna, E. F., and Ford, D. L., "The Characteristics and Pollutional




    Problems Associated with Petrochemical Wastes,"  for FWPCA, Contract




    No. 14-12-461, February, 1970.






    Austin, G. T., "Industrially Significant Organic Chemicals  -  Part  1,"




    "Chemical Engineering," January 21,  1974, p.  128,129-






    Sittig, M., Acetic Acid and Anhydride, Noyes  Development  Corporation,




    Pearl River, N. Y., 1965, p. 24-29-
                            6-498

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7.   References (continued)




    Lowenheim, F. A., and Moran, M. K.,  Industrial Chemicals,  4th Edition,




    John Wiley and Sons, New York, N.Y., 1975, p.  10,11.
                               6-499

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  202




                                 Formaldehyde




                     (catalytic air oxidation of methanol)
                            CH3OH + air
1.  Function - All formaldehyde in the United States  is  produced from




    methanol by either vapor-phase catalytic oxidation or by a combination




    oxidation-dehydrogenation process.   The  product is usually marketed




    as formalin — a 37% solution stabilized with  9%  methanol.




         The catalytic conversion of methanol to formaldehyde involves the




    reaction of a mixture of methanol vapors and air  over a stationary




    catalyst at appr&ximately atmospheric pressure.   Because methanol and




    air form explosive mixtures in the range 6-37% by volume of methanol




    in air at 60°C,  the commercial processes operate  either at methanol




    concentrations of nearly 50% or 5-10% by volume of methanol in air.




    In the catalytic conversion of methanol  to formaldehyde, using silver




    catalyst, dehydrogenation and oxidation  of methanol  may occur




    s imultaneously.




                            CH3OH	>• HCHO  + H2                  -20 Kcal.





                    CH3OH + 1/2 02 	* HCHO + H20               +38 Kcal.







         Clean air is heated and mixed with  methanol  vapors in a controlled




    ratio (1:1).   Temperature may vary between 450°-700°C with the optimum




    around 635°C.   Gases from reactors are quenched and  the excess methanol




    in the resulting methanol-formaldehyde solution is removed by fractiona-




    tion.






                              6-500

-------
         In the direct oxidation of methanol to formaldehyde in the
    presence of iron-molybdenum oxide catalyst, a low  (5-10%) methanol
    concentration stream in air is used.  The product is essentially
    free of methanol.
         Formaldehyde may also be produced in a vapor-phase oxidation of
    propane-rich LPG.  However, this process has not been used since
    February 1973 when Celanese Corporation closed its Bay City, Texas
    plant.
2.  Input Materials-- (data for silver-catalyzed, oxidation-dehydrogenation
                      process)
    Methanol - 438 g/kg of 37% formaldehyde
    Air - 888 g/kg of 37% formaldehyde
3.  Operating Parameters
    1)  Oxidation - dehydrogenation
        Temperature:          635°C (600-700°C)  (1175°F)
        Pressure:             146 kPa  (1.44 atm)
        Catalyst:             crystalline silver
        Reaction time:        0.5 second
    2)  Direct oxidation
        Temperature:          300-400°C  (572-752°F)
        Pressure:             ~100 kPa (atmospheric)
        Catalyst:             iron-molybdenum oxide
4.  Utilities - Basis: 45.4Gg/yr (100 M Ib/yr) capacity for production
                       of 37% HCHo by silver-catalyzed dehydrogenation-
                       oxidation
                            3
    Water, cooling - 88.3 dm /sec (1400 gpm)
                           o
    Water, process - 2.4 dm /sec (38 gpm) (includes water for steam generation)
    Steam - 0.794 kg/sec (6300 Ib/hr)
    Power - 107 kW (143 hp)
                               6-501

-------
5.  Waste Streams - Off-gases from the absorber of the absorption and


    purification section will lead to the following atmospheric emissions:


    CO - 63.5 g/kg 37% formaldehyde


    H2 - 7.6 g/kg 37% formaldehyde


    CH^ - 1.25 g/kg 37% formaldehyde


    ECHO - trace


    CH OH - trace


    formic acid - in water


         The major wastewater sources are the  scrubber waters  and the


    dimethyl ether by-product.   The total aqueous  stream should not

                  o                                         o
    exceed 0.42 dm /kg (100 gal/ton) containing 1-5000 mg/dm  COD unless


    on-site truck washing is practiced.


6.  EPA Source Classification Code - None


7.  References


    "1973 Petrochemical Handbook," "Hydrocarbon Processing," November 1973,


    p. 135,136.


    "1975 Petrochemical Handbook," "Hydrocarbon Processing," November


    1975, p. 149,150.


    Hedley, W. H. , et al., Potential Pollutants From Petrochemical Processes,


    Technomic Publishing Co., Eastport,  Conn., 1975.


    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,


    Interscience Publishers, New York, N.Y., Vol.  10 (1966), p. 86-88.
                               6-502

-------
7.   References (continued)




    Austin, G. T., "The Industrially Significant Organic Chemicals -




    Part 6," "Chemical Engineering," May 27, 1974, p. 101.





    Chemistry in The Economy - American Chemical Society Publication,




    1973, p. 32.





    Walker, J. F., Formaldehyde, 3rd Edition, ACS Monograph 159, 1964,




    p. 16-24.





    Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,




    John Wiley & Sons, New York, N.Y., 1975, p. 422.
                                6-503

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 203



       Ethylene Glycol (from formaldehyde & CO via glycolic acid)






                       BF                H

       CH00 + CO + H00 —	> HOCH0C00H —	>• HOCH-CH-OH
         2.          2             22  cat.       2  2




1.   Function - Although more than 90% of ethylene glycol produced is made



     by catalytic oxidation of ethylene to ethylene oxide, followed by



     hydration, a reaction of formaldehyde, water, and carbon monoxide



     is also being used.  These three chemicals combine at 200°C and



     about 70 MPa to form glycolic acid.



          This is followed by hydrogen reduction of the product glycolic



     acid in the presence of a copper oxide-magnesium oxide catalyst (at



     200°C and 10 MPa).



2.   Input Materials      Per kg ethylene glycol



     Formaldehyde                650 g



     Carbon monoxide             625 g



     Hydrogen                     75 g



     Sulfuric Acid                45 g



     Water



3.   Operating Parameters



     Temperature:  200°C  (392°F)



     Pressure:  70 MPa; 10 MPa for hydrogenation




     Catalyst:  BF  for acid formation CuO - MgO  (for hydrogenation)


                            4    -1
     Space Velocity:  2 x 10  hrs



4.   Utilities



     Not given
                             6-504

-------
5.   Waste Streams - Carbon monoxide fed to the primary reaction vessel




     is a possible, atmospheric emission.  Process slops may carry formal-




     dehyde, methanol, higher alcohols, and organic a"cids to waste water




     flow.




6.   EPA Source Classification Code - None




7.   References




     Faith, W. L. et al., Industrial Chemicals. 3rd Ed., John Wiley & Sons,




     New York, N.Y.,   1965  , p. 375, 376,  377.






     Chemical Technology, Barnes  and Noble Books, New York, N.Y.,




     Vol.  4  (1972),  p.  294.
                              6-505

-------
 INDUSTRIAL ORGANIC CHEMICALS                                 PROCESS NO.  204




          Methylenedianiline (condensation of aniline and formaldehyde)
                          HC1
                               NH4OlT  "2" ^y^y  ""2  V^/ ""2 '  3H2° + 2NH4C1






 1.    Function - The production of methylenedianiline is  a  two-stage




      process.   Aniline is  neutralized  with concentrated  hydrochloric




      acid in aqueous  solution at 100°C  to form aniline  hydrochloride.




      The solution is cooled  to 15°C  and  40% formaldehyde solution




      added,  followed by heating at 55  -  60°C for four hours.   The




      reaction mixture is then  chilled  again,  and the product  pre-




      cipitated out with dilute ammonium  hydroxide.  The  product  may




      be  further purified by  recrystallization from alcohol or water.




 2-    Input Materials




      Basis -  1 kg (Ib)  product




      Aniline - 1.66 kg (3.66 Ibs)




      Formaldehyde (40%)  -  0.68 kg (1.50  Ibs)




      Concentrated hydrochloric acid  -  1.68 &




      Ammonium  hydroxide




      Water - 3.57  £




3.    Operating Parameters




     Temperature:   55 -  60°C (131 -  140°F)




     Pressure:  not given




     Catalyst:  not given




4.   Utilities - Not given
                                6-506

-------
5.   Waste streams - Waste water streams may contain ammonium hydroxide,




     ammonium chloride, and aniline compounds in solution.  There will




     be no gaseous emissions.  Resinous materials formed on contact




     of aniline and formaldehyde will be disposed of in process wastes.




6.   EPA Source Classification Code - None




7.   References




     Scalon, J.T., J. Amer. Chem. Soc., _57, May, 1935, p. 890, 891.




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 2  (1963), p. 414.
                                6-507

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 205
                     Hexamethylenetetramine
           (condensation of formaldehyde with ammonia)
                                     N        ^
                                     I  CH2, xCH2 '
          6HCHO + 4NH, 	>•        I     N
                                          '     -CH2
1-   Function - Hexamethylenetetramine is a heterocyclic fused ring
     structure made by the condensation reaction of aqueous formaldehyde
     with liquid or gaseous ammonia.
          A slight excess of ammonia may be introduced to prevent side
     reactions which occur at pH values below 8.  The process is performed
     at 62-66°C and about 280 kPa (2.76 atm) in an aqueous solution within
     a steel, tower-type reactor.
          After addition of activated charcoal for the removal of impurities,
     the liquid is filtered and then evaporated at reduced pressure  (2-4
     kPa, 0.02-0.04 atm) to collect the crystalline product.  The crystalline
     solid mass is then centrifuged, washed, and dried to yield hexamethylene-
     tetramine, usually of a purity better than 99%.  According to industry
     sources, the yield is 97% from formaldehyde or 93.5% from ammonia.
2.   Input Materials
     Formaldehyde - 3.58 kg of 37% solution per kg of product  (based on
                    97% yield)
     Ammonia - 0.519 kg/kg product (93.5% yield)
3.   Operating Parameters
     Temperature:  62-66°C (144-151°F)
     Pressure:  280 kPa (2.76 atm)
                             6-508

-------
4.   Utilities - Not given



5-   Waste Streams - Reactor off-gases contain formaldehyde,  ammonia, and



     methanol (from formaldehyde production).   If this stream is  incinerated,



     NO  will be emitted to the atmosphere.   The bleed line  from  the centri-
       X


     fuge wash, a waste water stream, will contain dissolved formaldehyde,



     ammonia, methanol, and hexamethylenetetramine.  The drier used in



     final preparation of hexamethylenetetramine will emit formaldehyde,



     methanol, and ammonia vapors to the air.



6.   EPA Source Classification Code - None



7.   References



     Hedley, W. H., et al., Potential Pollutants from Petrochemical



     Processes, Technomic Publishing Company,  Westport,  Conn., 1975.





     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,



     Interscience Publishers, New York, N.Y.,  Vol. 10 (1966), p.  98.






     Austin, G. T., "The Industrially Significant Organic Chemicals -  Part 6,"



     "Chemical Engineering," May 27,  1974,  p.  104.






     U.S. Patent 3,288,790  (November  29,  1966).






     Sittig M., Organic Chemical Process  Encyclopedia - 1969, 2nd Edition,



     Noyes Development Corp., Park Ridge, N.J.,  1969, p. 364.






     Chemical Technology, Barnes and  Noble  Books, New York, N.Y., Vol. 4



     (1972), p. 563.
                             6-509

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  206




         Dimethyl Sulfide (from methanol/carbon disulfide)







          4CH3OH  +  CS2  	>  2(CH3)2S   +  2H20  +  C02






 1.   Function - Dimethyl sulfide may be  produced by the reaction of




     methanol with carbon disulfide in the vapor phase in a fixed bed




     catalyst of activated alumina.   Methyl  mercaptan is  the chief




     by-product.









 2.   Input Materials




     Methanol




     Carbon disulfide




     Catalyst (activated alumina)




 3.   Operating Parameters




     Temperature:  370-535°C (698-995°F)




     Pressure:  414 kPa (4.08 atm)




 4.   Utilities - Not given




 5.   Waste Streams - Unreacted methanol  and  carbon disulfide should be




     present along with some methyl mercaptan and possible  H_S.




 6.   EPA Source Classification Code - None




 7.   References




     Sittig, M.,  Organic Chemical Process Encyclopedia -  1969, 2nd Edi-




     tion,  Noyes Development Corp.,  Park Ridge, N. J., 1969, p. 266.





     U.  S.  Patent 2,930,816 (March 29, 1960).
                             6-510

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 207


          Dimethyl Sulfoxide (NC>2 oxidation of (City ,.5)





                                        0
               (CH3)2S + N02 	^-     II    + NO

                                        S

                                     /\
                                   CH3     CH3


                                     (DMSO)



1.   Function - Dimethyl sulfide is oxidized with a dimethyl sulfoxide


     solution of nitrogen dioxide in a reactor at 40-50°C.  The reactor


     contents pass into a 100°C zone where dimethyl sulfide is sparged


     from the crude product with nitrogen.  The crude dimethyl sulfoxide


     (DMSO) is then neutralized and distilled.


          The flow of nitrogen dioxide into the reactor is kept insuffi-


     cient to oxidize all of the dimethyl sulfide so that all the N0_


     is converted to NO, which is insoluble in DMSO and escapes the exit-


     gas stream.  This stream passes through a heat exchanger to condense


     some of the dimethyl sulfide for recycle back to the reactor.  The


     gases remaining are conducted to a second reactor where excess N0~


     converts the residual sulfide to the sulfoxide.  The gases from


     this reactor contain substantially no organic matter and are oxidized


     with oxygen in a third reactor to regenerate the N0».  The gases


     finally pass through a DMSO scrubber to remove nitrogen dioxide


     prior to venting to the atmosphere.


2.   Input Materials


     Dimethyl sulfide


     Nitrogen dioxide in dimethyl sulfoxide solution



                             6-511

-------
3.   Operating Parameters




     Temperature:   20-50°C (68-122°F)




     Pressure:  101 kPa (1 atm)




4.   Utilities - not given



5.   Waste Streams - The gas stream which is vented from the DMSO scrubber




     to the atmosphere will consist of C02,  02,  N2, and -0.3% nitrogen




     oxides (NO ) .  The liquid stream from the scrubber contains N02,




     but this is recycled back into the process.  There could also be




     emissions of NO, N02, N203, and N2 from the second and third reactors,




     where additional conversion was accomplished.  Some liquid waste




     could originate from the neutralization of crude dimethyl sulfoxide.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 19 (1969), p. 332, 333.






     U.S. Patent 2,935,533 (May 3, 1960).






     Sittig, M., Organic Chemical Process Encyclopedia - 1969. 2nd Edition,




     Noyes Development Corp., Park Ridge, N.J.,  1969 , p. 268.






     Chemical Technology, Barnes and Noble Books, New York, N.Y.,




     Vol. 4 (1972), p. 585.
                              6-512

-------
 SECTION VI
NAPHTHALENE
   6-513

-------
          COAL AND PETROLEUM RESIDUES
                                                                                   NAPHTHALENES
       208
Ui
                      Acenaphthene
                     Naphthalene .
                                    209
                    >Alkylnaphthalenes
Naphthalene
                                                                                 210
                                                                    213
                                                                    214
                                                                     217
                                                                           Chloronaphthalenes
                                                                           Bromonaphtha 1 enes
                                                                                                               1- Nitronaphthalene
                                                          211                           212
                                                         	>.  1-Naphthylamine  	.	1-Naphthol
                                                                                   1-Naphthalene sulfonic acid
                                                                            218                                   219'
                                                                            	^  2-Naphthalene sulfontc acid	^ 2-Naphthol
                                                                   220
                                                                          Phthalic anhydride
                                                                    215
                                                                    216
                                                                          > Tetrahydronaphthalene
                                                                           DecahydronaphthaleneJ
                                                                                                        221
                                                                -} Tetrachlorophthalic anhydride
                                                                                                        222
                                                                                                               Phthalonitrile
                                                                                                               223
                                                                                                                     -)Anthraquinone
                                                                                                                224
                                                                                                                       Anthraquinone
                                                                                                          225
                                                                                                                       Phthalimide
                                                                                                                                     226
                                                                                              kAnthranilic acid
                                                           Figure  11.   Naphthalene  Section Chemical Tree

-------
 I
Ui
t-1
Ul
        HN00
           Heat
             I
             Nitration
                     210
Steam
1
_ HCI
fn s
211
Hydrogenationi
Nj
jT
          213
Chlorlnatlon
                                       n2QU4
                                  Water  1  Heat
                                             212
Solvent
1
Heat
I
208
Separation
                                                                        Catalytic  209
                                                                      Desulfur1zat1on
                                                                                                                                      Steam
                                                                     214
                                                           Bromlnatlon
          215
Hydrogenatlon
                                                                                  /TetrahydroA
                                                                                  (naphthalene)
HSO
at , H
i I
NaOH
\ ,
219]
Substitution and
acidification
                                                         -*N( 1-Naphtol
                                                Figure  12.   Naphthalene Section Process  Flow Sheet

-------
 I
Ul
                                               Cooling
TetrachO
rophthallc
,anhydr1dey
Phthalo-^
nltrlle
h"

Heat Oleum Clz
i i 1 >x>
221
ChloHnatlon
XI

Heat «,
222
Ammonolysis and
dehydration
~<3

Benzene
Cooling water 1 H2S01,
^-^ ^nl\\i?>°^
A.nthra-
qulnone


224,223

-
-------
INDUSTRIAL ORGANIC CHECMICALS                                PROCESS NO. 208




              Separation of the Naphthalenes (Alkylnaphthalenes)




1.   Function - Alkylnaphthalenes are found in coal tar, lignite




     tar, crude oil, drip-oil, heavy petroleum reformate, and gas oil




     (4%).  The alkylnaphthanes are separated from the naphthalene




     fractions usually either by fractionation or solvent extraction,




     or both, depending on the purity desired.








     In the separation by fractionation, the coal tar or petroleum




     fraction feed is sent to a fractionator which produces a naphthalene




     concentrate, and a middle product of alkylnaphthalenes,  and heavy




     aromatics bottoms.  The more common present commercial sources




     of alkylnaphthalenes are aromatic petroleum fractions of appropriate




     boiling range 227 - 268°C (440 - 515°F) cut.








     The solvent extraction process consists of first distilling the




     feed to get a middle cut in the 204 - 285°C (400 - 550°F) from




     the light cycle oil cut.  A solvent extraction process known




     as the Unisorb process is then used to separate the naphthalene




     homologs (alkylnapthalenes) from the lower aromatics.  An extract




     is produced containing over 85% of the naphthalene homologs (including




     acenaphthene) from the charge stock while rejecting lower aromatics.









     The process contains a fixed absorbent bed which is operated




     isothermally and at constant pressure.
                                6-517

-------
2.   Input Materials




               coal tar




               light cycle oils




               catalytic gas oils




               drip-oil




               reformer bottoms




3.   Operating Parameters - not given




4.   Utilities - not given




5.   Waste Streams - The air vent streams may contain paraffins or olefins as




     well as low boiling aromatics and solvent vapors.   The solvents




     commonly used in solvent extraction of alkylnaphthalenes are




     furfural and sulfur dioxide.




6.   EPA Source Classification Code - None




7.   References




     Brownstein, A. M., "U.S. Petrochemicals, Technologies, Markets,




     and Economics," The Petroleum Publishing Company,  Tulsa, Oklahoma,




     1972, pp. 213-215.






     Kirk-Othmer, Encyclopedia of Chemical Technology," 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 13 (1967), pp. 678-690.






     Broughton, D. B. and Hardison, L. C., "Unisorb Extracts Naphthalene




     Homologs," Hydrocarbon Proc. and Petrol. Refiner, 1962, 41(5),




     125-128.
                               6-518

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 209


                 Desulfurization of Hydrocarbons



               RCH2SH + CuCl2 —*- (RCH2S)2 + CuCl                     (1)



                    CuCl + 02 —>• CuCl2 + CuO                         (2)




               RCH2SH + H2 molyMate*  RCH3 + H2S


 1.  Function - Hydrocarbon feeds from petroleum sources may contain signi-


     ficant amounts of sulfur containing compounds principally hydrogen


     sulfide and mercaptans.  If these stocks are to be used in reactions


     involving catalysts, which are "poisoned" by sulfur compounds, these


     compounds must then be removed.


          There are three methods of treating hydrocarbon feeds to eliminate


     the undesirable sulfur compounds.  These may be classified as 1) oxida-


     tion, 2) catalytic desulfurization and 3) extraction.


     Oxidation - Mercaptans are converted to disulfides by exposing the


     hydrocarbon stream to cupric chloride, CuCl-.  The copper salt may be


     deposited on an inert substrate and used as a slurry or as a fixed


     catalytic bed.  Sulfur compounds are converted to the inactive disul-


     fides, but are still present in the feed.  CuCLmay be regenerated


     with air either during or after the reaction.


     Catalytic desulfurization - Mercaptans are converted to the lower


     boiling hydrocarbons by loss of hydrogen sulfide.  Hydrogen and a


     cobalt molybdate or alumina catalyst are used.  Oxygen and nitrogen


     compounds behave similarly to sulfur compounds and thus this  catalytic


     desulfurization process has become important in the upgrading of


     reformer feed stocks.  Commercial processes use temperatures  of

                                                        o
     350-450°C with pressures up to 1500 psig (100 Kg/cm ).


                            6-519

-------
    Extraction - In some cases,  the sulfur containing organics are ex-




    tracted and recovered from the hydrocarbon stock by adding an organic




    solvent to the caustic soda (or potash) which is being used as the




    extraction liquid.   The solution is subsequently regenerated by air




    blowing to oxidize  mercaptans to disulfides.




2.  Input Materials




    Naphthalene feed




    Hydrogen




    Catalyst - cobalt molybdate




3.  Operating Parameters




    Temperature 350-450°C  (662-842°F)




    Pressure    up to 10.34 MPa (102 atm)




    Catalyst    cobalt  molybdate




4.  Utilities




    Not given




5.  Waste Streams - Hydrogen sulfide, ammonia, mercaptans




6.  EPA Source Classification Code - None




7.  References




    Chemical Technology, Barnes  and Noble, New York, N.Y., Vol. 4




    (1972),  p.  55-56.
                           6-520

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 210




                           1-Ni t ronaphthalene
1.  Function - 1-Nitronaphthalene is prepared by nitrating naphthalene




    with mixed acid at 50-60°C.  The organic phase is separated and washed




    with hot water until free of acids.  The product contains about 0.5-1%




    2,4-dinitronaphthalene and 3% 2-nitronaphthalene.  These are easily




    removed by crystallization or by sweating (partial melting).  The




    nitration of naphthalene gives a 94% yield of the 1-isomer.  The




    relatively small amount of 2-isomer is easily removed with the other




    by-products by crystallization from alcohol.




2.  Input Materials




    Naphthalene




    Mixed Acids (1 part 62% HN03 + 3 parts 80% H2S04>.




3.  Operating Parameters




    Temperature:  50-60°C  (122-140°F)




    Pressure:  100 KPa (1 atm)




4.  Utilities - Not given




5.  Waste Streams - Air vent streams may contain oxides of nitrogen.  Waste




    streams from the washing and purification processes contain nitric and




    sulfuric acids, naphthalene, a-nitronaphthalene, 6-nitronaphthalene,




    2,4-dinitronaphthalene, and alcohols.




6.  EPA Source Classification Code - None
                              6-521

-------
7.   References




    Kirk and Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers,  New York,  N.Y.,  Vol.  2  (1963),  p.  83.





    Ibid..  Vol.  13 (1967)  p.  704.





    Howe, A.  P.  and Hass,  H.B.,  Ind.  Eng.  ChemQS. 251,  (1946).





    Astle,  M.  J.,  Industrial  Organic Nitrogen Compounds, Reinhold Publishing




    Corp.,  New York,  N.Y.,  1961 ,  p.  320-21.
                              6-522

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 211
        1-Naphthylamine (reduction of 1-nitronaphthalene)
              NO
                 + HC1 + 4H00 + 9Fe
•'••   Function - 1-Naphthylamine is prepared by the catalytic reduction

     of 1-nitronaphthalene with iron powder and hydrochloric acid.  The

     product mixture is made alkaline and 1-naphthylamine is distilled

     out with superheated steam.  The yield in this process approximates

     96%.  By-products of this reaction are 2-naphthylamine, 1,5-naphthalene

     diamine and l,l'-binaphthylamine.

2.   Input Materials

     1-Nitronaphthalene

     Iron powder

     Hydrochloric acid (dilute)

3.   Operating Parameters

     Temperature:  80 ° C

     Pressure:  100 kPa (1 atm)

4.   Utilities - Not available

5.   Waste Streams - Air vent streams would include HC1 vapor and hydrogen.

     Waste water streams contain hydrochloric acid, iron salts (including

     chlorides), some 1-naphthylamine and 1-nitronaphthalene.

6.   EPA Source Classification Code - None

7.   References

     Kirk and Othmer, Encyclopedia of Chemical Technology,  2nd Edition,

     Interscience Publishers, New York, N.Y., Vol. 2  (1963),  p.  83.


     Chemical Technology, Barnes and Noble, New York, N.Y., Vol.  4

     (1972), p. 520.
                             6-523

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  212




                     1-Naphthol (from l-naphithylamine)
                          200° 14 atm




1.  Function - The best and most economical process for the production of




    1-naphthol is the hydrolysis of 1-naphthylamine in aqueous sulfuric




    acid at 200°C and 14 atm.  pressure.   The yield is 95% and the product




    is pure.  The purity of the product  gives this process a distinct




    advantage over the alkali fusion of  the sulfonic acid derivative,




    the method of choice for 2-naphthol, since the product purity from




    this process is often too low for many applications.




2.  Input Materials




    1-Naphthylamine  1.06 kg/kg product




    Sulfuric acid (aqueous)




3.  Operating Parameters




    Temperature - 200°C  (392°F)




    Pressure - 1.42 MPa  (14 atm)




4.  Utilities - not given




5.  Waste Streams - Effluents would contain ammonium sulfate, sulfuric acid,




    1-naphthylamine and 1-naphthol.




6.  EPA Source Classification Code - None




7.  References
    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd  Edition.




    Interscience Publishers, New York, N.Y., Vol. 13  (1967)  p.  717.





    Chemical Technology, Barnes and Noble, New York, N.Y., Vol.  4  (1972) p.  326.
                              6-524

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 213


                            CHLORONAPHTHALENES
                                                   + HC1              (1)
                                   >80°C
                                                 Polychl°ronaphthalenes
                                        3,     3



1.  Function - Commercial quantities of 1-chloronaphthalene and mixtures


    of polychloronaphthalenes are produced by passing chlorine gas into


    molten naphthalene (80° C) .  If 1-chloronaphthalene production is


    favored, catalysts are not normally required.


         If a polychloronaphthalene mixture is the desired product, ferric


    or antimony chloride catalyst  must be added to the reaction mixture


    to promote chlorine addition.  Chlorination is begun at 80°C, and the


    temperature is slowly raised as the reaction proceeds.  During the


    process, the chlorination mixture is continually agitated.


         When the desired point has been reached, the chlorination mixture


    is neutralized by stirring in the molten state with aqueous alkali,


    washed with water, and dried under vacuum.


2.  Input Materials


    Naphthalene


    Chlorine


    Sodium hydroxide


    Water
                               6-525

-------
3.  Operating Parameters




    Temperature - >_ 80°C (176°F)




    Pressure - not given




    Catalyst - for polychloronaphthalenes FeClg or SbCl3 (0.5%)




4.  Utilities - Not given




5.  Waste Streams - Wastewater streams from washing operations probably




    contain sodium chloride, sodium hydroxide,  and traces of naphthalene




    and chlorinated naphthalenes.   Chlorine gas may be discharged from




    various processing equipment.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol.  5  (1964)   p.  300.
                              6-526

-------
INDUSTRIAL ORGANIC CHECMICALS                                PROCESS NO.  214


                               Bromonaphthalenes
                                                           Br


                                                   f^Y^
                                                                + HBr



!•   Function - ^-Bromonaphthalene and lesser amounts of dibromonaphthalenes


     are produced by the interaction of naphthalene and bromine  in car-


     bon tetrachloride or water.  Iron catalysts are required if car-


     bon tetrachloride serves as the reaction medium.  Hydrogen  bromide


     by-product is allowed to escape, preferably being washed by in-


     coming raw material.  The crude product is then dried and frac-


     tionated, giving oc-bromonaphthalene in 72 - 75% yield.


2.   Input Materials


     Naphthalene - 0.82 - 0.86 kg/kg product


     Bromine


     Water or carbon tetrachloride


3.   Operating Parameters


     Temperature:  100°C  (212°F)


     Pressure:  not given


     Catalyst:  iron (in CCl^)


*•   Utilities - Not .given


5.   Waste Streams - Air vent streams contain hydrogen bromide,  the


     principal by-product of the reaction.  Carbon tetrachloride will


     be present in the air vent streams from solvent recovery systems,


     when this solvent is used as the reaction medium.  Waste streams


     will contain HBr, naphthalene, and some bromonaphthalenes when


     water is used as the solvent medium.  Sodium bromide will be


     present in waste water when caustic soda is used to neutralize


     the HBr absorbed in the water.

                                6-527

-------
6.   EPA Source Classification Code - None




7.   Reference




     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers,  New York,  N.Y.,  Vol.  3 (1964), p. 775.
                               6-528

-------
INDUSTRIAL ORGANIC CHECMICALS                                PROCESS NO. 215




                             Tetrahydronaphthalene
1.   Function - 1,2,3,4-Tetrahydronaphthalene, more commonly known




     as tetralin, is produced exclusively by the catalyic hydro-




     genation of naphthalene.  This reduction is carried out at 150°C*




     in the presence of nickel or modified nickel catalysts.








     Since active nickel catalysts are poisoned by sulfur compounds,




     represented predominatly in naphthalene by thianaphthene,




     commerical naphthalene must be desulfurized prior to hydro-




     genation.  This is accomplished by treatment with Sodium or by




     a catalytic dehydrosulfurizing process.




2.   Input Materials




     Naphthalene (desulfurized)




     Hydrogen




3.   Operating Parameters




     Temperature:  150°C  (302°F)




     Pressure:  100 - 200 KPa (1 - 2 atm)




     Catalyst:  nickel or modified nickel




4.   Utilities - Not given








*    Heat-exchanges are necessary to control the temperature of this




     exothermic reaction, since destructive hydrogenation occurs




     at high temperatures.
                                6-529

-------
5.    Waste Streams - Air vent streams from the reactor contain hydrogen




     and may have small quantities of tetrahydronaphthalene and naphthalene.




     When the product is purified by extractive distillation the air




     vent streams may contain tetrahydronaphthalene,  naphthalene and some




     solvent (diethylene glycol for example).




6.    EPA Source Classification Code - None




7.    References




     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 13 (1967), p. 676-77.
                               6-530

-------
INDUSTRIAL ORGANIC  CHEMICALS                                PROCESS NO. 216




                            Decahydronaphthalenes
                                                  CO
L.   Function - Commercial decahydronaphthalene,  a mixture  of cis-




     and trans-isomers more commonly known as Decalin,  is prepared




     by the catalytic hydrogenation of naphthalene.* The reaction may




     be carried out in the fused-state (above 100°C) or in  the liquid




     phase at 2.5 - 4.0 MPa (25 - 40 atm) and 200 - 260°C.  Both pro-




     cess variations employ copper or nickel catalysts.




2.   Input Materials




     Naphthalene (desulfurized)




     Hydrogen




3.   Operating Parameters




     Temperature:  fused state - >100°C  (212°F)




                   liquid phase - 200 - 260°C  (232-500°F)




     Pressure:  fused state - not given




                liquid phase - 2.5 - 4.0 MPa  (25-40 atm)




     Catalyst:  copper or nickel




4.   Utilities - Not given




5.   Waste Streams - Air vent streams from the reactor  will contain




     hydrogen and some naphthalene and decahydronaphthalene.  Air vent




     streams from the purification system contain naphthalene decahydro-




     naphthalene and solvent when extractive distillation is used to




     purify the product.









*    The naphthalene feed is desulfurized by the methods discussed in




     Process No.  209.



                               6-531

-------
6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience  Publishers,  New York,  N.Y., Vol. 13 (1967), p. 677.
                            6-532

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  217




                        1-Naphthalenesulfonic Acid
1.  Function - Commercially, 1-naphthalenesulfonic acid is prepared




    by sulfonating naphthalene with 98% sulfuric acid below 60°C.




    Isolation is accomplished by liming, conversion of the calcium salt




    to the sodium salt by soda ash, and drying.   The technical product




    contains about 77.5% 1-naphthalenesulfonate, 10.2% 2-naphthalenesulfonate,




    5.7% disulfonate, 2.7% sodium sulfate, and 3.7% water.




2.  Input Materials




    Naphthalene




    Sulfuric acid (98%)




    Lime




    Soda ash




3.  Operating Parameters




    Temperature - <60°C (140°F)




    Pressure - 101 kPa (1 atm)




4.  Utilities - Not given




5.  Waste Streams - Air vent streams from the reactor will contain some




    sulfur dioxide and small quantities of naphthalene.  The overhead




    gases from the concentrator contain sulfur dioxide and naphthalene.




    Calcium sulfate and calcium carbonate are recovered from neutralization




    and washing steps.  Waste wash water contains some sulfuric and




    naphthalene sulfonic acids.




                               6-533

-------
6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience  Publishers,  New York,  N.Y.,  Vol.  13  (1967),  p.  700.





    Chemical Technology,  Barnes  and Noble Books, New York,  N.Y.,  Vol.  4




    (1972),  p.  597.
                            6-534

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 218




                       2-Naphthalenesulfonic acid
1.  Function - 2-Naphthalenesulfonic acid is commercially prepared by




    treating naphthalene with about one part of 93-96% sulfuric acid




    at 160°C.




         1-Naphthalenesulfonic acid, which constitutes about 15% of the




    crude product, is hydrolyzed back to naphthalene by steam, and the




    latter is recovered by steam distillation.  The sulfonation mixture




    is then added to water, and 2-naphthalenesulfonic acid is precipi-




    tated as the sodium salt by the addition of sodium chloride.




2.  Input Materials




    Naphthalene




    Sulfuric acid (93-96%)




    Sodium chloride




    Water




3.  Operating Parameters




    Temperature - 160°C  (320°F)




    Pressure - Not given




4.  Utilities - Not given




5.  Waste Streams - Sodium chloride, sodium sulfate, and caustic acid may




    be present in process wastes.
                               6-535

-------
6.  EPA Source Classification Code - None




''•  References




    Klrk-Othmer,  Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience  Publishers,  New York,  N.Y.,  Vol.  13,  (1967),  p.  700.
                              6-536

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 219
              2-Naphthol (from 2-naphthalenesulfonic acid).
                        SO Na                            ^^  ^^  ^ONa
                                    NaOH, 325°C
                          ONa
•"-•  Function - In commercial practice, 2-naphthol is prepared by fusing

    the sodium salt of 2-naphthalenesulfonic acid with sodium hydroxide

    in a cast-iron or nickel-steel kettle at 325°C.  The melt is run into

    cold water, acidified with sulfuric acid, and the free 2-naphthol is

    separated.  The product is washed well with water, distilled jg. vacuo,

    and sublimed.  The yield is almost 80% of the theoretical.

2.  Input Materials

    2-Naphthalenesulfonic acid (sodium salt) - 1.80 kg/kg product

    Sodium hydroxide

    Sulfuric acid

    Water

3.  Operating Parameters

    Temperature:  325°C (617°F)

    Pressure:  not given

4*  Utilities - Not given

5.  Waste Streams - The waste water from washing operations probably contains

    quantities of sodium sulfate, naphthalenesulfonic acids,  and naphthols.
                               6-537

-------
6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology.  2nd Edition,




    Interscience Publishers,  New York, N.Y., Vol. 13 (1967)  p.  718.
                              6-538

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 220

              Phthalic Anhydride (from naphthalene)
                       + 902 (air) 	>-  2 K)l   0 + 4H20 4- 4C02

                                                 0
 1.  Function - As of January 1, 1975, 36% of the U.S. capacity for

     phthalic anhydride production was based on naphthalene feedstock.

     Both petroleum naphthalene (>80°C)  and desulfurized coal-tar naphtha-

     lene (78°) are converted to phthalic anhydride by vapor-phase air

     oxidation in the presence of a vanadium pentoxide catalyst.

          There are three processes in use for the air oxidation of

     naphthalene.  Two of these include a fixed catalyst bed process

     and these are adaptable to both naphthalene and o-xylene feed stocks.

     The third process involves a fluidized catalyst bed and has been

     applied only to naphthalene.  A significant by-product of all three

     processes is maleic anhydride and maleic acid.  Small amounts of

     benzoic acid are recovered from the fixed bed processes.

          The most widely used oxidation processes are the fixed bed pro-

     cesses.  These differ in the catalyst composition employed and the

     temperature range of operation.  The original process employed a

     catalyst consisting of 65% ^2°5' 30% Mo03 and 5% CuO or Mn^.  It

     operated at 400-475°C and gave yields of phthalic anhydride of

     approximately 65%.

          The von Heyden process, a low-temperature, fixed-bed air oxidation,

     also accounts for considerable naphthalene-based phthalic anhydride

     production.  Reaction temperatures are maintained in the 350-360°C

     range with 4-5 sec contact time.  The catalyst is usually vanadium


                            6-539

-------
    pentoxide on silica with 20-30% potassium sulfate.  Yields in the




    neighborhood of 82% are obtained by this process with limited by-




    production of maleic anhydride, maleic acid, etc.




         The third process employs an air-fluidized bed of V^O,- into which




    is injected naphthalene in vapor form.  The bed is maintained at




    340-380°C and 1 atmosphere.  The air/feed ratio can be maintained at




    2 to 3x a lower value than in the fixed bed system.  It is not possi-




    ble to use o-xylene as a feedstock in this system and as a result




    the use of this system is decreasing as the difficulty in obtaining




    naphthalene feedstock increases.  Yields from this process approxi-




    mate 85%.  The vaporous effluent in all these processes is passed




    through heat exchangers where phthalic anhydride crystallizes and




    deposits on the walls.  Heat is then applied and the crude product




    is melted out and collected.  Using this procedure 98-99% of the




    phthalic anhydride in the effluent is recovered.




         The crude product is purified by a chemical soak   in sulfuric




    acid and caustic followed by a heat soak at 150-250°C.  This heat




    treatment removes water and other impurities such as maleic acid




    and anhydride as well as benzoic acid.  The residual phthalic anhydride




    is vacuum distilled in batch or continuous operation.




2.  Input Materials - Basis - 1 metric ton phthalic anhydride




    Naphthalene (>80° or desulfurized) 1,250 kg (2,756 Ibs)




    Air (15°C, 59°F) 26,000 m3 (918, 181 ft3)




    Sulfuric acid




    Sodium hydroxide




    Water
                          6-540

-------
3.   Operating Parameters


     Temperature:  High temperature, fixed bed


                   Von Heyden


                   Fluidized bed


     Pressure:     Von Heyden


                   Fluidized bed


     Catalyst:     High Temperature, fixed bed





                   Von Heyden
                                                 400-475°C (752-887°F)


                                                 350-360°C (662-680°F)


                                                 340-380°C (644-716°F)


                                                  48-55 kPa (0.47-0.54 atm)


                                                 101 kPa (1 atm).


                                                  65° V205, 30% Mo03, 5%


                                                  (CuO or Mn_0.)
                                                       on Si02 + 20-30%
     Reaction
     Time:
                   Fluidized bed


                   Fluidized bed


                   Von Heyden


                   Fixed bed
Finely divided


19-20 sec


4-5 sec


0.1-0.6 sec
4.   Utilities  - Basis 0.72 kg/sec capacity (50M Ib/yr)


     Water


          Cooling, makeup (stream generation), makeup (cooling) - 61,000 gph


     Electricity


     Process  - 2.0 MW


     Utilities - 88 kW

                  o
     Fuel - 3.3 dm /sec average (420 cfh)

                  *
5.   Waste Streams


     Spray scrubber effluent (water)


     Phthalic anhydride - trace


     Maleic anhydride - 16.7 Kg/Mg phthalic anhydride


     Spray scrubber effluent (air)
  These values are characteristic of the first fixed-bed process.
                             6-541

-------
5.   Waste Streams (continued)




     Naphthalene - trace




     Phthalic anhydride - 9.5 Kg/Mg  phthalic  anhydride product




     Maleic anhydride - 26 Kg/Mg  phthalic  anhydride




     Other - 23.7 Kg/Mg phthalic  anhydride (assumed  to be organic in nature)




     Phthalic anhydride recovery  columns  (solid)




     Phthalic anhydride - 69.3  kg/Mg phthalic anhydride




     Other - 51 kg/Mg phthalic  anhydride  (assumed  to be organic in nature;




     specific compound information not  available)




6.   EPA Source Classification  Source - None




7.   References




     Austin, G. T.,  "The Industrially Significant  Organic Chemicals -




     Part 8," "Chemical Engineering," July 22, 1974, p. 109.






     Sittig, M.,  Chemicals from Aromatics,  Noyes Development Co.,




     Park Ridge,  N.J.,  1966, p. 50.






     Kirk-Othmer,  Encyclopedia  of Chemical Technology. 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 15  (1968), p. 450.







     "1971 Petrochemical Handbook," "Hydrocarbon Processing," November




     1971, p. 189.






     Sittig, M., Pollution Control  in the  Organic Chemical  Industry.




     Noyes Data Corp., Park Ridge,  N.J.,  1974, p. 186-188.






     Lowenheim, F. A. and Moran, M. K., Industrial  Chemicals,  4th Edition,




     John Wiley and Sons, New York,  N.Y.,  1975, p.  658-660.
                            6-542

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 221




                      Tetrachlorophthalic Anhydride
                          0 + 4C1,
0 + 4HC1
                                                 Cl
1.  Function - Tetrachlorophthalic anhydride is produced by the high-




    temperature chlorination of phthalic anhydride in fuming sulfuric




    acid.  Antimony pentachloride may be used as a catalyst.




2.  Input Materials




    Phthalic anhydride




    Chlorine




    Sulfuric acid (fuming)




3.  Operating Parameters - Not given




4-  Utilities - Not given




5.  Waste Streams - Wastewater from the acid scrubber may contain sodium




    hydroxide, and traces of phthalic anhydride, and various chloro-




    substituted phthalic anhydrides.




6.  EPA Source Classification Code -None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition, Inter-




    science Publishers, New York, N.Y., Vol. 15 (1968), p. 446.
                               6-543

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 222

                Phthalonitrile (from phthalic anhydride)
                                                     CN
                                                        + 3H 0
                                                     CN     Z
1.  Function - One competitive route to phthalonitrile involves the

    vapor-phase reaction of phthalic anhydride and ammonia.  This conver-

    sion takes place at high temperatures over an alumina catalyst.

         Phthalimide and/or phthalamide intermediates are probably involved.

2.  Input Materials

    Phthalic anhydride

    Ammonia

3.  Operating Parameters

    Temperature - Not given

    Pressure - Not given

    Catalyst - Alumina

4.  Utilities - Not given

5.  Waste Streams - Effluents from the ammonia stripper and/or separator

    probably contain ammonia, phthalic anhydride, phthalonitrile, and

    reaction intermediates such as phthalamide and phthalimide.

6.  EPA Source Classification Code - None
                              6-544

-------
7.   References




    Kirk-Othmer,  Ehcylcopedia of Chemical Technology,  2nd Edition,




    Interscience Publishers, New York, N.Y.,  Vol.  15  (1968), p.  447.





    Throdahl, M.  C., Zerbe, R. 0., and Beaver,  D.  J.,  Ind.  Eng. Chem.,




    43, 926 (1951).
                                6-545

-------
INDUSTRIAL ORGANIC CHEMICALS
                                                      PROCESS NO.  223
                       Anthraquinone (solvent method)
                .0 +
              CO
                               50-60°C
                               	!

                               2A1C1.
                                                     COC,H
                                                     COO-Aid,
                          100-110°C
                         cone.
1.  Function - The most frequently used route  to anthraquinone involves



    the condensation of phthalic anhydride and benzene to give o-benzoyl-



    benzoic acid which undergoes ring closure  by dehydration.   Overall



    this can be considered a modified Friedel-Crafts  reaction.  Two



    general methods are utilized to produce the product,  the solvent



    method and the ball mill method.



         In the solvent method,  phthalic anhydride is added to a cast-iron



    kettle containing aluminum trichloride and a large excess of benzene.



    An aluminum chloride complex of o-benzoylbenzoic  acid is formed with



    an evolution of heat.   The temperature is  regulated so that it slowly



    reaches 50-60°C.   Hydrogen chloride evolved during the reaction is



    discharged to a condenser-scrubbing system.



         When the evolution of HC1 is complete the reaction mass is trans-



    ferred to an acid proof reactor containing dilute H-SO, which decomposes



    the complex to o-benzoylbenzoic acid and water soluble aluminum sulfate.



    The water and benzene  solutions are separated and the o-benzoylbenzoic



    acid recovered by treating the benzene phase with aqueous sodium
                              6-546

-------
    carbonate.   The benzene is separated,  distilled and recycled.   The




    sodium salt of o-benzoylbenzoic acid is neutralized and filtered out




    of the aqueous phase.




         The o-benzoylbenzoic acid is washed,  dried and treated with




    concentrated l^SO^ or oleum at 100-110°C.   Practically quantitative




    yields of high-purity anthraquinone are obtained.   If further purifi-




    cation is required it may be done by sublimation.




2.  Input Materials




    Phthalic anhydride - 0.75 kg/kg product




    Benzene




    Aluminum chloride (anhydrous)




    Sulfuric acid




    Sodium carbonate




    Sodium hydroxide (HC1 scrubber)




    Water




3.  Operating Parameters




    Temperature:  condensation - 50-60°C  (122-140°F)




                  dehydration - 100-110°C (212-230°F)




    Pressure:  not given




4.  Utilities - Not given




5.  Waste Streams - The principal pollutant sources in this process are




    most likely wastewater effluents from the HC1 scrubber, phase  separations,




    and filtering and washing operations.




    Hydrogen chloride scrubber
                               6-547

-------
    Sodium chloride and caustic soda are probably present in this waste
    stream

    Aqueous phase separation

    The discarded aqueous phase of the aluminum chloride complex decom-
    position product is likely to contain sulfuric acid as well as various
    aluminum salts.

    Benzene extraction

    The extract water probably contains quantities of benzene and other
    organics, i.e., purification solvents.

    Filtering/washing operations

    Hydrochloric or sulfuric acid and various  sodium salts are probably
    the principal pollutants in the waste stream.

    Indeterminate quantities of phthalic anhydride,  benzene, and o-benzoyl-
    benzoic acid may be present in all wastewater effluents.

6.   EPA Source Classification Code - None

7.   References

    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed., Interscience

    Publishers, New York,  N.Y., Vol.  2, (1963), p.  435.
                              6-548

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  224




                     Anthraquirione (ball mill method)
                                   IUSO,
                                  5~20% oleum
                                                + H20 + 2A1C13




1.  Function - As mentioned in Process No. 223, the ball mill method is




    one of two general routes to anthraquinone from phthalic anhydride and




    benzene.  In this process, the reactants are mixed in practically




    stoichiometrical quantities with only a slight excess of benzene pre-




    sent.  Consequently, the product of the condensation reaction is




    discharged as a dry aluminum chloride complex of o-benzoylbenzoic acid




    which can be ring-closed directly to anthraquinone by treatment with




    strong sulfuric acid or 5-20% oleum.




         Alternately, the complex may be anhydrously decomposed to o-benzoyl-




    benzoic acid and subsequently dehydrated by the method described in




    Process No. 223 .  The yield and quality of the product obtained by this




    procedure are almost the same as in the solvent method.




         However, the ball mill operation has two distinct advantages over




    the solvent method.   Practically no solvent recovery is necessary, and




    the liberated hydrogen chloride is free of corrosive action since decom-




    position of the aluminum chloride complex is carried out anhydrously.




2.  Input Materials




    Phthalic anhydride - 0.75 kg/kg product




    Benzene
                               6-549

-------
2.  Input Materials (continued)




    Aluminum chloride (anhydrous)




    Sulfuric acid or oleum (5-20%)




    Aqueous sodium hydroxide (HC1 scrubber)




3.  Operating Parameters - see Process No.  224.




4-  Utilities - Not given




5.  Waste Streams - Wastewater from the HC1 scrubber probably contains sodium




    chloride, sodium hydroxide,  and traces  of phthalic anhydride and benzene.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed., Interscience




    Publishers, New York, N.Y.,  Vol. 2  (1963),  p. 436.
                               6-550

-------
INDUSTRIAL ORGANIC CHEMICALS
                               Phthalimide
PROCESS NO.  225
1.  Function - On an industrial scale, phthalimide is produced by




    saturating molten phthalic anhydride with dry ammonia and heating




    the mixture to 170-240°C under pressure.




         Alternately, the cyclic imide can be prepared in 95-97% yield




    by heating the anhydride with concentrated aqueous ammonia solution and




    eventually raising the temperature to 300°C.  Phthalimide is isolated




    by evaporating the product solution to dryness.




2.  Input Materials




    Phthalic anhydride - 1.05 kg/kg product




    Ammonia (anhydrous or aqueous)




3.  Operating Parameters




    Temperature - anhydrous process - 170-240°C  (338-464°F)




                  aqueous process - 300°C  (572°F)




    Pressure - anhydrous process - elevated




               aqueous process - atmospheric




4.  Utilities - Not given
                               6-551

-------
5.  Waste Streams - In the anhydrous process,  the principal pollutant




    source is probably the ammonia absorber off-gas,  containing ammonia




    and smaller quantities of phthalic anhydride.   In the aqueous




    process, waste gases from evaporation may  also contain quantities




    of ammonia and phthalic anhydride.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd Ed.,  Interscience




    Publishers, New York,  N.Y.,  Vol. 15  (1968),  p. 447.
                              6-552

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INDUSTRIAL ORGANIC CHEMICALS




                           Anthranllic Acid
                                   NaOH
                                                  PROCESS NO. 226
1.
2.
3.
                    COOH
                            + NaOCl
                                     NaOH
                                                             NaCl
4.
               •CONH-



Function - Anthranilic acid is prepared in high yield by the action




of sodium hypochlorite or hypobromite on phthalimide in alkaline




solution at 80°C.  The ring is opened by hydrolysis and the phthal-




amidic acid intermediate undergoes the Hofmann reaction.




     Anthranilic acid is precipitated on neutralization of the




alkaline solution.




     In commercial operations, sodium hypochlorite or hypobromite




is probably prepared in situ by passing chlorine or bromine into




the sodium hydroxide solution.




Input Materials




Phthalimide




Sodium hydroxide




Chlorine or bromine




Water




Mineral acid




Operating Parameters




Temperature:  80°C (176°F)




Pressure:  not given




Utilities - Not given
                             6-553

-------
5.   Waste Streams - Hypochlorous acid or the hypobromous acid may be




     detected in any air vent streams from the reactor.  Chlorine and/or




     bromine will also be present.   Waste water streams contain some




     sodium chloride and small quantities of anthranilic acid.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers,  New York,  N.Y.,  Vol.  3 (1964),  p. 434.
                            6-554

-------
SECTION VII
 PARAFFINS
 6-555

-------
ETHANE,PROPANE,BUTANE_
227
241
                   Butyraldehyde
                                    233
                Acetic acid

                Acetone

                - Butyric acid

                ' Ethyl acetate
              -^Ethyl  alcohol

              -^ Formic acid

              -} Methyl acetate

                 Methyl alcohol

                ^Methyl ethyl  ketone
              -^Propionic acid

              -> n-Propyl alcohol
      -^Butadiene
         234
                 Carbon  tetrachloride
                                              PARAFFINS
                                    -^Butyric acid
                                    228
                                         -$•  n-Propyl amines
                                          229!
                                                -^Propionaldehyde
                                          230
                                            n-Propyl chloride
                                        249
                                       -^Benzophenone
        235
 237
           Perch!oroethylene-

          ,Nitroethane

           Nitromethane
                               236
                                           -> Hexachloroetnane
238
 ^n-Butenes
           Nitropropanes
                   239
                                 Polybutenes
                         240
                              j> Butadiene
                                                                        231
n-Propylamines
                                                                               232
                                                                                      Butyronitrile
   PENTANE , ISOPENTANE
 242
248
              Amyl chlorides .
              Dichloropentanes
-^ Isoamylenes
                        247
                                    243
                                         > Amyl ami nes
                                                              244
                                    04 C
                                           Amy! mercaptans
                              ^Isoprene
       ^Isoprene
                                                                                        alcohols.
                                                                             Amyl ether
                                                                           ^ Pentylenes
                      Figure 13.   Paraffins Section Chemical Tree
                                      6-556

-------
 I
Ul
Ul
       Cooling water
           "Tit      1

                         227
                Oxidation
Acetic acid
Methyl ethyl  ketone
Propionic acid
Butyric acid
Formic acid
Ethyl acetate
Methyl acetate
Ethyl alcohol
Methyl alcohol
Acetone
Propyl alcohol
Butyraldehyde
                                                                                                                                                -WJJ
                                                                            Heat
                                                                                                                        Amination
                                                                                                                            n-Propyl ale.
                                                                                                                     st!am   I   Na'CN

                                                                                                                                 2321X1
                                                  Figure  14.    Paraffins  Section Process  Flow  Sheet

-------
 Benzene    Cooling
r 1T- iT
                                               Steam
Heat HN03
| I >O
Nitromethane " 	 237 Xj
Ml ti*nni"nn*inpfl ^*— ^ MIIIMII imi ^*i^m
NHrobutane

1
Ui
Ul
oo
Heat
e241j^
NaOH Cooling
H1T12 It
234.235
""• 	 "• Clilut iiidliuii
water
A
*B

Heat Quench water
238


N3**
O ^
{ Carbon \
•"1 tetra- 1 —
V chloride /
fc/Perchloro.- \ —
\ ethyl ene t
n-Butenes 1
»
249
Condensation
NaOH 'Heat C1,2
\ \ \ *
»»i



236
Chlorlnatlon
A1C13 Butane
239
Pnl vtnc^vi T/fUnn

CH3CN
TI n
Ox1dat1ve 24°
dehydrogenatlon
w Ben zophenon
< { ^
__BJHexachloro
^^ ethane
^_^
Jp x^ — ^>
^2S /
^^^j^ r
1 V_
<$ ^~"
•< /
V
Figure 14.  Paraffins  Section Process Flow Sheet (Cont.)

-------
Coolii
ig water
u
C12
242
Chlorlnatlon
I 1
Cooling water

Cooling water
Heat Water I I
* (S
248
Dehydrogenation

tiexane
1H2SO,,
HaOH^
246
Extraction
XI
Ui
Ui
HH3


243
Amonolysis
n Heat
XI

NaOH, aq. Alcohol
[ £ *
244
Hydrolysis
x|
NaSH
1 />
245 1X1
Substitution 1
Cooll
St
ng water
ea?J|
Heat Wat
\ \
247
Dehydrogenation
er
XJ
                                  Figure 14.   Paraffins Section Process Flow Sheet  (Cont.)

-------
 INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  227


            Acetic Acid and  by-products  (oxidationof n-butane)



                C4H10 + 02 (Air) 	* CH3COOH + by-products



 1.   Function -  The most economical  route to acetic acid, and one which


     accounted for 46%  of the total  1973 production in  the United States,


     is  the liquid-phase oxidation of a natural gas or  light petroleum


     fraction containing 95% n-butane.


         The oxidation  of n-butane  is carried out  at 150-225°C and 5.5 MPa


     (-800  psig) in the  presence of  a transition-metal  acetate, usually cobalt


     acetate.  Compressed air and liquid butane are fed to a liquid phase


     reactor.  Reaction  product is withdrawn, cooled and sent to a decanter


     for phase separation.  The hydrocarbon-rich phase  is recycled to the


     reactor.  The  aqueous phase is  sent to the recovery and purification


     system.  Off-gases primarily nitrogen, oxides  of carbon and n-butane,


     are scrubbed for butane recovery and vented through an expander turbine


     to recover energy.   Low boiling organics are separated from the crude


     acetic acid by conventional distillation.   Recovered by-products include

    methanol, acetone,   n-propyl alcohol and methyl ethyl ketone.  Depending


     on reaction conditions,  formic, propionic and  butyric acids and their


     esters  (methyl, ethyl) may also be recovered.  Azeotropic  distillation is


     used to purify  the  crude acetic acid to glacial acetic acid.




2.  Input Materials - Basis  - 1 metric ten  products

            *
    n-Butane  -  1.08 kg/kg acetic acid          965 kg (2127 Ibs/ton)


    Alr                                         3750 m3 (1.32 x 105 ft3/ton)
*
 The hydrocarbon feed also contains some propane, ethane,  isobutane,  and
 other lights.

                                6-560

-------
3.   Operating Parameters




    Temperature - 150-225°C (302-437°F)




    Pressure - 5.52 MPa (54.5 atm)




    Catalyst - cobalt acetate




*•   Utilities - Not given




5.   Waste Streams - Various wastewater streams from the purification section




    may contain acetic acid and a variety of alcohols,  aldehydes,  ketones,




    esters, other organic acids, ethers, and high-boiling impurities.




    Quantities of butane, propane, ethane, etc., are probably discharged  to




    the atmosphere from the reaction section.  No specific information was




    available.




6.  EPA Source Classification Code - None




7.  References




    Austin, George T., "The Industrially Significant Organic Chemicals -




    Part 1," "Chemical Engineering," January 21, 1974,  p. 128,129.





    Ibid., Part 4, April 15, 1974, p. 89,90.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Interscience




    Publishers, New York, N.Y., Vol. 8  (1965)  p. 396,397.







    Lowry, R. P. and Aguilo, A.,  "Hydrocarbon Processing," November, 1974, p. 105.





    Lowenheim, F. A. and Moran, M.  K.,  Industrial Chemicals, 4th Edition, John




    Wiley and Sons, New York, N.Y., 1975, p. 11,12.
                                6-561

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 228




                n-Propyl Amines (from n-prbpyl alcohol)
1.  Function - Propyl alcohol reacts with ammonia at moderately high



    temperature (300-500°C) and pressures of 1-20 MPa (10-200 atm) to yield



    mono-, di- and tripropyl amines.  The mixture of amines formed is thought




    to be in equilibrium and the yield of each of them can be increased by



    recycling the others.   The product ratio may also be controlled by the



    ratio of reactants and the operating temperature-  A catalyst consisting



    of activated alumina is commonly used in these reactions.  Silica, and



    magnesium oxide as well as alumina containing Fe_0_, TiO_ and cobalt,
                                                    Z. j     £•


    nickel and chromium oxides have been used to promote amine formation.



2.  Input Materials



    n-Propyl alcohol



    Ammonia



3.  Operating Parameters



    Temperature:  300-500°C  (572-932°F)



    Pressure:  1-20 MPA (10-200 atm)



    Catalyst:  alumina
                               6-562

-------
4.  Utilities - Not given




5.  Waste Streams - Waste effluents from strippers,  separators,  etc.,




    may contain ammonia, n-propyl alcohol,  and all of the n-propylamines.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.-Y., Vol.  2 (1963),  p.  117.







    Astle,  M.J.,  Industrial Organic Nitrogen Compounds,  Reinhold Publishing




    Corporation, New York, N.Y.,  1961 , p. 8-9.
                               6-563

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 229
                 Propiorialdehyde .(from n-propyl alcohol)
!•  Function - Small quantities of propionaldehyde are produced by the




    dehydrogenation of n-propyl alcohol.  This conversion is carried




    out at 200- 300° C in the presence of copper compounds or iron oxide.




         Reaction equipment is usually stainless steel, but aluminum




    is also satisfactory.




2.  Input Materials - n-propyl alcohol




3.  Operating Parameters




    Temperature - 200-300°C  (392-572 °F)




    Pressure - Not given




    Catalyst - copper compounds (copper chromite) or iron oxide




4.  Utilities - Not given




5.  Waste Streams - Waste gases from this process may contain hydrogen,




    n-propyl alcohol,  and propionaldehyde.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Ed. , Interscience




    Publishers, New York, N.Y. , Vol. 16   (1968), p. 550.
                               6-564

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 230

               n-Propyl Chloride (from n-propyl alcohol)
                                 ZnCl2
                            HC1  	
1.   Function - n-Propyl chloride is produced by heating n-propyl alcohol

     in concentrated hydrochloric acid.  Zinc chloride catalyzes the re-

     action.

2.   Input Materials

     n-Propyl alcohol

     Hydrochloric acid  (cone.)

3.   Operating Parameters

     Temperature:  not  given

     Pressure:  not given

     Catalyst:  ZnCl2

4.   Utilities - Not given

5.   Waste Streams - Water-spent catalyst, propyl chloride, and tars

     may be present in  the separator waste effluents.

6.   EPA Source Classification Code - None

7.   Reference

     Chemical Technology, Barnes and Noble Books, New York, N.Y., Vol. 4

     (1972), p. 192, 270.
                            6-565

-------
 INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  231



                n-Propyl Amine (from n-propyl chloride)
                            2NH2
                                     NH

          CH.CH0CH0NH_ + CH.CH.CH-Cl —^ (CH,CHOCH_) 9NH + NH, Cl
            3  i  L  L     3  /  2.           j  £.  & *.       n
                                     m
^--  Function - n-Propyl amine is commercially produced by the reaction of



    n-propyl chloride and ammonia.  The reaction is carried out under



    pressure at moderately high temperatures (160-170°C).  Normally the



    primary, secondary and tertiary amine derivatives are formed.  The



    primary amine yield may be maximized by operating at excess ammonia



    concentrations.  Yields of secondary and tertiary amines are  increased



    by recycling the primary amine.



2.  Input Materials



    n-Propyl chloride



    Ammonia



3.  Operating Parameters



    Temperature:  160-170°C (320-338°F)



    Pressure:   2.7 MPa (27 atm)



4-  Utilities - Not given



5.  Waste Streams - Waste effluents from the ammonia stripper may contain



    quantities of ammonia, propyl chloride, and primary, secondary, and



    tertiary propyl amines.
                               6-566

-------
6.  EPA Source Classification Code - None
7.  References
    Astle, M.J., Industrial Organic Nitrogen Compounds, Reinhold Publishing




    Corp., New York, N.Y.,  1961 , p. 5.
                               6-567

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  232

                 Butyronitrile (from n-propyl chloride)
                            aq. CELCH CH2OH
                      NaCN  -  ~ - >  CHCHCHCN + NaCl
1.  Function - Butyronitrile is prepared by the reaction of n-propyl

    chloride and sodium cyanide in aqueous n-propanol.

2.  Input Materials

    n-Propyl chloride

    Sodium cyanide

    n-Propyl alcohol

    Water

3.  Operating Parameters - Not given

4.  Utilities - Not given

5.  Waste Streams - Waste streams from the purification section probably

    contain sodium chloride, propyl alcohol, propyl chloride, butyronitrile,

    and sodium cyanide.   Some air emissions of propyl chloride, propanol,

    and hydrogen cyanide may also occur.

6.  EPA Source Classification Code - None

7.  References

    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed., Interscience

    Publishers, New York, N.Y., Vol. supplement  (1971), p. 598.
                              6-568

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 233




          n-Butyric Acid (oxidation of n-butyraldehyde)
                           1/2
1.   Function - Some butyric acid is prepared commercially by the oxi-




     dation of n-butyraldehyde.  In this process, air or oxygen is




     passed into n-butyraldehyde in the presence of a catalyst such as




     manganese butyrate or a cobalt salt.




          Yields of about 90% are possible over a wide range of tempera-




     tures.




2.   Input Materials




     n-Butyraldehyde - 0.91 kg/kg butyric acid




     Air or oxygen




3.   Operating Parameters




     Temperature:  30-50°C (86-122°F)




     Pressure:  not given




     Catalyst:  0.5% manganese butyrate




                Cobalt salts




4.   Utilities




     Not given




5.   Waste Streams - Although no information was available, some n-




     butyraldehyde and butyric acid are probably present in the reactor




     off-gas.  Process slops may also be a source of these pollutants,




     as well as reaction by-products.




6.   EPA Source Classification Code - None
                             6-569

-------
7.   References




     Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience  Publishers,  New York,  N.Y.,  Vol.  3 (1964).  p.  880.






     Chemical Technology.  Barnes and  Noble Books, New York, N.Y.,




     Vol.  4 (1972),  p.  426.






     Goldstein, R. F.,  The Petroleum  Chemicals Industry,  2nd  Edition,




     John Wiley and  Sons,  New  York, N.Y.,   1958 , p.  331.
                           6-570

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 234

           Carbon Tetrachloride and Perchloroethylene
                   (hydrocarbon chlorinolysis)
    C» - C, Hydrocarbons + Cl™ 	> mixed chlorocarbons and

                                      chlorohydrocarbons + HC1


1.   Function - Large quantities of perchloroethylene, carbon tetra-

     chloride, and other chlorohydrocarbons are co-produced by the

     simultaneous chlorination and pyrolysis of paraffinic hydrocar-

     bons.  In commercial practice,  this conversion is carried out by

     reacting ethane, propane, LPG,  or natural gas with an excess of

     chlorine at 500 -  700°C.

           Gaseous reaction products  are quenched and most organics con-

     densed.  Any HC1 remaining  in the condensed crude is neutralized

     with dilute caustic, and the product  is decanted from the aqueous

     phase, dried,  and  distilled.

           Light  end organics such as carbon  tetrachloride and trichloro-

     ethylene are  condensed and purified  by further distillation.   Per-

     chloroethylene, hexachloroethane, and higher-boiling bottoms  are

     separated,  and the saleable compounds are neutralized,  dried,  and

     inhibited  (if  an  olefinic  linkage is  present).   Depending  on  econo-

     mic factors,  any  of the various products may be  recycled  to the

     reactor.
   Generally, trichloroethylene production is favored by lower reaction
   temperatures, i.e., 300-500°C.
                             6-571

-------
2.   Input Materials




     Ethane,  propane,  LPG,  or natural  gas




     Chlorine




     Sodium hydroxide




     Polymerization inhibiters




     Water




3.   Operating Parameters




     Temperature:  500-700°C (932-1292°F)




     Pressure:  not given




4.   Utilities




     Not given




5.   Waste Streams - Generally,  the same types of  pollution would be




     expected as in Process Nos.  235 and 236.




6.   EPA Source Classification Code - None




7.   References




     Austin,  G. T., "The Industrially Significant  Organic Chemicals -




     Part 2,""Chemical Engineering," February 18, 1974,  p. 127.






     Ibid, Part 7, June 24, 1974, p. 156.






     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers, New York, N.Y.,  Vol. 5 (1964), p. 132, 199.








    "1973 Petrochemical Handbook," "Hydrocarbon  Processing," November




    1973, p.  114.
                             6-572

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  235



     Perchloroethylene (chlorinatidn of mixed hydrocarbons)





        Hydrocarbons + Cl» - >• mixed chlorohydrocarbons





      mixed chlorohydrocarbons - > CC1, + CC12=CC12 + HC1





                   2CC1. :sj=^. CC10=CC1_ + 2C10
                       4         22      2.




 1.  Function - Perchloroethylene is now produced from a mixture of hydro-



     carbons.  The usual starting materials are methane, ethane, ethylene,



     LPG, propane, ethylene dichloride, or process wastes from vinyl



     chloride manufacture, which are chlorinated to yield saturated chloro-



     hydrocarbons.  These are then pyrolyzed to yield mixtures of predomi-



     nantly trichloroethylene, carbon tetrachloride, and perchloroethylene .



     The desired product may be separated and the rest returned to the



     reactor.



          The formation of the mixed chlorohydrocarbons is carried out at



     100-125°C and 5-10 atm; the pyrolysis is carried out at 400-700°C.



          Perchloroethylene is also produced in a modified Deacon process



     which uses HC1 and air:
            CH2=CH2 + 4HC1 + 202             Cl.C - CC1, + 4H.O
     With an excess of oxygen, the mixed product is typically 5-10%



     dichloroethylene, 25-35% trichloroethylene, and 50-60% perchloro-



     ethylene, which can be separated by fractionation.  Fluid catalysts



     are commonly used; chlorination, oxychlorination and dehydrochlori-



     nation may proceed simultaneously in the same vessel.
                            6-573

-------
         In the past,  the dominant  process started with acetylene and




    chlorine:
            HC=CH + C12 - >• CHC12CHC12 + CC13CHC12 + HC1
    CHC12CHC12 + CC13CHC12 + Ca(OH>2 -






    This process is no longer economical.




2.  Input Materials (typical)




    Basis - 1 metric ton perchloroethylene and 1,350 kg HC1




    Propane, kg     200 (441 Ibs)




    Chlorine, kg  2,500 (5,512 Ibs)




3.  Operating Parameters




    Step one:




    Temperature, °C      100-125  (212-257°F)




    Pressure, MPa        0.507-1.01 (5-10  atm)




    Step two:




    Temperature, °C      400-700  (752-1292°F)




4.  Utilities




    Not given




5.  Waste Streams - Although no information was available, mixed chloro-




    hydrocarbons and hydrogen chloride may be present in the waste gases




    of various production steps.  Heavy ends from distillation columns




    are usually incinerated.




6.  EPA Source Classification Code - None




7.  References




    Austin, G. T., "The Industrially Significant Organic Chemicals -




    Part 7," "Chemical Engineering," June  24, 1974, p. 156.
                           6-574

-------
Hahn, A. V., The Petrochemical Industry - Market and Economics,




McGraw-Hill Book Co., New York, N.Y., 1970, p. 312,313.






Faith, W. L., et al., Industrial Chemicals. 3rd Edition,




John Wiley & Sons, New York, N.Y., 1965, p. 577,578.





Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,




John Wiley & Sons, New York, N.Y., 1975, p. 606.
                       6-575

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 236

            Hexachloroethane (from perchloroethylene)
            Cl     Cl          Fed,
              **C=C     + C19  	=+  CC1-CC1.
            cr   vci      z              J
1.   Function - In commercial practice, hexachloroethane is produced by

     the chlorination of perchloroethylene at 100-140°C.  This reaction

     is carried out in a lead-lined vessel in the presence of ferric

     chloride.

          When 50-60% conversion to hexachloroethane is attained, the

     reaction is halted.  After treatment with alkali to neutralize

     dissolved hydrogen chloride, the product solution is allowed to

     crystallize.  The crystals are removed by centrifuging, and unre-

     acted perchloroethylene is recovered and recycled to the chlorinator.

2.   Input Materials

     Perchloroethylene

     Chlorine

     Sodium hydroxide

     Water

3-   Operating Parameters

     Temperature:  100-140°C  (212-284°F)

     Pressure:  not given

     Catalyst:  FeCl3

4.   Utilities

     Not given
                             6-576

-------
5.   Waste Streams - Waste water from the purification section probably




     contains sodium chloride, caustic, various chlorinated by-products,




     and traces of perchloroethylene and hexachloroethane.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 5  (1964), p. 200.
                              6-577

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 237



              (L  ^C- Nitroparaffins (from propane)





CH,CH0CH, + HNO,  	* C,  - C, nitroparaff ins + oxygenated by-products
  J  £  J      J        J.     J




1.   Function - Propane is oxidized in the vapor phase with 65% nitric



     acid.  The nitration is carried out in a silica-clad stainless steel



     reactor at 390-450°C and 0.8-1.2 MPa (8-12 atm).   Approximately 40%



     of the nitric acid is converted to nitroparaffins, the remainder acts



     as an oxidizing agent, resulting in the oxygenated by-products, and



     is reduced to nitric oxide (NO).  This is reoxidized to nitrogen



     dioxide which is utilized to produce additional nitroparaffins. The



     combined yield of HNO_ to organic nitrates is 90%.



          The temperature affects the reaction rate of reaction, the pro-



     duct composition  (high temperature favors 1-nitro compounds), and  the



     yield of oxidation products.  High pressure increases rate but not



     product composition.  The yield of nitromethane and 2-nitropropane



     may be increased at  the expense of the other nitroalkanes by the use



     of 0.03-0.2  moles of an oxygenated sulfur compound.



          The nitroalkanes, aldehydes and ketonesare condensed leaving



     unreacted propane and nitric oxide in the gas phase.  Propane is



     separated and recycled, the NO is oxidized with air to N02 which



     is absorbed  in water to produce HNO-.  This nitric acid solution



     is brought up to strength by the addition of concentrated HNO,  and



     returned to  the process.  The aldehydes and ketones are separated



     from the nitroalkanes by solvent extraction with chlorinated aromatics.



     The nitroalkanes are separated and purified by fractional  distillation.
                             6-578

-------
2.   Input Materials



     Propane - 0.68 - 0.91 kg/kg product



     Nitric acid - 0.98 - 1.30 kg/kg product



     Water



     Air



3.   Operating Parameters



     Temperature:  370-450°C  (698-842°F)



     Pressure:  0.8-1.2 MPa (8-12 atm)



4.   Utilities



     Not given



5.   Waste Streams - Waste water from washing operations probably contains



     a number of by-product aldehydes, ketones, acids, alcohols, and ole-



     fins.  These same pollutants plus carbon monoxide, NO ,  and propane
                                                          'X.


     may be present in waste gases from separators and other  purification



     equipment.



6.   EPA Source Classification Code - None



7.   References



     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,



     Interscience Publishers, New York, N.Y., Vol. 13  (1967), p. 873-874.





     Chemical Technology, Barnes and Noble Books, New York, N.Y., Vol.  4



     (1972), p. 546-550.
                             6-579

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 238
                      n-Butenes (dehydration of n-butane)



                        CH,CH.CH,,CH,	> n-C.HQ + H0
                          J  Z  £.   J         l\ O    i



1.  Function - In the Phillips process,  n-butenes are produced by the


    dehydrogenation of n-butane to  serve as  intermediates  en route to

              *
    butadiene.    The feed,  preferably 98% n-butane,  is dried carefully


    over bauxite and charged to externally heated tubular  reactors filled


    with alumina-chromia catalyst.   The  dehydrogenation is carried out at


    566-593°C and 108-239 kPa (1-20 psig)  with 30% n-butane conversion


    per pass and 80% selectivity to n-butenes.   The process operates


    cyclically,  alternate reactors  being used one hour for dehydrogenation


    and one  hour for catalyst regeneration.


         Hydrogen,  C..  - C~  hydrocarbons,  and other conversion by-products


    are separated from the  reactor  effluent  by fractionation.   The remaining


    C,  hydrocarbon  mixture  is separated  by extractive distillation with


    aqueous  furfural or acetonitrile in  two  fifty-plate columns.   Unreacted


    n-butane is  collected overhead,  washed with water,  and recycled.   The


    n-butenes remain in the solvent bottoms,  from which they are  separated


    by  subsequent distillation and  washed with water.   Recovery of n-butenes


    as  a 90-95%  concentrate usually runs  on  the order of 80-90%.
    *
     n-Butenes produced by  this process may  also  be used in the preparation
   of other derivatives.

   **
     This is carried out at 791 kPa  (100  psig)  with an air-flue gas mixture
   containing 2-3% oxygen.


                              6-580

-------
2.  Input Materials




    n-Butane (98%) - 1.44-1.62 kg/kg product




    Furfural or acetonitrile




    Water




3.  Operating Parameters




    Temperature:  566-593°C (1050-1099°F)




    Pressure:  108-239 kPa (1-2.3 atm)




    Catalyst:  alumina-chromia




    Space Velocity:  700




4.  Utilities - Not given




5.  Waste Streams - Furfural or acetonitrile and various C,  hydrocarbons




    are probably present in air and wastewater emissions from extractive




    distillation and washing operations.   Quench waters from the dehy-




    drogenation section may also contain C/  hydrocarbons  as well  as residue




    gas, tars, and oils.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical  Technology,  2nd Ed., Interscience




    Publishers, New York, N.Y., Vol. 3  (1964), p.  834.






    Friedman, L., Womeldorph, D.E.  and Stevenson,  D.  H., Proc.  Am.  Petrol.




    Inst.,  Sec. Ill, 38, 202-218, 1958.
                              6-581

-------
 INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO  239




                               Polybutenes





 1.  Function - Commercial polybutenes are viscous, tacky liquids with




    molecular weights ranging from 300-3,000.  They are produced by the




    aluminum chloride-catalyzed polymerization of dried, desulfurized butane/




    butylenes refinery streams obtained from catalytic or thermal cracking




    operations.  The isobutylene in the feed is polymerized to the greatest




    extent, so the product is composed predominantly of polyisobutylenes with




    indeterminate but minor quantities of poly(n-butenes) and  insignificant




    amounts of n- and isobutane.




         The yield of polybutenes from this process is about 83%, based on




    butylene feedstock.   Unreacted butanes and the butylenes may be recycled




    or returned to the refinery.




2.  Input Materials




    Butane/butylenes refinery stream butylenes -1.2 kg/kg product




3.  Operating Parameters




    Temperature - Not given




    Pressure - Not given




    Catalyst - A1C1




4-  Utilities - Not given




5.  Waste Streams - Air emissions from this process may contain quantities




    of C, hydrocarbons,  dimers,  trimers, etc., and polymerization solvents,




    i.e., alcohols, ethers, alkyl halides.  Spent A1C1  catalyst and




    reaction by-products may be  present in solid or liquid process wastes.




    However,  no specific information was available.
                              6-582

-------
6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Ed. ,  Interscience




    Publishers, New York, N.Y., Vol. 3  (1964), p.  946-55.





    Ibid.. Vol. 14 (1967).
                               6-583

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 240




             Butadiene (oxidative dehydrogenation of n-butenes)
                    n-^,ng	  CH2=€HCH=CH2






1.  Function - Since 1971, the Phillips process has employed an oxidative




    dehydrogenation in the production of butadiene from n-butenes.  In




    this process, a compressed air/steam mixture is heated, mixed with




    n-butene, and passed over the oxidative dehydrogenation catalyst.




         The C, components are recovered and the butadiene is extracted




    and purified by the methods described in Process No. 59.




         The significant attribute of this process is the savings in fuel:




    oxidative dehydrogenation is an exothermic rather than an endothermic




    process, and so requires significantly less energy than other dehydro-




    genation processes.




2.  Input Materials




    n-Butenes - (90-95%)




    Air - 10% of butylene feed




    Water - (18 vols/vol butadiene)




    Hydrogen - (acetylenics removal)




    Furfural or acetonitrile




3.  Operating Parameters




    Temperature - 620-675°C (1148-1247°F)




    Pressure - low partial pressures




    Space velocity - 400 vols/hr per volume catalyst




    Catalyst - Ca, Ni, PO.
                               6-584

-------
4.  Utilities - Not given


5.  Waste Streams - Waste flows from butadiene production facilities were


    417 m /Gg (100 gal/ton) of product.


         The principal pollutant sources should be the quench waters con-


    taining tars, oils and soluble hydrocarbons and the solvent extract


    and wash waters (if acetonitrile or  furfural is used)  containing


    acetonitrile, furfural and C, hydrocarbons.  Some  air emissions of


    furfural or acetonitrile may also occur.


    PH:  8-9


    TOG:  100-200 g/m3


    Filtered COD:  250-375 g/m3

                                  3
    Suspended solids:  200-500 g/m

                           3
    Total solids:  3-4 kg/m


6.  EPA Source Classification Code - None


7.  References
    Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th Edition,


    John Wiley and Sons, New York, N.Y., 1975, pp. 164-167.


    Waddams,  A. L., Chemicals from Petroleum, 3rd Edition, John Murray


    Ltd., London, 1973, pp. 156-157.
                               6-585

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  241




                        Butadiene (Houdry process)
                                                CH2=CH-CH=CH2
1.  Function - In the Houdry process, 95+% n-butane is dehydrogenated




    in one step to a mixture of butenes and butadiene.  Fresh feed and




    recycle C, hydrocarbons are preheated to 593°C and passed over an




    activated alumina catalyst bed impregnated with 18-20% chromic oxide.




    The reactors are brick-lined horizontal drums operating at pressures




    of 13.8-20.7 kPa (0.14-0.2 atm) and a space velocity of about 2 (liquid



    volume of feed per hour per volume of catalyst space).




         Butadiene is separated from the reactor effluent by the methods




    described in Process No.  59, and unreacted butane and butenes are




    recycled.  Depending on economic considerations, Houdry units can be




    run to maximize production of butadiene or butenes.  Maximum production




    of butadiene corresponds to a yield of 57-63%.



2.  Input Materials




    n-Butane (95+%) - 1.7-1.9 kg/kg butadiene




    Hydrogen (acetylenics removal)




    Furfural or acetonitrile




3.  Operating Parameters




    Temperature - 593°C (1099°F)




    Pressure - 13.8 - 20.7 kPa (0.14-.20 atm)




    Catalyst - alumina with 18-20% chromic oxide




    Space Velocity - 2 (see above)
                              6-586

-------
4.  Utilities - Not given


5.  Waste Streams -  A typical waste water flow from a butadiene production

                      3
    facility was 417 m /Gg (100 gal/ton) of product.


         The principal sources of pollutants should be the quench waters


    containing tars, oils, and soluble hydrocarbons and the solvent extract


    and wash waters (if acetonitrile or furfural are used as extractants)


    containing acetonitrile or furfural and C,  hydrocarbons.  Some air


    emissions of furfural or acetonitrile may also occur.


    TOC:  100-200 g/m3


    Filtered COD:  250-375 g/m3

                                  3
    Suspended solids:  200-500 g/m


    Total solids:  3-4 kg/m3


6.  EPA Source Classification Code - None


7.  References


    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,  Inter-


    science Publishers, New York, N.Y., Vol. 3 (1964), p.  800-



    Lowenheim, F. A., and Moran, M. K., Industrial Chemicals,  4th Edition,


    John Wiley & Sons, New York, N.Y., 1975, p. 167-168.
                              6-587

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 242.
                Amyl Chlorides (from pentane/isopentane)









                     C5H12 + C12	*  C5HUC1 + HC1






-*-•  Function - Mixtures of isomeric amyl chloride are produced by the




    continuous vapor-phase chlorination of a n-pentane-isopentane re-




    finery cut.  In this process, the pentane feed is dried with hydrogen chloride




    to prevent corrosion of the steel equipment, combined in excess with




    chlorine gas, and passed through a heated pipe still.  Conversion takes




    place in the absence of light and catalysts.




         The mixed vapors from the reactor are cooled rapidly and passed




    through a series of four continuous fractionation columns.  Hydrogen




    chloride and most of the pentane are stripped in the first two columns.




    Amyl chloride is taken overhead and polychloropentanes from the bottom




    of the third column. Any residual pentane is removed from the amyl




    chloride in the fourth column.  With additional equipment, dichloropentane




    may be isolated from the polychloropentane mixture as a saleable by-product.




2.  Input Materials




    Pentane/isopentane




    Chlorine




3.  Operating Parameters - Not given




4-  Utilities - Not given




5.  Waste Streams - Process leaks may result in the discharge of hydrogen




    chloride, chlorine, pentanes, and various C  chlorohydrocarbons  to  the




    atmosphere.  No specific information was available.
                               6-588

-------
6.  EPA Source Classification Code - None




7.  References



    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Ed.,  Interscience




    Publishers, New York, N.Y.,  Vol. 2  (1963),  p.  375.
                               6-589

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 243




                  Amyl Amines (from amyl chloride)
       (C5H1;L)2NH + C5HnCl + NH3 	> (C5H11)3N + NH4C1






1.   Function - One commercial route to amyl amines involves the reaction




     of ammonia and amyl chloride.




          As in all reactions between ammonia and alkyl halides, quantities




     of di- and tri- substituted amines are also formed.




2.   Input Materials




     Amyl chloride




     Ammonia




3.   Operating Parameters




     Not given




4.   Utilties




     Not given




5.   Waste Streams - Effluents from the ammonia stripper may contain




     amyl chloride, ammonia, and various amyl amines.  Ammonium chloride




     and heavier organics are probably present in some waste stream




     from the purification section, but no specific information was




     available.




6.   EPA Source Classification Code - None
                             6-590

-------
7.   References




     Astle, M. J., The Chemistry of Petrochemicals, Reinhold Publishing




     Co., New York, N. Y.,  1956 , p. 245.
                             6-591

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  244



               Amyl Alcohols (from amyl chlorides)




                               Oleic
                CJH....C1 + NaOH   .7"   C,.HniOH + NaCl
                 5 11          acid    5 11



 1.   Function - Isomeric amyl alcohols are produced by the high-temperature



     hydrolysis of mixed amyl chlorides.   This continuous hydrolysis  is



     carried out with aqueous sodium  hydroxide in the presence of sodium



     oleate catalyst.   In most process variations,  the reaction slurry is



     passed through two digesters.  Amyl alcohols,  pentylenes, chlorides,



     and minor amounts of amyl ether  distill overhead from the second



     digester and brine is drawn from the bottom.  The remaining slurry



     is recycled to the first digester so that the  initial charge of  oleic



     acid,  which is converted to sodium oleate,  does not  need constant



     replenishment.



         Pentylenes and unreacted  amyl chlorides are stripped from the



     alcohol by steam distillation, and the chlorides are recycled.   The



     alcohol is fractionated into commercial compositions and sold  along



     with the pentylene and amyl ether by-products.



 2.   Input  Materials



     Amyl chlorides, mixed



     Sodium hydroxide



     Water



     Oleic  acid



 3.   Operating  Parameters



     Temperature:   not  given



     Pressure:  not given



     Catalyst:  oleic acid
                           6-592

-------
4.  Utilities




    Not given




5.  Waste Streams - The principal pollutant source in this process is




    probably the waste water from the brine decanter, containing sodium




    chloride, sodium hydroxide, and traces of amyl alcohols, amyl chlorides,




    pentylenes, and amyl ether.  All of these organics may also be present




    in the waste water from the amyl alcohol recovery column.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 2  (1963)  p. 375.
                            6-593

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 245




              Amyl Mercaptans (from amyl chloride)
                       NaSH alc°hol>  CHSH + NaCl
1.   Function - A mixture of isomeric amyl mercaptans is produced by




     the interaction of amyl chloride and sodium or potassium hydrosul-




     fide in alcohol.




2.   Input Materials




     Amyl chloride




     Sodium or potassium hydrosulf ide




     Solvent alcohol




3.   Operating Parameters




     Not given




4.   Utilities




     Not given




5.   Waste Streams - Indeterminate quantities of sodium or potassium




     chloride, amyl chloride, amyl mercaptans, sodium or potassium




     hydrosulf ide, the solvent alcohol, and reaction by-products such




     as diamyl sulfide may be present in process wastes.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 20  (1969), p. 212-13.






     Ibid., Vol. 2  (1963), p. 375.
                             6-594

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  246

                   Isoamylenes Cfrom C,. hydrocarbons)


1.  Function - Isoamylenes (2-methyl-l-butene and 2-methyl-2-butene) are

    extracted from a catalytically cracked C^ gasoline stream with 65%

    aqueous sulfuric acid.  This extraction is carried out in multiple

    absorption stages at temperatures of 0-10°C.

         The isoamyl alcohols formed dissolve in the aqueous phase and are

    washed with caustic and water to remove residual acid.  This aqueous

    phase is separated and contacted with hexane or a similar solvent at 50°C

    to reconvert the isoamyl alcohols to isoamylenes.  After caustic and

    water washings, hexane is stripped from the solution to recover the

    isoamylene concentrate.  Recovery from the C,. hydrocarbon feed is about

    22.5%.   However, this figure may be as low as 7.5%, depending on the

    amylene concentration of the feed.
                   **
2.  Input Materials

    C_ hydrocarbons - 3.72 kg/kg isoprene

    Sulfuric acid - 8.50 kg/Mg isoprene

    Sodium hydroxide - 10.0 kg/Mg isoprene

    Hexane - 31.5 kg/Mg isoprene
     The GC hydrocarbons feedstocks usually contain about 30% isoamylene
    by weight, but concentrations may be as low as 10%.  About  75% of  the
    isoamylene in the feed is recovered.

     The data given is based on isoprene production for which the isoamylene
    serves as an intermediate.
                               6-595

-------
3.  Operating Parameters


    Temperature - extraction - 0-10°C   (32-50°F)

                  Hexane treatment - 50°C  (122°F)


    Pressure - not given


4.  Utilities - see Process Nos. 235 and 236.

                 **
5.  Waste Streams


    Amylene recovery section - separation vessel  (water)


    Sodium hydroxide - 3.05 kg/Mg isoprene


    Sodium sulfate - 14.0 kg/Mg isoprene


    Amylene recovery section - amylene recovery column (water)


    n-Hexane - 19.0 kg/Mg isoprene


6.  EPA Source Classification Code - None


7.  References


    "1973 Petrochemical Handbook," "Hydrocarbon Processing," November, 1973,


    p.  101.
                              6-596

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 247
                        Isoprene (from isoamylenes)


            ?3     -
     CH CH -C=Ci

                                                       f 3
                                                CH-0=CH-C=CH0 + H,
       CH3-CH=C-CH3
                                  600°C
1.  Function - One of the most popular routes to isoprene involves the

    dehydrogenation of isoamylenes extracted from C,- gasoline (see Process

    No. 246).  in this process, the amylene feed and a C_ recycle stream

    from a downstream purification unit are mixed with steam passed to a

    catalytic reactor operating at 600°C and atmospheric pressure.  A

    mixture of iron oxide, K~CO_, and Cr-O, catalyzes the conversion to

    isoprene with by-production of hydrogen, carbon dioxide, and a variety

    of C» - C,. hydrocarbons.

         The C, and C,. hydrocarbons are recovered from the reactor

    effluent in an absorber-stripper section.  The dry gas from the

    absorber usually serves as fuel gas, typically containing:  hydrogen,

    methane, ethylene, ethane, propylene, propane, butylene, butane,

    butadiene, isoprene, t-amylenes, piperylenes, other C 's and absorber

    oil.  Approximately 322 kg of fuel gas are produced per Mg of isoprene.

         Upon leaving the stripper, the overhead product is processed for

    light ends removal.  The light ends (mainly C^'s) are fed to a debutanizer

    which recovers the C, fraction overhead for use as fuel gas and a bottom

    product for recycle to the reactor.  The bottom product of the light ends

    column is the crude isoprene, which is fed to a Shell Acetonitrile

    process unit for purification.


                               6-597

-------
2.  Input Materials

    Isoamylenes - see Process No. 246.

3.  Operating Parameters

    Temperature - 600°C  (1112°F)

    Pressure - 100 kPa (1 atm)

    Catalyst - Iron oxide, K2CO~, Cr-O™ mixture

**'  Utilities  - basis:  1.15 kg/sec capacity (80 M Ib/yr)
                          o          _
    Cooling water - 1.05 m /sec (1.0 M gph)
                           3
    Process water - 16.0 dm /sec (15,200 gph)

    Steam - 6.36 kg/sec (50,500 Ib/hr)

    Electrical power - 9.72 EJ (2.7  MW)

    Fuel - 2.16 m3/sec (275,000 cfh)

5.  Waste Streams

    Dehydrogenation section - partial condensers (water)

    Isoprene - 0.5 kg/Mg product

    Amylenes - 1.5 kg/Mg product

    Isoprene recovery section - extractive distillation column (air)

    Acetonitrile - 5.0 kg/Mg product

6.  EPA Source Classification Code  - None

7.  References

    "1973 Petrochemical Handbook Issue," Hydrocarbon Processing, Nov.  1973, p.  140.

    Hedley, W. H., et al., Potential Pollutants from Petrochemical Processes,

    Technomic Publishing Co., 1975.
    *
      Includes utilities for isoamylene extraction—Process No.  247.
                               6-598

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 248
         Isoprene (direct dehydrogenation of isopentane)

                     CH3
               CH,CH2CH-CH3 Catal7st >  CH2=CHC=CH2
                                            CH3
1*   Function - A promising, new route to isoprene involves a single-
     step, fixed-bed dehydrogenation of isopentane or a C,. fraction
     obtained by catalytic cracking.  In this process, fresh C- feed-
     stock is combined with recycle from the isoprene recovery section
     and heated to 540-620°C.  The dehydrogenation takes place over a
     chromia-alumina catalyst in a cyclic series of three reactors
     operating at 74-81 kPa (0.7-0.8 atm) partial vacuum.
          The product stream is quenched by direct contact with a quench
     oil stream and compressed before passing into the recovery section.
     In the recovery section, a conventional absorber, stripper, and
     debutanizer system recovers the C,. compounds which are then charged
     to the isoprene purification section.  The purification section
     (Shell acetonitrile process) gives isoprene product (99% + pure),
     1,3-pentadiene, and recycled isopentane-pentylenes.
          This process had been used for the manfacture of isoprene
     only on a pilot plant scale.  Yields of 51.5% based on
     isopentane and 58.6% based on a C_ gasoline fraction have been re-
     ported.
2.   Input Materials
     C,. hydrocarbons
     Isopentane - 2.06 kg/kg isoprene
     CL gasoline fraction -1.76 kg/kg isoprene

                             6-599

-------
3.   Operating Parameters




     Temperature:  540-620°C (1004-1148°F)




     Pressure:  74-81 kPa (0.72-0.81 atm)




     Catalyst:  chromia-alumina




     Space velocity:  1.5-3.5 hr




4.   Utilities




     Not given




5.   Waste Streams - Generally, the same types of pollution would be




     expected as in Process No. 247-




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 12  (1967), p. 75.
                             6-600

-------
INDUSTRIAL ORGANIC CHEMICALS
        PROCESS NO. 249
                Aid,
        + CC1,
                           Benzophenone
H20
 1-  Function - Benzophenone is manufactured principally by the Friedel-




     Crafts reaction of benzene and carbon tetrachloride.  Carbon tetra-




     chloride and anhydrous aluminum chloride are charged to a jacketed




     agitated, iron vessel and thiophene-free benzene is fed in over a




     period of three to five hours with cooling.  The hydrogen chloride




     evolved is removed by an absorption tower that is coupled with a




     settling tank where carbon tetrachloride is recovered.




          The temperature of the mixture is allowed to rise to 35°C




     (95°F) for 0.5 hour after the benzene has been added.  The viscous




     mass is transferred to a still containing water, heated to boil




     with a steam injector, and held at that temperature by the heat of




     reaction.  The vapors are fed to the absorption system mentioned




     above.




          The crude benzophenone is vacuum distilled and crystallized




     from a solvent.




 2.  Input Materials - Basis:  113.4 kg (250 Ib) batch




     Benzene - 115.7 kg (255 Ib)




     Carbon tetrachloride - 476 kg (1,050 Ib)




     Aluminum chloride - 104.3 kg (230 Ib)




     Water (hydrolysis) - 378.5 dm3 (100 gal)
                             6-601

-------
3.  Operating Parameters

    Temperature:  reaction - 20°C (68°F)
                  final reaction - 35°C (95°F)

    Equipment:  jacketed, iron reactor

4.  Utilities - Not given

5.  Waste Streams

    Water:  Waste streams may contain some acid,  small amounts of car-

    bon tetrachloride, some aromatic residues, aluminum chloride hydrol-

    ysis products.

    Solids:  Aluminum hydroxide by hydrolysis of  aluminum chloride-

    aromatic complexes, tars from still bottoms,  and still bottoms from

    recovery of recrystallizing solvent.

    Air:  Possible hydrogen chloride vapors.

6.  EPA Source Classification Code - None

7.  References

    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

    Interscience Publishers, New York, N.  Y., Vol.  3 (1964), p. 439-

    444.
                            6-602

-------
SECTION VIII
 PROPYLENE
6-603

-------
            PROPYLENE
                                                                                    PROPVLENE
ON


ON
O
251A
                                                252
                                    alcohol
                                                                 253
                                                      »Glycerol - )• Dlchlorohydrin
                         ,254                      255
                         	^Glyceraldehyde 	
                          251B
                              -)Acetone-
                                                256
                             _}B1sphenol A
                           )0iacetone alcohol
                                                                          259
                                              262
                                                      Isophorone
                                                        263A
                                                                  Ketene
                                                        263 B
                                                                  Diketene
                                                                                    Hexylene glycol
                                                                                        oxide — — — ) Methyl isobutyl ketone — 2Q - ^Methyl Isobutyl  carbinol
         264
                            Nonene
                           , Dodecene
                                               Isodecyl alcohol

              ^Heptanes   266     )lsooctyl alcohol           ^^  ^    Propylene  Section Chemical  Tree

-------
      PROPYLENE
     267
            -^ Isopropyl  alcohol-
                                         ogg                      272

                                        	) Isopropyl chloride	^Isopropyl phenol
                                          269,370
               ' Acetone
                                         271
                                        _lii_\ Isopropyl  amine*
    273
               >Aceton1trile
               i Acrylonitrile.
                                      274
    Aery1 amide
                                      275
                                           . Succinonitrile
         ^Acrylic acid——^ Butyl  acrylate
  278
                • Isobutyraldehyde
                                                    279
                                                            Isobutanol
                                   280
                                         • Isobutyl acetate
                                                    281
                                                        -^Isobutyic acid
               ^n-Butyraldehyde
                                  282
n-Butanol
                                 	> n-Butyric acid	) n-Butyric  anhydride
                                  284
                                        , Butyl amines
—-—^Propylerte chlorohydrin ———>Propylene oxide—,	—
                                                                  i	) Propylene glycol
                                                                       . Dipropylene glycol
                                                         288
                                                        -=22—^Polypropylene glycol
                                                                                         Epichlorohydrin
                                                       289                 290                 291
                                                         —> Allyl alcohol   i    ) 01chlorohydrin
                                                                             292|
                                                                                  tGlycerol
                                                         293
                                                              -^Glycerol  tri(polyoxypropylene) ether
      Figure 15.   Propylene  Section Chemical Tree  (Cont.)



                                      6-605

-------
PROPYLENE
ON
ON
O
OS


1 	 ^ Acetone
36 294 .. 295
	 \Cumcnc 	 '— 	 ^Cumpnp hydroperoxide • - 	 -
296
—^rt-Mpfrhvl itwnno .— — n\ Phenol
• — 21£i — ^ Propylene chlorohydrin
>Allyl chloride ) Dichlorohydrin - • • » Epichlorohydrin
317 318 J- 319'
\A11vl alrnhnl , ? \riurnrr.l
320
321
\ i 9 T Tri rhlnronrnnflnp
322
	 	 ,_,„, ^Propylene dirhlorldp
323
	 ^nifhlorop»-npenes
297
... ^26 Xylcnol
pop ?99
"D s Chlorophenols 	 	 ^Chloranll
— 30D ) Aniline
301i ^ Sodium phenate 3°2A'B )Ani-olc
30-yi 303B
. .."T!: ..) Salicylic acid 9.
304 305
v ri«-irthpyarml 	 \ r vcl ohexanone

307 308
	 30? 	 .^Nitroanisolc- — ~- ) Anisidines
311
1 	 ) Nonyl phenol
11?
	 	 rf . 	 ^\ Octyl phenol
1131
	 _,„ 	 ,.\ Unrlnrvlnhrnnl
3141
Anhpnnl *ifi1 "fnnic acids

                        Figure  15.   Propylene Section Chemical Tree  (Cont.)

-------
CT\
O
               Cooling water
             Cooling water1
                  Steam'
               Refrig
                       Epoxidation 25Z
                       & Hydration
/
2-Butanol H2i°2
51A
V
Cooling water
•TO ,.^|[
254
Hydroxylatlon
0
Isopr
t
•pc ID]
Hydrogen *
transfer j
                                                       Acetic acid
                                                Steam   I HCI
                                                           253
                                                 Substitution
      HCI
                                                                                                      Cooli
        JH20
   pH [Phenol
                                                                                                           Alkylation
                                                                                                                    256
                                                                                                        Steam Cooling water
                                                                                                           i      n
   Aldol
condensation
                                                                                                                    257
                                                                                                         Heat
                                                                                                        Condensation  262
                                                                                                         & Dehydration
                                                                                                         Heat
        263 A.B
 Pyrolysis  '
                                              Figure  16.   Propylene Section  Process Flow Sheet

-------
O
oo
Cooli
nq water
it
C12
I J*
321 "
322 ^
Chlorinatlon
x-K
Cooling water
Steam f 1
"tllli
Isobutane
320
Epoxidatlon
^
Coolant
C,, Refinery gas Steaj" tl
1 Heat 1 1 1
I ~ t 1 It
Solvent
1 A1 Heat
HPO,
62 ^ 276 "^ 264
•Addition Oxidation Ol.lgomerization
x^"^""^ '
JL JL JL
                             Propylene"
                           [dlchloridel
Steam
CO H2
266
Oxo Process
Steam
1
»'
260
Hydrogenation
                                                                                     Benzene
                                      Figure 16.  Propylene  Section Process Flow Sheet  (Cont.)

-------
 I
(^
o
                                     Isopropyl
                                      alcohol


Water
Steam 1
Cooling wate
Steam
Heatl
H2SO,, Refrlgl 1
267 ^
Hydration

•



NH3
IT
273
Ammox1dat1on



Heat
Cooling water
271
Amnonolysis
^
Heat
270^269
Oxidation
^
HC1
268
Substitution

Phenol
272
Frledel -Crafts
reaction
 Aceto-  \ / Acrylo-
nltrlle  I I nltrile
                                       Solvent

                                         L
Addition
275
                                                                                                                 Sucdnonitrile
                                       Figure  16.   Propylene  Section Process  Flow  Sheet  (Cont.)

-------
 I

I-1
o
Heat
1
Toluene
C|2 .P t
Heat
CO 1
323 ^ Z7S
Chlorlnation Oxo Process
Acetic anhydride
                                         n-Butyr-  1   I Isobutyr-

                                         aldehyde  I   \ aldehyde
Cooll
SI
ng water
T tl
Alcohol
A1r 1 «¥*
J _n * *
233
Oxidation
?
f3 H2 P Stef
f * /A *
Reductive Z84j
ami nation |
Heat
1 *\ o
282
Hydrogenation

                                                                   Water


                                                                    11
                                                                       279
                                                            Hydrogenation
Cooling water
                Air

                 \
        Oxidation
                                                                                            281
HS04
Acetic
280
Esterlflcatlon
      Figure 16.   Propylene Section Process Flow  Sheet (Cont.)

-------
ON
                              Cooling
                               water
1             285T2
c s>
286 "0

\
)









288
AHHi+inn

Steam
289
Isomerizatlon

Glycerol
Heat 1 (COM
Polyether 293
formation
N3

/>



A
,|
!
                                                                                  Poly-
                                                                                propylene
                                                                                 glycol
                                                                                 Glycerol
                                                                               :ri(polyoxy
                                                                                prqpylene
                                                                                  ether

1
1


Hydroperoxide
Water 1 Na.CO,
J 1 \3J> x^\
292
Epoxidation
8 Hydrolysis
C12
290
Chlorlnatlon

** I \
f Glycerul 1
v_y
.0 ^~^\
_!Y, 	 ,./D1chlor
-------
H,PO,
1 "4
IHeat
*
Benzene
I
36
Alkylatlon
Water 1
,.He,at n Heat
Ar I R i
1 294
i Hydroperox 1 datl on

Steam „
296
Dehydrogenatlon

g wa ter ^™
team A 1
ill,
H2S04
295
Cleavage
                         ro-Methyl-
                         l  styrene  J
                                                         Heat
                                                Cooling water)
                                                Steam   41  jMethanolp
                   Figure 16.   Propylene  Section Process Flow Sheet (Cont.)

-------
(^
I-"
U>
NaOH
Steam I
Water _
[ Heat P
+ t /A
3171
Substitution
Tt2
290
Addition
                                                Salicylic
                                                  Acid &
                                             Methyl sal icy!ate
Dodecene
Nonene
Octene
                              311,312,313
                          Alkylation'
                                                              Na?H  Dimethyl
                                                           Steam I   sulate
So
Went
1 Heat
Alkali
Dehydro- 291
chlorination
                                          Figure  16.   Propylene  Section Process  Flow  Sheet  (Cont.)

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 250



                                 Acrolein
                                  n
                                  2.
                                          CH0=CH-CH + H00
1.  Function - Acrolein is produced by a limited vapor-phase oxidation


    of propylene in the presence of a catalyst.  Oxygenated by-products


    complicate the product recovery and purification.


2.  Input Materials


    Propylene (98%) - 1.161 Mg/Mg (2,322 Ib/ton) product


3.  Operating Parameters


    Temperature - 290-380°C (550-720°F)


    Pressure - 410-580 kPa (4.05-5.72 atm)


    Flow rates - not given


    Size of equipment - not given - fixed bed reactor


    Types of catalysts - copper-oxide and bismuth-molybdenum


4.  Utilities - Basis - 9.1 Gg/yr (20 M Ib/yr) capacity

                          o
    Cooling water - 378 dm /s (6,000 gpm)


    Steam - 4.1 Mg/hr (9,100 Ib/hr)


    Power - 12.3 GJ (3,430 kWh)


    Fuel - 350 kW (1.2 M Btu/hr)


5.  Waste Streams


    Propylene recovery section - propylene absorber off-gas


    Propylene - 71 kg/Mg (142 Ib/ton) product


    Propane - 3.5 kg/Mg (7 Ib/ton) product


    Carbon monoxide - 73.5 kg/Mg (147 Ib/ton) product
                                6-614

-------
6.  EPA Source Classification Code - None




7.  References




    Muller, R. G.,  "Glycerine and Intermediates," Report No.  53,




    Stanford Research Institute,  Menlo Park, California, 1969.





    U.  S.  Patent 2,451,485  and 2,846,842.





    Hancock,  E. G.,  Propylene and Its  Industrial  Derivatives, John Wiley




    and Sons, New York, N.Y.,  1973,  p.  23.





    Chemical Technology,  Barnes and  Noble Books,  New York, N.Y.,




    Vol.  4 (1972), p.  364-427.
                              6-615

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 251A.B



                 Allyl Alcohol; Acetone (from acrolein)



                       0                                   0

                       II                                   II
                CH2=CH-CH + R-CH2OH - >- CH2=CH2~CH2OH + R-CH
0       OH                            0

II       I                              II
       -CH-R  - >- CH=CH-CHOH + R--C-R
               CH2=CH-CH
1.  Function - Acrolein undergoes hydrogen transfer with either a primary


    or secondary alcohol in the presence of a metal alkoxide catalyst to


    form allyl alcohol and the aldehyde or ketone that corresponds to the


    donor alcohol.


         It is not possible for all manufacturers to use the optimum


    alcohol donor.  Alcohols used and the corresponding by-products


    are:  ethyl alcohol (acetaldehyde) , n-propyl alcohol


    (propionaldehyde) , isopropyl alcohol (acetone) , and secondary (2-)


    butanol (methyl ethyl ketone) .  2-Butanol is a typical example of


    an alcohol which gives high allyl alcohol selectivity while producing


    a valuable by-product.


2.  Input Materials


    Acrolein - 1.044 Mg/Mg (2,088 Ib/ton) product


    2-butanol - 1.310 Mg/Mg (2,621 Ib/ton) product


3.  Operating Parameters


    Temperature - 20-80°C  (68-176°F)


    Pressure - 100 kPa (1 atm)


    Flow rates - m. g.


    Types of catalyst - aluminum alkoxides
                                6-616

-------
4.   Utilities - Basis:  8.7 Gg/yr 0-9.2 M Ib/yr) capacity

                          3
    Cooling water - 156 dm /s (2,473 gpm)


    Steam - 14.06 Mg/hr C31,000 Ib/hr)


    Power - 922 MJ (256 kWh)


    Refrigeration - 29°C (-20°F) - 700 kW (2.4 M Btu/hr)

                     3
    Nitrogen - 140 dm /hr (5 scfh)


5.   Waste Streams -


    Product recovery and purification - light ends column (water)


    Acrolein - 1.25 kg/Mg (25 Ib/ton) product


    Methyl ethyl ketone - 12.5 kg/Mg (25 Ib/ton) product - some 2-butanol


    Product recovery and purification - heavy ends column (water)


    Butanol - 7.5 kg/Mg (15 Ib/ton)  product


    Allyl alcohol - 5 kg/Mg (10 Ib/ton) product


    Polymer - 53.5 kg/Mg (107 Ib/ton) product


    Aluminum hydroxide - 82 kg/Mg (164 Ib/ton) product


    Trace quantities of acrolein, hydroquinene, and methyl ethyl ketone,
     and 2-butanol


6.   EPA Source Classification Code - None


7.   References


    Muller, K. G., "Glycerine and Intermediates," Report No. 58, Stanford


    Research Institute, Menlo Park,  California, 1969-


    Waddams, A.  L., Chemicals from Petroleum, 3rd Edition, John Murray,


    London, 1973, p.  131.


    Chemical Technology, Barnes and Noble Books, New York, N.Y., Vol. 4,


    (1972), pp.  287,388.
                               6-617

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 252



                  Glycerin (from allyl alcohol)
              CH2=CHCH2OH
                -CH-CH0OH + H00 	> HOCH0CH-CH0OH
                      22             2j    2


                                            OH




1.   Function - Allyl alcohol is epoxidized with hydrogen peroxide to



     form glycidal which is hydrated to glycerin.  The overall process



     may be considered a hydroxylation catalyzed by tungstic acid.  The



     epoxidation reaction occurs in a three-section reactor maintained



     at 45°C for a period of 1.1 hours per section.  The product glycidal



     is purified, then hydrated in a tubular reactor, with a 10 minute



     residence time, at 145°C.



2.   Input Materials



     Allyl alcohol - 746.5 kg/Mg (1,493 Ib/ton) product



     Hydrogen peroxide - 447 kg/Mg (894 Ib/ton) product



     Caustic soda - 9 kg/Mg (18 Ib/ton) product



3.   Operating Parameters




     Temperature:  45°C (3-section reactor), 145°C (tubular reactor)



     Pressure:  not given



     Flow rates:  not given



     Size of Equipment:  not given



     Types of Catalysts:  tungstic acid
                            6-618

-------
4.   Utilities - Basis:  11.65 Gg/yr (25.7 M Ib/yr) capacity

                             q
     Cooling water - 86.69 dm /s (1,374 gpm)


     Steam - 1.1 MPa (10.8 atm) -20.487 Mg/hr (45,167 Ib/hr)


             380 kPa (3.75 atm)-11.747 Mg/hr (25,898 Ib/hr)


     Power - 510 MJ (141 kWh)

                          2
     Makeup Water - 3.6 dm /s (57 gpm)


5.   Waste Streams


     Hydroxylation section - allyl alcohol recovery column - to flare


     (air)


     Allyl alcohol - 6 kg/Mg (12 Ib/ton) product


     Butanol - 2 kg/Mg (4 Ib/ton) product


     Acrolein - 20 kg/Mg (40 Ib/ton) product


     Miscellaneous light impurities - 22 kg/Mg (44 Ib /ton) product


     Glycerin recovery and purification - light ends column (water)


     Allyl alcohol - 4 kg/Mg (8 Ib/ton) product


     Glycerin - 3.5 kg/Mg (7 Ib/ton) product


     Miscellaneous light impurities - 23.5 kg/Mg (47 Ib/ton) product


6.   EPA Source Classification Code - None


7.   References


     Muller, K. G., "Glycerine and Intermediates," Report No. 58,


     Stanford Research Institute, Menlo Park, California, 1969.



     Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, John


     Wiley and Sons, New York, N.Y., 1975, p. 436.



     Hancock, E. G., Propylene and Its Industrial Derivatives, John


     Wiley and Sons, New York, N.Y., 1973, p. 24-25.
                             6-619

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 253




                       Dichlorohydrin (from glycerol)






               HOCH2CHOHCH OH + 2HC1 	*  CIO^CHCICH^H




                                                     or




                                               C1CH2CHOHCH2C1 + 2H20






1.  Function - In the past, dichlorohydrin has been produced by the




    interaction of crude glycerol and an excess of hydrogen chloride.




    This reaction is normally carried out at 100-160°C in a 4% solution




    of acetic acid.




         The major by-products of this reaction are water, polyglyceride,




    and a mixture of acetates.  Polyglyceride formation may be inhibited




    by lower reaction temperatures (~ 100°C),  although this necessitates




    HC1 recycling.  Vacuum distillation is normally sufficient to reduce




    acetate production.




2.  Input Materials




    Glycerol - 0.79 kg/kg dichlorohydrin




    Hydrogen chloride - excess




    Water




3.  Operating Parameters




    Temperature - 100-160°C  (212-320°F)




    Pressure - Not given




    Catalyst - acetic acid - 16 g/kg dichlorohydrin




4.  Utilities - Not given
                              6-620

-------
5.  Waste Streams - Various waste streams may be present depending on




    the purification procedures employed (different reaction temperatures




    require different purification techniques).   However, tars, acetic




    acid, various acetates, dichlorohydrin, and other halides from the




    surge-tank wastes are probably the principal pollutants.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 5  (1964), p. 314.
                              6-621

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 254



                        Glyceraldehyde (from acrolein)





                    CH0=CHCHO + H,CL   ug '   CH,-CHCHO + H_0
                      2          £ £  pno     * / >        2.

                                              Ncr



                     CH_-CH-CHO + H.O 	>  HOCH0CHOHCHO

                      \2/         2             2
                      V0^


1.  Function - Synthetic glyceraldehyde is prepared by the hydroxylation



    of acrolein via glycidaldehyde intermediate.  If pH is maintained



    at 8 during the reaction, acrolein and hydrogen peroxide combine to



    form glycidaldehyde.



         The intermediate is then hydrolyzed to give nearly quantitative



    yields of glyceraldehyde.



         In some cases, acrolein may be converted directly to glyceraldehyde



    by treatment with hydrogen peroxide in the presence of OsO, catalyst.



2.  Input Materials



    Acrolein - 0.65 kg/kg glyceraldehyde



    Hydrogen peroxide



    Water



3.  Operating Parameters



    Temperature - Not given



    Pressure - Not given



    pH - 8



4-  Utilities - Not given



5.  Waste Streams - Wastewater from the separator may contain small quantities



    of acrolein, hydrogen peroxide, glycidaldehyde, and glyceraldehyde.
                              6-622

-------
6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience Publishers,  New York,  N.Y.,  Vol.  1  (1963),  p.  261.
                              6-623

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  255



                Glycerol (hydrbgenation of glyceraldehyde)





                                     Ni °
                  HOCH CHOHCHO + H2     >   HOCH2CHOHCH2OH




1.  Function - One route to glycerol starts with propylene  involving



    intermediates of acrolein, glycidaldehyde,  and glyceraldehyde.  The



    final intermediate, glyceraldehyde, is converted to glycerol by



    hydrogenation in the presence of nickel catalyst.



2.  Input Materials



    Glyceraldehyde



    Rydrogen



3.  Operating Parameters



    Temperature - 200°C (392°F)



    Pressure - Not given



    Catalyst - Nickel



4.  Utilities - Not given



5.  Waste Streams - Air vent streams would contain hydrogen gas.  Purification



    by vacuum distillation separates glyceraldehyde and glycerol.   Vents



    from purification system contain glycerol,  waste water  streams would



    contain glycerol and some glyceraldehyde.   Because of the low vapor



    pressures of the reactants and products the process should be essentially



    free of air pollution.



6.  EEA Source Classification Code - None



7.  References



    Kirk-Othmer, Encyclopedia of Chemical  Technology. 2nd Edition,



    Interscience Publishers, New York, N.Y., Vol. 1 (1963), p.  261-262.
                               6-624

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 256



                  Bisphenol-A (from phenol & acetone)








               2C,H,.OH + CH0COCH, 	>- C(C,H,OH)0 + H00
                 o _>       j    3       !   o 4   Z    £.







1.   Function - 2,2-Bis(4-hydroxyphenyl)propane, also known as bis-



     phenol-A, is produced by reacting phenol with acetone in the pre-



     sence of acid catalyst.



          A number of by-products are formed in conjunction with the



     main reaction.  The earlier processes eliminated these impurities



     by batchwise crystallization, while the new process, the Hooker



     process, employs a continuous distillation and extractive crystal-



     lization under pressure to purify the product.



          Phenol and acetone at a molar ratio of approximately 3 to 1



     are mixed, saturated with hydrogen chloride gas, and sent to the



     reaction vessel.  Reaction conditions are about 40°C, close to



     atmospheric pressure, with a mercaptan used as a catalyst.  The



     crude product is stripped of HC1 and water of reaction.  The over-



     head is decanted into an organic phase (consisting mainly of phenol



     which is recycled) and an aqueous phase.  The latter goes on to an



     HC1 recovery unit, and water is sent to disposal.



          Bottoms from the stripper are sent to a series of purification



     distillation chambers, where excess phenol, isomers, and heavy ends



     are removed from the system for either recycle or disposal.  Distil-



     late from the last chamber is sent to the extraction operation, which



     produces a slurry of pure crystals.  The filtrate from the centrifuge






                             6-625

-------
     is partially recycled to the crystallizer,  and the remainder is




     concentrated in an evaporator to produce liquid bisphenol-A.




2.   Input Materials




     Phenol - 862.5 kg/Mg (1725 Ib/ton)  product  (excluding recycled excess)




     Acetone - 265.9 kg/Mg (531.7 Ib/ton)  product




3.   Operating Parameters




     Temperature:  40°C  (104°F)




     Pressure:  Near atmospheric




     Flow Rates:  Not given




     Catalysts:  HC1, and mercaptan




4.   Utilities




     Water (process) - 250 kg/Mg (500 Ib/ton) product




     (gross cooling) - 197 Mg/Mg (394,000 Ib/ton) product




5.   Waste Streams - Aqueous waste streams are produced by the hydrogen




     chloride recovery unit, the crystallizer, and the final evaporator.




     Total water flow - 458.8 dm /Mg (133.6 gal/ton) product




     COD - 17.1 kg/Mg (34.2 Ib/ton) product




     TOC - 5.2 kg/Mg (10.3 Ib/ton) product




     Phenol - 7.1 kg/Mg  (14.2 Ib/ton) pressure




6.   EPA Source Classification Code - None




7.   References




     Anon., "Development Document for Effluent Limitations Guidelines




     and Standards of Performance:  Organic Chemical Industry,"  Contract




     No. 68-01-1509, prepared for Environmental Protection Agency,  June



     1973.





     Sittig, M., "Pollution Control in the Organic Chemical Industry,"




     Pollution Technology Review No. 9,  Noyes Data Corporation,  1974,



     p. 85-87.




                             6-626

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 257
                 Diacetone Alcohol (condensation of acetone)






                       2(CH3)2CO 	> (CH3)2COHCH2COCH3






1.  Function - Diacetone alcohol is prepared by the aldol condensation




    of acetone flowing over a solid alkali or alkaline earth catalyst in a




    fixed-bed catalytic reactor.  The reaction is normally carried out




    near room temperature or below.




         To secure good yields it is necessary to remove the diacetone




    alcohol as fast as it is formed.




         Once the product solution is out of contact with the catalyst,




    the dimer has little tendency to revert to acetone and accumulates.




    Acetone, being more volatile, is continually removed by distillation




    and recycled.  Acetone-free diacetone alcohol is obtained by fractional




    distillation under vacuum.




2.  Input Materials




    Acetone




3.  Operating Parameters




    Temperature - 10-23°C  (50-73°F)




    Pressure - Not given




    Catalyst - Ba(OH)_ or similar compounds




4.  Utilities - Not given




5.  Waste Streams - Some acetone and diacetone alcohol may be present in




    air emissions from various processing equipment.
                              6-627

-------
6.  EPA Source Classification Code - None




7.  References




    Austin, G. T., "The Industrially Significant Chemicals  - Part 7,"




    "Chemical Engineering,  June 24,  1974,  p.  153.





    Hedley, W. H., et al.,  Potential Pollutants  from Petrochemical




    Processes. Technomic Publishing  Co.,  1975, p.  309.





    Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience  Publishers,  New York, N.Y.,  Vol.  1   (1963),  p.  165-166,





    Ibid.,  Vol. 12 (1967).
                              6-628

-------
INDUSTRIAL ORGANIC CHEMICALS                                   PROCESS  NO.  258






                            Hexylene Glycol



                                  PAT
           (CH3)2COHCH2COCH3 + H2  ^A1>  >   (CH3)2COHCH2CHOHCH3



1.   Function - Hexylene glycol is commercially prepared by the hydrogenation


     of diacetone alcohol.



     In normal plant procedure, acetone is the raw material, undergoing


     preliminary condensation to diacetone alcohol.


2.   Input Materials^


     Diacetone alcohol (from acetone - 1.2 kg/kg hexylene glycol)


     Hydrogen


3.   Operating Parameters - Not given


4.   Utilities


     Not given


5.   Waste Streams - Air vent streams from the reactor contain hydrogen and


     acetone. Off-gas streams from the purification process contain acetone


     and some diacetone alcohol.


6.   EPA Source Classification Code


     None


7.   References
     Hancock, E. G., Propylene and Its Industrial Derivatives, John Wiley


     and Sons, Inc., New York,  1973,  p.  258.
                               6-629

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  259




            Mesityl Oxide (dehydration of diacetone alcohol)







             (CH3)2COHCH2COCH3 —	* (CH3)2C=CHCOCH3 + H20






1.  Function - Mesityl oxide is commercially produced by dehydrating




    diacetone alcohol at 100°C in the presence of sulfuric acid.




2.  Input Materials - Diacetone alcohol and H^SO,




3.  Operating Parameters




    Temperature - 100°C (212°F)




    Pressure - Not given




4.  Utilities - Not given




5.  Waste Streams - Wastewater from the dehydration column may contain some




    acetone and diacetone alcohol.




6.  EPA Source Classification Code - None




7.  References




    Hedley, W.  H., et al., Potential Pollutants from Petrochemical Processes,




    Technomic Publishing Co., 1975.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 12 (1967)  p. 136.







    Waddams, A. L., Chemicals From Petroleum,  3rd  Edition, John Murray




    Publishers, Ltd., London, Eng., 1973, p.  126.
                              6-630

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 260
            Methyl Isobutyl Ketone (hydrogenation of mesityl oxide)


                  (CH3)2C-CHCOCH3+ H2 	»• (CH3> 2CHCH2COCH3


1.  Function - Methyl isobutyl ketone is made commercially by the selective

    catalytic hydrogenation of the olefinic linkage in mesityl oxide.  The

    reaction may be run in the vapor phase at 150-170°C and 100 kPa

    (1 atm) or in the liquid phase at 60-130°C and 1-25 atm.  Copper or

    Raney nickel catalysts are used.

         In normal plant procedure, acetone is the raw material undergoing

    conversion to diacetone alcohol, mesityl oxide, and finally methyl

    isobutyl ketone (see Process Nos. 257 and 259).  Methyl isobutyl carbinol

    is a by-product of this reaction.

2.  Input Materials

    Mesityl oxide

    Hydrogen

3.  Operating Parameters

    Vapor Phase - Temperature:  150-170°C  (302-338°F)
                  Pressure:  100 kPa (1 atm)

4.  Utilities - Not given

5.  Waste Streams - Air emissions from the purification section may contain

    mesityl oxide, methyl isobutyl ketone, methyl isobutyl carbinol, and

    other by-products.

6.  EPA Source Classification Code - None
                               6-631

-------
7.   References




    Austin,  G. T.,  "The Industrially  Significant  Organic  Chemicals  -




    Part 7," "Chemical Engineering,"  June  24,  1974, p.  153.





    Hedley,  W- H.,  et al.,  Potential  Pollutants from  Petrochemical  Processes,




    Technomic Publishing Co.,  1975} p.  309.





    Kirk-Othmer, Encyclopedia  of  Chemical  Technology, 2nd Edition,




    Interscience Publishers, New  York,  N.Y., Vol.  12  (1967), p.  134.
                              6-632

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 261
           Methyl Isobutyl Carbinol (from methyl isobutyl ketone)






                                  catalyst v
1.   Function - Methyl isobutyl carbinol is produced on a commercial scale




     by the hydrogenation of methyl isobutyl ketone.




          It is also isolated and collected as a by-product of methyl




     isobutyl ketone synthesis (see Process No. 260).




2.   Input Materials




     Methyl isobutyl ketone




     Hydrogen




3.   Operating Parameters




     Temperature:  150-190°C (302-374°F)




     Pressure:  345-689 kPa (3.4-6.8 atm)




4«   Utilities - Not given




5.   Waste Streams - Some air emissions may be present.  The probable




     pollutants are methyl isobutyl ketones, methyl isobutyl carbinol,




     and reaction by-products.




6.   EPA Source Classification Code - None




7.   References




     Astle, M. J., The Chemistry of Petrochemicals, Reinhold Publishing




     Co., New York, N.Y., 1956, p. 202, 228.






     Hahn, A. V., The Petrochemical Industry, McGraw-Hill Book Co.,




     New York, 1970, p. 367.
                            6-633

-------
7.   References (continued)




     Hancock, E. G., Propylene, John Wiley and Sons, New York, 1973,




     p. 258-259.
                           6-634

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 262


        Isophorone  (vapor-phase condensation of acetone)
               3(CH3)2CO
 1.  Function


     Isophorone is prepared by the vapor phase condensation of three


     molecules of acetone in the presence of an alkaline catalyst.  A

          *
     liquid phase condensation may also be employed.  In the vapor phase


     process, acetone is passed over calcium oxide, hydroxide,or carbide


     at 350°C and atmospheric pressure to give isophorone, water and by


     products such as:  diacetone alcohol and mesityl oxide.  The iso-


     phorone is purified by vacuum distillation.


 2.  Input Materials - Acetone


 3.  Operating Parameters


     Vapor phase


     Temperature:  350°C (662°F)


     Pressure:  100 kPa (1 atm)


     Catalyst:  CaO, Ca(OH)  or CaC_



     Liquid phase


     Temperature:  140-170°C  (284-338°F)


     Pressure:  not given


 4.  Utilities - not given
                            6-635

-------
5.  Waste Streams - Air emissions from purification operations may con-




    tain unconverted acetone,  mesityl oxide,  diacetone alcohol, other




    reaction by-products and isophorone.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology,   2nd Edition,




    Interscience Publishers, New York,  N.Y., Vol.  1 (1963)  p.  166.







    Sherwood,  P. W., "Petroleum Refiner," .33 (12), 144  (1954).
                          6-636

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  263A




                      Ketene (pyrolysis of acetone)
                      (CH3)2CO         > CH2CO + CH4






1.  Function - On a commercial scale,  ketene is prepared by the straight




    pyrolysis of acetone.  In the noncatalytic process,  acetone is heated




    to 600°C where it cracks to ketene and methane.   Ketene is a highly




    reactive material, unstable in storage-  It is manufactured only for



    captive use in further synthetic operations.  Ketene dimerizes spon-




    taneously and is a commercial by-product of ketene synthesis.




2.  Input Material - Acetone




3.  Operating Parameters




    Temperature - 650-670°C (1202-1238°F)




    Pressure - not given




    Contact time - 0.25-5 sec.




4.  Utilities - Not given




5.  Waste Streams - The off-gas from the reactor should  contain large




    quantities of methane, and smaller amounts of acetone and possibly




    acetic acid (reaction of ketene and water) .




6.  EPA Source Classification Code - None




7.  References




    Austin, G. T., "The Industrially Significant Organic Chemicals -




    Part 1," "Chemical Engineering," January 21, 1974, p. 129.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 12 (1967), p. 91.
                               6-637

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7.   References (continued)




    Lowenheim, F.  A.  and Moran, M.  K.,  Industrial Chemicals, 4th Edition,




    John Wiley & Sons, New York, N.Y.,  1975, p.  18.
                               6-638

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 263B




                   Diketene (dimerization of ketene)
                     2CH2CO 	  CH2C CH2C(0) 0






1.   Function - Diketene is a commercial by-product of ketene synthesis




     from acetic acid (see Process No. 105) or acetone (see Process No.




     263A).   The dimerization occurs spontaneously.



          For description of the other items see Process No. 263A.
                             6-639

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 264




       Nonene and Dodecene (oligomerization of propylene)





                                  HPO

                       3CH =CHCH«       '  CqH,R
                          £^     ,j          ,7 J-xJ





                                  HPO

                       4CH0=CHCH, ——±-*- C, 9H,,
                          ^     J          J_.£. ^T-







1.   Function - Nonene and dodecene are coproduced when a C^ refinery




     stream  (40-60% propylene/propane) is oligomerized in the presence




     of a phosphoric acid catalyst at 200°C and 3.45-6.89 MPa.




          In some cases, the oligomerization is done with the intention




     of producing gasoline, from which cuts of nonene and dodecene




     can be fractionated.  In other cases, the tetramer and/or trimer are




     the primary products desired and the oligomerization is carried out




     in such a way as to maximize production of both or either of these.




     For instance, if the demand for dodecene exceeds the quantity con-



     tained in a once-through oligomerization product, some or all of




     the dimer and trimer are recycled to increase or maximize production




     of the tetramer.




          The trimer and tetramer cuts that are fractionated from the




     oligomerization product are not pure trimer and tetramer, but are




     mixtures of olefins that consist principally of polypropylene having




     average molecular weights corresponding to those of nonene and  dode-



     cene.




2.   Input Materials


              *

     Propylene  (component of C- Refinery Gas)
*

  The figures presented represent maximized production of nonene and

  dodecene.



                             6-640

-------
2.   Input Materials (continued)




     For nonene - 1.21 kg/kg




     For dodecene - 1.27 kg/kg




3.   Operating Parameters




     Temperature:  200°C (392°F)




     Pressure:  3.45-6.89 MPa (34-68 atm.)




     Catalyst:  H^PO,




*•   Utilities - Not given




5.   Waste Streams - Since all of the co-products of nonene and dodecene




     manufacture are utilized, there are no process wastes to be dealt




     with, except spent phosphoric acid catalyst.  However, propylene,




     nonene, dodecene, and other olefins may be leaked to the atmosphere




     by various processing equipment.




6.   EPA Source Classification Code - None




7.   References






     Hedley,  W. H.,  et al., Potential Pollutants  from Petrochemical




     Processes, Technomic Publishing Co., 1975,  p.  335.
                             6-641

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 265




                    Isodecyl Alcohol (oxo process)
                            CO
1.   Function - Isodecyl alcohol, actually a mixture of trimethyl




     heptanols, is prepared from nonene by the oxo process.  In this pro-




     cess, a mixed stream of nonylenes is combined with synthesis gas at




     160°C and 1.38 MPa (137 atm) in the presence of cobalt naphthenate




     catalyst to produce a mixture of C1f. aldehydes.




          The intermediate aldehydes are then hydrogenated to isodecyl




     alcohol at 150°C and 10.0 MPa (100 atm) over a nickel or copper




     chromite catalyst:
          Purification is carried out in the manner described in Process




     Nos. 278 and 282.  Yields in the neighborhood of 64% are obtained.



2.   Input Materials




     Nonene - 1.25 kg/kg product




     Synthesis gas



     Hydrogen




3.   Operating Parameters




     Aldehyde Production




     Temperature:  160°C (320°F)




     Pressure:  13.8 MPa (137 atm)




     Catalyst:  Cobalt naphthenate
                             6-642

-------
3.   Operating Parameters (continued)




     Hydrogenation




     Temperature:  150°C  (302°F)




     Pressure:  10.0 MPa  (100 atm)




     Catalyst:  Ni or Cu chromite




4.   Utilities - Not given




5.   Waste Streams - Generally, the same types of pollution would be




     expected as in Process Nos. 187 and 188.




6.   EPA Source Classification Code - None




7.   References




     Austin,  G. T., "The  Industrially Significant Organic Chemicals -




     Part 3," "Chemical Engineering," March 18, 1974, p. 92.






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 14  (1967), p. 373-89.
                             6-643

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 266




                    Isooctyl Alcohol (from heptane)
                            CO
1.   Function - Isooctyl alcohol, actually a mixture of isomeric Cft




     alcohols, is manufactured by the oxo process.  Heptene and synthesis




     gas are reacted at 150°C and 20.7 MPa (3000 psi) in the presence of




     a cobalt carbonyl catalyst, to yield a mixture of intermediate




     octaldehydes.




          After separation, the octaldehydes are hydrogenated to isooctyl




     alcohol at 150°C and 10.0 MPa (100 atm) over a nickel chromate catalyst.




          The intermediate aldehyde and the crude alcohol product are puri-




     fied by the methods described in Process Nos. 278 and 282.  This pro-




     cess gives a 57% yield based on heptene.




2.   Input Materials




     Heptene - 1.33 kg/kg product




     Synthesis gas




     Hydrogen




3.   Operating Parameters




     Temperature:  150°C (302°F)




     Pressure:  octaldehyde production - 20.7 MPa




                hydrogenation - 10.0 MPa




     Catalyst:  octaldehyde production - cobalt carbonyl




                hydrogenation - nickel chromate
                            6-644

-------
4.   Utilities - Not given




5.   Waste Streams - Generally, the same types of pollution would be




     expected as in Process Nos. 187 and 188.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers, New York, N.Y.,  Vol. 14  (1967).  p. 373-89.







     Austin, G. T., "The Industrially  Significant Organic Chemicals -




     Part 6," "Chemical Engineering,"  May  27,  1974,  p.  106.
                             6-645

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  267




    2-Propanol (Isopropyl Alcohol;  Indirect Hydration Process)
CH3CH=CH2  +  (CH3)2CHOS03H
           S02  +  CH3CHOHCH3  - >






 1.  Function - The basic reactions  of the indirect  hydration process




     for the production of isopropyl alcohol  are described in the above




     formulae.




          Crude propylene is scrubbed to  remove  mercaptans and hydrogen




     sulfide, distilled to remove higher  hydrocarbons  and  hydrogenated




     to remove the acetylenics.




          The liquefied propylene feed stock  is  combined with recycled




     propylene and passed into  a  sulfuric acid absorption  column.   Most




     of the propylene is absorbed.   The spent gas containing  propylene




     and propane is scrubbed with caustic and sent to  liquefied petrol-




     eum gas (LPG) .




          The extract is sent to  the hydrolyzer-stripper where it is




     diluted with water to obtain the sulfate esters.   The ester solu-




     tion is then stripped with steam to  remove  the  2-propanol and di-




     isopropyl ether.   The alcohol and ether  vapors  are scrubbed with




     caustic solution to remove acidic compounds and entrained acid.




          The alcohol and ether are  separated by distillation, the ether




     being taken overhead as a water-ether azeotrope.   The alcohol-water




     mixture is  distilled and the distillate  sent to a dehydrating




     column where the remaining water is  removed azeotropically.  The






                             6-646

-------
ternary azeotrope is condensed and sent to a decanter where two layers
are formed.  The upper layer consists of alcohol and azeotropic components,
the lower layer is water.
 2.  Input Materials
     Refinery propylene stream (>50% propylene)
     Sulfuric acid (70-80 wt %)
     Caustic soda
     Azeotropic agent (benzene, isopropyl ether or ethyl ether)
 3.  Operating Parameters
     Absorber (reactor) temperature:  60-90°C (140-190°F)
     Absorber (reactor) pressure:  791 kPa-28.6 MPa (7.8-28.3 atm)
 4.  Utilities - Not given
 5.  Waste Streams
     Air:  possible compressor seal leaks, recycle gas line leaks,
     spent gas vent on reactor would result in propylene emissions.
     Water:  Waste water from dehydration column and crude storage may
     contain small amounts of isopropyl ether, hydrocarbons,  and
     propanoic acid.  Spent caustic soda solution contains caustic soda,
     sodium sulfate, and 2-propanol.  Waste water from the decanter may
     contain isopropanol and azeotropic components.
 6.  EPA Source Classification Code - None
 7.  References
     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
     Interscience Publishers, New York, N. Y., Vol. 16 (1967), p.  568-
     570.

     Kent, J.  A., Riegel's Handbook of Industrial Chemistry, Ed.,  7th
     Edition,  Van Nostrand Reinhold Company, New York, N. Y., 1974, p.
     794.
                             6-647

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 268




                 Isopropyl Chloride (from isopropyl alcohol)







                   (CH3) 2CHOH 4- HC1 	*• (CKj 2CHC1 + H20





1.  Function - Isopropyl chloride is readily formed by the reaction




    of isopropyl alcohol and hydrochloric acid.




2.  Input Materials




    Isopropyl alcohol




    Hydrochloric acid




3.  Operating Parameters - Not given




4.  Utilities - Not given




5.  Waste Streams - Air and water effluents from the separator may contain




    isopropanol, isopropyl chloride, and hydrogen chloride.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York,  N.Y., Vol. 16  (1968), p. 567.
                               6-648

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 269




                  Acetone (oxidation of isopropanol)







               (CH3)2CHOH + 1/2 02 - >• (CH3)2CO + H20







1.   Function - A significant amount of acetone is produced by the




     catalytic oxidation of isopropyl alcohol.  In this process, iso-




     propanol is mixed with air and fed to a reactor maintained at 500 °C




     and 345 kPa (50 psi) .  Copper or silver catalysts are used.




          Reactor products are treated similarly to those from the straight




     dehydrogenation process .




          If run in the liquid phase, this process yields hydrogen peroxide




     as a by-product.
                 (CH3)2CHOH + 02 - >






2.   Input Materials




     Isopropanol - 1.15 kg/kg product




     Air




3.   Operating Parameters




     Temperature:  500°C (932°F)




     Pressure:  345 kPa (3.4 atm)




     Catalyst:  copper or silver




4.   Utilities - Not given




5.   Waste Streams




     Isopropanol stripping still and intermediate flush column  (water)
                            6-649

-------
5.   Waste Streams (continued)




     Water flow - 1.46 m3/Mg product (350 gal/ton)




     COD - 1.1 kg/Mg product (2.2 Ib/ton)




     BOD - 3.25 kg/Mg product (6.5 Ib/ton)




     TOC - 0.35 kg/Mg product (0.7 Ib/ton)




          The waste water contains acetone, isopropanol and traces of




     heavier organics.




          Vent on absorber (air) - acetone and isopropanol vapors.




6.   EPA Source Classification Code - None




7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 1," "Chemical Engineering," January 21, 1974, p. 130.






     Hedley, W. H. et al., Potential Pollutants from Petrochemical




     Processes, Technomic Publishing Co., 1975.






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 1 (1963), p. 161.
                            6-650

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  270
             Acetone (catalytic dehydrogenation of isopropanol)







                         (CH3)2CHOH 	> (CH3)2CO + HZ






•*••  Function - As of November 1974, 42% of the U. S. capacity for




    acetone production was based on the dehydrogenation or oxidation




    (see Process No. 269) of isopropyl alcohol.  In the dehydrogenation




    process, isopropanol is fed to a packed tubular reactor.   The




    reaction takes place at 380°C in the presence of brass or zinc oxide




    catalyst, with a yield of 95%.




         The hot reactor effluent contains acetone, unreacted isopropanol,




    hydrogen, and minor amounts of by-products, such as propylene and




    diiospropyl ether.  The mixture is cooled and the noncondensable gases




    are scrubbed with water.  Because the resultant gas stream is mainly




    hydrogen, a part of it can be recycled to control catalyst fouling.




    The liquids are fractionally distilled taking reconcentrated acetone




    overhead and a mixture of isopropanol and water as bottoms.  In a




    second fractionating column, the aqueous isopropyl alcohol is concen-




    trated for 'recycle to the reactor.  The water removed may be rejected




    or reused in the gas scrubber.




2.  Input Material - Isopropanol - 1.25 kg/kg acetone




3.  Operating Parameters




    Temperature - 380°C  (716°F)




    Pressure - Not given




    Catalyst - brass or ZnO
                              6-651

-------
4.  Utilities - Basis:  2.16 kg/sec (150 M Ib/yr)  capacity

                          3
    Cooling water - 379 dm /sec (6000 gpm)

                         3
    Makeup water - 6.3 dm /sec (100 gpm)


    Power -  1080 MJ  (300 kW)


    Steam - 10.1 kg/sec (80,000 Ib/hr)


    Natural gas - 8.8 MW (30 M Btu/hr)


5.  Waste Streams


    Isopropanol stripping still and intermediate flash column (water),

                       o
    Water flow - 1.46 m /Mg product (350 gal/ton)


    COD - 1.1 kg/Mg product (2.2 Ib/ton)


    BOD - 3.25 kg/Mg product (6.5 Ib/ton)


    TOG - 0.35 kg/Mg product (0.7 Ib/ton)


    The wastewater contains acetone, isopropanol,  and traces of heavier


    organics.


    Vent on absorber (air)


    Acetone and isopropanol vapors


6.  EPA Source Classification Code - None


7.  References


    Austin, G. T., "The Industrially Significant Organic Chemicals - Part 1,"


    "Chemical Engineering," January 21, 1974, p. 129.


    Hedley, W. H., et al.,  Potential Pollutants from Petrochemical Processes,


    Technomic Publishing Co., 1975.


    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Interscience


    Publishers, New York, N.Y., Vol. 1  (1963), p. 160.
                               6-652

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INDUSTRIAL ORGANIC CHEMI.CALS                          PROCESS NO. 271

            Isopropyl Amine (.from isopropyl alcohol or acetone)


                                  A1PO      1*2
                  CH3CHCH3 + NH3  -35Qof- CE
                     OH
                                            NH0
                                    Ni      I 2
1.  Fvinction - Isopropyl amine is made principally by two vapor phase

    catalytic processes.  The first involves the alkylation of ammonia by

    isopropyl alcohol.  This reaction is run at 350°C under a pressure

    of 100-200 atmospheres using an aluminum phosphate catalyst.  An

    excess  (3 to 5x) of ammonia is used in order to promote primary amine

    formation.  Secondary and tertiary amines are by-products and must be

    separated.  The amines appear to be in equilibrium and the secondary

    and tertiary amines are therefore recycled.

         Acetone, ammonia and hydrogen are combined at 140°C and 740 psi

    over Raney nickel to give a 97% yield of isopropylamine.  Secondary

    and tertiary amines are also present as by-products of this reaction.

2.  Input Materials

    Isopropyl Alcohol

    Ammonia

    Acetone

    Hydrogen

3.  Operating Parameters

    Ammonylsis

    Temperature - 350°C (662°F)

    Pressure - 10.1-20.3 MPa  (100-200 atm)

                               6-653

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3.  Operating Parameters (Continued)




    Catalyst - Aluminum phosphate




    Reductive Ammination




    Temperature - 130-180°C (266-356°F)




    Pressure - 0.507-10.1 MPa (5-100 atm)




    Catalyst - Raney nickel




4.  Utilities - not given




5.  Waste Streams - Waste water streams from strippers may contain ammonia,




    isopropyl alcohol, acetone,  isopropyl amines and more highly substituted




    amines.  Air effluents may contain ammonia, acetone, isopropyl amine and




    isopropyl alcohol.




6.  EPA Source Classification Code -  None




7.  References
    E. G. Hancock, Propylene and Its Industrial Derivatives, John Wiley




    and Sons, New York, N.Y., 1973, p. 223-234.





    A. L. Waddams, Chemicals from Petroleum, 3rd Edition, John Murray




    Publishers, Ltd., London, 1973, p. 128.
                              6-654

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 272




       Isopropyl Phenols (from isopropyl chloride and phenol)
                 (CH3)2CHC1



                                          ^                 CH(CH3)2



*••   Function - Isopropyl phenols are produced by Friedel-Craf ts re-




     action of phenol and isopropyl chloride in the presence of A1C1,,




     BF3, or H2SO, catalyst.




          Ortho- and para-isopropylphenol are the primary products,




     although some polysubstitution does occur.




2.   Input Materials




     Phenol




     Isopropyl chloride




3.   Operating Parameters




     Temperature:  not given




     Pressure:  not given




     Catalyst:  A1CL,, BF™, or H-SO,




4.   Utilities - Not given




5.   Waste Streams - Waste water from the HC1 scrubber should contain




     sodium chloride and caustic, phenol, isopropyl chloride, spent




     catalyst, and isopropylphenol .  The air effluent may contain HC1,




     isopropyl chloride, and reaction by-products.  Tars from the still




     bottoms are probably incinerated.




6.   EPA Source Classification Code - None




7.   References




     Chemical Technology, Barnes and Noble Books, New York, N.Y., Vol. 4




     (1972), p. 129, 269.




                            6-655

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 INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  273

         Acrylonitrile/Acetonitrile (ammoxidation of propylene)

CH2=CHCH3  +  NH3  +  02(air) 	»• CH2=CHCN  +  HCN  +  CH^N  + H20  +  C02

 1.  Function - The entire production of acrylonitrile in the United States
     is obtained by the ammoxidation of propylene.   In this vapor-phase process,
     refinery propylene (90f%),  fertilizer grade ammonia (99.5+%),  and air are
     combined in a fluidized bed reactor at 450°C and 200 kPa (2 atm).  The
     reaction is catalyzed by a  Sohio developed product,  Catalyst 41 (50-60%
     bismuth phosphonohydrate on A1?0,J , which increases the yield  of acryloni-
     trile and decreases the  production of acetonitrile and hydrogen cyanide.
     Approximately 15 kg of acetonitrile and 75 kg of hydrogen cyanide are
     produced per Mg of acrylonitrile.
          The reactor effluent is scrubbed in a countercurrent absorber,
     and excess ammonia is neutralized with sulfuric acid.   The organic
     materials are recovered from the absorber water by distillation.
     Hydrogen cyanide, water, light ends, and high boiling impurities are
     then removed from the crude acrylonitrile by fractionation at  atmospheric
     pressure.  Acetonitrile and hydrogen cyanide are collected as  saleable
     by-products.
 2.   Input Materials - Basis - 1 metric ton  acrylonitrile
     Propylene - 1.0 kg/kg product                1175 kg  (2,590 Ibs/ton)
     Ammonia - 0.5 kg/kg product                  475 kg (1,047 Ibs/ton)
     Air - 10.0 kg/kg product                     6090 m3  (2.15 x  105  ft/ton)
     Sulfuric acid
     Catalyst                                     small
                                6-656

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3.   Operating Parameters
    Temperature:  450°C  (842°F)
    Pressure:  200 kPa (2 atm)
    Reaction Time:  10-20 sec.
4.   Utilities - Basis:  2.87 kg/sec capacity (200 M Ib/yr)
    Cooling water - 1.89 m /sec (30,000 gpm)
    Refrigeration - 907 Mg (1000 tons)
                          3
    Process water - 315 cm /sec (5 gpm)
    Electricity - 3.6 GJ (1000 kW)
    Steam - 25.2 kg/sec (200,000 Ib/hr)
                                      3
    Inert gas, high pressure - 23.6 dm /sec (3000 scfh)
5.   Waste Streams - Reaction section - absorber off-gases to flare (air)
    Acrylonitrile - 5.0 kg/Mg product
    Carbon monoxide - 200 kg/Mg product
    Propane - 50.0 kg/Mg product
    Propylene - 100 kg/Mg product
    Acetonitrile - trace
    Ammonia - trace
    Purification section - off gas from drying column to flare (air)
        Hydrogen cyanide - 1 kg/Mg product
    Reaction section - neutralizer (water)
        Wastewater contains ammonium sulfate
    Purification section - stripper (water)
        Wastewater may contain acetonitrile.
6.   EPA Source Classification Code - None
7.   References
    Austin, G.  T., "The Industrially Significant Organic Chemicals -
    Part 1, "Chemical Engineering," January 21, 1974, p. 131.

    "1973 Petrochemical Handbook," "Hydrocarbon Processing," November, 1975, p.  99.
    Hedley, W. H., et. al., Potential Pollutants from Petrochemical Processes,
    Technomic Publishing Co., 1975.

                               6-657

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7.   References  (continued)







   Lowenheim, F.  A.,  and Moran,  M.  K.,  Industrial Chemicals. 4th Edition,




   John Wiley and Sons,  New York, N.Y.,  1975,  p.  46,47.
                             6-658

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 274




              Acrylamide (hydration of acrylonitrile)
          CH2=CHCN
                            HO
1.   Function - The hydratlon of acrylonitrile to acrylamide sulfate




     followed by dilution accounts for most acrylamide production at




     the present time.  This reaction is carried out at 155-175° by




     adding acrylonitrile to sulfuric acid at the concentration corre-




     sponding to its mono hydrate.  Dilution with water converts the




     acrylamide sulfate intermediate to acrylamide and sulfuric acid.




          To prevent hydrolysis to acrylic acid, free acid must be re-




     moved from the crude product solution.  This is most commonly




     achieved by neutralization with ammonia or sodium hydroxide to




     form water-insoluble sulfate salts.  The salts are then removed




     by filtration and the filtrate is concentrated and /or cooled to




     recover crystals of acrylamide.  The mother liquor is frequently




     purged and recycled to serve as the medium for further neutrali-




     zation.




          The sulfuric acid may be directly separated from the crude




     product mixture without neutralization.  This is accomplished by




     means of an ion exchange column which separates the product mixture




     into successive fractions of sulfuric acid, acrylamide-acrylic




     acid and acrylamide.




          In July 1974, one U.S. company began producing acrylamide by




     the direct hydrolysis of acrylonitrile over special catalysts.




     A number of catalysts have been developed  that allow  the hydrolysis





                              6-659

-------
     of acrylonitrile in aqueous solution to yield the acrylamide




     directly, obviating the need for the separation procedure necessary




     in the sulfuric acid hydrolysis.  These catalysts consit for the




     most part of activated metallic oxides and are regenerable.  These




     reactions are run at 100°C and it is necessary to include a water




     soluble inhibitor to prevent polymerization of the acrylamide.  In




     one case where the catalyst was 40% Cu salt - 25.5% Cr the inhibitor




     used was N-nitroso-N-phenyl hydroxyamine ammonium salt.  For a 7%




     aqueous solution of acrylonitrile 25 ppm was sufficient to inhibit




     the polymerization.




2.   Input Materials




     Acrylonitrile - 0.95 kg/kg acrylamide




     Concentrated sulfuric acid




     Water




     Ammonia or sodium hydroxide




3.   Operating Parameters




     Temperature - hydrolysis




                   reaction - 155-175°C (311-347°F)




                   neutralization 50°C (122°F)




                   catalytic - 90-105°C (194-221°F)




     Pressure - not given




4.   Utilities - not given




5.   Waste Streams - The principal pollutants from this process should be




     the impurities removed from the mother liquor following acrylamide




     separation.  Acrylic acid, acrylonitrile, ammonia or caustic  soda,




     inorganic sulfates, and traces of acrylamide may be present in this




     waste stream.





                             6-660

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          The principal pollutants from the catalytic process are the




     impurities remaining in the mother liquor following the recrystal-




     lization of acrylamide.  Unreacted acrylonitrile, inhibitor and




     some acrylamide are present.  Catalyst is recovered by filtration




     and except for fines does not present a problem.




6.    EPA Source Classification Code - None




7.    References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N. Y., Vol.  1.,  (1963), p. 278-280.





     U.S. Patent 3,699,194  (1974).





     U.S. Patent, 3,689,558 (Dow Chemical 1974).
                               6-661

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INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 275




               Succinonitrile (from acrylonitrile)






                CH =CHCN + HCN 	>-  NCCH2CH2CN






1.   Function - Succinonitrile, also known as ethylene cyanide, is




     manufactured by reacting acrylonitrile with HCN in the presence




     of a catalyst (~5 wgt % acrylonitrile) and an inert solvent  (tert-



     butyl alcohol).  The acrylonitrile is added gradually to prevent




     polymerization.




2.   Input Materials




     Acrylonitrile




     Hydrogen Cyanide




     Catalyst:  (Triton B) (benzyltrimethylammonium hydroxide)




     Solvent:   tert-Butyl Alcohol




3.   Operating Parameters




     Temperature:             55-60° C (131-140°F)




     Pressure:                101 kPa (1 atm)




     Reaction time:           5 hrs.




4.   Utilities - Not given




5.   Waste Streams - Wastewater streams from the purification section




     may contain alcohol and smaller quantities of acrylonitrile,




     hydrogen cyanide, catalyst, and polymers of acrylonitrile.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 6  (1965), p.  641.
                             6-662

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 276




              Acrylic Acid (oxidation of propylene)




               CH =CHCH3 + 02 	*• CH2=CHCHO + H20




                CH2=CHCHO + 1/2 02	»• CH2=CHCOOH




 1.  Function - The fastest-growing route to acrylic acid involves a




     one-or two-stage oxidation of propylene in the presence of a molybdenum




     oxide catalyst.




          In the two-step process, propylene, steam, and preheated air are




     fed to the first reactor filled with oxidation catalyst.  The tempera-




     ture is maintained at 330 - 370°C by circulating heat transfer medium.




     The crude acrolein product is fed directly to the second reactor where




     it is converted to acrylic acid at 260 - 300°C.  The reaction may be




     run in a single reactor by raising the temperature to 350 - 400°C and




     using a pressure of 98-196 kPa.




          Regardless of the conversion technique, the reactor effluent is




     introduced to an absorber where acrylic acid is scrubbed as an aqueous




     solution.  Acrylic acid in the solution is then extracted with a sol-




     vent.  After solvent separation and light ends removal, high purity




     acrylic acid is obtained at the final rectifier.  Some acetic acid




     by-product may be recovered.




 2.  Input Materials




     Propylene - 0.83 kg/kg acrylic acid




     Air




     Steam - see utilities




 3.  Operating Parameters




     Temperature:  one stage - 350 - 400°C  (662-752°F)




                   two stage - first reactor - 330 - 370°C   (626-698°F)




                               second reactor - 260 - 300°C  (500-572°F)





                             6-663

-------
     Pressure:  100 - 200 kPa (1-2 atm.)


     Catalyst:  MoCL

              A                                      ~
 4.  Utilities  - Basis:  0.31 kg/sec capacity (21.6 M Ib/yr)


     Steam - 3.11 kg/sec (24,700 Ib/hr)


     Power - 0.97 GJ (270 kW)


     Cooling water - 379.1 dm /sec (6,009 gpm)

                           3
     Makeup water - 20.3 dm /sec (322 gpm)


     Electricity - 3.9695 (1,100 kWh) metric ton


 5.  Waste Streams  - Overhead of solvent recovery column (air)


     Acetone - 0.35 kg/Mg product


     Acrolein - 1.85 kg/Mg product


     Ethyl acetate - 1.85 kg/Mg product




     Off-gas from the C- recovery system (air)




     Ethyl acetate - 36.8 kg/Mg product


     Propylene - 6.25 kg/Mg product


     Carbon monoxide - 502 kg/Mg product




     Heavy ends from acrylic acid finishing system (water)




     Acrylic acid - 4 kg/Mg product


     Polymers - 20.6 kg/Mg product


     Hydroquinone - 10.65 kg/Mg product




     Bottom from ethyl acetate recovery system (water)




     Acetic acid - 35.7 kg/Mg product


     Acrylic acid - 5.9 kg/Mg product


     Ethyl acetate - 27.25 kg/Mg product
*
  Data is based on the one-step oxidation.


                            6-664

-------
6.  EPA Source Classification Code - None


7.  References

    Austin, G.  T.,  "The Industrially Significant Organic Chemicals

           ii
    Part 1, Chemical Engineering,   January 21,  1974,  p.  130,313.



    "1973 Petrochemical Handbook,"  Hydrocarbon Processing,


    November, 1973, p. 96.



    Hedley, W. H., et al., Potential Pollutants from Petrochemical


    Processes, Technomic Publishing Co., 1975.
                            6-665

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 277




              n-Butyl Acrylate (from acrylic acid)
        CH2=CHCOOH + n-C4H9OH - KIH






*•   Function - One competitive process for making n-butyl acrylate




     involves the direct esterification of acrylic acid with n-butanol.




          Sulfuric acid is normally used as the catalyst and benzene is




     used as a water entrainer to assist in driving the reaction to




     completion.




2.   Input Materials




     Acrylic acid




     n-Butanol




     Benzene




3.   Operating Parameters




     Temperature:  not given




     Pressure:  not given




     Catalyst:  H^SO,




4.   Utilities - not given




5.   Waste Streams - Waste water streams, if present, may contain acrylic




     acid, sulfuric acid, n-butanol, n-butyl acrylate, and benzene.




6.   EPA Source Classification Code - None




7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 2," "Chemical Engineering," February 18, 1974, p. 126, 127.






     Kirk-Othmer, Encyclopedia of Chemical Technology.  2nd  Edition,




     Interscience Publishers, New York, N.Y.,Vol. 1 (1963),  p.  299.






                             6-666

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 278
                        n-Butyraldehyde (oxo process)
                     CH2=CHCH3 + CO 4- H2 - >• CH3CH2C






1.  Function - In the oxo process, propylene is reacted with synthesis




    gas in the liquid phase at 140-170°C and 20-30 MPa (200-300 atm) .




    An aromatic liquid such as toluene is used as the solvent, and cobalt




    carbonyl compounds catalyze the reaction.  n-Butyraldehyde , isobutyral-




    dehyde, and some butanol are produced.  In modern plants the ratio of




    n-butyraldehyde to isobutyraldehyde is 4:1.  The cobalt catalyst is




    separated from the crude oxo product and recycled to the reactor with-




    out any loss.



         The two aldehydes may be hydrogenated and the corresponding




    alcohols separated by distillation, or the aldehydes may be separated




    and hydrogenated individually.




         The remainder of the product mixture, containing butanols, esters,




    and heavy ends, is separated in a third column to yield small quantities




    of butanol and a residue which is used as fuel.




2.  Input Materials




    Propylene - 0.75 kg/kg n-butyraldehyde




    Synthesis gas (CO and H )




    Toluene (or other solvents)




3.  Operating Parameters




    Temperature - 140-170°C (284-338°F)




    Pressure - 20-30 MPa  (197-296 atm)




    Catalyst - Cobalt carbonyl compound
                              6-667

-------
4.  Utilities




    Not given




5.  Waste Streams




    Catalyst recovery section (air, water)




    Air vents discharge carbon monoxide, propylene, and propane.  Some




    catalyst recovery systems have a wastewater stream.




    Purification section (air)




    Various light end by-products may be flared to the atmosphere.




6.  EPA Source Classification Code - None




7.  References
    Austin, G.  T.,  "The Industrially Significant  Organic  Chemicals -




    Part 2",  "Chemical Engineering," February  18,  1974,  p.  126.





    "1973 Petrochemical Handbook,"  "Hydrocarbon Processing," November




    1973, p. 107.





    Hedley, W.  H.,  et. al.,  Potential Pollutants  from Petrochemical Processes,




    Technomic Publishing Co., 1975.
                              6-668

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 279




         Isobutanol (hydrogenation of isobutyraldehyde)






              (CH3)2CHCHO + H2 	*• (CH3)2CHCH2OH






1.   Function - Isobutanol is produced by the catalytic hydrogenation of




     isobutyraldehyde in a process similar to that used to make n-butanol




     from n-butyraldehyde.  The reaction is carried out at 10.0 MPa  pres-




     sure, and water is added to suppress ether formation.




          Some n-butanol is also produced by this reaction due to aldehyde




     isomerization.  The isobutanol, n-butanol, and other by-products




     are separated by the methods described in Process No. 282.




2.   Input Materials




     Isobutyraldehyde - 1.10 kg/kg product




     Hydrogen




     Water




3.   Operating Parameters




     Temperature:  130-250°C (266-482°F)




     Pressure:  10.0 MPa (100 atm)




     Catalyst:  nickel, copper chromite, or molybdenum sulfide




*•   Utilities - Not given




5.   Waste Streams - The same general types of pollution would be ex-




     pected as in Process No.




6.   EPA Source Classification Code  - None




7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals  -




     Part 6," "Chemical Engineering," May 27, 1974, p. 104.
                             6-669

-------
7.   References (continued)




     "1973 Petrochemical Handbook Issue," Hydrocarbon Processing,




     November 1973, p. 107.






     Hedley, W. H., et al.,  Potential Pollutants from Petrochemical




     Processes. Technomic Publishing Co., 1975.






     Waddams,  A.  L.,  Chemicals from Petroleum, 3rd Edition,  John Murray,




     Ltd.,  London,  England,  1973,  p.  205.
                            6-670

-------
INDUSTRIAL ORGANIC CHEMICALS                             PROCESS NO. 280

                       Isobutyl Acetate  (from  isobutanol)
                                    H SO,
            CH3COOH
!•   Function - Isobutyl acetate is formed by tlie esterification of acetic

     acid with isobutyl alcohol in the presence of sulfuric acid.  The

     reaction is carried out at the reflux temperature of the ternary azeo-

     trope of isobutyl alcohol, isobutyl acetate and water.  The vapor

     mixture distilling at this temperature is sent to a separator where

     the water is separated into an aqueous and alcohol-ester fraction.

     The alcohol-ester layer is distilled giving an alcohol-ester azeotrope

     and pure ester.

2.   Input Material - basis 1 kg is'obutyl acetate


     Isobutyl alcohol        .9 kg/kg

     Acetic acid             .94 kg/kg

     Sulfuric Acid          0.1%


3.   Operating Parameters


     Temperature:     85-89°C (185 - 192°F)

     Pressure:        100  kPa  (1 atm.)

     Catalyst:        Sulfuric acid


4.   Utilities

     Not available

5.   Waste Streams - Isobutyl alcohol and isobutyl acetate will  be emitted

     from the reflux condenser.  Waste water streams from the separator

     contain acetic acid, dilute sulfuric acid, isobutyl alcohol and

     isobutyl acetate.  Air vent streams from the purification system

                               6-671

-------
     (distillation) will contain isobutyl alcohol and isobutyl acetate.




6.   EPA Source Classification Code - None




7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 2,""Chemical Engineering," February 18, 1974, p. 126.





     Faith, W.  L., et  al.,  Industrial Chemicals,  3rd  Ed.,  John Wiley and




     Sons,  Inc.,  New York,  1965,  p.  176-78.
                               6-672

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 281




         Isobutyric Acid (oxidation of isobutyraldehyde)






            (CH3)2CHCHO + 1/2 02 	1-  (CH3)2CHCOOH






-1--   Function - Isobutyric acid is prepared in 95% yield by the air




     oxidation of isobutyraldehyde at 30-50°C.




          The crude product is best purified by azeotropic distillation




     with water followed by fractional distillation.




          In some cases, ispbutyl alcohol may be the raw material for




     this oxidation.




2.   Input Materials




     Isobutyraldehyde - 0.86 kg/kg product




     Air




     Water




3.   Operating Parameters




     Temperature:  30-50°C




     Pressure:  not given




4.   Utilities - Not given




5.   Waste Streams - Waste water from distillation procedures may contain




     isobutyraldehyde, traces of isobutyric acid, and isobutanol, if used




     as the raw material in the synthesis.  Waste gases from the purifi-




     cation section probably contain isobutyraldehyde and/or isobutanol.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 3   (1964), p.  880.
                             6-673

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.   282





                               n-Butanol
1.  Function - About half of the commercial n-butanol is produced by the




    hydrogenation of n-butyraldehyde.   In nearly all plant processes, the




    butyraldehyde feedstock is prepared by the oxo-reaction of propylene,




    so it contains isobutyraldehyde as  well (see Process No.  278).   In




    modern processes the hydrogenation  reaction tends to isomerize the




    mixture to n-butanol.




         A number of operating parameters have been reported for this




    reaction.  In most cases, the butyraldehyde feed is converted with




    hydrogen over a fixed-bed catalyst  such as nickel, copper chrom^te,




    or molybdenum sulfide at 130-250°C  and 3-20 MPa (30-200 atm) .




         The crude n-butanol is purified by rectification in two columns.




    In the first column, the low boiling impurities, isobutanol and water,




    are separated as overhead.  The higher-boiling impurities are removed




    in the second column by continuous  discharge of the bottoms, product,




    and pure n-butanol is taken overhead.




2.  Input Materials




    n-Butyraldehyde (+ some isobutyraldehyde) -  1.09  kg/kg n-butanol



    Hydrogen
                              6-674

-------
3.  Operating Parameters

    Temperature - 130-250°C

    Pressure - 3-20 MPa (30-200 atm)

    Catalyst - nickel, copper chromite, or molybdenum sulfide

4.  Utilities - Not given

5.  Waste Streams

    Hydrogenation reactor (air)

    Tail gas vent discharges hydrogen and some organic vapors

    Distillation column (organic liquid)

    Heavy ends are usually burned.

    This process involves no waste water and minimal air pollution.

6.  EPA Source Classification Code - None

7.  References

    Austin, G. T., "The Industrially Significant Organic Chemicals - Part 2,"

    "Chemical Engineering," February 18, 1974, p. 126.


    "1973 Petrochemical Handbook Issue," "Hydrocarbon Processing,"

    November 1973, p. 153.


    Hedley, W. H., et al., Potential Pollutants from Petrochemical Processes,

    Technomic Publishing Co., 1975.
         \

    Waddams,  A.  L.,  Chemicals from Petroleum,  3rd Ed.,  John Murray,  Ltd.,

    London,  England,  1973,  pp.  204-206.
                              6-675

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  283




                      n-Butyric Anhydride
        2C3H?COOH + (CH3CO)20
                    2CH2CO - KC






1.   Function - Butyric anhydride may be prepared by an exchange between




     butyric acid and acetic anhydride,  or by the spontaneous reaction




     of butyric acid and ketene.




          Since ketene may be synthesized from acetic acid (see Process




     No. 105), these reactions may be run in conjunction with each other.




     This system would require an initial input of either acetic acid




     or acetic anhydride.




2.   Input Materials




     Butyric acid




     Acetic acid or acetic anhydride




3.   Operating Parameters - Not given




4.   Utilities - Not given




5.   Waste Streams - Effluents from separation and purification operations




     may contain acetic acid, acetic anhydride, unreacted butyric acid,




     and butyric anhydride.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,




     Interscience Publishers, New York,  N.Y., Vol. 3,  (1964), p. 880.
                             6-676

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 284




            n- Butyl. Amines (from n-butyraldehyde)
•"••   Function - The most common route to n-butylamine involves the hydro-




     genation of n-butyraldehyde and alcoholic ammonia.  The reaction is




     carried out at 90-125°C and elevated pressure in the' presence of a




     nickel catalyst.




          The yield of n-butylamine is about 80% with smaller amounts of




     di- and tri-n-butylamine by-products.




2.   Input Materials




     n-Butyraldehyde - 1.23 kg/kg n-butylamine




     Ammonia




     Hydrogen




     Alcohol (solvent)




3.   Operating Parameters




     Temperature:  90-125 °C




     Pressure:  -500-1000 kPa (5-10 atm)




     Catalyst:  nickel




4-   Utilities - Not given




5.   Waste Streams - The separator effluent may contain quantities of




     ammonia, n-butyraldehyde, alcoholic solvent, spent catalyst, various




     butylamines , and by-product n-butanol.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 2  (1963), p. 117,  124.





                             6-677

-------
7.   References (continued)




     Ibid., Vol. 3 (1964), p. 868.






     Koddo, N., Chem. Eng.. 50(9), 149-68 (1952)
                              6-678

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 285



             Propylene Chlorohydrin (from propylene)
                    C10 + H00 spfc HOC1 + HC1
                      L    2
                      HOC1
CH,CH-CH9OH +
Jf f.
Cl
10%
OH
90%
1.   Function - The bulk of propylene chlorohydrin produced in this



     country is made by the hydrochlorination of propylene.  The method



     involves passing chlorine, propylene and water into a rubber-lined



     steel or acid-proof brick reactor at 35-50°C.  The chlorine and



     water react to form hypochlorous acid and hydrochloric acid in a



     reversible reaction.  The olefin is added to the hypochlorous acid



     at a rate which is maintained to produce a chlorohydrin of 3-5%.



     More concentrated solutions promote side reactions which yield



     bis(chloroisopropyl) ether and propylene dichloride.



          The vent gases from the chlorohydrin tower are passed through



     a partial condenser to remove propylene dichloride and bis(chloro-



     isopropyl) ether.  The residual gas is scrubbed to remove HC1 and



     in some cases recycled to the tower to recover any residual propy-



     lene.  The propylene dichloride is purified and sold.



2.   Input Materials



     Propylene



     Chlorine



     Water
                             6-679

-------
3.   Operating Parameters




     Temperature:  35-50°C (95-122°F)




     Pressure:  110-130 kPa (1.14-1.27 atm)




4.   Utilities - not available




5.   Waste Streams - Waste water from scrubbing operations may contain




     sodium chloride and caustic soda.  Reaction by-products, such as




     bis(chloroisopropyl) ether, may be present in air and waste water




     emissions from other purification sources.  A portion of the re-




     cycled propylene may be vented to control the concentration of




     inert gases in the propylene feed.  These emissions may contain




     ethylene, propylene, butane, hydrogen chloride and chlorine.




6.   EPA Source Classification Code - None




7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 8,""Chemical Engineering," July 22, 1974, p. 111.






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 16 (1968) > p. 600-602.






     Waddams,  A.  L., Chemicals from Petroleum, 3rd Ed.,  John Murray, Ltd.,




     London, England,  1973,  p. 137, 138.
                             6-680

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 286




             Propylene Oxide (chlorohydrin process)
    2CH3CHOHCH2C1 + Ca(OH)2 - >• 2CH3CH-CH2 + CaCl2
1.   Function - As of July 1973, 70% of the U.S. capacity for propylene




     oxide production was based on the chlorohydrin process.   In normal




     plant procedure, the propylene chlorohydrin feedstock is synthesized




     as described in Process No, 285.   This dilute chlorohydrin solution




     is mixed with a 10% slurry of lime and pumped to a steam-heated flash




     hydrolyzer for conversion to propylene oxide.  The reaction is carried




     out under ambient conditions.




          The oxide is flashed out of the reaction zone as quickly as pos-




     sible to prevent its further hydrolysis to propylene glycol.  The




     lime slurry is used in excess and this excess may be recovered for




     recycle in thickeners which provide for the removal of the spent cal-




     cium chloride brine by decantation.  This effluent consists of 5%




     aqueous CaCl? containing traces of lime and propylene glycol.




          The overhead from the hydrolyzer is largely propylene oxide




     and water.  It is contaminated with propylene dichloride, chloro-




     prenes from dehydrochlorination of propylene dichloride, and propional-




     dehyde from isomerization of propylene oxide.  This crude product  is




     purified by fractionation in multiple distillation columns.




2.   Input Materials




     Propylene chlorohydrin




     (from propylene - 0.94 kg/kg propylene oxide)




     10% Calcium hydroxide - 1.17 kg/kg product
                             6-681

-------
3.   Operating Parameters


     Temperature:  25°C  (77°F)


     Pressure:  -atmospheric (100 kPa)


4.   Utilities* - Basis - 0.72 kg/sec capacity (30 M Ib/yr)


     Cooling water - 259 dm /sec (4100 gpm)


     Nitrogen - 23.6 dm3/sec (3000 cfh)


     Power - 648 MJ (180 kW)


     Refrigeration - 1.109 Gg (1222 tons)


     Steam - 7.31 kg/sec (58,000 Ib/hr)

                  *
5.   Waste Streams


     Purge gas from caustic absorber (air)


     Ethane - 8.5 kg/Mg product


     Butane - 8.5 kg/Mg product


     Propylene - 8.5 kg/Mg product


     Hydrogen chloride - 0.5 kg/Mg product


     Chlorine - 0.5 g/Mg product


     Off gas from tail gas absorber (air)


     Propylene oxide - 4.1 kg/Mg product


     Hydrogen chloride - 0.5 g/Mg product


     Chloride - 0.5 g/Mg product


     Water effluent


     The major waste stream would probably contain calcium chloride and


     traces of lime and propylene glycol.


6.   EPA Source Classification Code - None
  Includes Process No. 285



                             6-682

-------
7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals -




     Part 8," "Chemical Engineering," July 22, 1974, p. 111.






     Hedley, W. H., et al., Potential Pollutants from Petrochemical




     Processes, Technomic Publishing Co., 1975, p.  147-148.






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol.  16 (1968), p. 600.
                            6-683

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  287


                     Mono- and Dipropylene Glycols
                  CH0OCHCH, + ELO 	>• CH CHOHCIUOH
                    L |   j    /           J      f-
         CH3CHOHCH2OH
1*   Function - Propylene glycol is produced by hydration of propylene


     oxide under pressure at temperatures up to 200°C.   No catalysts are


     used.


          Some dipropylene glycol, tripropylene glycol, and minor quantities


     of higher glycols are co-produced by the continued reaction of propy-


     lene oxide.


          The proportion of higher glycols is controlled by the molar


     ratio of propylene oxide to water in the initial reaction mixture:


     the greater the dilution, the greater the production of propylene


     glycol and the higher the cost of recovering the pure products from


     solution.  Usually about 15 moles of water are used per mole of


     propylene oxide in order to maximize propylene glycol production.


     This yields about 13% by weight dipropylene glycol and 1.5% tri-


     propylene glycol.



          Although most dipropylene glycol is recovered as a by-product


     of this process, some is produced by reacting propylene glycol with


     propylene oxide.


2-   Input Materials


     Propylene oxide



     For propylene glycol - 0.77 kg/kg




                            6-684

-------
2.   Input Materials (continued)




     For dlpropylene glycol - 0.95 kg/kg




     Water - 3.7 kg/kg product




3.   Operating Parameters




     Temperature:  ~200°C




     Pressure:  not given




4.   Utilities - Not given




5.   Waste Streams - The principal pollutant source in this process is




     waste water flow from the dehydrator, containing quantities of




     propylene oxide and propylene glycol.




6.   EPA Source Classification Code - None




7.   References




     Hedley, W. H., et al., Potential Pollutants from Petrochemical




     Processes, Technomic Publishing Co., 1975.







     Austin, G. T., "The Industrially Significant  Organic Chemicals -




     Part 8," "Chemical Engineering," July  22,  1974,  p.  110-111.
                             6-685

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 288




                        Polypropylene Glycol
          CH3CHOHCH2OH + nCHOCHCH - > HO(CH0)    H
1.   Function - Polypropylene glycol is produced by the base-catalyzed




     addition of propylene oxide to propylene glycol.  The reaction




     takes place around 150°C.




          Commercial polypropylene glycols have molecular weights ranging




     from 400 to 4000.




2.   Input Materials




     Propylene oxide




     Propylene glycol




3.   Operating Parameters




     Temperature:  150°C




     Pressure:  Not given




     Catalyst:  KOH or other bases




4.   Utilities - Not given




5.   Waste '.Streams - The same types of pollution would be expected as in




     Process No. 287.  Spent catalyst may also be present.




6.   EPA Source Classification Code - None




7.   References




     Austin, G. T-, "The Industrially Significant Organic Chemicals -




     Part 8," "Chemical Engineering," July 22, 1974, p. 110.
                              6-686

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 289


           Ally! Alcohol (isomerization of propylene oxide)
                   CH3CH-CH2 - ~> CH2=CHCH2OH
1.   Function - Allyl alcohol is produced in 80-85% yield by the

     catalytic isomerization of propylene oxide.  This rearrangement is

     carried out in the liquid phase in jacketed, stirred tank-type

     reactors at 200-300°C and 1-25 atm.  Both lithium phosphate and

     lithium arsenate catalysts are used.

2.   Input Material - Propylene oxide - 1.21 kg/kg allyl alcohol

3.   Operating Parameters

     Temperature:  200-300°C (392-572°F)


     Pressure:  0.1-2.5 MPa (1-25 atm)

     Catalyst:  lithium phosphate or arsenate

4.   Utilities - Basis - 284 g/sec capacity (19.8 M Ib/yr)

     Steam - 1.16 kg/sec (9200 Ib/hr)

     Power - 302.4 MJ (84 kW)

     Fuel -  1159 MJ (1.1 M Btu/hr)

                       o
     Nitrogen - 157 scm /sec (20 scfh)


5.   Waste Streams

     Isomerization section - product column (water)


     Allyl alcohol - 13 kg/Mg product


     plus traces of n-propyl alcohol, tars, and xylene


     Catalyst tar removal section - auxiliary liquid column  (water)


     Terphenyls - 12.5 kg/Mg product


     Lithium phosphate - 5 kg/Mg product


     Tars - 25.5 kg/Mg product

                             6-687

-------
6.   EPA Source Classification Code - None




7.   References




     Hedley, W. H., et al.,  Potential Pollutants from Petrochemical




     Processes, Technomic Publishing Co.,  1975,  p. 151.






     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers,  New York,  N.Y.,  Vol. 10 (1966), p.  624.
                            6-688

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 290




                            Dichlorohydr in






               CH2=CHCH2OH + C12 	*-  ClCH2-CHCl-CH2OH              (1)






               CH2=CHCH2C1 + HOC1 	>-  HOCH2CHC1CH2C1               (2)






1.   Function - Dichlorohydrin is an intermediate in the production of




     glycerine.  There are two principal processes used in the synthesis




     of dichlorohydrin.  The starting materials in both processes are




     derived from propylene.




          Allyl alcohol is chlorinated with chlorine gas to the dichloro-




     hydrin.  The product mixture contains 1,2-dichlorohydrin and 1,3-




     dichlorohydrin which need not be separated if this is the intermediate




     step in the synthesis of epichlorohydrin.




          Allyl chloride is used as the starting material in a continuous




     chlorohydrination process.  Chlorine, water and allyl chloride are




     fed to a stirred-reactor operating at 30-80°C and atmospheric pressure.




     The allyl chloride is kept low to inhibit side reactions which form




     1,2,3-trichloropropane and chloroethane.  The reaction yields a mix-




     ture of 1,2- and 1,3-dichlorohydrin in a  70-30 ratio.




          The reactor effluent is lead to a separator where the aqueous




     and organic phases are separated.  The aqueous phase is recycled to




     the reactor after additional chlorine is  added.  The organic phase




     is converted to epichlorohydrin.




2.   Input Materials




     Allyl alcohol




     Chlorine





                              6-689

-------
2.   Input Materials (continued




     Allyl chloride - 0.98  kg/kg epichlorohydrin




     Chlorine/water - 0.90  kg/kg epichlorohydrin




3.   Operating Parameters




     Temperature:  30-80°C  (86-176°F)




     Pressure:  100 kPa (1  atm)




4.   Utilities - Not given




5.   Waste Streams - Vent gases from the  reactor may contain allyl  alcohol,




     allyl chloride, chlorine,  dichlorohydrin and  reaction by products




     such as propylene dichloride.




6.   EPA Source Classification  Code - None




7.   References







     Kirk-Othmer, Encyclopedia  of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol.  5  (1964),  p.  316-317.






     Hancock, E. G., Propylene  and  Its Industrial Derivatives, 'John




     Wiley and Sons, New York,   N.Y.,  1973, p.  24.
                             6-690

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 291



             Epichlorohydrin (from dichlorohydrin)




C1CH0CHC1CH«OH + 1/2 Ca(OH)0 -  CH0-CHCH0C1 + 1/2 CaCl, -I- H00
    i.      L               Z       \Z i   2.             t.    /
     C1CH,CHC1CH9OH + NaOH -  CH0-CHCH0C1 + NaCl + H,0
         i,      Z                ^Z i   /             i.
 1.  Function - Epichlorohydrin is commercially produced by the dehydro-



     chlorination of dichlorohydrin.  In this process, crude dichloro-



     hydrin (see Process No . 290)  is treated with a lime slurry or



     caustic soda in a column-type reactor at 70-100°C and atmospheric



     pressure.  The solvent is trichloropropane .



          The crude epichlorohydrin is removed from the reaction mixture



     as a water azeotrope by steam stripping.  Final purification is



     accomplished by a two-column distillation train.



          If the product is to be used in glycerol production, it need



     not be purified.



 2.  Input Materials



     Dichlorohydrin (crude mixture)



     Calcium hydroxide - 1.01 kg/kg epichlorohydrin or



     Sodium hydroxide - 1.09 kg/kg epichlorohydrin



 3.  Operating Parameters



     Temperature:  <60°C (<140°F)



     Pressure - 101 kPa (1 atm)



 A.  Utilities



     Not given



 5.  Waste Streams



     Tail gas absorber vent (air)




                            6-691

-------
    Chlorine - 0.5 g/Mg product




    Hydrogen chloride - 0.5 g/Mg product




    Allyl chloride - 2 kg/Mg product




    Reactor vent (air)




    Allyl chloride - 2 kg/Mg product




    Epichlorohydrin - 1.5 kg/Mg  product




    Trichloropropane - 0.5 kg/Mg product




    Chlorine - 0.5 g/Mg product




    Hydrogen chloride - 0.5 kg/Mg product




         The major water pollution problem would probably be a slurry




    containing lime or caustic soda, calcium chloride or sodium chloride,




    and small amounts of epichlorohydrin.




6.  EPA Source Classification Code - None




7.  References




    Hedley, W. H., et al., Potential Pollutants from Petrochemical




    Processes, Technomic Publishing Co., 1975.






    Sittig, M., Pollution Control in the Organic Chemical Industry,




    Noyes Data Corp., Park Ridge, N.J., 1974, p. 131, 132.






    Lowenheim, F. A. and Moran, M. K., Industrial Chemicals, 4th Edition,




    John Wiley and Sons, New York, N.Y., 1975, p. 335, 336.
                           6-692

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 292

            Glycerol (from peroxidation of allyl alcohol)
       CH7=CHCH0OH + (CH,),C-OOH  - >•  CH0-CH-CH0OH -f (CH.)
         *•     £•        j j              ^z, if.        j
                                           0
                                   Na2CO
                CH-CH-CHOH + H0 — - —
 22
\
                   Q                             OH

1.  Function - This process has become competitive with the hydrochlorination

    of allyl alcohol in the synthesis of glycerin.  The trend has been away

    from chlorination to peroxidation because in the former process the

    chlorinated products are discarded, for lack of markets, while the

    products of hydroperoxidation are all saleable.

         Allyl alcohol is epoxidized by reaction with a hydroperoxide.  The

    hydroperoxide that is used is chosen carefully so that its degradation

    product is saleable or useable in an allied process.  The hydroperoxides

    commonly used are t-butyl hydroperoxide (degradation product, t-butyl-

    alcohol) and ethyl benzene hydroperoxide (degradation product, phenyl

    methyl carbinol) .  The glycidol produced is hydrolyzed to produce

    glycerin.  Although the reactants in this process are more expensive

    than those in the chlorohydrin-glycerin process, their cost is recoverable

    since all products are utilized.

2.  Input Materials

    Allyl alcohol - 0.67 kg/kg glycerol

    t-Butyl hydroperoxide - 1.1 kg/kg glycerol

3.  Operating Parameters

    Temperature:  25-30°C  (77-86°F)

    Pressure:  1.6-3.6 KPa (16-35 atm)

                              6-693

-------
4.  Utilities - Not given




5.  Waste Streams - Air streams may contain allyl alcohol and degradation




    products of the hydroperoxide (t-butyl alcohol, for example).  Waste




    water streams may contain allyl alcohol, glycidol, sodium carbonate and




    t-butyl alcohol or methyl phenyl carbinol depending on the hydroperoxide




    used.




6.  EPA Source Classification Code - None




7.  References




    R. G. Muller, "Glycerin and Intermediates," Report No. 58, Stanford




    Research Institute, Menlo Park, California, 1969.





   "Hydrocarbon Processing," Nov. 1961, p. 249.





    Hedley, W. H. et al.,  Potential Pollutants From Petrochemical Processes,




    Prepared for EPA, Final Report MRC-DA-406,  Contract 68-02-0226, Dec. 1973,




    p. 149-150.
                              6-694

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INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO.  293
             Glycerol Tri(polyoxypropylene) Ether (GTPE)
           HOCH2CHCH2  + 3

                OHOH          (T
1.   Function - Glycerol tri(polyoxypropylene) ether is formed by the

     base-catalyzed reaction of glycerol and propylene oxide.  The con-

     version is normally carried out at 125°C and 446 kPa (4.4 Atm) .

          Near the end of the reaction, some ethylene oxide is usually

     added to impart certain desired properties characteristic of poly-

     oxyethylene linkages.

          GTPE is prepared in a variety of molecular, weights.



2.   Input Materials

     Glycerol
     Propylene oxide
     Ethylene oxide

3.   Operating Parameters

     Temperature:  125°C (257°F)
     Pressure:  446 kPa (4.4 atm)
     Catalyst: KOH

4.   Utilities - Not given.

5.   Waste Streams - Waste streams from purification operations are likely

     to contain quantities of propylene oxide, spent catalyst, glycerol,

     GTPE, and by-products such as propylene glycol.
                             6-695

-------
6.   EPA Source Classification Code - None.




7.   References




     Austin,  G. T.,  "The Industrially Significant Organic Chemicals




     Part 6", "Chemical Engineering", May 27,  1974,  p.  103.
                             6-696

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 294




                             Cumene Hydroperoxide
                                                          0-OH
1.  Function - The hydroperoxide ts made from cumene by an air oxidation




    process.  A mixture of cumene, water, sodium carbonate, sodium stearate




    and a small amount of cumene hydroperoxide, which functions as an




    oxidation initiator, is fed to a liquid phase oxidation vessel.   The




    oxidizing agent is air, and the reaction is carried out at 130°C and




    274-446 kPa  (2.70-4.40 atm) until 35-50% of the cumene is converted to the




    hydroperoxide.  The oxidation product is distilled so that most of the




    unreacted cumene goes overhead, and the cumene hydroperoxide to bottom.




    As of January 1, 1975,  almost 91% of synthetic phenol capacity was




    based on the acid-catalyzed cleavage of cumene hydroperoxide.









2-  Input Materials




    Cumene




    Air




    Sodium carbonate




    Sodium stearate




    Water




3.  Operating Parameters




    Temperature - 130°C  (266°F)




    Pressure - 274-446 kPa (2.70-4.40 atm)




4.  Utilities - Not given
                              6-697

-------
5.  Waste Streams - Waste water contains  sodium carbonate,  sodium stearate,

    phenol and acetone.   The air vents  may emit cumene,  acetone and  traces

    of mesityl oxide.

                          Plant 1                       Plant  2

    Flow           2.33  x 10~3 m3/kg (279-6       1.37 x 10~3m /kg (164  gal/
                     gal/1000 Ibs)                   1000 Ibs)

    COD                   4,700 mg/1                    84,304 mg/1
                           11.1  g/kg                     11.4  g/kg

    BOD,.                  2,410 mg/1                    17,575 mg/1
       5
                            5.6  g/kg                       24  g/kg
    TOG                     194 mg/1                    77,406  mg/1
                            0.45 g/kg                     105.6 g/kg

    Lower values for plant 1 due to installation of  dephenolizer facilities
    (steam strippers).

6.  EPA Source Classification Code - 3-01-034-01

7.  References

    Austin, G. T.,  "The Industrially Significant Organic Chemicals - Part 1,"

    "Chemical Engineering," January 21,  1974,  p.  130.


    Ibid., Part 8,  July 22, 1974, p. 107,108.


    "1973 Petrochemical Handbook," "Hydrocarbon Processing," November 1973,

    p.  158.


    "1975 Petrochemical Handbook," "Hydrocarbon Processing," November 1975,

    p.  170.


    Hedley, W. H.,  et al., Potential Pollutants from Petrochemical Processes,

    Technomic Publishing Co., 1975.


   Sittig, M.,  Pollution  Control in the Organic Chemical Industry. Noyes

   Data  Corp.,  Park Ridge, N.J., 1974, p. 182,183.
                               6-698

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  295



              Phenol (decomposition of cumene hydroperoxide)
                                                        0


                                                OH + CH3CCH3
1.  Function - Cumene hydroperoxide decomposes under the influence of



    sulfuric acid to acetone and phenol.  Approximately 88% of the phenol



    produced in the United States in 1974 was made by this process.   The



    hydroperoxide is usually made from crude cumene and may contain benzene



    and a-methyl styrene.



2.  Input Materials



    Cumene hydroperoxide



    Sulfuric acid



3.  Operating Parameters



    Temperature - 70-80°C (158-176°F)



    Pressure - 50-152 kPa (0.5-1.5 atm)



    Catalyst -  Sulfuric acid



4-  Utilities - Not given



5.  Waste Streams



    Crude Phenol surge (water)



    Cumene trace



    Acetone - 4.5 x 10~  kg/kg phenol



    Phenol - 7.5 x 10~  kg/kg phenol



    Evaporator Residue



    Acetophenone - .00175 kg/kg phenol



    Phenol - 7.5 x 10~  kg/kg phenol



    Polymeric matter - 0.11 kg/kg phenol

                           -4
    Cumyl phenol - 8.5 x 10   kg/kg phenol


                              6-699

-------
6.  EPA Source Classification Code - None




7.  Reference




    Lowenheim, F.  A., and Moran,  M. K.,  Industrial Chemicals, 4th Edition,




    John Wiley and Sons, New York, N.Y.,  1975,  pp. 612-613.





    Hedley, W. H., et al., "Potential Pollutants from Petrochemical Processes,"




    for Control Systems Laboratory, NERC, Environmental Protection Agency,




    Contract No. 68-02-0226, Task No. 9,  pp.  121-122.
                              6-700

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INDUSTRIAL ORGANIC CHEMICALS                    PROCESS NO. 296
            g-Methylstyrene (dehydrogenation of cumene)




                            A
                                   > C6H5C(CH3)=CH2 + ^






1.   Function - Most conmercial a-methylstyrene is produced by the




     dehydrogenation of cumene.  In a typical operation, a mixture




     of three parts steam to one part cumene is passed rapidly over




     an iron oxide catalyst at temperatures of 500-600 °C.




          The crude dehydrogenation mixture contains cumene and a-




     methylstyrene, as well as small amounts of benzene, toluene,




     ethylbenzene, styrene, and tars.  All of the usable components




     are separated and purified through a series of fractional




     distillations and recycled.




2.   Input Materials




     Cumene




     Steam




3.   Operating Parameters




     Temperature:   550-600°C (1022-1112°F)




     Pressure:       not given




     Catalyst:       iron oxide




4.   Utilities - Not given.




5.   Waste Streams - Wastewater streams from the separators and super-




     heater probably contain a variety of heavy-end aromatic hydro-




     carbons,  tars, and spent catalyst.  Organic solids from still




     bottoms are usually incinerated.




6.   EPA Source Classification Code - None.




                             6-701

-------
7.   References




     Klrk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N. Y-, Vol. 19, (1969)  p. 81.
                            6-702

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.  297
                   2,6-Xylenol (methylation of phenol)
1.  Function - 2,6-Xylenol is a by-product of the methylation of phenol




    to produce o-cresol.  The xylenol isomer is present in approximately




    25% of the yield.  Phenol is reacted with methanol at about 300°C and a




    pressure of 4.13 MPA (41 atm) over an alumina catalyst.   Small amounts




    of meta and para alkylated products are formed as well as some phenyl




    ethers formed by oxidative coupling.  The crude product is separated and




    purified by crystallization.




2.  Input Materials




    Phenol




    Methanol




    Alumina




3.  Operating Parameters




    Temperature:  300°C  (572°F)




    Pressure:  4.13 MPA (41 atm)




    Catalyst:  Al_03




4.  Utilities - Not given




5.  Waste Streams - Air vent streams would contain methanol and small




    quantities of phenol.  Wastewater effluents from purification operations




    probably contain small quantities of ethers and m- or p- substituted




    cresols and xylenols.  Unreacted methanol and phenol may also be present




    in trace amounts.






                              6-703

-------
6.   EPA Source Classification Code - None




7.   References




    Kirk-Othmer,  Encyclopedia of  Chemical Technology, 2nd Edition,




    Interscience  Publishers,  New  York, N.Y., Vol. 6  (1965)  p.







    Hahn,  A.  V.,The Petrochemical Industry, McGraw-Hill Book Co., New York




    1970,  p.  576-78.
                              6-704

-------
INDUSTRIAL ORGANIC CHEMICALS
                                             PROCESS NO. 298
                                CHLOROPHENOLS

                           (Chlorination of phenols)
                           OH         OH        OH
                                Cl
+ Cl,
                                                                         (1)
                   Cl
                             or
                                                      + HC1
                                                                (2)
               Cl                              Cl

1.  Function - The most widely used method for the preparation of mono-

    chlorophenols is the direct chlorination of phenol in the absence of a

    solvent.  The product is a mixture of o- and p-chlorophenols with

    preponderance of the para isomer.  The reaction will proceed step-

    wise to the di-, tri- and tetrachloro- products although the rate slows

    with each additional atom of chlorine added to the phenol substrate.

         The dichlorophenols can be produced by direct regulated action of

    chlorine in a solvent such as glacial acetic acid or chloroform.

    Chlorination in aqueous solution gives 2,4,6-trichlorophenol rapidly

    and quantitatively.

         Pentachlorophenol is produced by chlorinating the more highly

    substituted chlorophenols in the presence  of FeCl_ or A1C1- since the

    rate of chlorination has decreased to the  point that the uncatalyzed

    reaction becomes prohibitably slow.
                              6-705

-------
         The chlorophenols can be separated from unreacted phenol by




    adding potassium carbonate which reacts with the chlorinated phenols




    to form the water-soluble salts.  Phenol is not basic enough to react




    and can therefore be extracted from the water solution.




         The chlorophenol isomers can be separated by fractional distillation.




    Pentachlorophenol, 2,4-dichlorophenol,  2,3,4,6-tetrachlorophenol,  2,4,6-




    trichlorophenol and p-chlorophenol are  all soluble products.  o-Chloro




    and 2,6-dichlorophenol have no commercial use and are recycled for




    further chlorination.




2.  Input Materials




    Phenol




    Chlorine




    Potassium carbonate




    AtimiiTHim trichloride or ferric chloride




3.  Operating Parameters




    Temperature - 50-155°C  (122-311°F)




    Pressure - not given




    Catalyst - for pentachlorination - A1C1  or *eCl_  (0.05-1.0%)




4.  Utilities - Not given




5.  Waste Streams - Waste water streams from washing operations  and still




    bottoms probably contain quantities of potassium chloride,  HC1, phenol




    chlorine and chlorophenols.  Chlorine, HC1 and extraction solvents  are




    present in air emissions.




6.  EPA Source Classification Code - None
                              6-706

-------
7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience Publishers,  New York, N.Y., Vol.  5  (1968)  p.  300.
                               6-707

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INDUSTRIAL ORGANIC CHEMICALS                 PROCESS NO.  299


         Chloranil (from 2,4,6-trichlorophenol)
                                    C3T  Nf  NCI
                                          0
1.   Function - Chloranil or 2,3,5,6-tetrachloro-l,4-benzoquinone is

     prepared by the action of chlorine and fuming sulfuric acid on

     2,4,6-trichlorophenol.

2.   Input Materials

     2,4,6-Trichlorophenol
     Chlorine
     Sulfuric acid (fuming)

3.   Operating Parameters - Not given.

4.   Utilities - Not given.

5.   Waste Streams - Effluents from purification operations may contain

     2,4,6-trichlorophenol and other chlorophenols,  chlorine, sulfuric

     acid, chloranil and a variety of reaction by-products.

6.   EPA Source Classification Code - None.

7.   References

     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

     Interscience Publishers,  New York, N.Y., Vol. 5   (1964), p.  334.
                             6-708

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 3QQ




                 Aniline (ammonolysis of phenol)
 1.  Function - Currently, the most economical route to aniline is the




     ammonolysis of phenol.  In this process, ammonia and phenol are




     preheated and fed to a fixed-bed catalytic reactor where the con-




     version takes place over alumina.  The reactor effluent is partially




     condensed and unconverted ammonia is compressed and recycled.  The




     water of reaction is removed from the crude aniline stream by distil-




     lation, at the same time unreacted phenol distills as an azeotrope




     with water and is recycled.  High purity aniline product is recovered




     by distillation from heavies.  This process offers less by-products




     than other commercially used processes.




 2.  Input Materials




     Phenol - 1.05 kg/kg product




     Ammonia - 0.20 kg/kg product




 3.  Operating Parameters




     Temperature:  not given




     Pressure:  not given




     Catalyst:  alumina




 4.  Utilities




     Not given




 5.  Waste Systems - Off-gases from the separator ,may contain hydrogen,




     nitrogen, and some ammonia.  Traces of aniline and phenol may be




     present in the waste gas from the dryer.  The rejected heavies from




                            6-709

-------
    the final distillation could be present in waste water streams, but




    are probably incinerated.  Overall, waste disposal problems are




    considered minimal.




6.  EPA Source Classification Code - 3-01-034-01




7.  References




    Austin, G. T., "The Industrially Significant Organic Chemicals -




    Part 1, "Chemical Engineering," January 21, 1974, p.  132.






    "1973 Petrochemical Handbook Issue," "Hydrocarbon Processing,"




    November 1973, p. 105.






    "1975 Petrochemical Handbook", Hydrocarbon Processing," November




    1975, p. 114.
                          6-710

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 301




                              Sodium Phenate
                               + HaOB
1.  Function - In the commercial production of sodium phenate, phenol




    and a slightly greater than equimolar quantity of hot aqueous sodium




    hydroxide (concentration about 50%) are mixed in thermocoil autoclaves.




    The solution is heated to approximately 130°C and is evaporated to




    dryness, first at atmospheric pressure and in later stages by the




    application of a vacuum.  This operation is sometimes carried out in




    heated ball milla in order to yield a dry, powdered product.




2.  Input Materials




    Phenol




    50% aqueous sodium hydioxide




3.  Operating Parameters




    Temperature - 130°C




    Pressure - Not given




4.  Utilities - Not given




5.  Waste Streams - The principal source of air pollutions in this process




    is the evaporation step when a mixture of water vapor and phenol is




    emitted.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 17 (1968) p. 148.
                               6-711

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INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 3Q2A,B




                                   ANISOLE


1.  Function - Anisole is made by the Williamson reaction which is the




    alkylation of a phenate salt.  The most economical route to anisole




    is described by equation (1) and involves the reaction of sodium




    phenate and methyl chloride.  An alternate method, utilized more in




    the past, was based on the use of dimethylsulfate as the alkylating



    agent (2).




         In both methods, the sodium phenate is prepared in situ by combining




    molten phenol and sodium hydroxide at 45-60°C.  The alkylating agent




    is added and the temperature is then increased to 100°C.  The yield in




    both processes approximates 95%.




2.  Input Materials




    Phenol (2) 0.92 kg/kg anisole




    Sodium hydroxide




    (1) methyl chloride




    (2) dimethyl sulfate




3.  Operating Parameters




    Temperature - 45-100°C   (113-212°F)



    Pressure - not given




4.  Utilities - not given
                              6-712

-------
5.  Waste Streams - Waste streams from purification processes may contain




    sodium chloride or sodium sulfate, depending on the process used,




    sodium hydroxide, phenol, sodium phenate, anisole and methyl chloride




    or dimethyl sulfate, depending on the process utilized.   Methyl




    chloride may also be present in the off-gases of various processing




    equipment.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 15 (1968)   p. 167.
                              6-713

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INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 303A.B



                Salicylic Acid and Methyl Salicylate
              C,HcONa + CO- - »•  C,H. (OH) (COONa)
               o 5        i         o 4
       CfiH4 (OH) (COONa)  + HC1 - »-  CgH^OH) (COOH) + NaCl




1.   Function - In the  preparation of salicylic acid, an excess of



     carbon dioxide at  5 - 6 atm.  pressure is charged to a thermocoil



     autoclave containing dry,  powdered sodium phenate (see Process



     No.  301) .  The conversion to  sodium salicylate requires several



     hours at 140 - 170°C.  Any regenerated phenol is recovered by



     vacuum distillation.



          The crude product is  then cooled, dissolved in water,



     and filtered to remove impurities.  Acidification of this sodium



     salicylate solution with hydrochloric acid or sulfuric acid



     results in the precipitation  of salicylic acid.



          Further purification of  the technical product to yield USP



     salicylic acid is  achieved by sublimation.  In order to eliminate



     the risk of dust explosions,  caused by frictional electricity during



     this operation, a  stream of inert gas (nitrogen with some carbon



     dioxide) is circulated through the sublimation chamber.  The products



     obtained are USP salicylic acid and a slightly colored technical



     grade sublimed acid.  The yields of technical-grade and USP salicylic



     acid from this entire process are 88% and 84%, respectively.
                              6-714

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          Methyl salicylate is an Important commercial product in the




     perfume and flavoring industries.  Production in 1972 was in ex-




     cess of 5,000,000 pounds.  It is produced from salicylic acid,




     which has been purified by sublimation, by esterification with




     methyl alcohol in the presence of catalytic amounts of sulfuric




     acid.  The ester product is purified by vacuum distillation with




     the water and unreacted methanol recycled to the system.




2.   Input Materials




     Sodium phenate (from phenol - 0.74 kg/kg salicylic acid)




     Carbon dioxide




     Water




     Hydrochloric acid or sulfuric acid




     Nitrogen




3.   Operating Parameters




     Temperature:  carboxylation - 140 - 170°C (252 - 338 °F)




                   acidification - not given




     Pressure:  carboxylation - 500 - 600 kPa (5-6 atm)




                acidification - not given




4.   Utilities




     Based on production of 4,000 pounds of salicylic acid/day




     Steam - 0.158 kg/sec (1,250 Ib/hr)




     Power - 3,600 MJ (1,000 kWh)




5.   Waste Streams - The principal pollutant source in this process




     should be the waste water stream from centrifuging operations.




     The mother liquor is likely to contain sodium chloride or sulfate,




     hydrochloric or sulfuric acid, various reaction by-products, and




     traces of phenol and salicylic acid.




                              6-715

-------
          The wash water stream contains salicylic acid, sulfuric acid




     and methanol.  The vent streams from the esterification and distil-




     lation steps will contain some methanol.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers,  New York, N. Y., Vol. 17, (1968),




     p. 723-25.






     "Phenol," in Chemical Economics Handbook, Stanford Research Institute,




     Menlo Park, California.






     Shreve,  R. N., Chemical Process Industries, 3rd Edition, McGraw




     Hill Book Company, New York, N. Y., 1956, p. 864.






     Groggins, Unit Processes  in Organic Synthesis, 5th Edition,




     McGraw Hill Book Company, New York, N.Y., 1958, p. 367.
                              6-716

-------
INDUSTRIAL ORGANIC CHEMICALS                    PROCESS NO.  304





              Cyclohexanol (hydrogenation of phenol)






                   C-H-OH + 3H0	>C,HinOH
                    O J       2.           D 11




-*-•   Function - Some cyclohexanol is produced by the catalytic hydro-



     genation of phenol.  The reaction takes place over active nickel



     at 70-80°C and elevated pressure.



          Cyclohexanone is a by-product of this reaction,  and may be



     removed by condensation with benzaldehyde in the presence of



     alkali.



2.   Input Materials



     Phenol



     Hydrogen



     Benzaldehyde



     Alkali



3.   Operating Parameters



     Temperature:   70-80°C (126-176°F)



     Pressure:      not given



     Catalyst:      activated nickel



4.   Utilities - Not given



5.   Waste Streams



         Some phenol,  cyclohexanol,  and cyclohexanone



     may be present in air emissions from purification processes.



     Wastewater streams, if present, may contain alkali, benzaldehyde,



     cyclohexanone, and condensation products.



6.   EPA Source Classification Code - None




                             6-717

-------
7.    References




     Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience  Publishers,  New York,  N.Y.,  Vol.  6 (1965), p.  684.
                            6-718

-------
INDUSTRIAL ORGANIC CHEMICALS                         PROCESS NO. 305
                Cyclohexanbne (oxidation of  cyclohexanol)
                   O"
1.  Function -  Small quantities of cyclohexanone may be produced by parsing




    cyclohexanol over copper catalyst with air at 140"C.




2.  Input Materials




    Cyclohexanol




    Air




3.  Operating Parameters




    Temperature -  140 °C




    Pressure -  Not given




    Catalyst -  Copper




4.  Utilities - Not given




5.  Waste Streams  - Waste water streams contain sodium hydroxide and




    dissolved organics.  Light ends column vent emits cyclohexane,




    cyclohexanol and cyclohexanone.




6.  EPA Source  Classification Code - None




7.  References




    Hedley,  W.  H. , et al. , Potential Pollutants from Petrochemical Processes,




    Final Report,  Contract 68-02-0226, Task 9, December 1973, p. 224.






    Waddams,  A. L., Chemicals from Petroleum, 3rd Ed., John Murray Ltd.,




    London,  England, 1973, p. 136.
                              6-719

-------
INDUSTRIAL ORGANIC  CHEMICALS                          PROCESS NO.  306


                 Cyclohexanone (hydrogenation of phenol)
                                           O"
                                 2


1.  Function - Some cyclohexanone is produced by a hydrogenation reaction


    similar to that employed  to make cyclohexanol from phenol.   The dis-


    tinguishing variation  is  the milder catalyst used in this process.


         Phenol and hydrogen  are fed to a hydrogenator, where they are


    reacted in the liquid  phase at 100-200°C and 1-4 atm pressure in the


    presence of a palladium-on-carbon catalyst.  After scrubbing and


    cooling, the reaction  mixture is removed to a distillation  column,


    where high boilers  are removed and cyclohexanone is recovered.   This


    method accounts for approximately 20% of the total of cyclohexanone


    produced commercially  in  the United States.


2.  Input Materials - Basis kg cyclohexanone


    Phenol - 1.005 kg

                    3
    Hydrogen - 0.64 m


    Palladium-on-charcoal  - small


3.  Operating Parameters


    Temperature - 100-200°C (212-392°F)


    Pressure - 101-404  kPa (1-4 atm)


    Catalyst - Palladium-on-charcoal


4.  Utilities - Not given
                              6-720

-------
5.   Waste Streams - Air vent systems contain some  hydrogen.  Waste water




    from the scrubber will contain phenol,  small quantities  of  cyclo-




    hexanol and cyclohexanone.   Vents from  the overhead  take-off  system




    in the distillation process will emit cyclohexanol and cyclohexanone.




6.   EPA Source Classification Code - None




7.   References




    Austin, G. T., "The Industrially Significant Organic Chemicals - Part  3,"




    "Chemical Engineering," March 18, 1974, p. 92.





    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol.  6  (1965),  p.  686.






    Waddams,  A.  L.,  Chemicals  From Petroleum, 3rd Edition,  John Murray,




    London, England,  1973,  p.  136.





    Lowenheim,  F.  A.,  and Moran,  M.  K.,  Industrial Chemicals,  4th Edition,




    John Wiley  and Sons,  Inc., 1975, p.  306-307.
                               6-721

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.307
                      o- and p-Nitfophenols  (from phenol)
                  OH                  OH          OH


                                                  N02
1.  Function - Some o- and p-nitrophenol is produced by the nitration of
    phenol with dilute nitric acid at low temperatures.  The presence of an
    OH group on the ring activates it and permits a significant amount of
    oxidation resulting in a relatively large proportion of by-products.
    The nitration produces the ortho-isomer in about a 4x excess.  The over-
    all yield however, is 40% ortho, 13% meta, 14% para, and 33% oxidation
    products.  The more volatile ortho isomer is almost quantitatively
    stripped from the crude product by steam distillation.  The residue
    is heated and recrystallized in dilute acid to obtain the para isomer.
2.  Input Materials
    Phenol - for o-nitrophenol - 1.69 kg/kg product
             for p-nitrophenol - 5.20 kg/kg product
             total product     - 1.28 kg/kg product
    Nitric acid (20% aqueous)
3.  Operating Parameters
    Temperature - ~20°C (~68°F)
    Pressure - 101 kPa (1 atm)
4.  Utilities
    Not given
                              6-722

-------
5.  Waste Streams - Process waste effluents probably contain a variety




    of resinous by-products, dinitrophenols and trinitrophenols,  oxalic




    acid, nitric acid, phenol, and small amounts of p-nitrophenol.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 13 (1967) , p. 892, 893.
                               6-723

-------
INDUSTRIAL ORGANIC CHEMICALS
         PROCESS NO. 308
              o- And p-Phenetidiiie (from o- and p-nitrophenol)
      OH
         NO.
                  OCH CH
                      NOJ
                                                                      + NaCl
1.  Function - Ortho- and para-phenetidine are usually prepared from nitro-

    phenol isomers by ethylation (Williamson Reaction) and reduction.  The

    initial step is the formation of the ethyl-phenyl ether by the displace-

    ment of chloride from the ethyl chloride by the o- or para-nitrophenate

    ion.  Either ethyl chloride or diethyl sxilfate may be used as the

    alkylating agent.

         The nitrated phenol ether is then reduced to the corresponding

    amine using iron turnings and hydrochloric acid as the reducing system.

2.  Input Materials

    o- and p-Nitrophenol

    Ethyl sulfate or ethyl chloride

    Sodium hydroxide

    Hydrochloric acid

    Iron filings

    Water

3.  Operating Parameters

    Alkylation                               Reduction

    Temperature - 20-30°C (68-86°F)
    Pressure - 101 kPa (1 atm)
Temperature - 200°C  (392°F)

Pressure - 101 kPa  (1 atm)
                              6-724

-------
4.  Utilities




    Not given




5.  Waste Streams - Aqueous wastes from separation probably contain sodium




    chloride, ethyl chloride, ethyl alcohol, nitrophenol and phenetidene




    isomers, and a variety of reduction by-products.  Ethyl chloride, ethyl




    alcohol, and HC1 may be discharged from reactor vents and various types




    of purification equipment.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,




    Interscience Publishers, New york, N.Y., Vol. 2 (1963), p. 422, 423.
                               6-725

-------
INDUSTRIAL ORGANIC CHEMICALS




                 Nitroanisoles (from nitrophenol)
                                                       PROCESS  NO.  309
3.




4.




5.
6.




7.
                                                     OCH
                                                        3
                                                                     OCH0
                                                           2H20
     Function - The o- and p-isomers of nitroanisole are produced by




     methylating the corresponding isomers of nitrophenol with a




     reagent such as dimethyl sulfate.   The reaction is carried out in




     hot aqueous sodium hydroxide.



     Input Materials




     o- and p-Nitrophenol




     Dimethyl sulfate




     Sodium hydroxide




     Water




     Operating Parameters - not given




     Utilities - not given




     Waste Streams - Air and water effluents from separation probably




     contain quantities of sodium hydroxide and sodium sulfate  (water




     only), dimethyl sulfate, and reaction by-products such as methanol.




     EPA Source Classification Code - None




     References




     Kirk-Othmer, Encyclopedia of Chemical Technology,  2nd Edition,




     Interscience Publishers, New York, N.Y., Vol.  15  (1968),  p.  148,  168.




                             6-726

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 310

                                  ANISIDINE

                          (reduction of nitroanisole)
       OCR
                         OCHfl
OCH
                                  Fe or Sn
                                  HC1
OCH,
1.  Function - Ortho- and para-anisidines are produced from o- and p-

    nitroanisole by reduction with tin or iron filings and hydrochloric

    acid.

         The ortho and para isomers are separated by steam distillation.

2.  Input Materials

    o- and p-Nitroanisole

    Hydrochloric acid

    Tin or iron filings

3.  Operating Parameters

    Not given

4.  Utilities

    Not given

5.  Waste Streams - Liquid and/or solid wastes from purification may contain

    iron or tin salts and other reaction by-products.

6.  EPA Source Classification Code - 3-01-034-01

7.  References

    Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,

    Interscience  Publishers,  New York,  N.Y.,  Vol.  2 (1963), p. 422.
                              6-727

-------
INDUSTRIAL ORGANIC CHEMICALS                    PROCESS NO.  311






                            Nonylphenol
1-   Function - Nonylphenol Is commercially prepared by the alkyla-




     tion of phenol with a mixture of isomeric nonylenes (propylene



     trimers).   The reaction is carried out at 50-100°C and 345 kPa




     (3.4 atm)  in the presence of boron trifluoride catalyst.




          The conversion takes place in the liquid phase and yields a




     mixture of isomers, mostly para- with some 2,4-dinonyl substi-




     tution.  Both continuous and batch processes are used.




          Following alkylation, the crude product is washed several




     times and heated under vacuum to remove traces of reactants and




     water.  The final purification step is a vacuum distillation at




     10-20 mm Hg.




2.   Input Materials




     Phenol - 0.46 kg/kg product




     Nonene - 0.76 kg/kg product




3.   Operating Parameters




     Temperature:   50-100°C (122-212°F)




     Pressure:       345 kPa (3 atm)




     Catalyst:       BF_




4«   Utilities  - Not given.




5.   Waste Streams - The main source of pollution is the wastewater from




     the product washing step.  The water contains spent catalyst,




     phenol, and traces of product.






                             6-728

-------
6.   EPA Source Classification Code - None




7.   References




     Austin, G. T., "The Industrially Significant Organic Chemicals




     Part 7", "Chemical Engineering", June 24,  1974,  p.  155.








     Hedley, W. H., ^t al., Potential Pollutants from Petrochemical




     Processes, Technomic Publishing Co., 1975.








     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 1  (1963), p.  908.
                              6-729

-------
INDUSTRIAL ORGANIC CHEMICALS                    PROCESS NO.  312






                            Octylphenol
                C6H5OH + CgH16 - *






!•   Function - Octylphenol is prepared  by alkylating phenol with iso-




     butylene dimer.   The product is a mixture of isomers.




          The reaction conditions and purification procedures are




     similar to those used in nonylphenol production.




2.   Input Materials




     Phenol




     Diisobutylene




     H2S04




3.   Operating Parameters




     Temperature:    120°C (248°F)




     Pressure:     Not known




     Catalyst:     Hos°4




4.   Utilities - Not  given.




5.   Waste Streams -  The principal waste stream from this process is the




     product wash  water.  This may contain phenol, sulfuric acid and




     traces of Octylphenol.




6.   EPA Source Classification Code - None.




7 .   References




     Goldstein, R. F. , The Petroleum Chemicals Industry. John Wiley and




     Sons, Inc., New York, N.Y. ,  1958, p. 191-2.









     Chemical Technology, Barnes  and Noble Books, New York, N.Y.,




     Vol. 4 (1972), p. 149.




                              6-730

-------
INDUSTRIAL ORGANIC CHEMICALS                    PROCESS NO.  313






                           Dodecylphenol
1.   Function - Dodecylphenol is produced from phenol and  propylene




     tetramer (dodecene) ,  and consists mainly of a mixture of  p-




     alkylphenols derived from various isomeric branched-chain dodecy-




     lenes .




          The alkylation process is quite similar to that  used to




     make nonylphenol.




2.   Input Materials




     Phenol - 0.38 kg/kg product




     Dodecene - 0.86 kg/kg product




3.   Operating Parameters




     Temperature:   50-100°C (122-212°F)




     Pressure:      345 kPa (3 atm)




     Catalyst:      BF




4.   Utilities - Not given.




5.   Waste Streams - The main source of pollution is the waste water




     from the product washing step.  The water contains spent  catalyst,




     phenol and traces of dodecylphenol.




6.   EPA Source Classification Code - None.




7.   References




     Austin, G.  T., "The Industrially Significant Organic  Chemicals  -




     Part 7", "Chemical Engineering", June 24, 1974, p. 155.
                             6-731

-------
Hedley, W. H., jit al., Potential Pollutants from Petrochemical




Processes, Technomic Publishing Co., 1975.








Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




Interscience Publishers, New York, N.Y., Vol.  1  (1963), p. 908.
                        6-732

-------
INDUSTRIAL ORGANIC CHEMICALS
                                                PROCESS NO.  314
                 Phenolsulfonic Acids (from phenol)
                                          H
                                        O]    +
                                                                   + H20
1.   Function - Phenolsulfonic acid is commercially prepared  by  the




     direct sulfonation of phenol with concentrated sulfuric  acid  at




     100°C.




          The yield based on phenol is approximately 94%.   Although




     the p-isomer predominates (96%), some o-phenolsulfonic acid is




     also produced.




2.   Input Materials




     Phenol - 0.57 kg/kg product




     Sulfuric acid (cone.) - 0.60 kg/kg product




3.   Operating Parameters




     Temperature:   100°C (212°F)




     Pressure:      Not given




4.   Utilities - Not given.




5.   Waste Streams - The principal pollutant from this process should




     be spent caustic, present in the waste water from caustic washing




     operations.




6.   EPA Source Classification Code - None.




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers,  New York, N. Y.,  Vol. 15 (1968), 211 and




     Vol.  19,  (1969)   p.  311-18.



                             6-733

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  315




                         Allyl Chloride
               CH3CH=CH2 + C12      » C1CH2CH=CH2 + HC1





 1.  Function - Allyl chloride is made by chlorinating propylene at




     400-500°C.  At temperatures of 300°C and less, addition to the




     double bond is the predominant reaction and 1,2-dichloropropane is




     formed.




          The reaction is carried out in an adiabatic reactor designed to




     provide rapid and intimate mixing.  The reaction temperature is con-




     trolled by balancing the mole ratio of the feed (usually 4 moles of




     propylene to one mole of chlorine) and the propylene preheat tempera-




     ture.  The commonly used temperature range is 500-510°C, at 200 kPa




     (1.9 psig).




 2.  Input Materials




     Propylene - 723 kg/Mg product 1^71%)




     Chlorine - 1.323 Mg/Mg product (70%)




 3.  Operating Parameters




     Temperature:  500-510°C (932-950°F)




     Pressure:  200 kPa (1.97 atm)




 4.  Utilities




     Not given




 5.  Waste Streams




     Absorber vent (air)




     Propylene - 13.5 kg/Mg product




     Ethyl chloride - 13.5 kg/Mg product
                            6-734

-------
         The water pollution source from the allyl chloride process would




    probably be spent caustic from the absorber.




6.  EPA Source Classification Code - None




7.  References




    Anon., "Air Pollution from Chlorination Processes," prepared for OPA,




    Environmental Protection Agency, Contract No. CPA 70-1, March 1972.






    Muller, R. G., "Glycerine and Intermediates," Report No. 58, Stanford




    Research Institute, Menlo Park, California, 1969.




    Sittig, M., Pollution Control in the Organic Chemical Industry,




    Noyes Data Corp., Park Ridge, N.J., 1974, p. 75,76.
                           6-735

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 316
                Prbpylerie Chlbrohydrirt (from allyl chloride)^
                                                   OS02OH
                    CH2=CH-CH2C1 + H2S04	> CH3-CH-CH2
                                                  r
                                                ,-CH-C
CH3-CH-CH2C1 + H20 	»• CH3-CH-CH2C1
1.  Function - Small quantities of propylene chlorohydrin are produced
    by the acid catalyzed hydration of allyl chloride.  This system
    yields l-chloro-2-propanol free of 2-chloro-l-propanol.
2.  Input Materials
    Allyl chloride
    Water
    Sulfuric acid
3-  Operating Parameters
    Temperature - 3.55-4.56 MPa (35-46 atm)
    Pressure - 170-240°C  (338  - 464°F)
    Catalyst - sulfuric acid
4.  Utilities
    Not given
5.  Waste Streams - Although no specific information was available,
    wastewater streams from the purification section may contain traces
    of sulfuric acid, allyl chloride, and propylene chlorohydrin.
6.  EPA Source Classification Code - None
                              6-736

-------
7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 5 (1964), p. 310.






     G. Frosberg and L. Smith, Acta Chem. Scand., !_, 578 (1947).






     Hancock, E. G., Propylene and Its Industrial Derivatives, John Wiley




     and Sons, New York, N.Y., 1973, p. 225.
                             6-737

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 317


                     Allyl Alcohol (from allyl chloride)



                                     H.O
                 H2C=CHCH2C1 + NaOH —2—>• H2C=CHCH2OH + KaCl


1.   Function - Some allyl alcohol is prepared from propylene glycol.


          One competitive route to allyl alcohol involves the


     hydrolysis of allyl chloride with dilute (5%) caustic solution.


     The reaction is run at 150-160° C and a pressure of 1.38 MPa (14 atm).


          The alcohol is recovered by injecting steam to form the water-


     allyl alcohol azeotrope.  The water is removed by ternary allyl ether


     azeotrope.  A second distillation then yields pure allyl alco-


     hol.  The principal by-product is allyl ether which can be mini-


     mized by the addition of dilute caustic solution at a rate such


     that the pH is maintained in the range 8-11.


2.   Input Materials


     Allyl chloride


     Sodium hydroxide (5% aqueous solution)


     Allyl ether


3.   Operating Parameters


     Temperature:        150-160° C (302-320°F)


     Pressure:           1.38 MPa (14 atm)


4.   Utilities


     Not given


5.   Waste streams - The principal pollutant sources  in  this  process


     are probably distillation waste water and solvent handling.


     Allyl chloride and allyl alcohol, as well as diallyl  ether,  may
                            6-738

-------
     be involved.  Spent caustic waste streams from the reactor may




     also contain allyl chloride and allyl alcohol.




6.   EPA source Classification Code



     None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N. Y., Vol. 1  (1963), p. 588.











     Fanbaun, A. W., H. A. Cheney and A. J. Charniavsky, Chem. Eng.




     Prog., 43_, 280, (1947).






     U.S. Patent 2,318,033.











     Astle, M. J., The Chemistry of Petrochemicals, Reinhold Publishing




     Corp., New York, N.Y., 1956, p. 196-197.
                            6-739

-------
INDUSTRIAL ORGANIC CHEMICALS                 PROCESS NO. 318


        Glycerol (from allyl chloride via allyl alcohol)

          C12 + H20      y,    N      HOC1 + HC1


         CH =CHCH2OH + HOC1   	*•    CH2OHCHOHCH2C1

•*••   Function - Some glycerol is produced from allyl chloride via pre-

     liminary hydrolysis to allyl alcohol (see Process No. 317).  The

     allyl alcohol is then chlorohydrinated with aqueous chlorine solu-

     tion to yield a mixture of monochlorohydrins.

          The chlorohydrin intermediates are converted to glycerol in

     90% yield (based on allyl alcohol) by hydrolysis with sodium

     hydroxide:

     CH2OHCHOHCH2C1  +   NaOH   —*   CH2OHCHOHCH2OH + NaCl


          The crude product is a dilute aqueous solution containing 5%

     or less of glycerol.  To obtain a high purity product, the crude

     mixture is first concentrated to about 80% glycerol in multiple-

     effect evaporators.  Salt produced by the reaction is removed by

     centrifuging.   Additional concentration of the product, followed by

     final desalting, yields 98% glycerol.  Finally, colored substances

     are removed by solvent extraction and the product is refined by

     steam-vacuum distillation.

2-   Input Materials

     Allyl alcohol - 0.70 kg/kg product
     Chlorine
     Water
     Sodium bicarbonate 10% aqueous solution
                             6-740

-------
3.   Operating Parameters

     Temperature:  hydrochlorination - 14°C (57.2°F)
                   hydrolysis - 150°C (302°F)

     Pressure:  hydrochlorination - 100 KPa (1 Atm)
                hydrolysis - elevated

4.   Utilities - Not given

5.   Waste Streams - The vents from the acid scrubber may omit hydrogen

     chloride and chorine.  Waste water will contain some sodium salts,

     allyl alcohol and acids.

6.   EPA Source Classification Code - None.

7.   References

     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,

     Interscience Publishers, New York, N.Y., Vol.  10,  (1966)  p. 624.
                              6-741

-------
INDUSTRIAL ORGANIC CHEMICALS                    PROCESS NO. 319






                  Glycerol (from epichlorohydrin)
             CH2OCHCH2C1
     HOCH2CHOHCH2C1 + NaOH	> CH0OCH CH0OH + H00 + NaCl
             CH.OCHCH0OH + H.O	> HOCH-CHOHCH-OH
               2 |   2      2               i      z
1.   Function - The production of glycerol from epichlorohydrin involves



     a series of three reactions carried out at 157-180°C and 1.14 MPa



     (11.2 Atm).  First, epichlorohydrin is hydrated to monochlorohydrin



     in basic solution.



          Glycerol chlorohydrin is then dehydrochlorinated to glycidol



     by treatment with caustic.



          In the final reaction, glycidol is hydrated to glycerol.



          Pipe reactors are used in this process with residence times



     of 7-9 minutes.  The crude glycerol product is purified in the



     manner described in Process No. 318



2.   Input Materials



     Epichlorohydrin - 1.05 kg/kg product



     Sodium hydroxide - 0.49 kg/kg product



     Sodium carbonate - 73.0 g/kg product



     Toluene - 6.0 g/kg product



     HC1 - 83.5 g/kg product



3.   Operating Parameters




     Temperature:     157-180°C (315-356°F)



     Pressure:        1.14 MPa (11.2 Atm)



     Residence time:  420-540 sec.



                             6-742

-------
4-   Utilities - Basis:  0.361 kg/sec capacity (25.2 M  Ib/yr)

     Cooling water - 124 dm /sec (1960 gpm)

     Power - 547.2 MJ (152 kWh)

     Steam (300 psi) - 4.10 kg/sec (32,520 Ib/hr) (2.07  MPa)
                            3
     Process water - 3.03 dm /sec (48 gpm)

5.   Waste Streams -

     Glycerol purification section - second effect evaporator (water)
     Glycerol - 4.5 kg/Mg product

     Glycerol purification section - centrifuge (solid)
     Sodium chloride - 431 kg/Mg product

     Glycerol purification section - centrifuge (solid)
     Sodium chloride - 431 kg/Mg product

     Glycerol purification section - film evaporator (water)
     Glycerol - 9.5 kg/Mg product
     Sodium chloride - 82.5 kg/Mg product
     Miscellaneous impurities - 61 kg/Mg product

     Glycerol purification section - toluene recovery column  (water)
     Toluene - 4.5 kg/Mg product

     Glycerol purification section - light ends column (water)
     Glycerol - 0.95 kg/Mg product
     Toluene - 1.55 kg/Mg product

6.   EPA Source Classification Code - None.

7.   References

     Hedley,  W.  H. , et^ &L., Potential Pollutants from Petrochemical

     Processes,  Technomic Publishing Co., 1975.
     Kirk-Othmer,  Encyclopedia of Chemical Technology,  2nd Edition,

     Interscience Publishers,  New York,  N. Y.,  Vol.  10  (1966), p.  624.
                             6-743

-------
 INDUSTRIAL ORGANIC CHEMICALS                       PROCESS NO.  320






            Propylene  Oxide  (peroxidation  of  propylene)






                2(CH3)3CH 4- | 02    	*  (CH3)3COOH + (CH^COH.





                (CH3)3COOH + CH2=CHCH3  —* CH  -CHCH3  +  (CH^COH





 1-    Function  -  Increasing quantities of propylene oxide are now being




      produced  by  the  peroxidation of propylene.  The  organic peroxygen




      carrier is usually  t-butyl hydroperoxide, formed by  the liquid-phase




      air oxidation of isobutane at 125-150°C and 3.55 MPa (35 Atm) in




      the presence  of  soluble molybdenum catalysts.




           t-Butyl  alcohol is the principal by-product of  this reaction




      and also  functions  as a product.




          After separation, the t-butyl hydroperoxide is  used to  oxidize




      propylene  to  propylene oxide and is  reduced in the process to t-




      butyl alcohol.   Tungsten, vanadium,  or  molybdenum catalyst systems




      catalyze this liquid-phase epoxidation.




          It has been reported that the yield of propylene oxide  from




     propylene  is  about 93% of the theoretical.  However,  this process




     yields considerably more t-butyl alcohol than propylene oxide (2.2



     kg/kg propylene oxide).




2.   Input Materials




     Propylene - 0.78 kg/kg propylene oxide




     Isobutane 'v 3 kg/kg product




     Air
                             6-744

-------
3.   Operating Parameters

     Temperature:  isobutane oxidation - 125-150°C (257-302°F)
                   epoxidation - not given

     Pressure:  isobutane oxidation 3.55 MPa (35 Atm)
                epoxidation - not given

     Catalyst:  tungsten, vanadium, or molybdenum ([Mo(CO) ]
                systems

4.   Utilities - 100 kg/sec capacity (70 M Ib/yr)
                           3
     Cooling water - 1.89 m /sec (30,000 gpm)

     Refrigeration - 454 Mg (500 tons)

     Electricity - 3600 MJ (1000 kW)

     Steam - 12.6 kg/sec (100,000 Ib/hr) at 4.14 MPa (40.8 Atm)
                         3
     Inert gas - 23.6 sdm /sec (300 scfh)

5.   Waste Streams

     Hydroperoxide preparation section - absorber (air)

     Isobutane - 3.5 kg/Mg product

     n-Butane - 0.5 kg/Mg product

     Propylene oxide recovery section - vent from vaporizing
                                        column (air)

     Propylene - 10 kg/Mg product

     Solvent recovery section - evaporator waste (liquid and
                                (solid)

     Toluene - 1.0 kg/Mg product
     Heavy ends - 50.0 kg/Mg product

     Propylene oxide purification section - off gas from column to
                                            flare (air)

     Ethylene oxide - 2.0 kg/Mg product
     Acetalahyde, etc. - 3.5 kg/Mg product

6.   EPA Source Classification Code - None.
                              6-745

-------
7.   References




     Medley,  W. H., £t al.,  Potential Pollutants from Petrochemical




     Processes, Technomic Publishing Co.,  1975.
                            6-746

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO.  321
                1,2,3-Trichloropropane (from propylene)


             H3C-CH=CH2 + 2C12 	1- C1CH2-CH-CH2C1 + HC1
                                           Cl

1.   Function -  1,2,3-Trichloropropane is made by  chlorinating
     propylene at low temperature (25-40° C).  The principal product
     of this reaction is propylene dichloride.  In the absence of a
     catalyst however 20 percent of the product is 1,2,3-trichloropro-
     pane.  The products are easily separated by distillation.
2.   Input Materials
     Propylene
     Chlorine
     Propylene dichloride
3.   Operating Parameters
     Temperature:        25-40° C (77-104°F)
     Pressure:           100 KPa (1 atm)
4.   Utilities - Not available
5.   Waste streams - Overhead gas streams contain chlorine, propylene,
     hydrogen chloride some propylene dichloride.
6.   EPA Source Classification Code - None
7.   References
     Astle, M. J., The Chemistry of Petrochemicals, New York, N.Y.,
     Reinhold Publishing, 1956, p.  60-62.
                            6-747

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 322





                         Propylene Bichloride
                                         CH3CHC1CH2C1
1.   Function - Propylene dichloride is produced as a by-product of the




     propylene chlorohydrin process for the synthesis of glycerin.




     Some may also be produced as a by-product of the chlorination




     of propylene to produce allylchloride.  Propylene dichloride




     does not itself have industrial uses however it may be easily




     cracked to produce carbon tetrachloride and perchloroethylene.




          The chlorine necessary to react with the propylene is present




     as a result of the equilibrium HOC1 + HC1 £ Cl- + H-0.  The




     formation of propylene dichloride is promoted when the olefin




     concentration in the propylene chlorohydrin process falls too




     low or when the chlorohydrin concentration exceeds 5-6% in the




     system.  Under the usual operating conditions 0.1 kg of propylene




     dichloride is formed per kg of propylene oxide.




2.   Input Materials




     Propylene




     Chlorine




     Water




3.   Operating Parameters




     Temperature:        30-40° C (86-104°F)




     Pressure:           100 KPa (1 atm)
                            6-748

-------
4.   Utilities*




     Cooling water       259dm3/sec (4100 gpm)




     Nitrogen            23.6 dm3/sec  (3000 cfh)



     Power               648 MJ  (180 KW)




     Refrigeration       1.109 Gg  (1222 tons)




     Steam               7.31 Kg/sec (58,000 Ib/hr)




5.   Waste Streams* - Propylene dichloride is a by-product of propylene




     chlorohydrin production and as such the waste streams will be




     identical to this process. Air vent streams contain propylene




     and chlorine.  Waste water contains HC1, HOC1, some chlorohydrin.




6.   EPA Source Classification Code -  None.




7.   References




     Waddams, A. L., Chemicals from Petroleum, 3rd Edition, John




     Murray, London, 1973, p. 137-138.






     Astle, M. J., The Chemistry of Petrochemicals, Reinhold Publishing




     Corp., New York, 1956, p. 60-61.






     Kirk-Othmer, Encyclopedia of  Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 5  (1964), p. 2-3.








     *See propylene chlorohydrin waste streams.
                             6-749

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS HO.  323
                           Dichloropropenes
       CH2=CHCH, + 2C12 - »• CHC1=CHCH2C1 + CH2=CHCHC12 + 2HC1
                                   90%           10%
1.   Function - 1,3-Dichloropropene and 3,3-dichloropropene are the chief
     secondary products of allyl chloride manufacture, which involves the
     high-temperature reaction of propylene and chlorine.
          The dichloropropene yield may be increased by using an excess
     of chlorine or smaller amounts of propylene.  Chlorination at tempera-
     tures below 300°C yields the addition product, 1,2-dichloropropane.
          The reaction is carried out in the vapor phase under conditions
     similar to those used in the production of allyl chloride, temperature
     500-510°C (932-950°F) and 142-284 kPa (1.4-2.8 atm) .  The propylene
     is preheated to 250-350°C (482-662°F) to prevent the addition of
     chlorine to the double bond on mixing.  The product ratio can be
     controlled to some extent by the ratio of reactants charged.  The
     use of excess chlorine to increase the product ratio of 1,3-dichloro-
     propene to allyl chloride is limited, however, by the possibility of
     over chlorination of the propylene.
          The product mixture is separated by passing the effluent gas
     stream into an HC1 absorption column.  Next the gas is passed
     into an organic absorbing solvent to remove propylene.  The  chlori-
     nated propylenes are separated by fractional  distillation.
2.   Input Materials - Basis - 1 kg product
     Propylene - 0.723 kg/kg
     Chlorine - 1.32 kg/kg
                             6-750

-------
3.   Operating Parameters




     Temperature:  preheater - 340°C (650°F)




                   reactor - 500-510°C (932-950°F)



     Pressure:  142-284 kPa (1.4-2.8 atm)




4.   Utilities - Not given




5.   Waste Streams - The principal sources of pollution are the air vent



     stream on the absorber which may emit propylene and the wastfe water




     from the absorber which contains spent caustic.




6.   EPA Source Classification Code - None




7.   References



     Astle, M. J., The Chemistry of Petrochemicals, Reinhold Publishing




     Corp., New York, 1956, p. 60-61.






     Hedley, W. H., et al., "Potential Pollutants from Petrochemical




     Processes," prepared for Control Systems Laboratory, NERC,



     Environmental Protection Agency, Contract No. 68-02-0226, Task




     No. 9, 1973, p. 136.
                             6-751

-------
SECTION IX
 TOLUENE
  6-752

-------
                                                TOLUENE
     TOLUENE
  W&
  J     •) Benzonitrile
  333i
  345!
 349
	^ Benzoic  acid
                                  326
                                	> Phenol
                                  327                               328
                                	>3,5-Dinitrobenzoic acid	^3,5-Oiaminobenzoic acid
                                329'                            330
                               	;—^m-Nitrobenzoic acid  	^ m-. or p-Aminobenzoic acids
                                  331
                                 	) Sodium benzoate
                               i


                -4 Benzyl chloride
                                332
                            	••) Benzyl benzoate


                                                        |

                                                Benzyl alcohol
                                           335
                                         —_—> Benzyl ami ne
                -} Benzyl  dichloride


                                       336i                         -337
                  > Benzotrichloride	^Benzoyl chloride	—	^Benzamide
  338
 ———^Nitrotoluene-
                                      339                           330
                                     	> Nitrobenzoic acids	—	^ Aminobenzoic acids
                                   	^D1nitrotoluene*i	» Dinitrobenzoic acids-328  ) Diaminobenzoic acids
                                                          343i
                                                                         ,4-Diaminotoluene




                                                                     -> 2,6-Diaminotoluene
                                      341                     344
                                     	.	^Toluidines  	> m-Chlorotoluene
               p-Chlorotoluenes —.——	^ p-Chlorobenzaldehyde
                                      .  •) o- & p-Chlorobenzoic acids           )  o- &  p-Chlorobenzoyl chlorides
             >Benzene



             i Xylene
	)  Hethylcyclohexane	^ Methylcyclohexanol	^ Methylcyclohexanone
353                       354                  355                356
                                ^Benzoin - — - ^Benzil - » Benzilic acid
        \ Benzaldehyde
  357
        -)p-Toluenesu1fonyl chloride-
                                        358
                                               p-Toluenesulfonaraide
                Figure  17.    Toluene  Section Chemical  Tree
                                         6-753

-------
Cooll
St
ng water
T II

Air
325
Oxidation
Heat
/> 1
*•«
NH3
1 P.
324 1
Anmonolysls 1
Heat
F,-HC11
V I
Benzyl C00lin9 **?
alcohol Heat f
; A i 11
332
Ester1f.1 cation

Cooling water
H2SO,, fl
I W* Hef 11
32?|
Nitration 1
Cooling water
Tr» Til
329!
Nitration
Heat
AiV i
326
Oxidation
'XJ
Na.CO,
1 P
* /A
33l|
Salt formation I
        3,5-
      Dinltrp-
       benzoic
        acid
leat
4
f
328
Reduction
        3,5-
      01amino-
      benzole
        acid
Figure 18.   Toluene  Section Process Flow Sheet

-------
Ul
Ui
Heat
Fe° Cooling water
|Cj2p Stef|l
345
Chlorlnatlon

Cooling water
"i» "til
350
Hydrogenation
^XJ
HS04
I Mater
ITfc
33ftl
Nitration 1
               Heat
eam I
           Steam
                     p-
              (Chlorobenz-
              ialdehyde
                            o- S p
                           Chloro-
                           benzoic
                            acids
            Chlorlnatlon  346
            & Hydrolysis
Cool
St
D
«3
ing water
rl

Chromic
acid Steam
I ftv t
339 1
Oxidation I

pe<> Cooling water
1HC1 Heat \ I
1 fc HI
341 1
Reduction 1
H2SOM
j HN03
340
Nitration
Chlorobenzojtr
«
ichloride
iteam 1
i I
Cooling water
nrtO 1
Chlorination and 1
hydrolysis |
Air
352
Oxidation

f
330
Reduction
"T\ 2
uri Cooling water
FTP, II
344 1
Replacement 1
H2
343
Reduction
                                       O- i p-
                                       Chloro-
                                       benzoyl
                                     ichloride
                                                Methyl-
                                                eye lo-
                                                hexanone
(m- Chloro-1
f2,4 & 2,6-
 Diamino-
Ltoluenes
                                             Figure 18.   Toluene Section Process  Flow Sheet (Cont.)

-------
1 	
Cooll
Ste
ng water
T II
Fuel
1? „
349 ^
Transalkylatlon
1 1
Cooling water
s,T|J
Cooling water
02 Steam ||
1 J> 1 11-
Heat
1 Oleum
PC15
It ^>
Oxidation Sulfonation and
substitution
1 L
Steam
Cooling water
IICV A
3331
Chi or1 nation I

                                                                         fp-Toluene-i
                                                                           sulfonyl
                                                                           chloride
~J
Ui
Cool
t
Ing water
Til
Ethanol
IT
354
Condensation
Mater
Heat 1
NH3
* 0
358
Ammonolysls
^
                                              Cooling water
                                                 Steam 11
Acetic acid
   HN03
                                            Figure  18.   Toluene Section Process Flow Sheet  (Cont.)

-------
 I
-J
Ln
V
i
\
)
Steam
Hj

Hater
1 NaOH
4 » A
fdrolysls

Cooling water
Steam || NH3
33<
Amlnatlon
Benzole
acid
Cooling water
Heat Q Steam |j
1 /A 1 11
C|°3HNO
1 HNO
i ^ 336 1 342
Exchange I Oxidation
                                                             (BenzylamineI
                                                                               Steam
                                                                                       Cooling
                                                                                        water

                                                                                  Ammonolysls
                                                                                           337
                                                                                              ^1
                                                                                                      Heat
Reduction
         32
                                        Figure 18.  Toluene Section Process  Flow Sheet (Cont.)

-------
INDUSTRIAL ORGANIC CHECMICALS                                PROCESS NO, 324


                                 Benzonitrile
                            rtrr
                              n



                                 -3



1.   Function - Benzonitrile is produced in the United States chiefly


     by the ammonolysis of toluene in the vapor phase.  The reaction


     takes place in a reactor that consists of a shell containing a catalyst


     chamber heated with a heat transfer medium from outside the shell.


     Benzonitrile produced in each pass is stripped from the exit gases


     which are recycled with makeup toluene and ammonia.  The optimum


     operating conditions are described as employing molybdenum oxide on


     alumina as a catalyst, maintaining temperature between 524-552°C, and


     operating at pressures of 1 atm. of less.  Conversion per pass ranges


     from 5-10%.  Overall yields from 60-85% based toluene are reported.


2.   Input Materials - Basis:  1 kg benzonitrile


     Toluene - 0.89 kg


     Ammonia - 0.16 kg


     MoOs catalyst - quantities not given


3.   Operating Parameters


     Temperature:  524-552°C  (975 - 1025°F)


     Pressure:  101 KPa (1 atm) or less


     Yield:  60-85% based on toluene


*•   Utilities - Quantities not given


5.   Waste Streams - Off gases contain ammonia, hydrogen cyanide and  toluene.


     Air vent streams from the purification system would contain toluene.


6.   EPA Source Classification Code - None
                                  6-758

-------
7.    Reference



     Astle,  M.J.,  Industrial Organic Compounds,  Reinhold Publishing Cor-




     poration, New York, 1961, p. 227-228.
                                   6-759

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INDUSTRIAL ORGANIC CHEMICALS                                 PROCESS NO. 325




                       CH,       Benzoic Acid     COOH
1.   Function - The preferred industrial process in the manufacture




     of benzoic acid, in the United States, is the air oxidation of




     toluene.








     The reaction is carried out in the liquid phase at 110 - 150°C




     at pressures of 273 - 490 kPa (2.7 - 5 atm) using a cobalt salt




     usually the naphthenate as the catalyst.  The heat of reaction




     is controlled by refluxing toluene and water-jacketed cooling.




     Water of reaction is removed from condensed off gas before the




     toluene is returned to the reactor heel.  Material in the autoclave




     heel continously overflows to a stripper where toluene is re-




     cycled.  The bottoms, which contains the crude benzoic acid, are




     sent to a crystallizer, or a distillation tower.  Yields of




     relatively pure material of 90% based on toluene are cited.




2.   Input Materials - Basis 1 kg benzoic acid.




     Toluene              .83 kg/kg




     Air                 1.71 kg/kg




     Cobalt naphthenate   .008 - .024 kg/kg




3.   Operating Parameters




     Temperature:  110 - 150°C (230-302°F)




     Pressure:  273 - 490 kPa (2.7 - 5 atm)




     Catalyst:  0.1 - 0.3% of toluene
                                6-760

-------
4-   Utilities - Based on 100 M Ib/yr capacity




     Water - .545 m3/sec (518,000 gPh)




     Steam - 5.93 kg/sec. (47,000 Ibs/hr)




     Power 2,320




5.   Waste Streams - Air vent stream from the purification contains




     toluene, some benzaldehyde and some benzyl alcohol.  The air




     vent from the separator (centrifuge) contains toluene vapors.




     The waste water contains benzoic acid, benzaldehyde and benzyl




     alcohol.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 3  (1967), p. 420-439.






     Sittig, M., Organic Chemical Process Encyclopedia, 2nd Edition,




     Noyes Development Corporation, Park Ridge, New Jersey, 1969, p. 101.






     Hedley,  W.H. et. al., Potential Pollutants from Petrochemical




     Processes, Final Report, Contract 68-02-0226, Task 9, MRC-DA, 406,




     December 1973, p. 111-112.
                                6-761

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 326
                      Phenol (oxidation of Benzole acid)
                    OOH              copper
                         + 1/2  02   catalyst       Ik-^J     +  C02
1.  Function - Benzoic acid is melted in biphenyl, mixed with a small
    amount of manganese-promoted cupric benzoate and fed to an oxidizer
    (reactor).  A mixture of air and steam is sparged into the reactor,
    where the benzoic acid is oxidized to phenol.
         Purification is accomplished by distillation.  Phenol and water
    are taken off overhead and benzoic acid is taken from the column
    bottom and returned to the reactor.  The bottoms may be extracted
    firstjto recover organics for recycle.  The phenol and water are
    separated by  azeotropic distillation.
2.  Input Materials
    Benzoic acid
    Air
    Catalyst
3.  Operating Parameters
    Temperature - 230°C (446°F)
    Pressure - 138-172 kPa (1.36-1.7 atm)
    Mn-cupric benzoate - not given
4.  Utilities - Not given
5.  Waste Streams
    Centrifuged separator (solid)
    Tar -0.10 kg/kg phenol (204 Ib/ton)
    Phenyl benzoate -0.0015 kg/kg phenol  (3.1 Ib/ton)

                              6-762

-------
5.   Waste Streams (continued)




    Acetone -0.0018 kg/kg phenol (3.6 Ib/ton)




    Manganese benzoate -0.005 kg/kg phenol (10 Ib/ton)




    Copper benzoate -0.002 kg/kg phenol (4.3 Ib/ton)




    Separator effluent




    Toluene -0.0011 kg/kg phenol (2.14 Ib/ton)




6.   EPA Source Classification Code - None




7.   References




    Lowenheim, F. A., and Moran, M. K., Industrial Chemicals,  4th Edition,




    John Wiley & Sons, New York, N.Y., 1975, p. 618-619.





    Hedley, W. H., et al., "Potential Pollutants from Petrochemical Processes,"




    Prepared for Environmental Control Systems Laboratory, NERC, Environmental




    Protection Agency, Contract No. 68-02-0226, Task No.  9, 1973, p. 111-112.
                               6-763

-------
INDUSTRIAL ORGANIC CHEMICALS                                 PROCESS NO.  .327




                            3 t5-Dinitrobenzoic Acid
                                                     ;QOH


                                   H0SO,    n    7/N
                               ,     9.   a.^  O_N -C I   1

                               3
1.   Function - 3,5-Dinitrobenzoic acid is primarily manufactured by




     nitrating benzoic acid with a mixture of fuming nitric and sulfuric




     acids.  The sulfuric acid forms a hydrated molecule and removes the




     water of reaction.  The nitration occurs at elevated temperatures




     (70-90°C).




2.   Input Materials - Basis:  1 kg 3,5-dinitrobenzoic acid




     Benzoic acid - 0.6 kg




     HN03 - 0.6 kg (99+% acid)
3.   Operating Parameters




     Temperature:  70-90°C (158 - 194°F)




     Pressure:  atmospheric




4.   Utilities




     Quantities not given




5.   Waste Streams - Off -gas will contain oxides of nitrogen and some




     sulfur dioxide.  Waste water from the purification process contains




     nitric and sulfuric acids, benzoic acid and some 3,5-dinitrobenzoic




     and 3-nitrobenzoic acid.




6.   EPA Source Classification Code - None




7.   References




     Astle, M.J., Industrial Organic Nitrogen Compounds, American Chemical




     Society Mongraph Series, Reinhold Publishing Corporation, New York,




     1961, p. 334.
                                  6-764

-------
INDUSTRIAL ORGANIC CHECMICALS                                PROCESS NO.  .328

                            3,5-Diaminobenzoic Acid
                        COOH                      COOH

                                                      + 4H2°

1.   Function - 3,5-Diaminobenzoic acid is commercially produced by the

     catalytic reduction of dinitrobenzoic acid.  The process is similar

     to that used to manufacture m,p-aminobenzoic acids.   The reaction

     occurs in the liquid phase at about 1 atmosphere pressure.   The hydro-

     gen is fed in large excess to a slurry of catalyst,  dinitrobenzoic acid

     and water at temperatures greater than 85°C.  The product acid is then

     filtered to remove catalyst and cooled to precipitate the product.

2.   Input Materials - Basis:  1 kg diaminobenzoic acid

     Dinitrobenzoic acid - 1.5 kg

     Hydrogen - >0.03 kg

     Catalyst - quantities not given

3.   Operating Parameters

     Temperature:  85°C (185°F)

     Pressure:  lOOKPa  (1  atm).

     Catalyst:  Pd, Cu, Pt, or Ni

4.   Utilities

     Not given

5.   Waste Streams - Off-gas from the reactor contains hydrogen.  Waste

     water contain 2,5-dinitrobenzoic acid and 3,5-diaminobenzoic acid.

6.   EPA Source Classification Code - None

7.   References

     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-

     science Publishers, New York,  N.Y., Vol.  3, (1964)   pp. 435-436.
                                  6-765

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 329





                          m-Nitrobenzoic Acid
                              +   HN03-H2S04
!•  Function - The product of the nitration of benzoic acid is m-nitro-




    benzoic acid with the principal byproduct being ortho-nitrobenzoic




    acid.  Almost no p-nitrobenzoic acid is formed and the ortho isomer




    can be minimized by proper selection of the reaction temperature.




         The rate of reaction increases with temperature, however the




    amount of m-isomer decreases with temperature while the amount of



    ortho isomer increases.   The operating temperature must be a




    compromise between optimum rate of production and purity of




    product.




         The reaction is carried out in sulfuric acid and a maximum




    in rate of nitration is found at 89-90% sulfuric acid.




2.  Input Materials




    Benzoic acid




    Nitric acid




    Sulfuric acid




3.  Operating Parameters




    Temperature - 25-45°C




    Pressure - Atmospheric




    Sulfuric acid - 90%
                             6-766

-------
4.   Utilities - Not given




5.   Waste Streams - Air vent streams contain oxides of nitrogen.




    Waste water streams will contain benzoic acid, some m-nitrobenzoic




    acid.




6.   EPA Source Classification Code - None




7.   References




    Hoggett, J. G., Moodie, R. B., Penton, J. R. , and Schofield,  K.,




    Nitration and Aromatic Reactivity, Cambridge University Press,




    London, 1971, pp. 16, 18, 151, 160, 178.
                              6-767

-------
INDUSTRIAL ORGANIC CHEMICALS                                PROCESS NO. 330





                           m-or p-Aminobenzoic Acids
                    •C°°H + 3H2 -£*S—     yP-jV     + 2H20
1.   Function - These acids are manufactured chiefly by the reduction of




     m-or p-nitrobenzoic acids by catalytic hydrogenation or, less fre-




     quently, by reduction with tin or iron and HC1.  One patent for




     p-aminobenzoic acid claims an 85% yield when hydrogenating p-nitro-




     benzoic acid with a Pt or Pd catalyst in water.





     A thin slurry of p-nitrobenzoic acid and catalyst in water is agitated




     at about 800 RPM and held at 85°C.  Hydrogen is then introduced until




     no more absorption is noted and the p-nitrobenzoic acid dissolves as




     the reaction proceeds.  The partial pressure of H_ is from 200-700 mm Hg




     in the atmospheric pressure process.  The product acid is filtered and




     cooled to precipitate a 99% product.  The mother liquor from pre-




     cipitation is reused in the next batch.




2.   Input materials - Basis:  1 kg of aminobenzoic acid




     Nitrobenzoic acid (m-, or p-) - 1.2 kg




     H2 - >0.04 1.2 kg




     Catalyst:  Pt, Mi, Pd, or Cu - quantities not given




3.   Operating parameters




     Temperature:  85°C




     Pressure:  atmospheric




     Agitation:  800 RPM




4.   Utilities




     Quantities not given





                                 6-768

-------
5.    Waste streams - The off gas from the hyd rogenation reactor contains




     hydrogen,  when iron powder and hydrochloric acid is used hydrogen




     chloride is present in the off gas.  Waste wash water from the




     centrifuge contains aminobenzoic acid, ferric chloride and HC1.   The




     product contains some m-or p-nitrobenzoic acids.




6.   EPA Source Classification Code




     None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Inter-




     science Publisher, New York, N.Y., Vol. 3  (1967)  p. 434-436.
                                  6-769

-------
INDUSTRIAL ORGANIC CHEMICALS                                  PROCESS NO. 331
                                Sodium Benzoate

                          COOH
                          + NaOH   	ft, Ifl       + HOH
1.   Function - Sodium benzoate is generally produced by the addition of

     benzole acid to a hot solution of sodium carbonate or sodium hydr-

     oxide.  The resulting solution is treated with charcoal or, in some

     cases, potassium permanganate, and is filtered and dried.

2.   Input Materials - Basis:  1 kg sodium benzoate

     Benzoic acid - 0.85 kg

     NaOH - >0.3 kg

     NafiC03 (alternate) - >0.74 kg

     Charcoal - quantity not given

     KMnO^ - quantity not given

3.   Operating Parameters

     Quantities not given

4.   Utilities

     Quantities not given

5.   Waste Stream - Waste water streams contain sodium hydroxide or

     sodium carbonate and water use to wash the benzoate product contains

     NaOH, Na2C03, NaHC03 and some sodium benzoate.  There will be some

     carbon dioxide in the off-gas.

6,   EPA Source Classification Code

     None

7.   References

     Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,  Inter-

     science Publishers, New York, N.Y., Vol.  3   (1967),  p.  433.

                                  6-770

-------
INDUSTRIAL ORGANIC CHEMICALS
      PROCESS NO. 332
            C=0
                         Benzyl Benzoate
COOH
          COOH
     Function - Benzyl benzoate is produced commercially by two routes.




     The most commonly used commercial process is the Cannizaro reaction




     in which benzaldehyde, catalyzed by sodium hydroxide, undergoes an




     oxidation-reduction reaction giving benzyl alcohol and benzoic




     acid.  These compounds undergo an esterification catalyzed by the




     NaOH to produce benzyl benzoate.  The second process involves a




     direct esterification of benzoic acid and benzyl alcohol catalyzed




     by a boron trifluoride hydrochloric acid complex.  The reactions




     are carried out at 75-90°C at 1 atm pressure.




     Input Materials - Basis:  1 kg benzyl benzoate (benzaldehyde




     route)




     Benzaldehyde - 2 kg




     NaOH catalyst/reactant - quantities not given




     Operating Parameters




     Temperature:  75-90°C  (167-194°F)
                            6-771

-------
     Pressure:  100 kPa (1 atm)




     Catalyst:  NaOH or any strong base




4.   Utilities




     Quantities not given




5.   Waste Streams - Waste water contains sodium hydroxide, sodium ben-




     zoate and some benzaldehyde.  No significant quantities of air pollu-




     tants would result from this process.




6.   EPA Source Classification Code - None




7.   References




     Shreve, R. N., Chemical Process Industries, McGraw-Hill Book Co.,




     New York, 1967, p. 512.
                           6-772

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 333
          Benzyl Chloride, Benzyldichloride, Benzotrichloride



          CH3                 CH2C1             CHC1
              ' C12  	*"  VJ + Cl2-****> lyi + C12	*• ILJJ + HC1



1.   Function - The chlorination of toluene to the three products,




     mono-, di-, and tri-chloromethyl benzene, can be considered as a




     single process since the extent of chlorination cannot be exactly




     controlled.




          The use of excess toluene will result in a predominance of




     benzyl  chloride.  Stopping the reaction when the product density




     reaches 1.283 will result in a product that is predominantly




     benzyl chloride and allowing the reaction to continue until the




     product density reaches 1.38 will yield benzotrichloride.




          The reaction must be carried out in glass or polymer lined




     reactors since iron catalyses nuclear substitution.  The tempera-




     ture is controlled in this exothermic reaction by the reflux of




     toluene.




2.   Input Materials




     Toluene




     PCI- or PC15  (optional)




3.   Operating Parameters




     Temperature:        110° C




     Catalyst:           PCI  or PCI.  (optional)
     Spec. Eqpt.:        Cl? resistant container for benzyl - glass




                         for benzotrichloride
                            6-773

-------
4.   Utilities - Not given




5.   Waste streams - HC1 is neutralized with a weak base before disposal,




     so chloride salts will be waste.




6.   EPA Source Classification Code -  None




7.   References




     Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers,  New York, N.Y.,  Vol.  5(1969), p. 281-287.






     Austin,  G. T.,  "The Industrially  Significant Organic Chemicals-




     Part 1," "Chemical Engineering,"  January  21, 1974, p.  132.
                           6-774

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 334


                          Benzyl Alcohol


              CH2C1
                    +  NaOH     - >              +  NaCl
 1.  Function - Benzyl alcohol Is manufactured in the United States


     exclusively by hydrolysis of benzyl chloride.  Sodium hydroxide or


     sodium carbonate is usually employed but use of the carbonate


     minimizes formation of by-products such as dibenzyl ether.


          A charge consisting of 1349.4 kg (2,975 Ib) of water, 1428.8


     kg (3,150 Ib) benzyl chloride, and 714.4 kg  (1,575 Ib) sodium car-

                                 3
     bonate is put into a 3.785 m  (1,000 gal) steel jacketed reactor,


     agitated, and heated to reflux for 24 hours.  The reaction is


     cooled, sodium chloride added to saturation, and the layers allowed


     to separate.  The lower aqueous layer is drained to the sewer while


     the upper layer of crude benzyl chloride is purified by vacuum dis-


     tillation.


 2.  Input Materials


     Benzyl chloride - 1.34 kg/kg alcohol


     Sodium carbonate - 0.67 kg/kg alcohol


     Water - 1.27 kg/kg alcohol


 3-  Operating Parameters


     Temperatures:  210°C (410°F)


     Reaction Time:  24 hours

                       3
     Equipment:  3.75 m  (1,000 gal) steel-jacketed reactor
                             6-775

-------
4.  Utilities - Not given




5.  Waste Streams - Aqueous layer saturated with sodium chloride and




    containing sodium carbonate used to be discharged to the sewer but




    may be disposed of differently now.  Waste water may contain




    traces of benzyl chloride.




6.  EPA Source Classification  Code - None




7.  References




  '  Kirk-Othmer,  Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience  Publishers,  New York,  N. Y.,  Vol.  3 (1964), p.  443-




    444.
                            6-776

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 335




                             Benzyl Amine
                                                ,CH2NH2
                                                       + NH^Cl
1.   Function - Benzylamine is produced commercially by the ammonolysis




     of benzyl chloride.  The reaction is carried out at elevated




     temperatures (100-200° C) and pressure (100 KPa-2.76 MPa) and a




     4 to 10 X excess of aqueous ammonia.  The major product under these




     conditions of excess ammonia is the primary amine, although some




     secondary, tertiary and quaternary salts are formed.  The water




     and ammonia are separated and recycled and the amines separated




     and purified by distillation.




2.   Input Materials




     Benzyl chloride




     65% aqueous ammonia




3-   Operating Parameters




     Temperature:        150-200° C (302-392°F)




     Pressure:           100 kPa-2.76 MPa (1-27 atm)




4.   Utilities - Not given




5.   Waste streams - by-product secondary and tertiary amines quaternary




     salts are formed.  Ammonium chloride sent to other processes.




6.   EPA Source Classification Code - None




7.   References




     Astle, M. J., Industrial Organic Nitrogen Compounds, Reinhold




     Publishing Corp., New York, N.Y., 1961, p. 6-8.
                            6-777

-------
7.    References (continued)




     Shreve,  R. N.,  Chemical Process Industries^ McGraw Hill Book



     Company, New York,  N.Y., 1967,  p.  815-816.
                            6-778

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  336




                         Benzoyl Chloride




            CC13               COOH
 1.  Function - Benzotrichloride and catalyst (zinc chloride impregnated




     on pumice) are run into a glass-lined steel reactor which has




     previously been half filled with molten benzoic acid.   A glass-




     coated agitator is used to stirr the mixture and tank temperature




     is maintained at 122-130°C for about eight hours.   A Karbate (impreg-




     nated carbon) condenser removes the hydrochloric acid formed in the




     reaction.  The benzoyl chloride is purified by distillation.




 2.  Input Materials




     Benzotrichloride




     Benzoic acid




 3.  Operating Parameters




     Temperature:  122-130°C (252-266°F)




     Pressure:  101 kPa (1 atm)




     Catalyst:  zinc chloride on pumice




 4-  Utilities - Not given




 5.  Waste Streams - Waste waters may contain traces of benzoic acid,




     benzotrichloride,  and zinc chloride.




 6.  EPA Source Classification Code - None




 7.  Kirk-Othemer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers,  New York, N. Y., Vol. 3 (1964), p. 424.
                             6-779

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 337




                                  Benzamide
^-  Function - Benzamide is produced by the acylation of ammonia with




    benzoyl chloride.  The reaction may be carried out under anhydrous




    conditions by passing anhydrous ammonia into a solution of benzoyl




    chloride in an inert solvent such as diethyl ether.  In a commercial




    operation it is more usual to add the benzoyl chloride to a cold




    (0°C), concentrated aqueous solution of ammonia from which the benza-




    mide percipitates.   The crude benzamide is washed with water and




    purified by recrystallization.




2.  Input Materials




    Benzoyl chloride




    Ammonia (anhydrous  or concentrated aqueous solution)




3.  Operating Parameters




    Temperature - 0°C (32°F)




    Pressure - 101 kPa (1 atm)




4.  Utilities - Not given




5.  Waste Streams - Air streams may contain ammonia and some hydrogen




    chloride.  Waste water from product recovery and purification contains




    ammonia, HCl, NH.C1 and benzoic acid.




6.  EPA Source Classification Code - None
                               6-780

-------
7.   References




    Kirk-Othmer,  Encyclopedia ot Chemical Technology,  2nd Edition,




    Interscience Publishers, New York,  N.Y.,  Vol.  2  (1963), p.  69-71.
                              6-781

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 338




                           Nitrotoluene
                           H2S04/HN03
1.   Function - Nitrotoluenes are manufactured by nitration of toluene




     by a nitrating agent usually consisting of a mixture of sulfuric




     and nitric acid and recycled fortified acid.  The ratio of H-SO,,




     HNO_ and H»0 as well as the temperature and rate of agitation has




     to be controlled to ensure high yield, favorable ratio of desired




     isomer, and to minimize dangerous side reactions.  Nitration is




     done at relatively low temperatures (<40°C) .  The crude product is




     washed with water, alkali, and water.  The isomeric nitrotoluenes




     are then separated from toluene and other organics by steam dis-




     tillation and subsequently dried.  Separation of the o-, m-, and p-




     isomers is done by a series of vacuum distillations.




2.   Input Materials - basis:  1000 kg yield of nitrotoluene




     Toluene - 690 kg




     Nitric acid - 450 kg




     Sulfuric acid - 810 kg




     Water - 240 kg




     10% NaOH solution - 22 kg




3.   Operating Parameters




     Temperature:  25°C [initially] (77°F)




                   35-40°C [final] (95-104°F)
                             6-782

-------
     Equipment:  Toluene nitration is normally carried out in cast-




     iron or stainless-steel nitrators sized for 3,000 gal batches of




     toluene.




4.   Utilities - None given




5.   Waste Streams - Heavy tar residues from final fractionation




     stage are disposed of and would contain a complex mixture of




     organic by-products in the amount of approximately 40 kg/1000 kg




     nitrotoluene.  Waste waters may contain also alkali used in wash-




     ings, spent acid, and soluble organic by-products.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N. Y., Vol. 13 (1967), p. 844-^




     848.



     Albright, L.F. and Hanson, C., "Industrial and Laboratory Nitrations,"




     ACS Symposium Series 22, 1976, p. 190-218.
                             6-783

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 339


                        Nitrobenzoic Acids



                                              :OOH


                                [0]
 1-  Function - m,  and p-Nitrotoluene may be oxidized with chromic



     acid to yield  the corresponding m-,  and p-nitrobenzoic acids,  o-



     Nitrotoluene is not affected by chromic acid.  o-Nitrotoluene is oxidized


     by potassium permanganate to give o-nitrobenzoic acid.



 2.  Input Materials


     Nitrotoluene


     Potassium permanganate (to oxidize o-nitrotoluene or p-nitrotoluene)
         /

     Chromic acid (to oxidize m- and p-nitrotoluene)



 3.  Operating Parameters



     Temperature:  25-50°C (77-122°F)



     Pressure:  101 kPa (1 atm)



 4.  Utilities - Not given



 5.  Waste Streams  - Neutralization of reaction waste liquors would give



     wastewater streams containing salts of the acid or alkali used.



 6.  EPA Source Classification Code - None



 7.  References



     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,



     Interscience Publishers, New York, N. Y., Vol. 13 (1967), p. 848-


     850.
                              6-784

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 340



                Dinitrotoluene (nitration of toluene)
              CH~  + HNC- -H9SO. - *• mixed nitrotoluenes
              CH«  "» J.J.i*W« — LLfJ\J\J I      '  UOi"1|~\V  ]F~*>JH'\
                J       J  ^  H-         ,Z  ^^^*^r   -^



1.   Function - The reaction of nitric acid and toluene to produce



     dinitrotoluene can be thought of as a two stage reaction.  The



     first stage being the mononitration of toluene.  The nitrating



     agent is the acid mixture 48% sulfuric, 18% nitric, 14% nitro-



     sylsulfuric, 12% water and 8% nitroorganics, which is typical



     of the fortified spent acid from the dinitration stage.  The



     temperature is initially 25° C raised to 40° C to complete the



     reaction.  The reactor must be vigorously agitated since the



     toluene is not very  soluble in the mixed acids.  A typical pro-



     duct mix is 62% ortho, 33% para and 3% meta.  The mixture may



     be separated or used as is in the second nitration step.



          The acid  mixture used in the second stage contains, for a



     typical mixture, 50% sulfuric,  20% nitric, 12% nitrosylsulfuric



     6% water and 12% nitroorganics.  The  temperature must be



     increased to 55 to  85° C at 1 atm pressure.  Nitration  of  the



     pure p-isomer  yields 2,4-dinitrotoluene with no significant



     amounts of by-product.  Nitration of  the unresolved  product  of



     the mononitration yields an 80-20 mixture  of  2,4  and 2,6-




     dinitrotoluene,  respectively.   The  product mixture may be separated



     into the pure  isomers by crystallization or used  directly  for



     the manufacture of  toluenediisocyanate.
                             6-785

-------
2.   Input Materials



     Toluene:             506.25 kg/Mg of product




     Nitric Acid:         721.25 kg/Mg of product




     Sulfuric  Acid:       1311 kg/Mg of product



     Nitrosyl  sulfuric acid:   262 kg/Eg of product




?.   Operating Parameters



     Temperature:         mononitration  25-40° C   (77-104°F)



                         dinitration    50-85° C   (122-185°F)




     Pressure:           100  KPa




4.   Utilities - Not available



5.   Waste Streams



     Decantors (water) - Wastewater from the decanters, containing




     small amounts of nitrated toluene, is discarded and may end up




     in sewer  lines.




     Absorber  (air)  - Reactor vents go to the absorber to oxidize




     the NO to NO- which is absorbed in water to produce nitric acid.




     Vent from absorber discharges air and unabsorbed oxides of nitrogen.




     Washer vents (air) - Air saturated with water and some nitrated




     toluenes  will be discharged from the washer vent.




6.   EPA Source Classification Code - None




7.   References




     Austin, G. T.,  "Industrially Significant Organic Chemicals,"




    "Chemical  Engineering," April 15, 1974.






     Sittig, M., "Pollution Control in the Organic Chemical Industry,"




     Noyes Data Corporation,  Park Ridge, N.J., 1974, p. 126-27.






     Brownstein, A.  M., "U.S. Petrochemicals - Technologies, Markets




     and Economics," The Petroleum Publishing Company, Tulsa, Oklahoma, 1972.




                             6-786    -

-------
INDUSTRIAL ORGANIC CHEMICALS
                             PROCESS NO. 341
                           Toluidines
NO,
                                           NH,
                             Fe
                                HC1_L
                       '2                   ^2
     Function - The toluidines are made from the nitrotoluenes by reduc-
     tion.  The process most commonly used is the metal-acid process,
     the most widely utilized combination being iron and hydrochloric
     acid.  Nitrotoluene, powdered iron, and a small amount of
     water are mixed in a reaction vessel.  Hydrochloric acid is added
     at a rate such that the heat of reaction will maintain a brisk
     rate of reaction.  The converted toluidine is steam distilled,
     from the reactor, separated, and purified by distillation.  Approx-
     imately 3.1% of the toluidine remains in the aqueous layer most
     of which may be recovered by solvent extraction.
          Catalytic hydrogenation has been replacing the iron-acid
     method in recent years yielding a purer product at lower cost.  The
     reduction is done in the vapor phase, passing hydrogen and the
     nitrotoluene vapor through a fluidized bed of copper clad silica
     gel.
     Input Materials
     Iron reduction:          Nitrotoluene
                              Hydrochloric acid - iron powder
     Catalytic reduction.     Nitrotoluene
                              Hydrogen
                             6-787

-------
3.   Operating Parameters



     Iron reduction:          Temperature:   100° C (212°F)




                              Pressure:      100 kPa (1 atm)




     Catalytic reduction:     Temperature:   250-300° C  (482-572°F)




                              Pressure:      238 kPa (2.5 atm)




                              Catalyst:      Copper on silica




4.   Utilities - Not available




5.   Waste streams - the major waste water stream is from the steam




     stripper for the aqueous layer and contains approximately 0.2%




     toluidine as well as some HC1.  Some toluidine hydrochloride is




     lost in the waste water from the reactor after steam distillation.




     Air streams contain hydrogen chloride and some particulates.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




     Interscience Publishers, New York, N.Y., Vol. 2  (1963), p. 79, 421.






     Ibid.,  Vol. 13 (1967} p. 852.




     Kent,  J. A., Riegel's Handbook of Industrial Chemistry, 7th




     Edition, Van Nostrand-Reinhold Company, New York, N.Y., 1974.
                            6-788

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO.  342
                         Dinitrobenzoic Acids
                                             COOH
(N02)   --H    IVjJ— 
                                                      22
1.   Function - 2,4-Dinitrotoluene and 2 , 6-dinitrotoluene are obtained



     by the dinitration of toluene by conventional nitrating process.



     The corresponding benzoic acids may be obtained by nitrating in the



     presence of CrO_ or Na2Cr?07.



2.   Input Materials



     Toluene
3.   Operating Parameters



     Temperature:  0°C (32°F)



     Pressure:  101 kPa (1 atm)



     Time:  1 to 2 hr



4.   Utilities - not given



5.   Waste Streams - Typical nitration waste streams (NO , spent acid)
      ~"~                                                  X


     should be present as well as some chromium salts in the sludge.



6.   EPA Source Classification Code - None



7.   References



     Kirk-Othmer , Encyclopedia of Chemical Technology, 2nd Edition,



     Interscience Publishers, New York, N.Y. , Vol. 13 (1967), p. 851.
                             6-789

-------
7.  References (continued)




    Tadeuz, Urbanski,  et al.,  Biul.  Wojskowej Akad. Tech. 9, No. 97,




    73-83 (1960).






    Adolph, E. et  al.,  Tetrahedron,  19(6),  801-7 (1963).
                           6-790

-------
INDUSTRIAL ORGANIC CHEMICALS              PROCESS NO.  343
                   2,4- and 2,6-Diaminotoluenes
1.   Function - The usual industrial dinitration of toluene gives a


     mixture of 2,4- and 2,6-dinitrotoluenes in a 80:20 ratio.   A


     conventional liquid phase hydrogenation yields the 2,4- and


     2 , 6-diamino toluenes .  The mixture of the diamines is used to


     manufacture the corresponding diisocyanates used in urethane


     manufacture.


2.   Input Materials


     Dinitrotoluenes - 1.57 kg/kg Diaminotoluenes


     Hydrogen - 0.106 kg/kg Diaminotoluenes


3.   Operating Parameters


     Temperature:             90-190°C (194-374°F)


     Pressure:                606 kPa (6 atm)


     Catalyst:                palladium on carbon


     Phase:                   liquid


     Reactor type:            jacketed kettle


     Solvent:                 water


4.   Utilities - Basis:  9.41 Gg (20.75 M lb)/yr. capacity (based on


                         DuPont patents)

                          3
     Cooling water - 568 m  (150,000 gal.) /hour

                                3
     Demineralized water - 681 m  (180,000 gal.) /hour


     Steam - 5.94 Mg (13,100 lb)/hour


     Fuel - 5.9 GJ (5.6 M BTU)/hour


     Electricity - 634 MJ (176 kWh)/hour

                             6-791

-------
5.   Waste Streams



     Recovery section (water),  Toluidlne - 11 gm/kg Diaminotoluenes




     Purification section (water),  Toluenediamine - 9.8 gm/kg




     Diaminotoluenes




6.   EPA Source Classification  Code -  None




7.   References




     Kirk-Othmer,  Encyclopedia  of Chemical Technology,  Interscience




     Publishers,  New York,  N.Y.,  2nd Edition,  Vol.  20 (1969), p.  562.








     Yen,  Y.  C.,  Isocyanates  -  Part I,  Report No.  1-A,  Stanford Research




     Institute,  Menlo Park, California,  June 1968.








     Sittig,  M.,  Organic  Chemical Process Encyclopedia  - 1969,  Noyes




     Development Corp., Park  Ridge,  N.J.,  1969.








     Albright,  Lyle F., and Hanson,  Carl,  "Industrial and Laboratory




     Nitrations",  ACS Symposium Series 22,  1976,  p.  314.
                             6-792

-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 344
                         m-Chlorotoluene
                    NaNO,
                                              CuCl
                                                                  + N,
1.   Function - m-Chlorotoluene is made by the replacement of the amino




     group of m-toluidine with a chlorine by formation of a diazonium




     salt and the reaction of the diazonium salt with cuprous chloride.




     The reaction is carried out by dissolving the m-toluidine in a 2.5X




     excess of aqueous hydrochloric acid containing the cuprous chloride.




     A solution of sodium nitrite is added giving nitrous acid in situ.




     The product is insoluble in water and separates as a nonaqueous




     layer.  Purification is accomplished by distillation.  Urea may be




     added to remove excess nitrous acid.




2.   Input Materials - Basis:  1 kg m-chlorotoluene




     meta-Toluidine - 0.85 kg




     Hydrochloric acid (2.5X excess)




     Sodium nitrite




     Cuprous chloride




3.   Operating Parameters




     Temperature:  0.5°C




     Pressure:  100 kPa (1 atm)




4.   Utilities - Not available




5.   Waste Streams - Air vent streams contain hydrogen chloride, nitrogen,




     nitric oxide and nitrogen dioxide.  Waste water streams contain




     hydrochloric acid, m-toluidine hydrochloride, some copper salts and




     small quantities of m-chlorotoluene.



                            6-793

-------
6.   EPA Source Classification Code - None




7.   References




     Astle,  M.  J.,  Industrial Organic Nitrogen Compounds, Reinhold




     Publishing Corp.,  New York,  1961, p.  198-200.
                           6-794

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 345
                     o- and p-Chlorotoluenes
                                         CH
                                                       Cl

1.   Function - Ortho-and para-chlorotoluenes are prepared by direct

     catalytic chlorination of toluene.  The reaction is carried out in

     a liquid phase reactor at a temperature of 110-130°C and 1 atmos-

     phere pressure, in the presence of iron powder to facilitate ring

     chlorination.  By-products of the reaction are dichlorotoluenes

     and higher chlorinated derivatives.  These are separated from the

     mono-chloro products by distillation.  The o- and p- isomers are

     separated by fractional crystallization.

2.   Input Materials - Basis:  1 Kg chlorotoluene

     Toluene - .91 Kg/Kg

     Chlorine - .70 Kg/Kg

     Iron Turnings

     Sodium hydroxide (10% aqueous to neutralize chlorinated toluenes)

3.   Operating Parameters

     Temperature - 110-130°C

     Pressure - 100 kPa (1 atm)

4.   Utilities - Not available

5.   Waste Streams - Air vent streams contain chlorine, hydrogen chloride

     and some toluene.  Vent on absorber emits chlorine, some toluene.

     Water from decanter contains sodium hydroxide, sodium chloride some

     dichlorotoluenes.  Vent stream from stripping column contains

     toluene.
                            6-795

-------
6.   EPA Source Classification Code - None




7.   References





     Faith, W.L. et al.,  Industrial Chemicals, 3rd Edition, John Wiley




     and Sons, New York,  N.Y., 1965, p. 261-263.





     Sittig,  M.,  Pollution  Control  in the Organic Chemical Industry,




     Noyes  Data Corporation,  Park Ridge,N.J., 1974, p. 103.
                           6-796

-------
INDUSTRIAL ORGANIC CHEMICALS




                      p-Chlorobenzaldehyde
                           HCC1
              + Cl
                                             PROCESS NO.  346
                                                    HCO
Function - p-Chlorobenzaldehyde is produced by hydrolyzing p-




chlorobenzalchloride, a side chain chlorination product of p-




chlorotoluene.  p-Chlorotoluene is chlorinated at 160°C and




1 atmosphere pressure in a glass lined reactor, to prevent metal




catalyzed ring chlorination.  The extent of chlorination is




estimated by measuring  the density of the reaction product.




This method of control results in by-product of chlorobenzylchloride




and chlorobenzotrichloride.




     The crude chlorobenzal chloride is hydrolyzed by boiling water




yielding chlorobenzaldehyde and by-products of chlorobenzylalcohol, and




chlorobenzoic acid.




Input Materials - Based on 1 Kg chlorobenzaldehyde




Chlorotoluene - 0.9 Kg




Chlorine - 70.5 Kg




Water - 70.13 Kg




Operating Parameters




Temperature - 160°C




Pressure - 100 kPa (1 atm)




Utilities - Not given
                       6-797

-------
5.   Waste Streams - Vent on gas absorber emits hydrogen chloride and




     chlorine.  Waste water streams may contain hydrochloric acid,




     benzoic acid, chlorobenzylalcohol and some chlorobenzaldehyde.




     Because the heat of reaction for the chlorination is controlled




     by the reflux of chlorotoluene some chlorotoluene vapors may be




     emitted.




6.   EPA Source Classification Code - None




7.   References




     Faith, W.L. et al., Industrial Chemicals, 3rd Edition, John Wiley and




     Sons, New York, N.Y., 1965, p. 120,121.
                            6-798

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 347




                  Chlorobenzoic Acids (o- and p-)
                  CC1,
                           + 3C1,
                                   Fe
                                          CC1,
+ 3HC1
                                                    + 3HC1
     Function - Chlorobenzoic acids may be prepared by a variety of




     methods based on well-known reactions.  The ortho and para acids




     can be made from o-chlorotoluene and p-chlorotoluene, respectively,




     by chlorinating the substituted toluene in the side chain to the




     chloro-benzotrichloride stage (indicated by the density of the




     reaction product), and then hydrolyzing.




          Mixed o, p-acids are manufactured by reacting mixtures of o,




     p-chlorotoluenes.  The meta acid can be made by direct chlbrination




     of benzoic acid.



     Input materials - Basis:  1 kg p-chlorobenzoic acid




     p-chlorotoluene - 0.81 kg




     Chlorine - >1.3 kg






                            6-799

-------
     Water - >0.23 kg




     Catalyst - quantity not given




3.   Operating parameters




     Temperatures:  160°C chlorination;  100°C hydrolysis




     Pressure:  100 kPa (1 atm)




     Catalyst:  zinc chloride




4.   Utilities - none available




5.   Waste Streams - Hydrogen chloride is emitted from the vent in




     the gas absorber, possibly  some chlorine is also emitted.   Waste




     water streams may contain sodium hydroxide, sodium chloride,




     sodium  chlorobenzoate,  zinc  chloride and by-products of chloro-




     benzaldehyde and chlorobenzylalcohol depending upon the purity of




     the chlorobenzotrichloride  hydrolyzed.




6.   EPA Source Classification Code - None




7.   References




     Kirk-Othmer, Encyclopedia of  Chemical Technology, 2nd Edition,




     Interscience Publishers, New York,  Vol. 3  (1967), pp. 436-437.






     Faith, W. L., D. B. Keyes and R. L. Clark, Industrial Chemicals,




     3rd Edition, John Wiley and Sons Inc., New York, 1965, pp. 141-142.
                            6-800

-------
INDUSTRIAL ORGANIC CHEMICALS
PROCESS NO. 348
                    Chlorobenzoyl Chlorides (o- and p-)
                                                                HC1
                            COOH
   COC1 + HC1
1.   Function - Chlorobenzoyl chloride Is made by the reaction of chloro-




     benzoic acid and chlorobenzotrichloride.  This may be operated as




     part of the process for producing benzole acid.  The product, benzole




     acid, is mixed with unhydrolyzed benzole acid precursor, chloro-




     benzotrichloride and heated.




2.   Input Materials




     Chlorobenzoic acid




     Chlorobenzotrichloride




3.   Operating Parameters




     Temperature:  150-250°C  (302-482°F)




     Pressure:  100 kPa (1 atm)




4-   Utilities - Not available




5.   Waste Streams - Vent from gas absorber emits some hydrogen chloride




     and chlorine.  Bottoms from the distillation column contain unreacted




     chlorobenzoic acid and chlorobenzochloride.




6.   EPA Source Classification Code - None




7.   References




     Staff, Chemical Origins and Markets, Chemical  Information Services,




     Stanford Research Institute, Menlo  Park, California  (1967),  p.  21.
                             6-801

-------
References (continued)




Hahn, A. V., The Petrochemical Industry, McGraw-Hill Book Co.,




New York, (1970), p. 518.
                       6-802

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS NO. 342



     Benzene and Xylenes (disproportionation; hydrodealkylation)
                                92% H9^r   1     +      — (CH3)2   (1)
                                                 + CH,                (2)

                                80% H2 ^   •*  "

1.   Function - Benzene and xylene are formed by the disproportionation



     of toluene.  Benzene can be produced by the hydrodealkylation (2)



     of toluene.  Both of these processes are becoming increasingly



     important because of the rising demand for benzene in industry.   Petrol-



     eum stocks have been the principal  sources of benzene  in recent



     timesj hut the ratio of benzene/toluene/xylenes produced by the



     catalytic reformer processes is almost exactly opposite to the



     demand for these products.  It was  necessary therefore to develop



     process to produce benzene from toluene and xylene.  Both catalytic



     and thermal processes are employed.



          There are four major processes used  to convert alkyl benzenes



     to benzene:  Howdry  (a fixed bed catalytic process), Hydeal



     (catalytic dealkylation) , Hydrodealkylation, and the Thermal



     Hydrodealkylation (a non-catalytic, elevated temperature and



     pressure) .



2.   Input Materials



     Hydrogen



     Toluene



     C0 Aromatics
      o


     Alkylbenzenes
                            6-803

-------
3.   Operating Parameters




     Detol:         temperature - 538-649° C (1000-1200° F)




                    pressure - 3.5-8.3 MPa (34-82 atm)




                    catalyst - poison resistant,  non-noble metal




                               compound pellets




     Hydeal:        Not given




     Hydrodealkylation:  temperature - 593-760° C (110-1400° F)




                         pressure - 3.5-7.0 MPa (34-68 atm)




     THD:            Not given




4*   Utilities - disproportionation of toluene




     Electric power - 263 MJ (73 kWh)




     Steam - 1.2 Mg (1.5 short tons)




     Cooling water (AT 10° C) - 2.1 Mg (3.6 short tons)




     Fuel - 2.0 GJ (0.7 x 106 kcal)




5.   Waste streams - C- aromatic hydrocarbon plus  diphenyl and higher




     condensed aromatics as bottoms.  Lighter paraffins and olefins




     as overhead or raffinate.  By-product formation 29 kg (64 lb)/




     1000 kg (metric ton) product.




6.   EPA Source Classification Code - None




7.   References




     Anon., "Detol," "Hydeal," "Hydrodealkylation," and "Thermal




     Hydrodealkylation," Pet. Refiner, 40(11), 236, 251, 252, 298  (1961),






     Mager, E. M., "Aromatics Production," U.S. Petrochemicals,




     Technologies, Markets, and Economics, Brownstein, A. M., Ed.,




     The Petroleum Publishing Company, Tulsa, Okla.,  1972, pp.  123-125.
                            6-804

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 350
                           Methylcyclohexane

                        3
                            , „  catalyst  .
1.   Function - Methylcyclohexane is produced commercially by the

     catalytic reduction of toluene.  Since the reaction is catalyzed

     by Raney nickel, a catalyst which is severly poisoned by sulfur

     compounds, it is necessary to desulfurize the toluene or to use

     sulfur-free toluene as the starting material.  The reaction is

     carried out in the liquid phase at 220° C and pressures of 25-

     34 atm.  It is usually carried out in a series of reactors to

     reduce the amount of recycle, cooling methylcyclohexane in order

     to avoid excessive catalyst bed temperatures which can lead to

     isomerization.

2.   Input Materials

     Toluene

     Hydrogen

3.   Operating Parameters

     Temperature:        220° C to 270° C (428-518° F); average

                         conditions 220° C (428° F)

     Pressure:           2.5-3.6 MPa (25-34 atm)

     Catalyst:           Supported nickel or platinum catalyst

4.   Utilities - Not given

5.   Waste Streams - rearrangement by-products such as dimethylcyclo-

     pentanes, ethylcyclopentanes, and paraffinic residues as still bottoms

     or overheads.
                            6-805

-------
6.   EPA Source Classification Code - None
7.    Reference
     Hydrocarbon Processing and Petroleum Refiner .40(11^. 234, 1961.
                          6-806

-------
INDUSTRIAL ORGANIC CHEMICALS                                 PROCESS NO. 351




                              Methylcyclohexanol
1.   Function - Large scale manufacture of methylcyclohexanol employs




     the oxidation of methylcyclohexane.  The process can start by




     the direct oxidation of methylcyclohexane.  The oxidation is most




     preferably carried out in the presence of metaboric acid, although




     other special boron compounds can be used.  Oxygen reacts with




     methylcyclohexane to form methylcyclohexyl hydroperoxide, which




     on reaction with metaboric acid is believed to form a peroxyborate.




     This peroxyborate is thought to react subsequently to make cyclohexyl




     borate esters.  Caustic may be used in neutralization of product.




     The water of reaction must be maintained at very low levels or




     product yield is decreased.  The process for producing methyl-




     cyclohexanol is similar, if not identical, in some cases to that




     used to produce cyclohexanol.  Methylcyclohexanol is also pro-




     duced by the hydrogenation of o, p-cresols.




2.   Input Materials - Basis:  1 kg methylcyclohexanol




     Methylcyclohexane - 0.98 kg




     Oxygen  - 0.16 kg




     Metaboric acid - quantity not given




     Caustic - quantity not given




3.   Operating Parameters




     Temperature:  185 - 200°C (365-392°F)




     Pressure:  2040 - 4800 (20 - 47 atm)




     Catalyst:  boric acid or none (5% of Hydrocarbon)






                               6-807

-------
4.   Utilities - Quantities not given




5.   Waste Streams - The principal source of air pollution occurs during




     the removal of the water of reaction by azeotropic distillation




     of cyclohexane-water.   Boric acid is recovered and cyclohexane is




     recycled.  Some cyclohexane may be present in the air vent streams.




     Spent caustic from hydrolysis of borate esters as well as small




     quantities of cyclohexanol will be present in the waste process




     water.




6.   EPA Source Classification Code - None




7.   References




     Considine, D.M., Chemical and Process Technology, McGraw-Hill




     Book Company, New York, 1974, pp. 337-338.






     Sittig,  M., Organic Chemical Process Encyclopedia 1969, 2nd Edition,




     Noyes Development Corporation, Park Ridge, New Jersey, 1969, p. 203.






     Waddams, A.L., Chemicals from Petroleum, 3rd Edition, John Murray,




     London,  1973, p. 240-241.
                                6-808

-------
INDUSTRIAL ORGANIC CHEMICALS                           PROCESS  NO.  352





                          Me thylcyclohexaaene
CH,
           _/    \-OH + 1/2 o2 -£2i:—+-  CH3-\    Vo + H2
1.   Function - Conmercial processes employ air oxidation of methylcyclo-




     hexanol to produce methylcyclohexanone.




          The reaction occurs in a fixed bed multitubular reactor in the




     vapor phase.  A silver or copper catalyst is used.




2.   Input Materials - Basis - 1 kg methylcyclohexanone




     Methylcyclohexanol - 1 kg




     Air - >0.14 kg




     Catalyst - quantity not given




3.   Operating Parameters




     Temperature:  ~630°C  (1166°F)




     Pressure:  atmospheric




     Catalyst:  silver or copper




4.   Utilities - Not given




5.   Waste Streams - No specific information was found.  Gaseous emissions



     would include methylcyclohexanol, methylcyclohexanone, and a host




     of by-products from side reactions depending on catalyst efficiency.




     The condensed water which is separated and disposed of may contain




     methylcyclohexanone as well as  other  organic impurities from the




     high temperature oxidation.
                             6-809

-------
6.   EPA Source Classification Code - None




7.   References




     Sittig, M., Organic Chemical Process Encyclopedia, 2nd Edition,




     Noyes Development Corporation, Park Ridge, N.J., (1969), p. 433.






     U.S.  Patent 2,930,679 (March 29, 1960).
                           6-810

-------
INDUSTRIAL ORGANIC CHEMICALS              PROCESS NO. 353

                           Benzaldehyde
                 + 02(air)
                                       CHO
                              Cat.
!•   Function - Toluene can be directly oxidized in the vapor phase
     to benzaldehyde by using a mixture of air and toluene vapors
     (14:1 weight ratios) in the presence of a 93% uranium oxide,
     7% molybdenum oxide catalyst.  Small amounts of CuO are added
     to minimize oxidation to maleic anhydride.
          Direct oxidation of toluene is not the only process used.
     Some quantities are manufactured by hydrolyzing benzal chloride.
2.   Input Materials - Basis:  1 kg Benzaldehyde (direct oxidation
     route)
     Toluene - 2.2 kg
     Air - 30.2 kg
     Catalyst - quantity not given
3.   Operating Parameters
     Temperature:   500°C (932°F)
     Pressure:      101 kPa (1 atm)
     Catalyst:      molybdenum oxide - 7%/uranium oxide - 93% with
                    cuprous oxide
4*   Utilities - quantities not given
5.   Waste Streams - By-products such as benzoic acid, maleic anhydride,
     CO,  C0»,  anthraquinone, and high boiling oils; scrubber wastes.
6.   EPA Source Classification Code - None
                             6-811

-------
7.   References




     Faith,  W-  L.,  et  al.,  Industrial Chemicals,  John Wiley and  Sons,




     Inc., New York,  N.Y.,  3rd  Edition,  1965,  p.  120-124.





     Hahn, A.  V., The Petrochemical Industry;   Market  and  Economics,




     McGraw-Hill Book Co., New  York,  N.Y.,  1970,  p.  519-518.
                             6-812

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 354




                                   Benzoin






                   JCHO




                         KCN
                         EtOH






1.  Function - Benzoin is manufactured by the reductive condensation of




    benzaldehyde in an alkaline cyanide solution.  The reaction occurs in




    the liquid phase in alcohol (commonly ethyl alcohol) which will




    solubilize benzaldehyde, cyanide,and benzoin.  The reaction is carried




    out at reflux conditions.




2.  Input Materials - Basis - 1 kg benzoin




    Benzaldehyde - 1 kg




    Potassium cyanide catalyst - quantity unknown




3.  Operating Parameters




    Temperature - 80°C (reflux temperature of ethyl alcohol) (176°F)




    Pressure -  101 kPa (1 atm)




    Time for reaction - 1-3 hours




    Catalyst - potassium cyanide




4-  Utilities - Not given




5.  Waste Streams - The reflux of ethyl alcohol to control the heat of




    reaction may cause the presence of ethanol and HCN in the vent streams.




    Potassium cyanide, ethanol,  and benzaldehyde will be found in the waste




    water streams.




6.  EPA Source Classification Code - None
                               6-813

-------
7.   References




    Kirk-Othmer,  Encyclopedia  of  Chemical  Technology.  2nd Edition,




    Interscience  Publishers, New  York, N.Y.,  Vol.  3  (1967),  p.  365.
                              6-814

-------
INDUSTRIAL ORGANIC CHEMICALS
                                   Benzil
                                CuSO,
                                aq. Py.
PROCESS NO.  355
1.  Function - The a-diketone benzil is obtained in high yield by oxidation




    of benzoin with nitric acid in acetic acid solution or with copper




    sulfate in aqueous pyridine.  Reaction occurs at reflux conditions.




2.  Input Materials - Basis:  1 kg benzil




    Benzoin - 1 kg




    CuSO., pyridine - quantities not given




    Water or HNO




    Acetic acid




3.  Operating Parameters




    Temperature - 230°C (reflux condition) (446°F)




    Pressure - 101 kPa (1 atm)




    Catalyst - CuSO,




4.  Utilities - Not given




5.  Waste Streams - Pyridine, acetic acid, HNO™, as well as products and




    reactants may be present in wastewater.  The reaction occurs at reflux.




    Thus, pyridine, acetic acid, and nitric acid may be present in vent gas\



6.  EPA Source Classification Code - None
                              6-815

-------
7.   References




    Kirk~0thmer,  Encyclopedia of Chemical Technology,  2nd Edition,




    Interscience  Publishing  Co.,  New York, N.Y.,  Vol.  12 (1967),  p.  146-147.





    U.  S.  Pat.  2,377,749  (June 5,  1945).
                              6-816

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO.   356


                               Benzilic Acid
                                    KOH     HO-C-
                                   140°C


                                                             P

1.  Function - Benzilic acid is produced from benzil by a base catalyzed
                                                                    »

    rearrangement.  The reaction is run in water at slightly elevated


    pressure and a temperature of 140°C (melting point of benzil =  137°C).


    Alternately a sodium hydroxide-sodium bromate catalyst mixture  is


    employed at a temperature of 85-90°C and ambient pressure.


         At the conclusion of the reaction (4-5 hours) the sodium salt


    of benzilic acid is neutralized with hydrochloric acid and crystallized


    from the solution as it cools to room temperature.  The product


    separated  after washing, is of sufficient purity for use in most


    applications.  Crystallization from benzene can be employed to  produce


    a benzilic acid of superior purity.


2.  Input Materials


    Potassium hydroxide - 0.2 kg


    Benzil - 1 kg


    Hydrochloric acid - 0.16 kg


3.  Operating Parameters


    Temperature - 140°C


    Pressure - Not  given


4.  Utilities - Not given
                             6-817

-------
5.  Waste Streams - Air vent streams may contain some hydrogen chloride.




    Waste water contain potassium chloride, potassium hydroxide, sodium




    benzilate, minor amounts of benzilic acid.




6.  EPA Source Classification Code - None




7.  References




    Doering and Urgan,  J.  Am.  Chem.  Soc., 78,  5938 (1956).





    Ballard, D.  A.,  and Dehn,  W.  M., Org. Syn. Coll., Vol.  1, 89 (1941).
                             6-818

-------
INDUSTRIAL ORGANIC CHEMICALS
   PROCESS NO.  357
                      p-Toluenesulfonyl Chloride
                           + so.
                              J3
                          (oleum)
                             PC1
  + POC1- + HC1
1.   Function - p-Toluenesulfonyl chloride is produced, industrially

     from toluene, oleum and phosphorus pentachloride.  The first stage

     produces p-toluenesulfonic acid.  Toluene and oleum are combined

     to give o- and p-toluene sulfonic acid.  The p-isomer is favored

     at higher temperatures, however the o-isomer can be isomerized to

     the p- by heating to 140°C.  The solution is neutralized with

     or BaCO,, percipitating BaSO. and leaving the sulfonic acids in

     solution from which they are recovered by crystallization.

          The sulfonic acids are converted to the sulfonyl chlorides

     through the action of phosphorous pentachloride.  The use of PCI-

     instead of Cl« obviates the need for non-ferrous reaction vessels

     and reaction in  the absence of light.

          An alternate route to p-toluenesulfonyl chloride is also  a  two

     step process using chlorosulfonic acid as both  the  sulfonating and

     the chlorinating reagent.
                              C1S03H
                             6-819
+ HC1

-------
                                             so2ci
          An excess of chlorosulfonic acid is used to drive the reaction
     to completion.
2.   Input Materials - Basis - 1 kg p-toluenesulfonyl chloride (SO^,  PClj
     route)
     Toluene - 0.48 kg
     Oleum - 2.1 kg
     PC15 - .31 kg
3.   Operating Parameters
     Temperature:  sulfonation - 30-40°C (86-104°F)
                   chlorination - 80°C  (176°F)
     Pressure:  100 kPa (1 atm)
4.   Utilities - Not given
5.   Waste Streams - The air vent stream from the gas absorber will con-
     tain hydrogen chloride.  Barium sulfate and. phosphate will precipi-
     tate on neutralization of the sulfonating solution.  Waste wash water
     streams may contain small amounts of sulfuric and phosphoric acids
     and their salts as well as p-toluenesulfonic acids.
6.   EPA Source Classification Code - None
7.   References
     Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,
     Interscience Publishers, New York, N.Y., Vol. 19  (1969),  p. 298-99.

     Chemical Technology, Barnes and Noble Books, New York, N.Y.,
     Vol. 4 (1972), p. 595, 612.
                             6-820

-------
INDUSTRIAL ORGANIC CHEMICALS                             PROCESS NO.  358




                         p-Toluenesulfonamide


                                                    /^\
                                                            S02NH2 +  NH4C1



1.   Function - Toluenesulfonamide is prepared by reacting toluenesulfonyl

     chloride with ammonia*


2.   Input Materials - Basis:  1 kg toluenesulfonamide


     Ammonia - 0.1 kg


     Toluenesulfonyl chloride - 1.1 kg


     Catalyst - quantity not given


3-   Operating Parameters


     Temperature:  room temperature or lower


     Pressure:  atmospheric





4.   Utilities


     Quantities not given


5.   Waste Streams - Hydrogen chloride may appear in the air vent streams as


     well as ammonia although most of the HC1, reacts with the excess ammonia


     gas used, to form ammonium chloride.  The NH.C1 will be present in the


     waste water streams as well as small amounts of toluenesulfonamide.


6.   EPA Source ClassificationCode


     None


7.   Reference


     Chemical Technology.  Barnes and Noble Books, New York, N.Y., Vol. 4


     (1972), p.  611-613.
                                6-821

-------
Kirk-Othmer, Encyclopedia of Chemical Technology. 2nd Edition,




Interscience Publishers, New York, N.Y.., Vol. 19  (1969), p.  255-260.
                          6-822

-------
SECTION X
 XYLENES
6-823

-------
                                                                                    XYLENES
           XYLENES
CX>
NJ
-e-
359


\
/
\
/
	 X
                                   } Ethylbenzene
                                   ^ o-Xylene
^p-Xylene-
                                                360
                                                361
                  -> Phthalic anhydride
                                                        Isophthalic  acid
                                                362 A.B
                                                    *
                                                        Terephthallc acid *  Dimethyl.Terephthalate
                                     Xyienes	—	) Nitroxylenes  	^Xylidines
                                                        Figure 19.   Xylenes  Section  Chemical Tree

-------
cr>
 I
oo
K3
Ul
     1


I  Xylenes  I




       if
                            Nitration    363
                                          XI
1 *

Reduction
364

                                                    I  p-Xylene  J
                                                   Water
Acetic acid

 [Air  .
                                                     Oxidation
                              362 A.B
                                                       Tere-
                                                      phthalic
                                                    .  acid & .
                                                Dimethyl Terephthaiate
            Acetic acid
Cooling water
III



Air
* ./*
360
Oxidation
XI

                                                                Ethyl-
                                                                benzene
                                                   Figure  20.   Xylenes Section Process Flow  Sheet

-------
INDUSTRIAL ORGANIC CHEMICALS                            PROCESS NO.  359



                o-t m-,  and p-Xylenes and Ethyl Benzene



 1.   Function - Over 90% of the  domestic  production  of  xylenes is the



     result of catalytic reforming  or hydroforming of certain petrol-



     eum fractions.   Disproportionation and  transalkylation of toluene



     is a minor source of xylenes.  A typical cut of C0 stock has the
                                                     o


     following composition:

ethyl benzene
p-xylene
m-xylene
o-xylene
Wt. % in
distillate
9-13%
17-20%
45-53%
18-24%
M.P., °C
-95.0
13.2
-47,9
-25.2
B.P., °C
136.2
138.4
139.1
144.4
         By a process  termed  super-fractionation, ethyl benzene  (99.7%



     purity) can be  separated  from the xylenes.   In addition, o-xylene



     can  be separated from  the other xylenes by fractional distillation.



         The differences in melting points allow for practical separa-



     tion of the m-  and p-isomers.



         The dried  feedstock  (^ 10 P.P.M. H20) is cooled to -40°C  and



     passed to a crystallizer  at -62°C to -66°C.  Crystals of p-xylene



     formed are centrifuged, partially melted and recrystallized  at



     -31°C.  The mother liquor (rich in m-xylene) can be recycled or



     isomerized to yield more  p-xylene.



         Isomerization processes may employ a platinum on a  silica-



     alumina support as a catalyst.  Isomerization occurs in  the  vapor
                             6-826

-------
    phase in the presence of hydrogen at temperatures around 450°C

    and pressures in the 10-25 atm range.  The product of isomeriza-

    tion is recycled to the crystallization unit.

         Other processes of interest in the isolation of xylenes in-

    clude:

          1.  Preferential adsorption of p-xylene  on a solid absorbent

    from a mixture of CQ aromatics (Parex process).
                       o

          2.  Separation of pure m-xylene via sulphonation,  formation

    of clathrates, or formation of an HF-BF3 complex.

          3.  Separation of m- and p-isomers by formation of Werner-

    type complexes.

2.  Input Materials

    CQ aromatics
     o

3.  Operating Parameters

    Separation of ethyl benzene

    (Three 200 ft column in series containing 350  plates.  Reflux ratio

    25:1 to 50:1.)

    Crystallization (p-xylenes)

    1st - Temperature:  -62°C-66°C (144-151°F)
          Pressure:  not given

    2nd - Temperature:  -31°C (88°F)
          Pressure:  not given

    Isomerization

         Temperature:   -450°C (842°F)
         Pressure:  1.01-2.53 MPa (10-25 atm)
         Catalyst:  Platinum on a silica-alumina support
                            6-827

-------
4.    Utilities

     Distillation of  ethylbenzene  and  o-xylene:   Not given

     Crystallization  of  p-xylene  (Chevron Process,  Crude Feed)


     Basis:     45.4 Og/yr  (100 M lb/yr)  capacity
                            o
               water  - 40  dm /s  (600 gpm)

               steam  - 2.3 Gg/hr (5 M  Ib/hr)

               power  - 10.8GJ  (3,000 kWh)

     Isomerization of m-xylene (alumina-silica catalyst,  Crude Feed)


     Basis:     45.4 Gg/yr  (100 M lb/yr)  capacity
                            3
               water  - 44  dm /s  (700  gpm)

               steam - 7.3 Mg/hr (16,000 Ib/hr)

               power  - 1.4 GJ (400 kWh)

               fuel - 30 MW (100 M Btu/hr)


5.   Waste Streams

     Distillation - Not  given.
                                       o
     Crystallization - Sludge 0.3-1.7 m /Mg (100-500 gallons/ton of
                                                      3
                       p-xylene) containining 3g-5kg/m   (3-5,000 mg/1)


                       of organic material is produced.

     Isomerization - Separator has an off-gas vent  that would expel

                     organic vapors.


6.   EPA Source Classification Code - None.


7.   References

     Brownstein, A. M.,  U. S. Petrochemicals, The Petroleum Publishing

     Company, Tulsa, Oklahoma, 1972.



     Gloyna, E. F., and Ford, D. L.,  "The Characteristics and Pollution


     Problems Associated with Petrochemical Wastes",  for TWPCA, Contract


     No. 14-12-461, February, 1970.


                             6-828

-------
Ries, H. C., "Xylenes Separation", Report No. 25, Stanford Research




Institute, Menlo Park, California, 1967.






Anon., "Development Document for Effluent Limitations Guidelines




and Standards of Performance", prepared for Environmental Protection




Agency, Contract No. 68-01-1509, June, 1973.






Austin, G. T., "The Industrially Significant Organic Chemicals -




Part 9", "Chemical Engineering,"August 5, 1974, p. 99.






Waddams, A. L., Chemicals From Petroleum, 3rd Edition, John Wiley




and Sons, New York, N. Y., 1973, p. 209-221.
                        6-829

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO.  360



                Phthalic Anhydride (from o-xylene)
!•   Function - Phthalic anhydride (PAN)  is manufactured by air oxida-



     tion of o-xylene in a fixed catalyst bed reactor.   Oxidation is



     achieved by feeding the mixture of vaporized o-xylene and preheated



     air (1:10) to a reactor containing a V?0,- based propietary catalyst.



     The reaction takes place at a temperature of V550°C with a contact



     time of the order  of .10 to .15 seconds.  Heat is removed by cir-



     culating molten salts across the reactor.  Many plants can operate



     at will on o-xylene or naphthalene feedstock.



          The vapors leaving the reactor are condensed, then melted and



     fed into a pre-decomposer.  In the pre-decomposer maleic and benzoic



     acid are removed and any phthalic acid present is dehydrated.



     Final purification is done by distillation in vacuum.



2.   Input Materials



     o-xylene            975 kg/metric ton product



     air                 25,000 m  at 15°C/metric ton product



3.   Operating Parameters



     Temperature:             550°C (1022°F)



     Pressure:                not given



     Catalyst:                propietary catalyst based on 7,0,.
                                                             £  .J


     Contact Time:            0.10 to 0.15 sec



     Av. Plant Capacity:      18 to 45 million kg/yr



                             6-830

-------
4.   Utilities - not given

5.   Waste Streams - Waste gas - Most waste gas is scrubbed with water.

     Removal rates have been shown to be in excess of 99% of all organic

     acids, however total aldehydes removal is poor with concentrations

     in the effluent varying between   8 and 26 ppm as formaldehyde.

     The scrubbing water discharges at 115 - 130°F with 1.7 - 2.5% total

     acidity as maleic acid.

          A phthalic anhydride plant producing 100 million pounds of  PAN

     a year could have a scfubbet effluent with an ultimate oxygen

     demand of from 400 to in excess of 1200 Ibs/hr.

6.   EPA Source Classification Code - None

7.   References

     Sittig, M., Pollution Control in the Organic Chemical Industry,

     Noyes Data Corp., Park Ridge, N. J., 1974, p. 186-188.


     Fawcett, R. L., "Air Pollution Potential of Phthalic Anhydride

     Manufacture," Journal of the Air Pollution Control Associationr  JO

     (7):  461-465, 1970.

                                                                         M
     Austin, G. T., "Industrially Significant Organic Chemicals - Part 8,

     "Chemical Engineering", July 22, 1974, p. 109-110.


     "1973 Petrochemicals Handbook", "Hydrocarbon Processing", November,

     1973, p. 159-160.


     Waddams, A. L., Chemicals from Petroleum, 3rd Edition, John Wiley

     and Sons, New York, N. Y., 1973, p. 228-230.



     Lowenheim, F. A. and Koran, M. K., Industrial Chemicals, 4th Edition,

     John Wiley and Sons, New York, N. Y., 1975, p. 661-664.


                             6-831

-------
Hedley, W- H. et al.,  "Potential Pollutants from Petrochemical




Processes", Prepared for Control Systems Laboratory,  NERC,  Environ-




mental Protection Agency, Contract No.  68-02-0226,  Task No.  9,




1973, p. 95-96.
                       6-832

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO. 361
                                              OOH
                          CH3




1.   Function - As of 1971 Amoco and Arco were the only two producers of




     isophthalic acid in the U.S.  In the Amoco process m-xylene is oxi-




     dized in the liquid phase at 150-250°C and a pressure of 15-30 atm.




     Air is used as the oxidizing agent and the reaction is carried out




     in acetic acid as solvent, in the presence of a bromine-promoted




     cobalt salt as catalyst.  The isophthalic acid produced will con-




     tain varying amounts of terephthalic acid depending on the purity




     of the m-xylene feedstock.




2.   Input Materials




     m-xylene




     Acetic acid




     Catalyst




3.   Operating Parameters




     Temperature:             150-250°C (301-481°F)




     Pressure:                1.52-3.04 MPa (15-30 atm)




     Catalyst:                cobalt salt activated by bromine




4.   Utilities - not given




5.   Waste Streams - Potential water wastes are IPA, terephthalic acid,




     and acetic acid.




6.   EPA Source Classification Code - None
                            6-833

-------
7.   References




     Hedley,  W. H.,  et.  ai,,  Potential Pollutants  from Petrochemical




     Processes, Prepared for  Control Systems  Laboratory,  NERC,  Environ-




     mental Protection Agency,  Contract No. 68-02-0226,  Task No.  9,




     1973.





     Waddams, A.  L.,  Chemicals  From Petroleum,  3rd Edition,  John  Wiley




     and Sons,  New York, N, Y,,   1973 ,  p. 232-235.
                           6-834

-------
INDUSTRIAL ORGANIC CHEMICALS                      PROCESS NO.  362.A.B


          Terephthalic Acid and Dimethyl Terephthalate

                                            COOH
                                          ^   "X
                                           o.
                                            COOH


1.   Function - Terephthalic acid (TPA) is produced by the air oxidation

     of p-xylene in the liquid phase.

          p-Xylene dissolved in acetic acid reacts with air in the pre-

     sence of a cobalt proprietary catalyst in a reactor at 200°C and

     400 p.s.i.  The hot slurry from the reactor effluents is fed into a

     crystallizer.  Acetic acid, unreacted p-xylene and water are removed

     at this step and by further centrifugation.  Acetic acid and p-

     xylene are recycled.  The crude TPA is leached with acetic acid at

     high temperature.  The resulting TPA of better than 99% purity is

     washed with hot water to remove traces of catalyst and acetic acid.

     Subsequent hydrogenation in fixed-bed reactors, crystallization and

     drying yield fiber grade TPA.  A new route to TPA involves the

     ammoxidation of p-xylene and the subsequent hydrolysis of terephthalo-

     nitrile to terephthalic acid.  The Hercules-Witten process produces

     dimethyl terephthalate from p-xylene without isolation of TPA.

2.   Input Materials

     p-xylene - 680 kg/metric ton polymer grade TPA

     air - not given

     acetic acid - not given
                             6-835

-------
3.   Operating Parameters


     Temperature:              200°C (392°F)


     Pressure:                2.76 MPa (27.2 atm)


     Catalyst:                Bromine promoted cobalt catalyst


4.   Utilities - not given


5.   Waste Streams - Off-gas from scrubber contain some organic vapors;


     wastewaters contain acetic acid, traces of catalyst,  and terephth-


     alic acid.

                                 /             *3
     Water flow rate - 3.62 x 10~  - 9.09 x 10~  m/kg


                       (86.8 - 2180 gal/ton)


     COD        5,400 - 24,950 g/m3     (1.95 - 227 lb/1000 Ib)


     BOD5       3,600 - 7,500 g/m3      (1.30 - 68.3 lb/1000 Ib)


     TOG        4,200 - 3,730 g/m3      (1.52 - 34 lb/1000 Ib)


6.   EPA Source Classification Code - None


7.   References


     Sittig, M., Pollution Control in the Organic Chemical Industry


     Noyes Data, Park Ridge, N.J., 1974, p.  198-203.


     "1973 Petrochemical Handbook", "Hydrocarbon Processing", November,


     1973, p. 183-185.


     Hedley, W. H., et. al., Potential Pollutants in the Petrochemical


     Processes, Prepared for Control Systems Labotatory, NERC, Environ-


     mental Protection Agency, Contract No.  68-02-0226, Task No. 9,


     1973.


     Waddams, A. L., Chemicals from Petroleum, 3rd Edition, John Wiley


     and Sons, 1973, p. 232-237.
                            6-836

-------
Lowenheim, F. A., and Moran, M. K., Industrial Chemicals, 4th




Edition, John Wiley and Sons, 1975, p. 807-813.
                        6-837

-------
INDUSTRIAL ORGANIC CHEMICALS                          PROCESS NO. 363




                                Nitroxylen.es





            GIL
1.  Function - Xylenes, o-,  m-  or p-isomers,  can be nitrated to place nitro




    groups on the benzene ring. Ortho-xylene gives the 4-nitro and the




    4,6-dinitro isomers; meta-xylene gives the 4-nitro isomer, and para-




    xylene the 2,3-dinitro-or 2,6-dinitro-p-xylene, or the 2-nitro-p-xylene.




         The extent of nitration, the number of nitro groups placed in the




    ring, is a function of acid strength and temperature.  The extent of




    side chain oxidation is dependent on the same two factors; therefore,




    with polynitrated products a compromise must be reached.




         Mononitration of xylenes is carried out near room temperature,




    25°C  (77°F) with a mixture of nitric 30% and sulfuric (55%) acids




    and at atmospheric pressure.




2.  Input Materials




    Xylenes




    Nitric-sulfuric acid mixture




3.  Operating Parameters




    Temperature - 25-40°C (77-104°F)




    Pressure - 100 kPa (1 atm)




4.  Utilities - Not given
                              6-838

-------
5.  Waste Streams - Spent acid is recovered and recycled to the system.




    Air emissions from the reactor may contain oxides of nitrogen.  Waste




    water from the product washing procedure contains sodium carbonate,




    some nitroxylenes and nitrate salts.




6.  EPA Source Classification Code - None




7.  References




    Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition,




    Interscience Publishers, New York, N.Y., Vol. 22 (1970), p.  484.





    Chemical Technology, Barnes and Noble Books, New York, N.Y.,




    Vol. 4  (1972), p. 172-174.
                               6-839

-------
INDUSTRIAL ORGANIC CHEMICALS                         PROCESS NO. 364

                  Xylidines (reduction of nitroxylenes)



                                catalyst  __
                       2 + H2


                                                  \
                                                    3

1.  Function - The xylidines are made by the reduction of nitroxylenes.

    The only technical process used at present is hydrogen reduction.

    A molybdenum sulfide catalyst is used for this reaction.

2.  Input Materials

    Nitroxylenes

    Hydrogen

    MoS_ on an inert support

3.  Operating Parameters

    Temperature - 165-170°C (330-340°F)

    Pressure - 20.7 MPa (205 atm)

    Catalyst - MoS-

    Nitroxylene feed - 0.44 vols/vol catalyst/hr.

    Recycle feed - 1.2-1.6 vols/vol

    Recycle gas - 80-85% H» and 0.6% H S

4.  Utilities - Not given

5.  Waste Streams - Waste water from product wash contains sodium carbonate.

    Vents emit some hydrogen.

6.  EPA Source Classification Code - None

7.  Reference


    Brown, C. L., and Smith, W. W., "Production of Xylidines by High Pressure

    Hydrogenation," Ind. Eng. Chem.. Vol. 40, (1948), pp. 1538-42.



                               6-840

-------
            APPENDIX A
INDUSTRIAL CHEMICALS AND SOLVENTS GLOSSARY
            6-841

-------
Table A-l lists specific industrial compounds and their
uses.  Also included are the major producers listed in
alphabetical order for each compound, the plant locations,
plant capacities, and total annual production where
available.  Capacities given are for 1975 and total
chemical production is for the specific year noted.
Capacity and production estimates are given in millions
of kilograms per year (MM kg) and millions of pounds
per year (MM Ibs).
                        6-842

-------
References

1.  Hawley, G. G. (ed.).  The Condensed Chemical Dictionary.  8th Edition,
    Van Nostrand Reinhold Company, 1971.

2.  Staff.  Directory of Chemical Producers - U.S.A. Chemical Information
    Services, Stanford Research Institute, Menlo Park (California), 1975.

3.  Staff.  Chem. Sources.  Directories Publishing Co., Flemington, New
    Jersey, 13th Edition, 1972.

4.  Staff.  "Recession Stifles Output of Top 50 Chemicals." Chemical and
    Engineering News, American Chemical Society, May 5, 1975, p. 31.

5.  Staff.  "Facts and Figures - The U.S. Chemical Industry." Chemical
    and Engineering News, American Chemical Society, June 2, 1975, p.  33.
                                6-843

-------
                                                                   Table A-l.  INDUSTRIAL CHEMICALS  AND  SOLVENTS.
00
                               Acenaphthene
                              Acetal
                              Acetalde-
                              hyde
                              Acetaldol
Dye intermediate;
Pharmaceuticals;
insecticide; fungi-
cide; plastics

Solvent; cosmetics;
organic synthesis;
perfumes; flavors

Acetic acid; acetic
anhydride; n-butanol;
2-ethylhexanol; per-
acetic acid; pentaery-
thritol; pyridlnes;
chloral; 1,3-butylene
glycol; trimethyl-
propane manufacturing
intermediate
                                             Rubber accelerators;
                                             age  resistors;  synthesis;
                                             perfumery;  engraving;  ore
                                             flotation;  solvent; sol-
                                             vent mixture  for  cellu-
                                             lose acetate; fungicides;
                                             organic synthesis;
                                             printer's rollers; cad-
                                             mium plating; dyes;
                                             drugs; dyeing assis-
                                             tant; synthetic polymers
Manufacturer(s)z>^


Hoffmann - La Roche,
Inc., Burdick & Jackson
Labs., Inc., subs id.
                                                                          Fritzche  Dodge  &  Olcott
                                                                          Inc.
Celanese Corp.  -
Celanese Chem,  Co., dlv.


Eastman Kodak Co. -
Eastman Chem. Products ,
Inc-, subsld, Texas
Eastman Co., div.

Monsanto Co. -  Monsanto
Polymer & Petrochems. Co.

Publicker Indust. Inc.

Shell Chem. Co. -
Base  Chems.

Union Carbide Corp. -
Chems. & Plastics Div.
                            Union Carbide Corp. -
                            Chems. & Plastics Div.
Location(s)2*3
Muskegon, Mich.
1975
Capacity2
KM kg (MM Ib)
_
Total1*'5 '
production
MM kg (MM Ib)
for year of estimate
.
                                                                                                      East Hanover, N.J.
Bay City, Tex.
Clear Lake, Tex.
Pampa, Tex.

Longview, Tex.
                                                                                                     Texas  City, Tex.


                                                                                                     Philadelphia, Pa.

                                                                                                     Norco, La.


                                                                                                     Institute & South
                            Institute & South
                            Charleston, W.  Va,
 90.8  (200)     731.6   (1611.10-1970



227    (500)




  2.3  (5)


  2.3  (5)

  2.3  (5)

 90.3  (200)


   Total •
67^.2  (1H85)

-------
                                Chemical
                                                                            Table  A-l.  (Continued)


                                                                           Manufacturer(s)2 »3          Location(s)2J3
                                                                                                1975
                                                                                              Capacity2
                                                                                            MM kg (MM Ib)
                                                                      Total1**5
                                                                      production
                                                                     MM kg (MM Ib)
                                                                  for year of estimate
00
4^
Ui
Acetamide      Organic synthesis
               (reactant, solvent,
               peroxide stabilizer);
               general solvent; lac-
               quers ; explosives;
               soldering flux;
               hygroscopic agent;
               wetting agent;
               penetrating agent

Acetanilide    Rubber accelerator;
               inhibitor in hydro-
               gen peroxide; stabilizer
               for cellulose ester
               coatings; manufacture of
               intermediate  (paranitro-
               aniline, paranitroace-
               tanilide, parahexylene-
               diamine); synthetic cam-
               phor; pharmaceutical
               chemicals; dyestuffs;
               precursor in penicillin
               manufacture; medicine
               (antiseptic)

Acetic         Acetic anhydride, cellu-
acld           lose acetate, and vinyl
               acetate monomer; acetic
               esters; chloroacetic
               production of plastics;
               Pharmaceuticals, dyes;
               insecticides, photo-
               graphic chemicals, etc.;
               food additive (as vine-
               gar) ; natural latex
               coagulant; oil-well
               acidizer; textile
               printing
                                                                           Heicos Inc.


                                                                           Mallinckrodt, Inc. -
                                                                           Indust. Chems. Div.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. Tennessee
Eastman Co., div.

Merck & Co. Inc. -
Merck Chem. Div.

Salsbury Labs

Syntex Corp. - Arapahoe
Chems. Div.
                                                                            Borden  Inc.  -  Borden
                                                                            Chem. Div. Petrochems.

                                                                            Celanese  Corp.  - Cela-
                                                                            nese Chem. Co., div.
                                                                           Eastman Kodak Co. -
                                                                           Eastman Chem. Prod. Inc.,
                                                                           subsid. - Tenn. Eastman
                                                                           Co., div.

                                                                           PMC Corp. - Chem. Group
                                                                           Indust. Chem. Div.

                                                                           Monsanto Co. - Monsanto
                                                                           Polymers & Petrochems. Co.

                                                                           Publicker Indust. Co.

                                                                           Union  Carbide Corp. -
                                                                           Chems. & Plastics Div.
                            Delaware Water
                            Gap, Pa.
                            St. Louis, Mo.
                                                                                                       Kingsport, Tenn.
Albany, Ga.

Charles City,  Iowa
Newport, Tenn.
                            Gelsmar, La.


                            Bay .City, Texas
                            Bishop, Tex.
                            Clear Lake, Tex.
                            Pampa, Tex.

                            Kingsport, Tenn.
                                                                                                                               52.2  (115)   930.7  (2050)-1971
                                                                                                                               50
                                                                                                                              181.6
                                                                                                                              250
                                                                                                                              181.6
                              (110)
                              (tfOO)
                              (550)
                              (JJOO)
Bayport, Tex.
Texas City, Tex.
Philadelphia, Pa.
Brownsville, Tex.
Taft, La.
Texas City, Tex.
18.2 (40)
181.6 (400)
36.3 (80)
268 (590)
111 (90)
15.4 (100)
Total -
1305 (2875)

-------
                                                                                 Table  A-I. (Continued)
                               Acetic
                               anhydride
00
                               Acetone
Cellulose acetate fi-
bers and plastics; vinyl
acetate; dehydrating
and acetylating agent in
production of Pharma-
ceuticals, dyes, per-
fumes, explosives, etc.;
aspirin
                                              Chemicals  (methyl  iso-
                                              butyl ketone, methyl
                                              Isobutyl carbinol
                                              methyl methacrylate
                                              bisphenol-A); paint;
                                              varnish; lacquer sol-
                                              vent; to clean & dry
                                              parts of precision
                                              equipment; solvent for
                                              potassium  iodide &
                                              permanganate; deluste-
                                              rant for cellulose
                                              acetate fibers; speci-
                                              fication testing of
                                              vulcanized rubber
                                              products
Celanese Corp. - Cela-
nese Chem. Co., div.
Celanese Fibers Co., div.
Eastman Kodak Co. -
Eastman Chem. Products.
Inc.. siibsid. -Ten- .
nessee Eastman Co., div.
PMC Corp. - Chem. Group
Indust. Chem. Div.

Union Carbide Corp.-
Chem. & Plastics Div.
                            Allied Chem. Corp. .-
                            Specialty Chems. Div.

                            Clark Oil & Refining
                            Corp. - Clark Chem.
                            Corp., subsid.

                            Dixie Chem. Co.

                            Dow Chem. U-.S.A.

                            Eastman Kodak Co. -
                            Eastman Chem. Products.,
                            Inc., subsid. - Tennes-
                            see Eastman Co., div.

                            Exx6n Corp. - Exxon
                            Chem. Co., div. - Exxon
                            Chem. Co. U.S»A.

                            Georgia-Pacific Corp. -
                            Chem. Div.

                            The Goodyear Tire &  Rub-
                            ber Co. - Chem. Div.
Location(s)2'3
Pampa, Tex. "1
Cumberland, Md. 1
Narrows , Va . 1
Rock Hill, S.O.
Rome , Ga . J
Klngsport, Tenn.
Meadville, Pa.
Brownsville, Tex.l
Texas City, Tex. J
Prankf ord , Pa .
Blue Island, 111.
Bayport , Tex .
Oyster Creek, Tex.
Kingsport, Tenn.
1975
Capacity2
MM kg (MM Ib)
386
272.4
27.2
102
Total
787.7
143
24
11
109
36
(850)
(600)
(60)
(225)
(1735)
(315)
(53)
(24)
(240)
(80)
                            Bayway, N.J.


                            Plaquemlne, La'.

                            Bayport, Tex.
                                                                     Total1*'5-
                                                                     Production
                                                                    MM kg  (MM Ib)
                                                                  for year  of estimate


                                                                  708.5   (1560.6)-1972
                                                                                              902.2   (1987.2)-1973
63.6 (140)


78.1 (172)

-------
                                                                                  Table A-l. (Continued)
                              Chemical

                              Acetone
                              (continued)
00
                               Acetone
                               Cyanohydrin
                               Acetonitrile
Usage1

(see previous page)
Insecticides;  inter-
mediate for organic
synthesis, especially
methyl methacrylate
                                              Solvent in hydro-
                                              carbon processes,
                                              especially for buta-
                                              diene; specialty sol-
                                              vent; intermediate;
                                              separation of fatty
                                              acids from vegetable
                                              oils; manufacture of
                                              synthetic Pharma-
                                              ceuticals
Manufac t urer (_s_ )..2_*_^


Monsanto Co. - Monsanto
Polymers & Petrochems. Co

Oxirane Chem. Co.

Publicfcer Indust. Inc.

Shell Chera. Co. -
Base Chems.


Skelly Oil Co.

Standard, Oil of Calif, -
Chevron Chem. Co., sub-?
sld.^Qronite Additives
& Indust. Chem&. Div. -
Indust, Chems.

Union Carbide Corp..-
Chems. & Plastics Div*
                                                                          Union Carbide Carlbe,
                                                                          Ine., s-ubsld.
                                                                          United States Steel Corp.
                                                                          USS Chems., div.
E. I. du Pont de Nemours
& Co. Inc. - Industrial
Chems. Dept,

Rohm & Haas Co. - Rohm &
Haas Texas Inc., subsid.

Eastman Kodak Co. - East-
man Chem, Products, Inc.,
subsid., Texas Eastman
Co., div.

The Standard Oil Co.
(Ohio) - Vistron Corp.,
subsid.4 Chems. Dept.
Locatlon(s)2'3
Chocolate Bayou,
Tex.
Bayport, Tex.
Philadelphia, Pa.
Deer Park, Tex.
Dominquez, Calif.
Norco, La.
El Dorado , Kans .
Richmond^ Calif.
Total1"5
1975 production
Capacity2 MM kg (MM lb)
MM kg (MM lb) for year of estimate
122.6
18.2
15.9
181.6
45.4
15.4
25-9
15
(270) 
-------
                                                                            Table  A-l.  (Continued)
oo
j>-
oo
                              Chemical
                              Ac e t o -
                              phenone
                              Acetylene
Perfumery; solvent;
intermediate for
Pharmaceuticals,
resins, etc.;
flavoring
Vinyl chloride &
vinylidene chloride;
vinyl acetate; welding
& cutting metals; neo-
prene; acrylonitrile;
acrylates; per- & tri-
chloro-ethylene; cyclo-
octatetraene; tetra-
hydrofuran;  carbon black
Manufacture(s)2*3

Allied Chem. Corp.
Speciality Chems-
Skelly Oil Co.

Universal Oil Pro-
ducts Co. - Chems.
& Plastics Group -
Chem, Dlv.
Chemical Use
Aircoa Inc.

Air Products & Chems.,
Inc., Specialty Gas
Dept.
Lo ca t ion (sj 2^3


Frankfort, Pa.


El Dorado, Kans.
East Rutherford
N.J.
Calvert City, Ky.
Louisville, Ky.
Hometown, Pa.
                            Rohm & Haas Co. - Rohm &
                            Haas Texas Inc., subsid.
                            Solox, Inc.
                            Tenneco Inc. - Tenneco
                            Chems., Organics &
                            Polymers Div.
                                                                                                                              Total
                                                                                                                            Capacity2
                                                                                                                          MM kg (MM Ib)
Chemetron Corp. -
Indus t . Gases Div.
Dow Chem. U.S.A.
Gaspro Inc.
Liquid Air Corp. of
North America — South-
western Region
Monochem. , Inc .
Northern Gases, Inc.
Occidental Petroleum
Corp. - Hooker Chem. Corp.
subsid., Hooker Chems. &
Plastics Corp. , subsid.
Electrochemical & Speci-
alty Chems. Div.
Pryor, Okla

Preeport , Tex.
Honolulu, Hawaii
Houston, Tex.


Geismar, La.
Waukesha, Wise.
Tacoma, Wash.





0.5

6.8
<0.5
_


81.7
_
4.5





(1)

(15)
(<1)



(180)

(10)





                            Deer Park,  Tex.

                            Chattanooga,  Tenn.
                            Houston, Texas
                                                                                                                           15-9   (35)
                                                                                                                           45- H
                                                                                                                                  (100)
                                                                                                  Total4*5
                                                                                                  production
                                                                                                 MM kg (MM  Ib)
                                                                                              for yearof estimate
 36.3  (80)     230.2  (507) -197**
109    (240)
                (chemical and non-
                 chemical use)

-------
                                                                                      Table A-l. (Continued)
                                Chemical        Usage1


                                Acetylene      (see previous page)
                                (continued)
00
-P-
VO
Acetylene
(continued)
                                           Manufacturer(s)2*3
                                           Union Carbide Corp, -
                                           Chems. & Plastics
                                           Div.
                                                                           Union Carbide Caribe,
                                                                           Inc., subsid.
Non-Chemical Us'age
Airco, Inc. - Arco
Indust, Gases Div,

Air Products & Chems.
Inc.
                                                                           American Cyanaraid Co. -
                                                                           Specialty Gas Dept. -
                                                                           Indust. Chems. & Plastics
                                                                           Dlv.

                                                                           Burdett Oxygen Co.

                                                                           Paul Carroll Oxygen Co.

                                                                           Chemetron Corp,  - Indust.
                                                                            Gases Div.
Location(s)2'3


Ashtabula, Ohio
Institute & South
Charleston, W. Va.


Seadrlft, Tex.
Taft, La.
Texas City, Tex.

Penuelas, P.R.
Houston, Tex.


Albany, Ga.
Bladensburg, Md.
Creighton, Pa.
Dallas, Tex.
Granite City, 111.
Greensboro, N.C.
Hampton, Va.
Iselin, N.J.
Kingsport, Tenn.
Memphis, Tenn.
Omaha, Neb.
Parkersburg, W. Va.
Rapid City, S.D.

New Orleans, La.
                                                                       Norristown. Pa.

                                                                        Abilene, Tex.

                                                                        Belton, Tex.
                                                                        Cleveland, Ohio
                                                                        Columbus, Ohio
                                                                        Conshohocken, Pa.
                                                                        Dallas, Tex.
                                                                        Denver, Colo.
                                                                        Detroit, Mich.
                                                    Total
                                                   Capacity2
                                                 MM kg (MM Ib)


                                                   3*   (75)
                                                   15-9 (35)

                                                    3.6 (8)
                                                    9.1 (20)
                                                    6.8 (15)
                                                    8.2 (18)
                                                   36.3 (80)
                                                     n.a.
                                                   Total (Chem.
                                                   use) =
                                                 
-------
                                                                                       Table  A-l.(Continued)
                                Chemical
                                Acetylene
                                (continued)
Usage1


(see previous page)
                                                                            Manufacturer(3)2 * 3
                            Cheiaetion Corp.  (cont'd)
00
                                                                            Welding & Indusfc.
                                                                            Products, Ltd.  - subsid.
                                                                            East  Texas Oxygen Co.
                                                                            Kansas  Oxygen,  Inc.
                                                                            Liquid  Air Corp.  of  North
                                                                            America - Northwestern
                                                                            Region
                                                                            •?•  Southeastern Region
                                                                                                        Location(s)2j3
   1975
 Capacity2
MM kg (MM Ib)
                                                        Evansville ,, Ind,
                                                        Hodgkins, 111.
                                                        Jackson, Miss.
                                                        Jacksonville, Pla.
                                                        Knoxville, Tenn.
                                                        McKees Rocks, Pa.
                                                        Memphis, Tenn.
                                                        Miami, Pla.
                                                        New Orleans, La.
                                                        North Grafton, Mass.
                                                        Peoria, 111.
                                                        Pryor, Okla.
                                                        Sty Paul, Minn.
                                                        Southaven, Miss.
                                                        Tampa, Pla.

                                                        Ewa,(0ahu), Hawaii
                                                        Tyler* Tex.

                                                        Hutchinson, Kans .

                                                        Anchorage , Alas .
                                                        Boise, Idaho
                                                        Fairbanks , Alas .
                                                        Medford, Ore.
                                                        Missoula, Mont.
                                                        Portland, Ore.
                                                        Spokane, Wash.

                                                        Augusta, Ga.
                                                        Decautur, Ala.
                                                        Lake Charles, La.
                                                        Orlando, Pla.
                                                                            -  Southwestern Region      Abilene,  Tex.
                                                                                                        Lubbock,  Tex.
                                                                                                        Odessa, Tex.
                                                                                                        Phoenix,  Ariz.
                                                                                                        Tucson, Ariz.
                                                                            -  Western Region
                                                                            Manitowoc Gases,  Inc.
                                                        Las Vegas, Nev,
                                                        Reno, Nev.
                                                        Sacramento, Calif.
                                                        San Bernardino,
                                                        Calif.
                                                        Santa Pe Springs ,
                                                        Calif.
                                                        Union City, Calif.

                                                        Hanitowoc, Wise .
    Total"*5
    production
   MM kg (MM Ib)
for year of estimate
                 (see previous page)

-------
                                                                                      Table A-l.(Continued)
                                Chemical
                                Acetylene
                                (Continued)
00
Oi
                                Aerolein
                                Aery1amide
Usage1


(see previous page)
Intermediate  for
synthetic glycerol,
polyurethane, poly-
ester resins,
methionine,
Pharmaceuticals;
herbicide; tear gas

Synthesis of  dyes, etc.;
polymers or copolymers
as plastics,  adhesives,
paper & textile sizes,
soil conditioning
agents; flocculants;
sewage & waste treat-
ment; ore processing;
permanent press fabrics
Manufacturer(s)2'3


Northern Gases, Inc.

Pacific Oxygen Co.

Selox, Inc.

Union Carbide Corp. -
Ferroalloys Div.
Linde Div.
                                                                            Shell  Chem.  Co.  -
                                                                            Base Chems.

                                                                            Union  Carbide  Corp.--
                                                                            Chems.  &  Plastics Div.
American Cyanamid Co.-
Indust. Chems. & plastics
Div.

Bio-Red Labs

Dow Chem. U.S.A.

The Standard Oil Co.
(Ohio) - Vistron Corp.,
subsid. - Chems. Dept.
Locatlon(s)2*3


Waukesha, Wise.

Oakland, Calif.

Greenville, S.C.


Ashtabula, Ohio
Albany, N.Y.
Albuquerque, N.M.
Altoona, Pa.
Amarillo, Tex.
Baltimore, Md.
Billings, Mont.
Birmingham, Ala.
Boise, Idaho
Butte, Mont.
Carter Lake, Iowa
Casper, Wyo.
Charlotte, N.C.
Columbus, Ohio
Dallas, Tex.
Denver, Colo.
Des Moines, Iowa
Duluth, Minn.
East Buffalo, N.Y,
East Chicago, Ind.

Norco, La.


Taft, La.
Linden, N.J.
New Orleans, La.
                                                                                                       Richmond, Calif.

                                                                                                       Midland, Mich.

                                                                                                       Lima, Ohio
                                                                                                                               1975
                                                                                                                             Capacity2
                                                                                                                            MM kg  (MM Ib)
                                          Total1**5
                                          production
                                         MM kg (MM Ib)
                                      for; _ye.ar of estimate


                                      (see previous page)
                                                                                                                                              27-7  (61)   -1974
                                                                                                                                              18.2  (40)   -1973

-------
                                                                                      Table  A-l.  (Continued)
                                Chemical
                                Acrylic
                                acid
Ui
to
                                Acrylo-
                                nitrile
                                Adipic
                                acid
Monomer for polyacrylic
& polymethacrylic acids
& other acrylic polymers
Acrylic & modacrylic
fibers & high-strength
whiskers; ABS & acrylo-
nitrlle-styrene copply-
mers; nitrile rubber;
cyanoethylation of cot-
ton; synthetic soil
blocks (aerylonitrile
polymerized in wood
pulp); organic
synthesis; grain
fumigant
Manufacture of nylon &
of polyurethane foams;
preparation of esters
for use as plasticisers
& lubricants; ingredient
of foods, as acldulant;
insecticides; adhesives
Manufacturer(s)2j 3


American Aniline & Ex-
tract Co,, Inc.

Celanese Corp. - Cela-
nese Chem, Co.,  div.

Dow Badische Co.

Rohm & Haas Co., Rohm &
Haas Texas Inc., subsid.

Union Carbide Corp. -
Chems. & Plastics Div.
American Cyanamid Co. -
Indust. Chems. & Plastics
Div.

E. I. du Pont de Nemours
& Co., Inc . -
Elastomer Chems. Dept.
Indust. Chems. Dept.

Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.

The Standard Oil Co.
(Ohio) - Vistron Corp.,
subsid. - Chems. Dept.

Allied Chem. Corp.

Celanese Corp. - Cela-
nese Chem. Co., div.

E. I. du Pont de Nemours
& Co., Inc.  - Plastics
Dept.

El Paso Natural Gas Co, -
El Paso Products Co.,
subsid.
                                                        Location(s)2'3


                                                        Philadelphia, Pa.


                                                        Clear Lake, Tex.
                                                        Pampa, Tex.

                                                        Freeport, Tex.

                                                        Deer Parkj Tex.


                                                        Taft, La.



                                                        New Orleans, La.
                                                                                                       Beaumont, Tex.
                                                                                                       Memphis, Tenn.
                                                                                                                               1975
                                                                                                                             Capacity2
                                                                                                                            MM kg (MM Ib)
                                                                               100   -(220)
                                                                                36.3 (80)

                                                                                18.2 (HO)

                                                                               181.6 (1)00)


                                                                                90.8 (200)
                                                                                Total =
                                                                              131-3  (950)

                                                                                90.8 (200)
                                                   136.2 (300)
                                                   113-5 (250)
                            Chocolate Bayou, La.   208.8 (160)
                                                                                                       Lima, Ohio
                                                        Hopewell, Va.

                                                        Bay City, Tex.


                                                        Orange, Tex.
                                                        Victoria, Tex,


                                                        Odessa, Tex.
                                                   177   (390)
                                                    Total =
                                                   726.il (1600)

                                                    11.3 (25)

                                                    56.7 (125)


                                                   136.2 (300)
                                                   136.2 (300)


                                                    36.3 (80)
                                                                                                  Total14'5
                                                                                                  production
                                                                                                 MM kg (MM Ib)
                                                                                              For year of estimate


                                                                                                37.5  (82.5) -1968
                                                                                                                                              611.2  (1352.9J-1973
                                                                                                                                              626.5  (1380) -1972

-------
                                                                              Table
                                                                                    A-l.
                                                                                          (Continued)
00
Ul
LO
                               Chemical

                               Adipic
                               acid
                               (continued)
                               Alkylnaph-
                               thalenes
                               (methyl)
                               Allyl
                               alcohol
                               Allyl
                               chloride
 (see  previous  page)
Organic synthesis;
insecticides
Esters for use in
resins & plastici-
zers; intermediate
for Pharmaceuticals &
other organic chemi-
cals; manufacture of
glycerol & acrolein;
military poison gas;
herbicide

Preparation of allyl
alcohol & other de-
rivatives ; thermo-
setting resins for var-
nishes , plastics, ad-
hesives; synthesis of
Pharmaceuticals, glycerol
ft insecticides
Manufacturer(s)2 * 3


Monsanto Co. - Monsanto
Indust. Chems. Co. -
Monsanto Textiles Co.
Crowley Hydrocarbon
Chems., Inc.
Koppers Co., Inc. -
Organic Materials Div.
Marathon Oil Co.

PMC Corp. - Chem. Group -
Indust, Chem. Div.
Shell Chem. Co. -
Base Chems.
Dow Chem. U.S.A.
Shell Chem. Co. -
Base Chems.
Location(s)2'3
Luling, La.
Pensacola, Pl'a.
1975
Capacity2
MM kg (MM Ib)
27.2 (60)
255 (562)
Total «
659.2 (1152)
Total*'5
production
MM kg (MM Ib)
for year of estimate
(see previous page)
Houston, Tex.
Kent, Ohio
Oklahoma City,
Okla.
Paulsboro, N.J.
Follansbee, W. Va.


Kobinson, 111.

Bayport, Tex.


Deer Park, Tex.
Freeport, Tex.

Deer Park, Tex.
NorcOj La.
                               Amino-
                               benzoic
                               acid
                               (m,o,p)
Dyes; drugs; perfumes
& Pharmaceuticals; dye
intermediates
Bofors Indust., Inc.

Salsbury Labs.
Linden, N.J.

Charles City, Iowa
Wilmington, N.C.
                                                                          Salsbury Labs.
                                                                          The Sherwin-Williams
                                                                          Co. - Sherwin-Williams
                                                                          Chems. Div.
                                                         Wilmington,  N.C.

                                                         St.  Bernard, Calif.

-------
                                                                                   Table A-l.  (Continued)
                                Chemical
                                                                           Manufacturer(s)2'3
                                                                       Locatlon(s)2'3
                                                                                 1975
                                                                              capacity2
                                                                             MM kg (MM Ib)
                                                                     Total1**5'
                                                                     production
                                                                    MM kg (MM Ib)
                                                                 for year of estimate
<&>
Ui
                                Amino-
                                benzoic
                                apid
                                (m,o,p)
                                (continued)
Amino-
ethyl-
ethanol-
amine
                                Amyl
                                acetates
                                Amyl
                                alcohols
                                (8  isomers)
                                Arayl-
                                amine
Textile finishing
compounds (antifuming
agents, dyestuffs,
eationic surfactants);
resins, rubber products,
insecticides, & certain
medicinals
               Solvent for lacquers &
               paints; extraction of
               penicillin; photographic
               film; leather polishes;
               nail polish; warning
               odor; flavoring agent;
               printing & finishing
               fabrics; solvent for
               phosphors in fluorescent
               lamps.

               Solvent; raw material for
               pharmaceutical prepara-
               tions ; organic synthesis;
               lubricants; plasticizers;
               additives for oils; &
               paints; flotation agent;
               medicine

               Chemical Intermediate;
               dyestuffsj rubber chemi-
               cals; insecticides;
               synthetic detergents;
               flotation agents; corro-
               sion inhibitors; solvent;
               gasoline additive;
               Pharmaceuticals
Bofors Indust.,  Inc.

Northern Pine Chems., Inc.

Salsbury Labs.

Warner-Lambert  Co.  -
Parke, Davis &  Co.,
subsid.

Dow Chem. U.S.A.

Hodag Chem. Corp.

Texaco Inc. - Jefferson
Chem. Co., Inc.,  subsid.

Union Carbide Corp. -
Chems. & Plastics  Div.


Commercial Solvents Corp.

Publicker Indust.  Inc.

Institute & South
Charleston, W.Va.
                            Union Carbide Corp. -
                            Chems. & Plastics Div.
                            Eastman Kodak Co. -
                            Eastman Organic Chems.

                            Pennwalt Corp., Chem. Div.

                            The Ames Labs., Inc.

                            Pennwalt Corp. - Chem.
                            Div.

                            Virginia Chems. Inc. -
                            Indust. Chems. Dept,
                                                                       Linden, N.J.

                                                                       Franklin, N.J.

                                                                       Wilmington, N.C.

                                                                       Holland, Mich.
Freeport,  Tex.

Skokie, 111.

Conroe, Tex.


Institute  & South
Charleston, W.  Va.
Texas City, Tex.

Terre Haute, Inc.

Philadelphia, Pa.
                            Institute & South
                            Charleston, W.  Va.
                            Texas City, Tex.

                            Rochester,  N.Y.
                            Wyandotte,  Mich.

                            Milford,  Conn.

                            Wyandotte,  Mich.


                            Portsmouth, Va.
                                                                                                                                                    (12)  -1973

-------
                                                                                   Table Arl. (Continued)
00
Ui
Ui
Amyl           Synthesis of other amyl
chloride       compounds; solvent;
               rotogravure ink vehiclesj
               soil fumigation


Amyl           Synthesis of organic sul-
tnercaptans     fur* compounds; chief
               constituent of odorant
               used in gas lines to
               locate leaks

Amyl           Dispersing & mixing
phenol         agent for paint pastes;
               antiskinning agent for
               paint, varnish, & oleo-
               resinous enamelsj organic
               synthesis; Manufacture
               of oil-soluble resins;
               plasticizer; germicidej
               fumigant

Aniline        Rubber accelerators &
               antioxidants ; dyes &
               intermediates; photo-
               graphic chemicals
               (hydroquinone); iso-
               cyanates for urethane
               foams; Pharmaceuticals;
               explosives; petroleum
               refining; diphenylaminej
               phenolics; herbicides,
               fungicides
                               Aniline         Dyes;  intermediates;
                               hydro-          dyeing & printing;
                               chloride        aniline black
                                                                         Manufacturer(s)2 * 3
                                                                         Columbia Organic Chem.
                                                                         Co.

                                                                         Eastman Kodak - East-
                                                                         man Organic Chems.

                                                                         Pennwalt Corp.
Pennwalt Corp.  -
Chem. Div,

Productol Chem. Co.
                                                                         American Cyanamid Co. -
                                                                         Organic Chems. Div.
                                                                         E. I. du Pont de
                                                                         Nemours & Co., Inc.
                                                                         Elastomer Chems. Dept.
                                                                         Indust. Chems. Dept.
                                                                         First Mississippi Corp.
                                                                         First Chem. Corp., subsid.
                                                                         Mobay Chem. Corp. -
                                                                         Indust. Chems. Div.
                                                                         Rubicon Chems. Inc.
                                            American Cyanamid Co. -
                                            Organic Chems. Div.
                            Locat-.ion(s)2'3


                            Columbia, S.  C.


                            Rochester, M.  Y.


                            Greens Bayou,  Tex.





                            Wyandotte, Mich
                                                                                                     Santa Fe Springs,
                                                                                                     Calif.
                            Bound Brook, N. J.
                            Willow Island, W. Va.
                            Beaumont,  Tex.
                            GIbbstown, N.  J.


                            Pascagoula, Miss.
                            New Martinsville,
                            W. Va.
                            Gelsmar,  La.
                                                                                                      Bound Brook, N. J.
                                                                                                1975
                                                                                              capacity2
                                                                                            MM kg (MM Ib)
                   Total*'5
                   production
                  MM kg  (MM Ib)
               foryear  of estimate
 27.2  (60)
 22.7  (50)
 90-8  (200)
 59    (130)

 45.4  (100)
 *»5.ll  (100)


 25    (55)
  Total =
315   (695)
                                                                                                                                           207.3  (456.6)  -1973

-------
                                                                                     Table  A-l.   (Continued)
                                                                          Manufacturer (s)2 * *
                                                        Locatlon(s)2 *_3
                                                    1975
                                                  Capacity2
                                                 MM kg (MM Ib)
                                         Total**5
                                         production
                                         MM kg  (MM  Ib)
                                      for year  of estimate
                               Anisidine
Intermediate for azo dyes
ft for quaiacol; azo
dyestuffs
00
Ln
                               Anisole
                               Anthranilie
                               acid
                               Anthraqui-
                               none
                                              Solvent ; perfumery ;
                                              vermicide; intermediate
Dyes; drugs; perfumes
& Pharmaceuticals
Intermediate for dyes;
& organics; organic
inhibitor; bird repel-
lent for seeds.
Aldrich Chem. Co., Inc.

Eastman Kodak Co. -
Eastman Organic Chems.

American Color & Chem.
Corp,

E. I, du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Dyes ft Chems. Div.

Monsanto Co. - Monsanto
Indust. Chems. Co,

Salsbury Labs.

Chem. Formulators, Inc.,
Chem. Div.

Continental Oil Co. -
Conoco Chems, - Pitt-
Consol Chems.

Eli Lilly & Co. -
Tippecanoe Labs.

Givaudan Corp. - Chems.
Div,

Salsbury Labs.

The Sherwin-Williams
Co. - Sherwin-Williams
Chems. Div.

American Cyanamid Co. -
Organic Chems. Div.

E. I. du Pont de Ne-
mours & Co. - Organic
Chems. Dept.

GAP Corporation

Sterling Drug Inc. -
                                                                                                      Milwaukee, Wise .
                                                                                                      Rochester, N. Y.

                                                                                                      Lock Haven, Pa.
Deepwater, N. J.

St. Louis3 Mo.


Wilmington, N. C.

Nitro, W. Va.


Newark, N. J.



Lafayette, Inc.


Clifton, N. J.


Wilmington, N. C.

St. Bernard, Ohio



Boundbrook, N. Y.


WiImington, Del.



Linden, N. J.
Rensselaer, N. Y.

-------
                                                                           Table A-l.  (Continued)
CO
Ln
                               Chemical
Benzalde-      Organic  synthesis  (es-
hyde           pecially of  dyes  &  dye
               intermediates); sol-
               vent  for oils, resins,
               some  cellulose ethers,
               cellulose acetate  &
               nitrate  flavoring  com-
               pounds;  synthetic  per-
               fumes; manufacture  of
               cinnamic acid, ben-
               zole  acid; Pharmaceu-
               ticals & soaps; photo-
               graphic  chemicals;
               baking chemicals;
               medicine


Benzamide      Organic  synthesis
                               Benzene        Styrene; phenol; syn-
                                               thetic detergents;
                                               cyclohexane for nylon;
                                               aniline; DDT; maleic
                                               anhydride; dichloro-
                                               benzene; benzene hexa-
                                               chloride; nitrobenzene;
                                               diphenyl; insecticides;
                                               fumigants; solvent;
                                               paint removers; rubber
                                               cement; antiknock
                                               gasoline
                                                                           Manufacturer(s)2'3
Alco Standard Corp. -
Monroe Ghem. Co., div.

Kalama Chem. Inc.
Northwest Indust.,
Inc. - Velsicol Chem.
Corp., subsid.
St'auffer Chem. Co. -
Specialty Chem. Div.
Tenneco Inc. - Organics
& Polymers Div.
Universal Oil Products
Co. - Chems. & Plastics
Group, Chem. Div.

Aceto Chem. Co., Inc. -
Arsynco, Inc., subsid.
Guardian Chem. Corp. -
Eastern Chem. Div.

Allied Chein. Corp. -
Union Texas Petroleum
Div.

Amerada Hess Corp. -
Hess Oil Virgin Islands
Corp.t subsid.
American Petrofina, Inc.
American Petrofina Co.
of Texas, subsid.

Cosden Oil & Chems.
Co., subsid.

Armco Steel Corp.


Ashland Oil, Inc. -
Ashland Chem. Co., div.
Petrochems. Div.
Atlantic Richfield Co. -
ARCO Chem. Co., div.
Location(s)2'3


Eddystone, Pa.


Kalama, Wash.
Chattanooga, Tenn.


Edison, N. J.


Fords, N. J.
                                                                                                       East Rutherford,
                                                                                                       N.  J.
                                                                                                       Carlstadt,  N.  J.

                                                                                                       Hauppauge,  N.  Y.


                                                                                                       Winnie,  Tex.
                                                                        St.  Croix,
                                                                        Virgin  Islands

                                                                        Port Arthur, Tex.
                                                                       Big Spring, Tex.

                                                                       Houston, Tex.
                                                                       Middletown, Ohio
                                                                       Ashland, Ky.
                                                                       North Tonawanda,
                                                                       N. Y.

                                                                       Houston, Tex.
                                                                       Wilmington, Del.
                                                                       Bethlehem, Pa.
                                                                       Lackawanna, N. Y.
                                                                       Sparrows Po1nt, Md.
                                                                                                 1975
                                                                                               capacity2
                                                                                             MM kg  (MM Ib)
                                                                      Total*1'5
                                                                      production
                                                                     MM kg (MM Ib)
                                                                  for jLearcj* estimate
                        10  (22)       3694   (8136)- 1971


                        50  -CllO.2)


                        50  (110,2)


                       100  (220.5)

                         3  (6.6)
                         6.7(1^.7)
                       166.8(367.5)
                        50  (110.2)

                       146.8(323-4)
                        53-4(117.6)
                        13-3(19.4)
                        25  (55-1)
                        50  (110.2)

-------
                                                                                     Table  A-l. (Continued)
                              Chemical


                             Benzene
                             (cont'd)
OO
Ui
00
                                                                         Man ufac t urer(s)2"
CF&I Steel Corp.

The Charter Co., Char-
ter Oil Co., subsid.

Cities Service Co.,
Inc. - North American
Petroleum Group

Coastal States Gas Corp.
Coastal States Market-
ing, Inc., subsid.

Commonwealth Oil Re-
fining Co., Inc. -
Commonwealth Petro-
chems., Inc., subsid,

Crown Central Petro-
leum Corp.

Dow Chem. U.S.A.
                                                                         Exxon Corp. - Exxon
                                                                         Chem. Co., div. -
                                                                         Exxon Chem. Co. U.S.A.

                                                                         Gulf Oil Corp. - Gulf
                                                                         Oil Chems. Co., div. -
                                                                         Petrochems. Div.
                                                                         Interlake, Inc. -
                                                                         Jones & Laughlin In-
                                                                         dust., Inc. - Jones &
                                                                         Laughlin Steel Corp.,
                                                                         subsid.

                                                                         Kerr-McGee Corp. - South-
                                                                         western Refining Co.,
                                                                         Inc., subsid.

                                                                         Marathon Oil Co.

                                                                         The Mead Corp. -
                                                                         Metals & Minerals Div.
Looation(s)2'3
Pueblo, Colo.
Houston, Tex.
1975
capacity2
MM kg (MM Ib)
10 (22)
16.7(36.7)
Total1"5
production
MM kg (MM Ib)
for year of estimate
(see previous page)
                                                                                                     Lake Charles, La.
                                                                                                     Corpus Christi,
                                                                                                     Tex.
                                                                                                     Penuelas, P.  H.
                                                                                                     Pasadena, Tex.
                                                                                                     Aliqulppa, Fa.
                            Corpus Chrlstl,
                            Tex.
                            Texas City, Tex.
                            Woodward, Ala.
 83.1(183.7)


233-6(511.5)


617  (1359.7)



 66.7(117)
Bay City, Mich.
Freeport, Tex.
Baton Rouge, La.
Baytown, Tex.
Alliance, La.
Philadelphia, Pa.
Port Arthur, Tex,
Toledo, Ohio
100.1(220.5)
133.5(291)
210.2(529.2)
206.9(155.7)
233.6(511.5)
110 (212.5)
126.8(279.3)
3.3(7.3)
                                                                                                                             33.1(73-5)
 26.7(58.8)


 20  (M.I)
  1.7(10.3)

-------
                                                                                Table  A-l.  (Continued)
                                Chemical

                                Benzene
                                (continued)
Usage1


(see 2nd prev. page)
CTs

00
Ul
Manufacturer(s)2 ' 3

Mobil Oil Corp. - Mobil
Chem. Co., div. -
Petrochems. Div.
Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.
Northwest Indust., Inc.
Lone Star Steel Co.,
subsid.
Penzoil Co. - Atlas
Processing Co., subsid.
Phillips Petroleum Co.
Phillips Puerto Rioo
Core Inc., subsid.
Republic Steel Corp. -
Iron & Chem. Div.
Shell Chem, Co. - Base
Chems.
                                                                            Skelly Oil Co.

                                                                            Standard Oil Co.  of
                                                                            California
                                                                            Standard Oil Co.  (Ind.)
                                                                            Amoco Oil Co.,  subsid.
                                                                            Sun Oil Co.  - Sun Oil
                                                                            Co. of Pa.,
                                                                            Suhtide Refining  Co.,
                                                                            subsid.
                                                                            Tenneco Inc.  -  Tenneco
                                                                            Oil Co., div.

                                                                            Union Carbide Corp. -
                                                                            Chems. & Plastics Div.
                                                                            Union Oil Co. of  Calif.
                                                                            Union Pacific Corp.  -
                                                                            Champlin Petroleum Co.,
                                                                            subsid.
                                                                            United States Steel
                                                                            Corp. -  USS Chems., div.
Location(s}2» 3
Beaumont , Tex.
Chocolate Bayou,
Tex.
1975
capacity2
MM kg (MM Ib)
200 (
-------
                                                                            Table A-l.  (Continued)
00
                                 Chemical

                                 Benzene-
                                 sulfonic
                                 acid
                                 Benzenedi-
                                 sulfonic
                                 acid
                                Benzil
                                Benzilic
                                acid
                                Benzole
                                acid
                                Benzoin
                                Benzo-
                                nitrile
Phenol; resorcinol;
organ!c synthesis;
catalyst
Organic synthesis;
insecticide

Chemical
Intermediate

Sodium & benzyl ben-
zoates; plasticizers;
alkyd resins;  vulcaniza-
tion retarder;  food
preservative;  season-
Ing tobacco; flavors,
perfumes;  dentifrices;
medicine  (germicide)
Organic synthesis;
intermediate; photo-
polymerization catalyst

Manufacture of benzo-
guanamlne; intermediate
for rubber chemicals;
solvent for nitrile
rubber, specialty lac-
quers, and many resins &
polymers, & for many
anhydrous metallic salts
Manufacturer(s)2^3

Nease Chem. Co., Inc.

Stauffer Chem. Co,,
Agricultural Chem. div.

Jim Walter Corp. - U.S.
Pipe & Foundry Co.,
subsid., Chem. Div-

Koppers Co., Inc. -
Organic Materials Div.

Jim Walter Corp. - U.S.
Pipe & Foundry Co.,
subsid., Chem. Div.

Napp Chems. Inc.
Stauffer Chem. Co. -
Specialty Chem. Div.

Kalama Chem., Inc.

Monsanto Co. - Monsanto
Indust. Chems. Co.

Northwest Indust.,
Inc. - Velsicol Chem.
Corp,, subsid.

Pfizer Inc. - Chems.
Div.

Tenneco Inc. - Tenneco
Chems., Inc., Organic s
& Polymers Div.

Napp Chems., Inc.

Stauffer Chem. Co. -
Specialty Chem. Div.

Northwest Indust.  Inc. -
Velsicol Chem. Corp.,
Subsid.
Location(s)2'3

State College, Pa

Henderson, Nev.


Birmingham, Ala.
Petrolia, Pa.


Birmingham, Ala.



LodI, N. J.


Edison, N. J.


Kalama, Wash.

St. Louis, Mo.
                                                                                                        Beaumont,  Tex.
                                                                                                        Chattanooga,  Tenn.
Terre Haute, Ind.


Garfield, N. J.



LodI, N. J.

Edison, N. J.


Chattanooga, Tenn.
                                                                                                                                                 Total1*'8
                                                                                                                                1975             production
                                                                                                                               capacity2         MM kg (MM Ib)
                                                                                                                             MM kg  (MM l.b)    for year of estimate
 5*1.5  (120

  ^.5  (10)


 22.7  (50)



  2.7.  (6)


  5.4  (12)

  Total =
117.1  (258)
                                                                                                                                                36.8  (81)    -197M

-------
                                                                                 Table *~1-   (Continued)
                               Chemical
                                                                           Manufacturer(s)2 *
                                                                                                       Location(s)2'
                                                                                 1975
                                                                               capacity2
                                                                             MM kg (MM Ib)
                                                                      Total1*'5
                                                                      production
                                                                     MM kg (MM Ib)
                                                                  for yeaj? of estimate
                               Benzo-
                               phenone
oo
                               Benzo-
                               quinone
                                Benzo-
                                trichlo-
                                ride
Organic synthesis;
perfumery; odor fixa-
tive; derivatives
are used as ultravio-
let absorbers; flavor-
ing; polymerization
inhibitor for styrene
Manufacture of dyes
& hydroquinone
Synthetic dyes;
organic synthesis
Aceto Chem. Co., Inc.-
Arsynco, Inc ., subsid.

GAP Corp. - Chem. Div.

Norda Inc.


Orbis Products Corp.

Universal Oil Products
Co. - Chems. & plastics
Group - Chem.  Div.

Warner-Lambert Co, -
Parke, Davia & Co.,
subsid.

Eastman Kodak Co. -
Eastman Chem.  Products,
Inc., subsid.  - Tenn.
Eastman Co., div.

Frank Enterprises

Northwest Indust., Inc.
Velsicol Chem. Corp.,
subsid.

Occidental Petroleum
Corp., Hooker Chem.
Corp., subsid - Hooker
Chems. & Plastics Corp.,
subsid, - Electrochemi-
cal & Specialty Chems.
Div.

Tenneco Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Div.
Carlstadt, N. J.


Rensselaer, N. Y.

Boonton, N. J.
East Hanover, N. J.

Newark, N. J.

East Rutherford, N. J.



Holland, Michigan
Kingsport, Tenn.




Columbus, Ohio

Chattanooga, Tenn,



Niagara Falls, N.  Y.
                                                                                                       Fords,  N.  J.

-------
                                                                                    Table A-l.  (Continued)
                                Chemical
                                                                           Manufacturer (_s_)2 *3
                                                        LocatlonCs)2*3
                                                     1975
                                                   capacity2
                                                 MM kg (MM Ib)
                                          Total1**5
                                          production
                                         MM kg (MM  Ib)
                                      for year of estimate
                                Benzoyl
                                chloride
00
                               Benzyl
                               alcohol
                               Benzl-
                               amlne
Medicine;  intermediate
for production  of ben-
zoyl groups; inter-
mediate for other
organ!cs
Perfumes & flavors;
photographic developer
for color movie films;
dyeing nylon filament,
textiles and sheet
plastics; solvent  for
dyestuffs, cellulose
esters, casein, waxes,
etc.; heat-sealing poly-
ethylene films; inter-
mediate for benzyl
esters & ethers; local
anesthetic; cosmetics,
ointments, emulsions;
ball point pen Inks;
stencil inks.
Chemical intermediate
for dyes, Pharmaceuti-
cals, & polymers
Northwest Indust., Inc. -
Velsicol Chem. Corp.,
subsld.

Occidental Petroleum
Corp., Hooker Chem.,
Hooker Chems. & Plastics
Corp., subsid. - Electro-
chemical & Specialty
Chems. Div.

Stauffer Chem. Co. -
Specialty Chem. Div.

Tenneco Chems., Inc. -
Tenneco Chems., Inc.,
Organics & Polymers Div.

Alco Standard Corp. -
Monroe Chem. Co., div.

Cloray NJ Corp.

Givaudan Corp. - Chems.
Div.

Northwest Indust.,
Inc. - Velsicol Chem.
Corp., subsid.

Orbis Products Corp.

Stauffer Chem. Co. -
Specialty Chem. Div.

Tenneco Inc. - Tenneco
Chems., Inc. — Organics
& Polymers Div.

Universal Oil Products
Co. - Chems. & Plastics
Group - Chem.  Div.

Aceto Chem. Co., Inc. -
Arsynco, Inc., subsid.

Miles Labs., Inc.  -
Sumner Div.

Uniroyal, Inc. - Uni-
royal Chem., div.
Chat tanooga, Tenn.


Niagara Falls,
Edison, N. J.


Fords, N. J.



Eddystone, Pa.


Newark, N. J.

Clifton, N. J.


Chattanooga, Tenn.



Newark, N. J.

Edison, N. J.


Fords, N. J.
                                                                                                       East  Rutherford,
                                                                                                       N.  J.
Carlstadt, N. J.


Zeeland, Mich.


Naugatuck, Conn.

-------
                                                                                 Table A-l.  (Continued)
                              Chemical
                                                                          Manufacturer(s)2'3
                                                                                                      Locations )2'3
                                                                                                 1975
                                                                                               capacity2
                                                                                             MM kg (MM Ib)
                                                                                                  Total1"5-
                                                                                                  production
                                                                                                 MM kg  (MM  Ib)
                                                                                              for year  of estimate
                              Benzyl
                              benzoate
0V

00
Benzyl
chloride
                              Benzyl
                              dichlorlde
                              Biphenyl
               Fixative & solvent  for
               musk in perfumes  &
               flavors; medicine
               (external); plasticizer;
               miticide
Dyes; intermediates;
benayl compounds; syn-
thetic tannins; per-?
fumery; Pharmaceuticals j
manufacture of photo-p
graphic developer;
gasoline gui? Inhibi-
tors ; penicillin
precursors; quaternary
ammonium compounds
                                              Dyes
               Organic  synthesis;  heat
               transfer agent;  fungi-
               cides; dyeing assistant
               for  polyester
Monsanto Co. - Monsanto
Flavor/Essence, Inc.
Monsanto Indust * Chems.
Co.

Northwest Indust,, Inc.-
Velsicol Chem. Corp.,
subsid.

Pfizer Inc. -
Chems. Div*

Universal Oil Products
Co. - Chems. & plastics
Group - Chem. Div-.

W, R. Grace & Co. -
Hatoo Group - Hatco
Chem. Div.

Monsanto Co. — Monsanto
Indust. Chems. Co.

Northwest Indust., Inc.
Velsicol Chem, Corp.,
sub S, id.

Sfcauffer Chem. Co. -
Specialty Chem. Div.,

Tenneoo Inc. - Tenneao
Chems,., Inc. - Organlcs
& Polymers Div.

GAP Corp. - Chem. Fiv.

Tenneco Inc. - Tenneco
Chems., Inc. - Organ!cs
& Polymers Div.

Bethlehem Steel Corp.

Chemol, Inc.

DQW Chem. U.S.A.


Monsa,nto Co. T Monsanto
Indust. Cheps. Co.

Pilot Chem. Co. -r Pilqt
Indust. of Texas, suhsid.

Sybron Corp. - The
Tanatex Chetiu Co., div.

Woonsocket  Color & Chem.
Co.
                                                                                                      St. Louis, Mo.
                                                                                                      St. Louis, Mo.


                                                                                                      Chattanooga, Tenn,
                                                                                                      Greensboro, N. C.
                                                                                                      East Rutherford,
                                                                                                      N. J.
                                                                        Fords,  N.  J.
                                                                        Rensselear,  N.  Y.

                                                                        Great  Meadows,
                                                                        N.  J.
                                                        Sparrows Point, Md.

                                                        Greensboro, N. C.

                                                        Bay City, Mich.
                                                        Freeport, Tex.

                                                        Anniston, Ala.


                                                        Houston, Tex.


                                                        Lyndhurst, N. J.


                                                        Woonsocket, R.- I,
                                                                                                    (15)
                                                                                                                 40.9  (90)
Bridgeport, N. J.
Chat1;anoqga, Tenn.
Edison, H. 1.
Fords, N. J[.
3* (75)
1.5 (10)
5 (11)
3^^ (7)
                                                                                                                              Total  -
                                                                                                                            536    (118)
                                                                                                                                                2.3 (  5)    -1971

-------
                                                                                     Table
                                                                                           A-l.
                                                                                                 (Continued)
                                Chemical
                                Bisphenol
                                A
00
                               Bromo-
                               benzene
                               Bromo-
                               naphtha-
                               lene
                               Butadiene
Epoxy, polycarbonate,
phenoxy, & polysul-
fone resins
Solvent; motor fuels;
top-cylinder com-
pounds; crystallizing
solvent; organic
synthesis

Organic synthesis;
microscopy;
refractometry
                                              Principally  in  sty-
                                              rene-butadiene  rubber,
                                              & to a lesser degree  in
                                              polybutadiene and
                                              nitrile elastomers;
                                              as the starting material
                                              for adiponitrile  (nylon
                                              66); in latex paints;
                                              resins; organic
                                              intermediate
Manufacturer(s)2' 3

Dow Chem. U.S.A.
Gen. Electric Co. -
Plastics Business Div,
Engineering Plastics
Product Dept.
Shell Chem. Co. -
Polymers & Detergent
Products
Union Carbide Corp. -
Chems. & Plastics Div.

Union Carbide Caribe,
Inc., subsid.
                                                                           Dow Chem.  U.S.A.
Eastman Kodak Co. -
Eastman Organic Chems.
Guardian Chem. Corp. -
Eastern Chem. Div,
R.S.A. Corp.

Atlantic Richfield Co.
ARCO Chem. Co., div.
Copolymer Rubber &
Chem. Corp.
Dow Chem. U.S.A.
                            El Paso Natural Gas Co. -
                            El Paso Products Co.,
                            subsid,
                            Exxon Corp. - Exxon Chem.
                            Co. U.S.A. - Exxon Chem.
                            Co., div.
                            The Firestone Tire & Rub-
                            ber Co., Firestone
                            Synthetic Rubber & Latex
                            Co., div.
Locations)2'3


Freeport, Tex.
Mount Vernon, Ind.
                                                                                                       Deer  Park,  Tex.
                                                                                                  Total4*5
                                                                                 1975             production
                                                                               capacity2         MM kg (MM  Ib)
                                                                             MM kg (MM 1'b)    for year of estimate
Midland, Mich.





Rochester, N. Y.

Hauppauge, N. Y.


Ardsley, N. Y.

Channelview, Tex.


Baton Rouge, La.


Bay City, Mich.
Freeport, Tex.
Odessa, Tex.


Baton Rouge, La.



Orange, Tex.
 U5-4 (100)

 32.7 (72)
                                                                                                                             68    (150)
                       (319-7)-1973
Marietta, Ohio
Penuelas, P. R.

18.2 (1)0)
31-8 (70)
Total -
196.1 (1132)
127   (280)

 58.1 (128)


 10.9 (21)
 39   (86)
 90.8 (200)



151.1 (310)



 99.9 (220)
                                                                                              1663   (3662.8)-1973

-------
                                                                              Table *-!•  (Continued)
                               Chemical

                               Butadiene
                               (continued)
Usage'


(see previous page)
OS
oo
                                                                          Manufacturer(s)2' 3
                            Qetty Oil Co.

                            Mobil Oil Corp. - Mobil
                            Chem. Co., div. -
                            Petrochems. Div.

                            Monsanto Co, - Monsanto
                            Polymers & Petrochems.
                            Co.

                            Neches Butane Products
                            Co.
                            Northern Natural Gas  Co.
                            Northern Petrochem. Co.,
                            subsid., Polymers Div.

                            Petro-Tex Chem. Corp. -
                            Petro-Tex Chem. Co.,
                            subsid.
                            Phillips Petroleum Co, -
                            Petrochem. & Supply Div.
                            Puerto Rico Olefins Co.

                            Shell Chem. Co. - Base
                            Chems.
                            Standard Oil Co. (Ind.) -
                            Amoco Chems. Corp., sub-
                            sid.
                            Union Carbide Corp. -
                            Chems. & Plastics Div.
                                                                          Union Carbide Carbide, Inc
                                                                          Subaid.
Location(s)2'3
Delaware City,
Del.
Beaumont, Tex.
Chocolate Bayou


Port Neches, Tex,

Morris, 111.


Houston, Tex.


Phillips, Tex.

Penuelas, P. R.
Deer Park, Tex,

Chocolate Bayou,
La.

Seadrift, Tex.
Taft, La.
Texas City, Tex.
Penuelas, P. R.
                      Total1"5
     1975             production
   capacity2         MM kg (MM Ib)
 MM kg (MM Ib)    for year of estimate
    9.1 (20)

   36.3 (80)


   511.5 (120)


  290.6 (640)

   29.5 (65)


  14119.5 (990)


  131.7 (290)

   90.8 (200)
  120.3 (265)

   10.9 (90)
   20.1 (15)
   10.9 (90)
   20.1 (15)
   70.1 (155)

    Total =
1,985.3 (1,373)
                                      (see previous page)

-------
                                                                                  Table  A-l.  (Continued)
                               Chemical
                               n-3utyl
                               acetate
I
sec-Butyi
acetate
                               tert-
                               Butyl
                               acetate
                               n-Butyl-
                               acrylate
               Solvent in production  of
               lacquers, lacquer enamels;
               pyroxylin solutions;
               leather dressings; per-
               fumes, flavoring extracts;
               solvent for natural gums &
               synthesis resins; dehy-
               drating agent
Solvent for nitro-
cellulose i Xacquers;
thinners; nail enamels;
celluloid products;
artificial leather;
leather finishes;
plastic wood;.washable
wallpaper
               Possible antiknock
               agent in gasoline
               Intermediate in organic
               synthesis; polymers &
               copolymers for solvent
               coatings, adheslves,
               paints, binders;
               emulsifier
                            Manufacturer(s)2*3


                            Celanese Corp. - Cela-
                            nesfe Chem. Cor.', div.

                            Eastman Kodak Co. -
                            Eastman Chem. Products,
                            Inc., subsid - ^enn.
                            Eastman Co., div.

                            Publicker Indust. Inc.

                            -Union Carbide Corp^ -
                                   & Plastics Div.
 EXxon Corp.  - Exxon
 £henu Co.
"Jtercules,  inc.

 Shell Chem,  Co.  -
 Jndust.  Cheras./Petro-
 chems.
 (See also  -  n-Butyl
 acetate)

 Exxon Corp.  - Exxon
 Chem\ po.
 (See also  -  n-Butyl
 acetate)

 Celanese Corp. - Cela-
 nese Chern. Co.,  div.

 Dow  Bad!sche Co,

 Rohm & Haas  Co.  - Rohm
 &  Haas Texas Inc.,
 subsid.

 Union Carbide Corp. -
 Chems. & Plastics Div.
                             Locatlon(s)2'3


                             Bishop,  Tex.


                             Klngsport!( Tenn.
                                                                                                      Philadelphia, Pa.

                                                                                                      Institute & South
                                                                                                      Charleston, tf. Va*
                                                                                                      Texas City, Tex.
Baton Rouge, ia.


Hattlesburg, Miss.

Deer Park, Tex.
                                                                                                       Baton Rouge, La.
                                                        Clear Lake, Tex.
                                                        Pampa, Tex.

                                                        Freeport, Tex.

                                                        Deer Park, Tex.
                                                                                                      Institute & South
                                                                                                      Charleston, W. Va.
                                                                                                      Taft, La.
                         1975
                       capacity2
                     MM kg (MM lb)


                        6.8 (15)


                        6.8 (15)
                                                                                               6.8 (15)

                                                                                              22.7 (50)
                                                                                                                              Total te
                                                                                                                             ^3-1 (95)
                                                                                                                 Total"*5-
                                                                                                                 preduction
                                                                                                                MM kg (MM lb)
                                                                                                             for jrear of estimate


                                                                                                               43.M (95.7)   -1972

-------
                                                                             Table &-!-•   (Continued)
                               Chemical.
                               n-Butyl
                               alcohol
00
ON
                               sec-
                               Butyl
                               alcohol
                               tert-
                               Butyl
                               alcohol
Preparation of esters,
especially Butyl ace-
tate; solvent for
resins & coatings;
plasticizers; dyeing
assistant; hydraulic
fluids; detergent
formulations; dehydrat-
ing agent (by azeo-
tropic distillation);
intermediate; "butyl-
ated" melamine
resins
Preparation of methyl
ethyl ketone; solvent;
organic synthesis
                                              Alcohol denaturant
Manufacturer(s)2 >3


Celanese Corp. - Cela-
nese Chem. Co., div.


Continental Oil Co. -
Conoco Chems.
Dow Badische Co.

Eastman Kodak Co. -
Eastman Chem. Products
Inc., subsid. - Texas
Eastman Co., div.
W. R. Grace & Co. -
Hateo Group - Hatco
Chem. Div.

Oxochem Enterprise
Publicker Indust. Inc.

Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Caribe,
Inc., subsid.
                                                                          Celanese  Chem,  Co.
                            Exxon Corp. - Exxon
                            Chem. Co.
                            Shell Chem. Co. -
                            Indust. Chems./Petro-
                            chems.

                            Shell Chem. Co. -
                            Indust. Chems./
                            Petrochems.
                            Oxirane Chem. Co.
Location(s)z*3


Bay City, Tex.
Bishop, Tex.
Clear Lake, Tex.
Westlake, La.

Freeport, Tex.

Longview, Tex.
Fords, N. J.



Penuelas, P. R.

Philadelphia, Pa
Deer Park, Tex.


Seadrift, Tex.


Penuelas, P. R.




Bay City, Tex.
Bishop, Tex.
Clear Lake, Tex.
Baton Rouge, La.


Deer Park, Tex.



Martinez, Calif.


Bayport, Tex.
                                                                                                                               1975
                                                                                                                             capacity2
                                                                                                                           MM kg (MM Ib)
                                                                                                                             68.1 (150)
                                                                                                                             20.I* (1(5)
                                                                                                                              2.3 (5)

                                                                                                                             43.1 (95)
                                                                                                                             31.8 (70)
                                                                                                                             36.3 (80)
                                                                                                                             15.9 (35)
                                                                                                                             36-3 (80)

                                                                                                                             27.2 (60)

                                                                                                                             18.2 (40)
                                                                                                                              Total =
                                                                                                                            299.6 (660)
                                                                                                  Total**5
                                                                                                  production
                                                                                                 MM kg (MM Ib)
                                                                                              for year of estimate


                                                                                               235.4 (518.6) -1973
                                                                                                                                             205.6 (453)  -1973
                                                                                                                                             508.5 (1120) -1973

-------
                                                                                 Table A-l-  (Continued)
                               Chemical
                                                                          Manufacturer(s)2 *
                                                                                                      Location(s)2*3
                                                                                                1975
                                                                                              capacity2
                                                                                            MM kg (MM lb)
                                                                     Total4*5
                                                                     production
                                                                    MM kg (MM lb)
                                                                 for year ofestimate
                               tert-
                               Butyl-
                               phenol
00
ON
00
tert-
Butyl-
toluene

n-Butyr-
aldehyde
Chemical intermediate
for synthetic resins,
plasticizers, surface-
active agents, perfumes,
& other products; a
permissible antloxi-
dant for aviation
gasoline; plasticizer
for cellulose acetate
intermediate for anti-
oxidants, special
starches, oil soluble
phenolic resins; pour-
point depressors &
emulsion breakers for
petroleum oils & some
plastics; synthetic
lubricants; insec-
ticides ; industrial
odorants

Solvent; intermediate
                                              Poly vinyl butyral;
                                              butyrate plastics
                                           Dow Chem. U.S.A.

                                           Ethyl Corp.
                                           Productol Chem. Co.
                                                                          Schenectady Chem.,
                                                                          Inc.

                                                                          Union Carbide Corp. -
                                                                          Chems. & Plastics Div.
                                                                          Shell Chem. Co. -
                                                                          Base Chems .
Celanese Corp. -
Celanese Chem. Co.,
div.

Eastman Kodak Co. -
Eastman Chem. Pro-
ducts, Inc., subsid. -
Texas Eastman Co., div.

Oxochem Enterprise
Shell Chem. Co. -
Base Chems.

Union Carbide Corp. -
Chems. & Plastics Div.
                                                                          Union Carbide Caribe,
                            Midland,  Mich.
                            Orangeburg,  S.  C.
                            Santa Fe  Springs,
                            Calif.

                            Rotterdam Junction,
                            N. Y.
                            Bound Brook, N. J.
                                                                                                      Martinez, Calif.
                                                        Bay City, Tex.
                                                        Bishop, Tex.
                                                        Freeport, Tex.

                                                        Longview, Tex.
                                                                                                      Penuelas,  P.  R.

                                                                                                      Deer Park, Tex.


                                                                                                      Institute  & South
                                                                                                      Charleston, W.  Va.
                                                                                                      Seadrift,  Tex.

                                                                                                      Penuelas,  P.  R.
                                                                                                                           136.2  (300)

                                                                                                                           227   (500)
                                                                                            158.9 (350)
                                                                                            111.2 (245)
                                                                                             68.1 (150)
                                                                                            136.3 (300)
                                                                                              Total »
                                                                                            837.6 (18«5>

-------
                                                                               Table  A-l.  (Continued)
 I
00
                               Chemical
                               n-Butyrlc
                               acid
                               n-Butyric
                               anhydride
                               n-Butyr-
                               onltrile
                               Carbon
                               disul-
                               fide
Synthesis of butyrate
ester perfume &
flavor ingredients;
Pharmaceuticals; de-
liming agent; dis-
infectants; emulsi-
fying agents;
sweetening gasolines
Manufacture of butyrates;
drugs; tanning agents
Basic material- in in-
dustrial, chemical &
pharmaceutical inter-
mediates & products;
poultry medicines

Viscose rayon; cel-
lophane ; manufacture of
carbon tetrachlorlde
& flotation agents;
veterinary medicine;
solvent
Man_uf_a c t u r e r (s)2 * _3


Celanese Corp. - Cela-
nese Chem. Co., div.

Eastman Kodak Co,  -
Eastman Chem. Products,
Inc., subsld. - Tenn.
Eastman Co., div.

Union Carbide Corp. -
Chems. & Plastics Div.

Eastman Kodak Co.  -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div,

Union Carbide Corp. -
Chems. & Plastics Div.

Eastman Kodak Co.  -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.

Lonza Inc.

FMC Corp. - Chem.
Group - Indust.
Chem. Div.

Pennwalt Corp. -
Chem. Div.

PPG Indust,, Inc.  -
Chem. Div. - Indust.
Chem. Div.

Stauffer Chem. Co. -
Indust. Chem. Div.
Location(s)2'3

Pampa, Tex.

Eastman, Terni.
                                                                                                      Institute  & South
                                                                                                      Charleston, W. Va.

                                                                                                      Klngsport, Tenn.
                                                        Institute & South
                                                        Charleston, W. Va.

                                                        Longview, Tex.
Mapleton, 111.

South Charleston,
W. Va.
                                                                                                      Greens  Bayou, Tex.

                                                                                                      Natrium, W. Va.
                                                                                                      Delaware City, Del.
                                                                                                      Le Moyne,  Ala.
                                                                                                                               1975
                                                                                                                              capacity2
                                                                                                                           MM kg  (MM  lb)
                                                                                                  Total"*5-
                                                                                                  production
                                                                                                 MM kg (MM lb)
                                                                                              f o ryear o f e s t i ma t e
81.7 (180)


 1.5 (10)

27.2 (60)
                                                                               158.9 (350)
                                                                               113-5 (250)
                                                                                Total =
                                                                               385.9 (850)
                                                                                                                                             351-8  (775)  -1972
                               Carbon
                               tetra-
                               bromide
                                              Organic  synthesis
                            Great Lakes Chem, Corp.

                            Olin Corp, - Designed
                            Products Div.
                            El Dorado, Ark.
                            Rochester, N. Y.

-------
                                                                              Table  A-l.  (Continued)
00
                              Chemical
                              n-Butyl-
                              amlne
                              sec-Butyl-
                              amine
                              tert-Butyl-
                              amine
                              p-tert-
                              Butyl-
                              benzoic
                              acid

                              1,3
                              Butylene
                              glycol
                              Butylenes
Intermediate for
emulsifying agents;
Pharmaceuticals, in-
secticides; rubber
chemicals; dyes;
tanning agents
Intermediate for rubber
accelerators; insec-
ticides; fungicides;
dyestuffs; Pharmaceu-
ticals
Polyesters; polyure-
thanes; surface active
agents; plasticlzers;
humectant; coupling
agent; solvent; food
additive & flavoring

Polymer & alkylate gaso-
line ; polybutenes;
butadiene; Intermediate
for Ci, & C5 aldehydes,
alcohols, St other
derivatives;
Solvent; cross-link-
ing agent; butadiene
synthesis; synthesis
of Ci, & C5 derivatives
Manufacturer(s) 2 * 3
Air Products & Chems .
Pennwalt Corp. -
Chem. Div.
Union Carbide Corp. -
Chems. & Plastics Div,
Va. Chems , Inc . -
1975
capacity2
Location(s)2'3 KM kg (MM Ib)
Pensacoia,
Wyandotte,
Institute
Charleston
Portsmouth
Fla.
Mich.
& South
, W. Va.
, Va.
Total1"5
production
MM kg (MM Ib)
for year of estimate
1.82 (i|) -1973

Indust. Chems.  Dept.

Pennwalt Corp.  -
Chem. Div.

Va. Chems. Inc.  -
Indust. Chems.  Dept.

Monsanto Co.  -  Monsanto
Indust. Chem. Co.

Rohm & Haas Co.  - Rohm
& Haas Tex Inc., subsid.


Shell Chem. Co.  -
Base Chems.
Celanese Corp. -
Celanese Chem. Co., dlv.
Dow Chem. U.S.A.


Gulf Oil Corp. - Gulf
Oil Chems,  Co., div. -
Petrochems div.

Petro-Tex Chem. Corp.
Petro-Tex Chem. Co.,
subsid.
Wyandotte, Mich.


Portsmouth, Va.


Texas City, Tex.


Deer Park, Tex.



Martinez, Calif.




Bishop, Tex.
Bay City, Mich.
Freeport, Tex.
Cedar Bayou,
Tex.
                                                                                                     Houston, Tex.
                                                                                                                                         10,074 (22,190>-1967

-------
                                                                       Table  A-l.  (Continued)
                              Chemical

                              Carbon
                              tetra-
                              chloride
00
Refrigerants & propel-
lants; metal degreasing;
agricultural fumigant;
chlorinating organic
compounds; production of
semiconductors
                                                                         ManufacturerCsl2^.3
Allied Chem. Corp. -
Specialty Chem. Dlv.

Dow Chemical U.S.A.
                            E. I. du Pont de
                            Nemours & Co,, Inc. -
                            Organic Chems. - Dept.
                            Freon® - Products Dlv.

                            PMC Corp. - Chem.
                            Group - Indust. Chem.
                            Div.

                            Inland Chem. Corp.

                            Stauffer Chem. Co, -
                            Indust. Chem. Div.
                                                                          Vulcan Materials,  Co.
                                                                          Chems. Div.
Loeationfs)2'3
Moundsville, W. Va .
Freeport, Tex.
Pittsburg, Oal.
Plaquemine , La .
Corpus Christi,
Tex.
South Charleston,
W. Va.
Hanati, P. R.
Le Moyne, Ala.
Louisville, Ky.
Niagara Palls,
N. Y.
Geismar, La.
Wichita, Kans.
Total lt>5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
3.6
59
20.4
15.1
136.2
90.8
31.8
68.1
(8) 158.3 (1009.D -1971
(130)
(15)
(100)
(300)
(200)
(TO)
(150)
15.9 (35)
18.2 (10)
Total =
716.1 (1578)

-------
                                                                               Table A-l.(continued)
                                Chemical
                                Cellulose
                                acetate
(Jo
                                Chloranil
                               Chloro-
                               acetic
                               acid
                               m-chloio-
                               aniline
                               o-chloro-
                               aniline
Acetate fiber; lacquers;
protective coating
solutions; photographic
film, transparent sheet-
ing, thermoplastic mold-
ing composition, cigaret-
te filters, magnetic
tapes, osmotic cell
membrane
Agricultural fungicide;
dye intermediate; ele-
trodes for pH measure-
ments ; vulcanizing
agent

Herbicide; Intermediate
in production of car-
boxymethylcellulose,
ethyl chloroacetate,
glycine, synthetic
caffeine, sarcosine,
thioglycolic acid,
EDTA, 2,4-D, 2,4,5-T

Intermediate for azo
dyes & pigments; Phar-
maceuticals; Insecti-
cides ; agricultural
chemicals

Dye intermediate; stan-
dards for colorlmetrlc
apparatus; manufacture
of petroleum solvents
& fungicides
                                                                           Manu f ac t ur e r ( s ) 2 * 3
Celanese Corp. -
Celanese Fibers Co.,
div.
E. I. du Pont de Ne-
mours & Co., Inc. -
Textile Fibers Dept.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
FMC Corp. - Chem.
Group - Fiber Div.
Dow Chem. U.S.A.
Hercules Inc. -
Coating & Specialty
Products Dept.
The Procter & Gamble
Co. - The Buckeye
Cellulose Corp., subsid.

E. I. du Pont de Nemours
& Co., Inc., Organic
Chems. Dept. - Dyes &
Chems-. Div.
GAP Corp. - Chem. Div.

E. I. du Pont de Nemours
& Co., Inc. - Organic
Chems. Dept, - Dyes &
Chems. Div.

Monsanto Co. - Monsanto
Indust.  Chems. Co.
Location (sj^2'^_


Narrows, Va.
Rock Hill, S.  C.
Rome, Ga.
Waynesboro, Va.


Kingsport, Tenn.



Meadville, Pa.
Midland, Mich.
Hopewell, Va.



Memphis, Tenn.



Deepwater, N. J.



Linden, N. J.

Deepwater, N. J.



Luling, La.
                                                                                 1975
                                                                               capacity.2
                                                                             MM kg (MM Ib)
22?  (500)

 27-2(60)


156.6(315)



 11-3(25)
  Total -
422.2(930)
                     Total **'5
                     production
                    MM kg  (MM  Ib)
                 for year,  of estimate

                  209.8 (462.2)  -1973
                                                                                                                                               29.1  (64.2)  -1969
  9.1(20)
                                                                                                                              1.1(3)
                                                                                                                              Total =
                                                                                                                             30.9  (68)

-------
                                                                           Table  A-l.  (Continued)
                                Chemical
                                p—chloro-
                                aniline
                                 Chloro-
                                 benzalde-
                                 hyde
00
*vj
u>
                                 Chloro-
                                 benzene
Dye intermediate;
Pharmaceuticals; agri-
cultural chemicals
Intermediate in the
preparation of tri-
phenyl methane &
related dyes; organic
intermediate
Phenol; chloronitro-
benzene; DDT; aniline;
solvent carrier for
methylene  diisocyanate;
intermediate  & solvent
Manufacturer(s)2'3


E. I. du Pont de Nemours
& Co., Inc., Organic
Chems. Dept. - Dyes &
Chems. Div.

Monsanto Co. - Monsanto
Indus t. Chems. Co.

Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. - Hooker
Chems. & Plastics Corp.
subsid - Electrochemi-
cal  & Specialty Chems.
Div.

Tenneco Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Div.

Allied Chem. Corp. -
Indust. Chems. Div.

Dow  Chem. U.S.A.

Monsanto Co. - Monsanto
Indust. Chems. Co.

Montrose Chem. Corp.
of California

Occidental Petroleum
Corp, - Hooker Chem.
Corp., subsid. - Hooker
Chems. & Plastics Corp.,
subsid. - Electrochemi-
cal  & Specialty Chems.
Div.

PPG  Indust., Inc. -
Chem. Div. - Indust.
Chem. Div.

Standard Chlorine
Chem, Co., Inc.
Location(s)2'3
1975
capacity2
MM kg (MM Ib)
1* 5
Total '
production
MM Kg (MM Ib)
for year of estimate
Deepwater, N. J,
                                                                                                        Luling,  La.
Niagara Falls,
N. Y.
                                                        Fords, N. J.
Syracuse (Solvay),
N. Y.
Midland, Mich.
Sauget, 111.

Henderson, Nev.
                                                                                                        Niagara Falls,
                                                                                                        N.Y.
                                                                                                        Natrium,  W.  Va.


                                                                                                        Delaware  City,
 11.3 (25)

136.2 (300)

 52.2 (115)

 31.8 (70)

  6.8 (15)
                                                                                                                               11-3  (91)
                                                                               31   (75)

                                                                                Total -
                                                                              313.7 (691)
                                                                                                                                               183.2  (403.5) -1972

-------
                                                                         Table A-l.  (Continued)
00
                               Chloro-
                               benzoic
                               acid
                               Chloro-
                               benzoyl
                               chloride
                               Chloro-
                               dlfluoro-
                               ethane
                               Chloro-
                               form
                              Chloro-
                              naphtha-
                              lene
 Intermediate  for  the
 preparation of  dyes,
 fungicides, Pharma-
 ceuticals  & other
 organic chemicals

 Intermediate  for
 Pharmaceuticals,  dyes
 6 other organic
 chemicals

 Refrigerant;  solvent;
 aerosol propellant;
 Intermediate
Pluorocarbon refrig-
ants & propellantsj
fluorocarbon plastics;
dyes & drugs; general
solvent; analytical
chemistry; fumlgant;
insecticides
Wax; condenser impreg-
nation; moisture-, flame-
acid- j Insect-proofing
of wood, fabric & other
fibrous bodies; mois-
ture-, & flame-proofing
covered wire & cable;
solvent (for rubber,
aniline & other dyes;
mineral & vegetable
oils, varnish gums
& resins, & other
waxes when mixed
in the molten state
Manufaeturer(s)2*3


Tenneco Inc. - Tenneco
Chems., Inc. - Organlcs
& Polymers Div.
Tenneco Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Div.
E. I. du Pont de Nemours
& Co., Inc., Organic
Chems. Dept. - Preon®
Products Div.
Pennwalt Corp. -
Chem. Div.

Union Carbide Corp. -
Chems. & Plastics Div,

Allied Chem. Corp. -
Specialty Chems. Div.

Diamond Shamrock Corp, -
Diamond Shamrock Chem.
Co. - Electro Chems. Div.

Dow Chem. U.S.A.

Stauffer Chem. Co. -
Indust. Chem. Div.

Vulcan Materials Co. -
Chems. Div.
American Color & Chem.
Corp.
GAP Corp. - Chem. Div.
JKoppers Co., Inc. -
Organic Materials
Div.
Location(s)2'


Fords, N. J.





Fords, H. J.
Antloch, Calif.
Deepw&ter, N. J.
East Chicago, Ind.
Louisville, Ky.
Montague, Mich.

Calvert City, Ky.
Institute & South
Charleston, W. Va.

Moundsvllle, ¥. Va.

Belle, W. Va.


Preeport, Tex.
Louisville, Ky.

Geismar, La.
Newark, N. J.
Wichita, Kans.
Lock Haven, Pa.

Linden, N. J.
Bridgeville, Pa.
                                                                                                                               1975
                                                                                                                            capacity2
                                                                                                                          MM kg  (MM Ib)
                                                                                                  Total ""S
                                                                                                  production
                                                                                                 MM kg  (MM  Ib)
                                                                                              fpr^rear  of est Imate
13.6 (30)

 8.2 (18)


45-4 (100)

34.1 (75)
                                                                                                                               4.5  (10)
                                                                                                                              13.6  (30)
                                                                                                                               Total  =
                                                                                                                             133    (293)
                                                                                                                                            106.8  (235.2)  -1972

-------
                                                                      Table  A-l. (Continued)
                               Chemical
                               o-
                               cresol
00
                               p-cresol
                               Cresylic
                               acid
                                              See m- eresol
                                              See m-cresol
Phosphate esters;
phenolic resins; wire
enamel solvent; plastici-
zers; gasoline additives;
laminates  coatings for
magnet wire for small
electric motors; dis-
infectants ; metal
cleaning cumpounds*
phenolic resins  flota-
tion  agents;  surfactants >
chemical intermediates;
oil additives; solvent
refining of lubricating
oils; scouring com-
pounds; pesticides
Marmfacturer(s)2*3


Continental Oil Co. -
Conoco Chems.  - Pitt
Consol Chems.
Koppers Co., Inc. -
Organic Materials Div.
The Merichem Co.
Productol Chem. Co.


Stimson Lumber Co. -
Northwest Petrochem.
Corp., div.

American Cyanamid Co, -
Organic Chems. Div.
The Sherwin-Williams
Co. - Sherwin-Williams
Chems. Div.

Continental Oil Co. -
Conoco  Chems. - Pitt-
Cons ol Chems.
Crowley Tar Products Co.
Ine.
Koppers Co., Inc. -
Organic Materials Div.
The Merichem Co.
Mobil Oil Corp. -
North American Div.
Productol Chem. Co.
                                                                          Stimson Lumber Co. -
                                                                          Northwest Petrochem.
                                                                          Corp.> div.
                                                                          U.S. Steel Corp. -
                                                                          USS Chems., div.
Locatlon(s)2'3
Newark, N. J.
1975
capacity2
MM kg (MM Ib)
.
Total"'5
production
MM kg (MM Ib)
for year of estimate
See m-cresol
                                                                                                      Follansbee, W. Va.


                                                                                                      Houston, Tex.

                                                                                                      Santa Fe Springs,
                                                                                                      Calif.
                                                                                                      Anacortes, Wash.
Bound Brook, N. J.

Chicago, 111.



Newark, N.  J.


Houston, Tex.


Follansbee, W. Va.

Houston, Tex.
Beaumont, Tex.
Paulsboro,  N. J.

Santa Fe Springs,
Calif.
Anacortes,  Wash.


Clairton, Pa.
                                                                                 22.7 (50)
 15-9 (35)

 15.ft (100)

  l._1 (3)

 13.6 (30)

 13.6 (30)


  9-1 (20)

   Total -
121.7 (268)
                                                                                                                                            See m-cresol
                                                                                                 31.7 (69.9)  -1971

-------
                                                                           Table  A-l.  (Continued)
oo
                                 Chemical


                                 Chloro-
                                 nitro-
                                 benzene
                                Chloro-
                                phenols
                                m-chloro-
                                toluene
                                 ochloro-
                                 toluene
                                p-chloro-
                                toluene
                                cresol
Intermediate, especially
for dyes; manufacture
of p-nitrophenol, from
which parathion is made
Intermediate in synthesis
of dyes & drugs; denatu-
rant for alcohol; selec-
tive solvent in refining
mineral oils
                                                Solvent;  Intermediate
Solvent & Intermediate
for organic chemicals
& dyes
Solvent & intermediates
for organic chemicals &
dyes

Disinfectant; phenolic
resins; tricresyl phos-
phate; ore flotation;
textile scouring agent;
organic Intermediate;
mfg. of salicylaldehyde;
coumarin, & herbicides;
in food antioxidants;
surfactant
Manufact ur e r (s)2 * 3


E, I. du Pont de Nemours
& Co., Inr. - Organic
Chems. Dept. - Dyes &
Chems. Div.

Monsanto Co. - Monsanto
Indust. Chems. Co.
Aldrich Chem. Co., Inc.
Dow Chem.  U.S.A.

Eastman Kodak Co, -
Eastman Organic Chems.

Monsanto Co. - Monsanto
Indus t. Chems. Co.

Specialty Organics, Inc.

R.S.A. Corp.
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsld., Hooker
Chems. & Plastics Corp.,
subsld, - Electrochemi-
cal & Specialty Chems.
Dlv.

Tenneco Inc. - Tenneco
Chems,, Inc. - Organics
& Polymers Div.

(See o-chlorotoluene)
                                                                            Koppers  Co.,  Inc. -
                                                                            Organic  Materials Dlv.
Location(s)2'3
Deepwater, N. J.
1975
capacity2
MM kg (MM Ib)
20.4 (45)
Total1" 5-
production
MM kg (MM Ib)
for year of estimate
_
                                                                                                        Sauget, 111.
Milwaukee, Wise.

Midland, Mich.

Rochester, N. Y.


Sauget, 111.


Irwindale, Calif.

Ardsley, N. Y.


Niagara Falls,
                                                                                                       Fords, N. J.
                                                                                                       Oil City, Pa.
                                                                                43.1 (95)

                                                                                 Total -
                                                                                63.5 (140)
                                                                                                                                                 Total m,p,p cresol
                                                                                                                                                 10.5 (23-1)  -1970

-------
                                                                                Table A-l.   (Continued)
                               Chemical
                                              Usage1
                                           Manufacturer (si.2..* 3
                            Location(s)2'3
                         1975
                       capacity2
                     MM kg (MM Ib)
    Total*'5-
    production
   MM kg (MM Ib)
foryearof estimate
ON

00
Croton-        Intermediate for n-
aldehyde       butyl alcohol & 2-
               ethyl-hexyl alcohol;
               solvent; preparation of
               rubber accelerators;
               purification of lubrica-
               ting oils; insecticides;
               tear gas; fuel-gas warn-
               ing agent; organic
               synthesis; leather tan-
               ning; alcohol denaturant

Crotonic       Synthesis of resins,
acid           polymers, plasticizers,
               drugs
                               Cumene          Production of phenol,
                                               acetone,  & alpha-
                                               methylstyrene; solvent
                                                                           Union  Carbide  Corp. -
                                                                           Chems,  &  Plastics  Div.
                            Institute &
                            Charleston, W. Va.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.

Ashland Oil, Inc. - Ash-
land Chem. Co., div, -
Petrochems, Div.
Clark Oil & Refining
Corp. - Clark Chem.
Corp., subsid.
Coastal States Gas Corp.
Coastal States Marketing,
Inc., subsid.
Dow Chem. U.S.A.
Gulf Oil Chems. Co.,
div. - Gulf Oil Corp. -
Petrochems, Div.
Marathon Oil Co.
Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.
Phillips Petroleum Co. -
Petrochem & Supply Div.
Skelly Oil Co.
Kingsport, Tenn.




Ashland, Ky.


Blue Island,  111.



Corpus Christi,
                                                                                                       Midland,  Mich.
                                                                                                       Philadelphia, Pa.
                                                                                                       Port  Arthur, Tex.

                                                                                                       Texas City, Tex.
                                                                                                       Chocolate Bayou,
                                                                                                       Phillips,  Tex.


                                                                                                       El  Dorado,  Kans,
                                                                                                                             136*2  (300)    1325.7 (2920)  -197*1
                                                                                                                               50    (110)
                                                                                                                              63.6  (140)
                                                                                                4.5 (10)

                                                                                              204.3 (^50)
                                                                                              204.3 (450)

                                                                                               95.3 (210)
                                                                                              290.6 (640)
                                                                                                0.5 (1)

                                                                                               63.6 (140)

-------
                                                                              Table A-l.  (continued)
GO
^4
00
                               Chemical

                               Cumene
                               (con* t)
                              Cumene
                              hydro-
                              peroxide
                              Cyano-
                              acetlc
                              acid

                              Cyanogen
                              chloride
                              Cyanuric
                              acid
                              Cyanuric
                              chloride
 (see previous page)
Production of acetone
& phenol; polymerization
catalyst, particularly
In redox systems, used
for rapid polymerization
                                              Organic  synthesis
Organic synthesis; tear
gas; warning agent in
fumigant gases

Organic synthesis
Chemical synthesis;
dyestuffs; Pharmaceuti-
cals; explosives;
surfactants
Manufact urer(s)2'3


Standard Oil of Calif. -
Chevron Chem. Co., sub-
sid., Oronlte Additives
& Indust. Chems. Div. -
Indust. Chems.

Standard Oil Co. (Ind.)
Amoco Chems. Corp.,
subsid.

Sun Oil Co. - Sun Oil
Co. of Penn., subsid. --
Suntide Refining Co.,
subsid.

Texaco Inc.

Union Carbide Corp. -
Union Carbide Carlbe,
Inc., subsid.

Allied Chem. Corp.  -
Specialty Chems. Div.

Hercules Inc., Organics
Dept. - Synthetics Dept.

Reichhold Chems., Inc. -
Specialty Chems. Div.

Kay-Fries. Chems., Inc.
                            Nilok  Chems., Inc.
PMC Corp. - Chem. Group-
Indus t . Chem, Div.

Monsanto Co. - Monsanto
Indust. Chems. Co.

Cib;a-Geigy  Corp. -
Agricultural  Div.

Nilok Chems., Inc.
Locatlon(s)2'3


El Segundo,  Calif.
                                                        Westville, N. J.

                                                        Penuelas, P. R.
Frankford, Pa.


Gibbstown, N. J.
Gibbstown, N. J.

Austin, Tex.
Stony Point, N. Y.



Memphis, Tenn.



South Charleston,


Everett , Mass .
Mclntosh, Ala.
St. Gabriel, La.

Memphis, Tenn.
                         1975
                       capacity2
                     MM kg (MM Ib)


                       45.4 (100)
                                                                                                      Texas City,  Tex.        22.7  (50)



                                                                                                      Corpus Christ!,        113-5  (250)
                       63.6 (140)

                      290.6 (640)

                        Total =
                     1648   (363D
    Total4'5
    production
   MM kg (MM  Ib)
for year of estimate

(see previous page)

-------
                                                                                 Table A-l-  (Continued)
                               Chemical
                               Cyclo-
                               hexane
oo
^j
vo
                               Cyclo-
                               hexanol
Manufacture of nylon;
solvent, for 'cellulose
ethers, fats, oils,
waxes, bitumens, resins,
crude rubber; extracting
essential oils; chemical
(organic synthesis, re-
crystallizing medium);
paint & varnish remover;
glass substitutes;
vapor has been u,sed as
lubricant for steel
(experimental)
Soap making; to in-
corporate solvents &
phenolic insecticides;
source of adipic acid
for nylon; textile
finishing solvent;
blending agent;lacquers;
paints & varnishes;
finish removers;, dry
cleaning; emulsified
products; leather
degreasing; polishes;
plasticizers; plas-
tics ; germicides
                                                                          Manufacturer(s)2 *3
American Petrofina, Inc.
Cosden Oil & Chem. Co.,
subsid.

Commonwealth Oil Refin-
Co., Inc. - Corco
Cyclohexane, Inc. -
subsid.

Exxon Corp. - Exxon
Chem, Co., div. - EXxon
Chem. Co. U.S.A.

Gulf Oil Corp. - Gulf
Oil Chems. Co., div. -
Petrochems. Div.

Phillips Petroleum Co. -^
                                                                          Phillips Puerto Rico
                                                                          Core Inc., subsid.
                                                                          Texaco Inc,
                                                                          Union OiJ Co. of Calif-.
                                                                          Union Pacific Corp, -
                                                                          Champlin Petroleum Co.,
                                                                          subsid.
Allied Chem. Corp. -
Fibers Div.
Celanese Corp. - Cela-
nese Chem, Co., div.
Dow Bad!sche Co.
El Paso Products Co.,
subsid, - El Paso
Natural Gas Co.
Monsanto Co. -- Monsanto
Indust. Chems. Co. -
Monsanto Textiles Co.
Nipro, Inc.
flohm & Haas Co. T Rohm
& Haas Ky. Inc.* subsid.
Location(s)2'3


Big Spring, Tex.



Penuelas, P. R.




Baytown, Tex.



Port Arthur, Tex.



Borger, Tex.
Sweeny, Tex.

Quayama, P. R.


Port Arthur, Tex.

Beaumont, Tex,

Corpus Christi,
Hopewell, Va.


Bay City, Tex.


Freeport, Tex.

Odessa, Tex.
                                                                                                      Luling, La.
                                                                                                      Pensacola, Pla.

                                                                                                      Augusta, Ga,
                                                                                                      Louisville,  Ky.
                     Total*'5
    1975             production
  capacity2         MM kg (MM Ib)
MM kg (MM Ib)    for year of estimate

   45.3 (99.8)   1062.lt (2340)  -1974


  117-7 (259.2)



  117.7 (259.2)


   97-1 (213.8)
                                                                               117.7 (259.2)
                                                                               252.8 (556.8)

                                                                               214.7
                                                                               m.7 (259.2)
                                                                               3,00   (220.3)
                                                                                67   (147.6)
                                                                                                                               Total =
                                                                                                                            1323.4 (2915.1)
                                                                                                                                             325.5 (716.9)  -1968

-------
                                                                                   Table A-l.  (Continued)
                                 Chemical
                                 Cycln-
                                 hex.,
00
00
o
                                 Cyclo-
                                 hexene
                                Cyelo-
                                hexyl-
                                amine
Organic synthesis;
particularly of adipic
acid & caprolactam  (about
95%}', polyvlnyl chloride
& its copolymers, &
methacrylate ester poly-
mers; solvent for DDT in
aerosol bombs; general
wood stains; paint &
varnish removers; spot
& stain removers; de-
greasing of metals;
in polishes; leveling
agent in dyeing & de-
lustering silk; lube
oil additive; general
solvent
Organic synthesis;
catalyst solvent; oil
extraction
Boiler-water treatment;
corrosion inhibitor
in boilers; rubber
accelerator; inter-
mediate
                                                                            Manufacturer's )_2 * 3
Allied Chem. Corp. -
Fibers Div.

Celanese Corp. - Cela-
nese Chem. Co., div.
Dow Badische Co.

El Paso Natural Gas Co. -
El Paso Products Co.,
subsid.
Monsanto Co. - Monsanto
Textiles Co.
Nipro, Inc.

Rohm & Haas Co. - Rohm
& Haas Ky. Inc. - subsid.
Union Carbide Corp. -
Cheras. & Plastics Div.
Phillips Petroleum Co. -
Petrochem, & Supply Div.
Uniroyal, Inc. - Uniroyal
Chem., div.

Abbott Labs. -
Chem. Div,
Monsanto Co. - Monsanto
Indust.  Chems. Co.

Virginia Chems., Inc. -
Indust.  Chems. Dept.
LocationCs)2 » 3
Hopewell, Va.
Bay City, Tex.
Freeport, Tex.
Odessa, Tex.
1975
capacity2
MM kg (MM lt>)
157.1 (316)
45.4 (100)
113-5 (250)
29 (64)
Total1" $•
production
MM kg (MM Ib)
for year of estimate
313-5 (756.5) -1971



Pensacolas Pla.

Augusta, Ga.
Louisville, Ky.


Taft, La.
Phillips, Tex.

Naugatuck, Conn.


Wichita, Kans.

Sauget, 111.

Portsmouth, Va.
                       227   (500)

                        68.1 (150)
                        18.2 (40)

                        31.8 (70)

                         Total -
                       701.4 (15115)
                         4.5 (10)

                         1   (2)

                         3.6 (8)

                         Total =
                         9-1 (20)

-------
                                                                                 Table A-l.   (Continued)
oo
CO
                              Chemical

                              Decahydro-
                              naphtha-
                              lene
                              Decanol
                              Diacetone
                              alcohol
Solvent for oils, fats,
waxes, resins, rubber,
etc.; substitute for
turpentine; cleaning
machinery; stain-re-
mover ; shoe creams,
floor waxes, etc. ;
cleaning fluids;
lubricants

Plasticizers; deter-
gents i synthetic lubri-
cants; solvents; per-
fumes; flavorings


Solvent for nitro-
cellulose, cellulose
acetate, variovis oils,
resins, waxes, fats,
dyes, tars; lacquers;
dopes, coating composi-
tion; wood preservatives;
stains; rayon & artifical
leather; imitation gold
leaf; dyeing mixtures;
antifreeze mixtures;
extraction of resins &
waxes; preservative for
animal tissues; metal-
cleaning compounds;
hydraulic  compression
fluids; stripping
agent (textiles); labora-
tory reagent; the techni-
cal grade, containing
acetone, has greater
solvent power
Manufacturer(s)2*3


E. I. du Pont de Ne-
mours S Co., Inc.  -
Organic Chems. Dept. -
Dyes & Chems. Div,

Lonza Inc.
Continental Oil Co. -
Conoco Chems.

The Proctor S Gamble
Co.

Celanese Corp. - Cela-
nese Chem. Co., div.

Shell Chem. Co. -
Base Chems.

Union Carbide Corp. -
Chems. & Plastics
Div.
LocationCs)2'3


Deepwater, N.  J.




Mapleton, 111.





Westlake, La.


Ivorydale, Ohio


Bishop, Tex.


Deer Park, Tex.
Dominguez, Calif.

Institute & South
Charleston, W. Va.
                                                                                 1975
                                                                               capacity2
                                                                             MM kg (MM Ib)
                                                                                                                                               Total1*'5
                                                                                                                                               production
                                                                                                                                              MM kg  (MM Ib)
                                                                                                                                           for  r ear  of estimate
                              Diamino-
                              benzoic
                              acid
                            Bofors Indust., Inc.

                            Salsbury Labs.
                            Linden, N.  J.

                            Wilmington, N.  C.

-------
                                                                                   Table A-l.  (Continued)
                                 Chemical
                                 Dichloro-
                                 aniline
oo
to
                                 Dichloro-
                                 ben?ene
                                 (m,p,p)
Usage1

Dye intermediate;
intermediate for
biologically active
compounds
Mfg. of 3,1-dichloro-
anilinej solvent for a
wl
-------
                                                                                  Table A-l.  (Continued)
                                Chemical
                                                                           Manufacturer(s)2 *3
                                                                                                       Location(s)2*3
                                                                                                1975
                                                                                              capacity2
                                                                                            MM kg (MM Ib)
                                         Total1"5
                                         production
                                        MM kg (MM  Ib)
                                     for year of estimate
00
00
Dichloro-      General solvent for
ethylene       organic materials; dye
(vinyl-        extraction; perfumes;
idene          lacquers; thermoplastics;
chloride)      organic synthesis;
               medicine; copolymerised
               with vinyl chloride or
               acrylonitrile to  form
               various kinds of
               saran; other copolymers
               are also made; adhesives;
               component of synthetic
               fibers

Dichloro-      General solvent;  selee-
ethyl          tive solvent for produc-
ether          tion of high-grade lubri-
               cating oils; textile
               scouring & cleansing;
               fulling compounds; wet-
               ting & penetrating com-
               pounds ; organic synthe-
               sis; paints, varnishes,
               lacquers; finish  removers;
               spotting & dry cleaning;
               soil fumigant

Dichloro-      General solvent;  inter-
hydrin         mediate in organic syn-
               thesis ; paints, varnishes,
               lacquers, celluloid
               cements; water colors'
               binder; photographic
               lacquers

Dichloro-      Solvent for oils, greases,
pentane        rubber, resins & bi-
               tuminous materials; removal
               of tar; reclaiming rubber;
               paint & varnish removers;
               degreasing of metals;
               insecticide; soil fumi-
               gant; removal of wax
               deposits on oil-well
               equipment
                                                                           Dow Chem. U.S.A.
                                                                           PPG Indust., Inc.  -
                                                                           Chem. Div.  - Indust,
                                                                           Chem. Div.
                                                                                                       Preeport,  Tex.
                                                                                                       Plaquemine,  La.

                                                                                                       Lake Charles,  La.
                                                                           Buckman Labs., Inc.
                                                                           Dow Chem. U.S.A.
                                                                           Union Carbide Corp.  -
                                                                           Chems.  & Plastics Div.
                                                                           Eastman Kodak Co.  -
                                                                           Eastman Organic Chems.
Cadet, Mo.
Memphis, Tenn.
Preeport, Tex.
Institute & South
Charleston, W. Va.
                                                                                                       Rochester,  N.  Y.

-------
                                                                                Table  A-l.   (Continued)
Chemical
Dichloro-
propene
Dicyclo-
hexyl-
amine



Usage1
Organic synthesis;
soil fumigants
Intermediate; insecti-
cides; plasticizer;
corrosion inhibitors;
antioxidants in rubber;
lubricating oils, fuels;
catalysts for paint,
varnishes & inks ;
detergents; extractant
Manufacturer^)2,1 3
Dow Chemical U.S.A.

Abbott Labs, - Chem.
Div,
Va. Chems. Inc. -
Indust . Chems . Dept .



LocationCs]2 *
Preeport , Tex

Wichita, Kans

1


.

Portsmouth, Va






00
00
Diethanol-     Liquid detergents for
amlne          emulsion paints, cutting
               oils, shampoos, cleaners,
               & polishes; textile
               specialties; absorbent
               for acid gases; chemical
               intermediate for resins &
               plasticizers, etc.;
               solubilizing 2,4-D
                              Diethylene      Polyurethane  &  unsatu-
                              glycpl          rated  polyester resins;
                                              triethylene glycol;  tex-
                                              tile softener;  petroleum
                                              solvent  extraction;  de-
                                              hydration  of  natural gas;
                                              plasticizers  &  surfac-
                                              tants; solvent  for
                                              nitrocellulose,  & many
                                              dyes & oils;  humectant
                                              for tobacco,  casein,
                                              synthetic  sponges, paper
                                              products;  cork  composi-
                                              tions; book-binding
                                              adhesives; dyeing as-
                                              sistant ; cosmetics
Allied Chem. Corp. -
Specialty Chems.  Div.
Dow Chem. U.S.A.

Olin Corp. - Designed
Products Div.
Texaco Inc. - Jefferson
Chem. Co., Inc.,  subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
                                           Allied Chem. Corp. -
                                           Specialty Chems. Div.
                                           BASF Wyandotbe Corp. -
                                           Indust. Chems. Group
                                           Celanese Corp. -
                                           Celanese Chem. Co., dlv.
                                           Dixie Chem. Co.

                                           Dow Chem. U.S.A.


                                           Eastman Kodak Co. - East-
                                           man Chem. Products, Inc.,
                                           subsld. - Texas East-
                                           man Co., div.
                                                                                                     Orange, Tex.
                                                                                                                              1975
                                                                                                                            capacity2
                                                                                                                          MM kg (MM Ib)
                                                                                                                Total1* '-
                                                                                                                production
                                                                                                               MM kg  (MM Ib)
                                                                                                             for year  of estimate.
                                                                                                                              9.1 (20)
                                                                                                                                              50.^t  (111)
                                                                                                                                                            -1971
Preeport, Tex.
Midland, Mich.
Brandenburg, Ky .
Port Heches, Tex.
Seadrift, Tex.
13.6
15.9
11.3
31
113.5
(30)
(35)
(25)
(75)
(250)
•Total =
197-5 (435)
Orange, Tex.
Gelsmar, La.
Clear Lake, Tex.
Bayport, Tex.
Freeport, Tex.
Plaquemine, La.
Longview, Tex.
1.5
9.5
10.9
_
10.9
21.3'
3.6
(10)
(21)
(21)

(21)
(17)
(8)
                                                                    122   (268.7)   -1973
                               Includes mono- and tri-ethanol  amines

-------
                                                                               Table  A-l.  (Continued)
00
00
                             Chemical

                             Diethylene
                             glycol
                             (Con't)
                             Diefchylene
                             glycol
                             mono-
                             butyl
                             ether
                             Diethylene
                             glycol
                             mono-
                             butyl
                             ether
                             acetate
Usage1

(see previous page)
Solvent for nitro-
cellulose, oils, dyes,
gums, soaps, polymers;
plasticizer intermediate
Solvent for oils, resins,
gums, also for cellulose
nitrate & polymeric
ings; plasticizers in
lacquers & coatings
Mamifacturer(s)^^3

Northern Natural Gas
Co - Northern Petro-
chem. Co., subsid. -
Polymers Div.
LocationCs)2*3

Morris, 111.
                                                                        Inc., subsid.
Dow Chem. U.S.A.

Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.

Olin Corp. - Designed
Products Div.

Shell Chem. Co. -
Base Chems.

Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.

Union Carbide Corp. -
Chems. & Plastics Div.

Eastman Kodak Co. - East-
man Chem. Products, Inc.,
subsid. - Tex. Eastman
Co., div.

Union Carbide Corp. -
Chems. & Plastics Div.
Midland, Mich.

Longview, Tex.
                                                                                                    Brandenburg, Ky.


                                                                                                    Geismar, La,


                                                                                                    Port Neches, Tex.


                                                                                                    Institute & South
                                                                                                    Charleston, W. Va.

                                                                                                    Longview, Tex.
                                                        Institute & South
                                                        Charleston, W. Va.
    1975
  capacity2
MM kg (MM Ib)

   13.6 (30)
    Total1"5
    production
   MM kg (MM Ib)
for year of production

(see previous page)
Olin Corp. - Designed
Products Div.
PPO Indust., Inc. -
Chem. Div. - Houston
Chem. Co., div. -
PPG Indust. (Caribe)
Shell Chem. Co. -
Base Chems.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. 8 Plastics Div.
Union Carbide Caribe,
Brandenburg, Ky.
Beaumont, Tex.
Guayanllla, ?. R.
Geismar, La.
Port Neches, Tex.
Seadrirt, Tex. T 	
Taft, La.
Penuelas, P. R. 1
2.3
1.5
18.2
1.5
16.3
97.6

(5)
(10)
(10)
(10)
(36)
(215)

                                                                                                                             Total -
                                                                                                                           218 (480)
                                                                                                                                              6.8 (15)
                                                                                                                                                           -1972

-------
                                                                                Table  A-l.   (Continued)
                              Chemical
                                                                         Manufacturer(s)2 * 3
                                                                                                     Location(s)2'3
                                                                                 1975
                                                                               capacity2
                                                                             MM kg (MM Ib)
                                                                     Total1" s-
                                                                     production
                                                                     MM kg  (MM Ib)
                                                                  for year  of estimate
oo
00
CTv
                              Diethylene
                              glycol
                              mono-
                              ethyl
                              ether
                              Diethylene
                              glycol
                              mono-
                              ethyl
                              ether
                              acetate

                              Diethylene
                              glycol
                              mono-
                              hexyl
                              ether
                              acetate

                              Diethylene
                              glycol
                              mono-
                              methyl
                              ether
Solvent Tor dyes, nitro-
cellulose, & resins, mu-
tual solvent for mineral
oil-soap & mineral oll-
sulfonated oil mixtures;
nonaqueous stains for
wood; for setting the
twist & conditioning
yarns & cloth; textile
printing; textile soaps;
lacquers; organic syn-
thesis; brake fluid
diluent
Solvent for cellulose
esters, gums, resins;
coatings & lacquers;
printing inks
Solvent; brake fluid
component; Intermediate
Dow Chem. U.S.A.

Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. -- Texas
Eastman Co., div.

Olin Corp, - Designed
Products Div.

Shell Chem. Co. -
Base Chems.

Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.

Union Carbide Corp. -
Chems. & Plastics Div.
Dow Chem. U.S.A.

Eastman Kodak Co. - East-
man Chem, Products, Inc.,
subsid. - Texas Eastman
Co., div.

Olin Corp. - Designed
Products Div.

PPO Indust., Inc. -
Chem. Div. - Houston
Chem. Co., div.

Shell Chem. Co. - Base
Chems.

Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.

Union Carbide Corp. -
Chems.  & Plastics Div.
Midland, Mich.

Longview, Tex.
Brandenburg, Ky.


Geismar, La.


Port Neches, Tex.


Institute & South
Charleston, W. Va.
                                         20.il  (il5)   -1972
Midland, Mich.

Longview, Tex,
                                                                                                     Brandenburg, Ky.


                                                                                                     Beaumont, Tex.



                                                                                                     Geismar, La.


                                                                                                     Port Neches, Tex.


                                                                                                     Institute & South
                                                                                                     Charleston, W. Va.
                                                                                                  6.8 (15)    -1972

-------
                             Chemical
                                                                               Table A-l.   (Continued)
                                                                        Manufa,cturer(s)2> 3
                                                                       Location(s)2*3
                                                                                 1975
                                                                               capacity2
                                                                             MM kg (MM Ib)
                                                                      Total1"5
                                                                      production
                                                                     MM kg (MM  Ib)
                                                                  for year^jxf estimate
00
oo
                             Diethylene
                             glycol
                             mono-
                             methyl
                             ether
                             acetate

                             Diethylene
                             glycol
                             dibutyl
                             ether
Diethylene
glycol
diethyl
ether
                             Diethylene
                             glycol
                             dimethyl
                             ether
                             Diethyl-
                             amine
                             Diethyl
                             sulfate
High-boiling, inert
solvent with applica-
tion in extraction pro-
cesses & in coatings
& inks; diluent in
vinyl chloride disper-
sions; extractant for
uranium ores

Solvent for nitrocellu-
lose ; resins, lacquers;
high-boiling medium &
solvent for organic
synthesis

Solvent; anhydrous reac-
tion media for organo-
metallic syntheses
               Rubber chemicals; tex-
               tile specialties;
               selective solvent; dyes;
               flotation agents; resins;
               pesticides; polymeriza-
               tion inhibitors; Pharma-
               ceuticals ; petroleum
               chemicals; electroplat-
               ing; corrosion
               inhibitors

               Ethylating agent in
               organic synthesis
                                           Union Carbide Corp. -
                                           Chems, & Plastics Div.
Union Carbide Corp. -
Chems. & Plastics Div.
The Ansul Co. - Chem.
Div,

Olin Corp. - Designed
Products Div.

Air Products & Chems.,
Inc.

Pennwalt Corp. - Chem.
Div.

Union Carbide Corp. -
Chems. & Plastics Div.

Va. Chems. Inc. -
Indust. Chems. Dept.
                            Union Carbide Corp. -
                            Chems. & Plastics Div.
                            Institute & South
                            Charleston, W. Va.
Institute & South
Charleston, W. Va.
Marinette, Wise.


Rochester, N. Y.


Pensacola, Pla.


Wyandotte, Mich.


Taft, La.


Portsmouth, Va.
                            Institute & South
                            Charleston, W. Va.
                                                                                                                                                 5 (11.1)  -1972

-------
                                                                                 Table A-l.   (Continued)
OO
00
00
                               Chemical
                               DIfluoro-      Refrigerant; aerosol
                               ethane         propellant; Intermediate
                               Diiso-         Alkylation; intermediates;
                               butylene       antioxldants; surfactants;
                                              lube additives; plastici-
                                              zers; rubber chemicals
                               DIketene       Production of aceto-
                                              arylamides; pigments &
                                              toners; pesticides; food
                                              preservatives; pharma-
                                              ceutical intermediates
Dimethyl-       Acid  gas  absorbent;  sol-
amine           vent;  antioxidants;  mfg.
                of  dimethylformamide &
                dimethylacetamide;  dyes;
                flotation agent;  gasoline
                stabilizers;  pharmaceuti-
                cals;  textile chemicals;
                rubber accelerators;
                electroplating; dehalring
                agent;  missile fuels;
                pesticide propellant;
                rocket  propellants;
                surfactants

N,N-dl-         Dyes;  intermediate's;
methyl-         solvent;  manufacture of
aniline         vanillin;  stabilizer
                (acid  accepter)
                                                                          Manufacturer(s)2*3
Allied Chem. Corp. -
Specialty Chems. Div.
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Preon® products div.

The B. P. Goodrich Co. -
B. F. Goodrich Chem.
Co., div.

Petro-Tex Chem. Corp. -
Petro-Tex Chem. Co.,
subsld.

Texaco Inc.

Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsld. - Tenn.
Eastman Co., div.

PMC Corp. - Chem. Group -
Indust. Chem. Div.

Air Products & Chems.,
Inc.

Commercial Solvents Corp.

E. I. du Pont de Ne-
mours & Co., Inc.,
Biochems. Dept.
GAF Corp. - Chem. Div.
                                                                          Allied Chem. Corp. -
                                                                          Specialty Chems. Div.
                                                                          American Cyanamid Co. -
                                                                          Organic Chems. Div.

                                                                          E, I. du Pont de Ne-
                                                                          mours & Co., Inc. -
                                                                          Organic Chems. Dept. -
                                                                          Dyes & Chems. Dept.
                                                                          Dye Specialities, Inc.
Location(s)2*3


Baton Rouge, La.

Louisville, Ky.




Port Neches, Tex.


Houston, Tex.



Port Arthur, Tex.

Kingsport,  Tenn.




Meadvllle,  Pa.


Pensacola,  Fla.


Terre Haute, Ind.
Belle, W. Va.


Calvert City,  Ky.
                            Buffalo,  N.  Y.

                            Bound Brook, N.  J.


                            Deepwater,  N.  J.




                            Jersey City, N.  J.
                                                     1975
                                                   capacity2
                                                 MM kg (MM Ib?
                                                                                                                 Total1**5
                                                                                                                 production
                                                                                                                MM kg (MM Ib)
                                                                                                             fgr_y_e_ar_._pf_ estimate
                                                                                                                                               55-2 (121.5)  -1973

-------
                                Chemical
                                                                                  Table A-l.  (Continued)
                                                                                                       Locations)2'3
                                                                                                1975
                                                                                              capacity2
                                                                                            MM kg (MM Ib)
                                                                     Totall|>5
                                                                     production
                                                                     MM kg  (MM Ib)
                                                                  for year  of estimate
oo
00
VO
                                Dimethyl       Refrigerant; solvent;
                                ether          extraction agent;  propel-
                                               lant for sprays; chemical
                                               (reaction medium); cata-
                                               lyst & stabilizer in
                                               polymerization

                                N,N-dl-        Solvent for vinyl  resins
                                methyl-        & acetylene, butadiene,
                                formamide      acid gases; catalyst
                                               in carboxylation reac-
                                               tions ; organic synthesis
Dimethyl       Methylating agent for
sulfate        amines & phenols
                                Dimethyl       Gas odorant; solvent
                                sulfide        for many inorganic
                                               substances; catalyst
                                               impregnator
                                Dimethyl       Solvent for polymeriza-
                                sulfoxide      tion & cyanide reactions;
                                               analytical reagent; spin-
                                               ning polyacrylonitrile &
                                               other synthetic fibers;
                                               industrial cleaners pesti-
                                               cides, paint stripping;
                                               hydraulic fluids;
                                               preservation of cells at
                                               low temperatures; diffu-
                                               sion of drugs, etc.,
                                               into blood stream by
                                               topical application;
                                               medicine; plant patho-
                                               logy & nutrition
                                           E. I. du Pont de Ne-
                                           mours & Co., Inc. -
                                           Biochems.  Dept.

                                           Union Carbide Corp. -
                                           Chems. & Plastics Div.
                                           Air Products & Chems.,
                                           Inc.
                                           E. I. du Pont de Ne-
                                           mours & Co., Inc.  -
                                           Biochems. Dept.

                                           Lachat Chems. Inc.
E. I. du Pont de Ne-
mours & Co., Inc. -
Biochems.Dept.  -
Indust. Chems.  Dept.

Crown Zellerbach Corp. -
Chem. Products Div.
Pennwalt Corp.  - Chem.
Div.
Phillips Petroleum Co. -
Petrochem. & Supply Div.

Crown Zellerback Corp. -
Chem. Products Div.
                            Belle,  W.  Va.



                            Institute  & South
                            Charleston, W.  Va.


                            Pensacola, Fla.


                            Belle,  W.  Va.
                                                                       Chicago Heights,
                                                                       111.

                                                                       Belle, W. Va.
                                                                       Linden, N,  J.

                                                                       Bogalusa, La.


                                                                       Beaumont, Tex.


                                                                       Phillips, Tex.
                                                                       Bogalusa, La.
                                                                       Camas, Wash.

-------
                                                                                  Table A-l.  (Continued)
                                Chemical
                                                                           Manufacturer(s ) 2 J 3
                                                        Location(s)2'3'
                                                     1975
                                                   capacity2
                                                 MM kg  (MM  Ib)
                                         Total1**5-
                                         production
                                        MM kg  (m Ib)
                                      for year  of estimate
oo
^o
o
                                Dinitro-
                                benzene
                                Dinitro-
                                benzoic
                                acid
                                Dinltro-
                                toluene
                                Dioxane
Organic synthesis;
dyes; camphor substitute
in celluloid ,production
                               Dioxo-
                               lane
Organic synthesis;
toluidines; dyes;
explosives
Solvent for cellulosics
& wide range- of organic
products; lacquers;
paints i varnishes;
paint & varnish re-
movers j wetting &  dis-
persing agent in tex-
tile processing, dye
baths, stain and print-
ing compositions;
cleaning & detergent
preparations; cements;
cosmetics; deodorants;
fuinigants; emulsions;
polishing compositions;
stabilizer for chlori-
nated solvents; scintil-
lation counter

Low-boiling solvent &
extractant for oils,
fats, waxes, dyes, &
cellulose derivatives
                            Ashland Oil, Inc. -
                            Ashland Chem. Co., dlv.
                            Chem. Products Div.

                            Bofors Indust., Inc.

                            Salsbury Labs.
Air Products & Chems,,
Inc.

E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Dyes & Chems. Div.

Rubicon Chems. Inc.

Dow Chem. U.S.A.

Ferfo Corp. - Grant
Chem. Div.

Union Carbide Corp. -
Chems. & Plastics Dlv.
Ferro Corp. - Grant
Chem. Div.
Great Meadows,



Linden, N. J,

Charles City,
Iowa

Pensacola, Fla.


Deepwater, N. J.




Geismar, La.

Freeport, Tex.

Baton Rouge, La.


Institute & South
Charleston, W. Va.
                                                                                                       Baton Rouge,  La.

-------
                                                                                  Table A-l.  (Continued)
                                Chemical
                                Diphenyl-
                                amine
oo
vo
                                Dlphenyl
                                oxide
Rubber antioxidants &
acceleratprs; stabiliz-
ers for plastics; solid
rocket propellants;
pesticides; explosives;
dyes; Pharmaceuticals
Organic synthesis;
perfumery, particularly
soaps; heat-transfer
medium; resins for
laminated electrical
insulation
Manufacturer (_s)_2_*_3


American Cyanamid Co,
Organic Chems. Div.

E. I. du Pont de Ne-
mours & Co., Indust.
Chems. Dept.

First Mississippi
Corp. - First Chem.
Corp., subs id,
Rubicon Chems. Inc.

Dow Chem. U.S.A.
Locatlon(s)2*3


Bound Brook, N.  J.


Gibbstown, N. J.



Pascagoula, Miss.


Geismar, La.

Midland, Mich.
                                                                                                                                1975
                                                                                                                              capacity2
                                                                                                                            MM kg (MM Ib)
                                                                                                  Total1*'5
                                                                                                  production
                                                                                                 MM kg (MM lb)
                                                                                              for ygar of estimate
                                Diphenyl-      Intermediates; dyes
                                thiourea       (sulfur colors, indigo,
                                               methyl indigo); vulcani-
                                               zation accelerator;
                                               synthetic organic
                                               Pharmaceuticals; flota-
                                               tion agent; acid
                                               inhibitor

                                Dipropy-       Solvent for nitrocellulose; Dow Chem. U.S.A.
                                lene           shellac; partial solvent
                                glycol         for cellulose acetate;
                                               solvent mixtures; lacquers; p^ducts Div.
                                               coatings; printing anks
                                                                           Oxirane Chem. Co.,
                                                                           Texaco Inc., Jefferson
                                                                           Chem. Co., Inc.,  subsId,
                                                                           Union Carbide Corp. -
                                                                           Chems. & Plastics Div.
                            American Cyanamid Co. -
                            Organic Chems. Div.
                            Monsanto Co. - Monsanto
                            Indus t. Chems. Co.
                            Olin Corp. - Designed
                            Bound Brook, N. J.

                            Nitro, W. Va.
                            Preeport, Tex.
                            Plaquemine,  La.
                            Brandenburg, Ky.


                            Bayport, Tex.
                            Port Neches, Tex.


                            Institute &  South
                                                                               15.9 (35)
                                                                                5.1 (12)
                                                                                2.3 (5)
                                                                                5.9 (13)
                                                                                3.2 (7)

                                                                                5.4 (12)

                                                                                Total =
                                                                               38.1 (84)
                                                                                                 24.2 (53-3)  -1973

-------
                                                                                   Table A-l.  (Continued)
                                 Chemical


                                 Dodecene
00
                                Dodecyl-
                                aniline

                                Dodecyl-
                                phenol
                                Epiehloro-
                                hydrln
                                                Flavors;  perfumes;
                                                medicine; oils; dyes;
                                                resins
                                                Intermediate
Solvent; intermediate
for surface-active
agents; oil additives;
resins; fungicides;
bactericides; dyes;
Pharmaceuticals, ad-
hesives; rubber
chemicals
Major raw material for
epoxy & phenoxy resins;
mfg. of glycerol; cur-
ing propylene-based
rubbers; solvent for
cellulose esters &
ethers; high wet-
strength resins for
paper industry
Manufacturer (s)2 ^3


Atlantic Richfield Co. -
ARCO Chem. Co., div.

Continental Oil Co. -
Conoco Chems.

Exxon Corp. - Exxon
Chem. Co., dlv. -
Exxon Chem. Co. U.S.A.

Gulf Oil Corp. - Gulf
Oil Chems. Co., div.
Petrochems. Div.

The Humphrey Chem. Co.

Sun Oil Co. - Sun Oil
Co. of Penn., subsid.


Texaco Inc.

Union Oil Co. of Calif.

Monsanto Co. - Monsanto
Indust. Chems. Co.

GAP Corp. - Chem. Div.

Monsanto Co. - Monsanto
Indust. Chems. Co.


Productol Chem. Co.
Union Carbide Corp. -
Chems. & Plastics Div.

Dow Chem. U.S.A.

Shell Chem. Co. - Base
Chems.
                                                        Locatlon(s)2'3


                                                        Wilmington, Calif.


                                                        Westlake, La.


                                                        Baton Rouge, La.



                                                        Cedar Bayou, Tex.
North Haven, Conn.

Duncan, Okla.
Marcus Hook, Pa.
Toledo, Ohio

Port Arthur, Tex.

Beaumont, Tex.

Sauget, 111.


Calvert City, Ky.

Kearnv, N. J.
                                                                                                        Santa Fe  Springs,
                                                                                                        calif.
                                                                                                        Marietta,  Ohio
Preeport, Tex.

Deer Park, Tex,
Norco, La.
                                                                                                                                1975
                                                                                                                              capacity2
                                                                                                                            MM kg  (MM Ib)
                                         Total1* >5
                                         production
                                        MM kg  (MM Ib)
                                      forvear  of estimate
12M.8 (275)
 72.6 (160)
 27.2 (60)

  Total -
224.7
                                                                                                                                                81.7 (180)  -1973

-------
                                                                                 Table  A-l.  (Continued)
                              Chemical


                              Ethanol
00
VO
co
                               Ethyl
                               acetate
                                             Solvent  for  resins,  fats,
                                             oils,  fatty,  acids, hydro-
                                             carbons,  alkali  hydroxi-
                                             des; extractive  medium;
                                             manufacture  of inter-
                                             mediates,  organic deri-
                                             vatives  (especially  ace-
                                             taldehyde),  dyes, syn-
                                             thetic drugs, elasto-
                                             mers ,  detergents, clean-
                                             ing  solutions, surface
                                             coatings,  cosmetics,
                                             -Pharmaceuticals» ex-
                                             plosives.,  anti-freeze;
                                             beverages5 antisepsis;
                                             medicine
General solvent in
coatings & plastics;
organic synthesis;
smokeless powders;
Pharmaceuticals
                            Manufacturer^ )2 *_j_


                            Commercial Solvents
                            Corp.

                            Eastman Kodak Co.  -
                            Eastman Chem. Products,
                            Inc.,  subsid. -  Texas
                            Eastman Co., div.

                            Georgia-Pacific  Corp. -
                            Chem.  Div.

                            Grain  Processing Corp.

                            Inland Chem. Corp.

                            National Distillers &
                            Chem.  Corp.  - Chems.
                            Div. - U.S.  Indust.
                            Chems. Co.,  div.

                            Publicker Indust.  Inc.


                            Shell  Chem.  Co.  -
                            Base Chems.

                            Union  Carbide Corp. -
                            Chems. & Plastics  Div.
Celanese Corp. -
Celanese Chem. Co., div,

Eastman Kodak Co. -
Eastman Chem, Products,
Inc., subsid. - Tenn.
Eastman Co., div.

Monsanto Co. - Monsanto
Indus t. Chems. Co. -
Monsanto Polymers &
Petrochems. Co.

Publicker Indust. Inc.
Union Carbide Corp.
Chems. and Plastics Div.
                            Location(s)2'3


                            Terre Haute,


                            Longview,  Tex.




                            Bellingham,  Wash.


                            Muscatine, Iowa

                            Juneau,  Wise-.

                            Tuscola, 111.




                            Gretna,  La.
                            Philadelphia,  Pa.

                            Deer Park, Tex.


                            Texas City,  Tex.
Bishop, Tex.
Pampa, Tex.

Kingsport,, Tex.
Longview, Tex.
                                                                                                      Trenton,  Mich.


                                                                                                      Springfield,  Mass.

                                                                                                      PhiladeIphis, Pa.
                                                                                                                               1975
                                                                                                                             capacity2
                                                                                                                           MM kg (MM Ib)
 71.1 (161)
 11.9 (26.3)
196.7 (133.2)
178.9 (39D
119.2 (262.6)

357.6 (787.7)

  Total •
938.8 (2067.8)

 27.2 (60)

  9   (20)
  9   (20)
                                                                                                                              6.8  (15)
                    Total"'5
                    production
                   MM kg (MM Ib)
                for year of estimate


                 862.6 (1900) -1971
                                                                                    (20)

                                                                                    (20)
                                                                                                      Brownsville,  Tx.
                                                                                                      Institute  and South
                                                                                                      Charleston, W.Va.       15.1  (100)
                                                                                                      Texas  City, Tex.

                                                                                                                              Total  =
                                                                                                                            115.8  (255)
                               Ethyl          Organic synthesis;
                               aceto-         antipyrine; lacquers;
                               acetate        dopes; plastics;
                                              manufacture of dyes,
                                              Pharmaceuticals, anti-
                                              malarials, vitamin B;
                                              flavoring
                            Eastman Kodak Co. -
                            Eastman Chem. Products,
                            Inc., subsid. - Tenn.
                            Eastman Co., div.

                            Lonza Inc.
                                                                                                      Kingsport,  Tenn.
                                                        Mapleton, 111.

-------
                                Chemical
                                                                                   Table  Art-   (Continued)
                                                                                                       LocationCs)2'3
                                                                                 1975
                                                                               capacity2
                                                                             MM kg (MM Ib]
                                                                     Total1**5
                                                                     production
                                                                    MM kg  (MM Ib)
                                                                  for  f_e ar _c> f . es t i ma t e
                                Ethyl
                                aery late
Polymers; acrylic
paints;  intermediates
oo
                                Ethyl-
                                ami ne
                                Ethyl
                                benzene
Dye intermediates;
solvent extraction;
petroleum refining;
stabilizer for rubber
latex; detergents;
organic synthesis
Intermediate in produc-
tion of styrene;
solvent
Celanese Corp. - Cela-
nese Chem. Co., div.

Dow Badisehe Co.

Rohm & Haas Co. - Rohm
& Haas Texas Inc.,
s ub s i d.

Union Carbide Corp. -
Chems. S Plastics Div,

Air Products & Chems.,

Pennwalt Corp. -
Chem. Div.

Union Carbide Corp. -
Chems. & Plastics Div.

Virginia Chems. Inc. -
Indust. Chems. Dept.

American Petrofina,
Inc. - Cosden Oil &
Chem. Co., subsld.

ARCO/Polymers, Ine.


The Charter Co. -
Charter Oil Co., subsid.
Charter International
Oil Co., subsid.

Commonwealth Oil Refin-
ing Co., Inc. - Styro-
chem Corp., subsid.
Clear Lake, Tex.
Pampa, Tex.
Freeport ,  Tex .
Deer Park, Tex.
Taft, La.


Pensacola, Pla.

Wyandotte, Mich.


Taft, La,


Portsmouth, Va.


Big Spring, Tex.
                                                                                                       Houston, Tex.
                                                                                                       Port Arthur, Tex.

                                                                                                       Houston, Tex.
                                                                                                       Penuelas, P. R.
                                                                     75    (165.2)-1968
                                                                           Gulf Oil  Chems.  Co.,
                                                                           div. - Petrochems.
                                                                           Div.
                                                                                                                                                25.2 (55.5)  -1972
61.3 (135)     2588   (5700)   -1974


     (100)
                                                                               245.2

                                                                                15.9 (35)
                                                                                                                               40.9  (90)
Cos-Mar, Inc.
Dow Chem. U.S.A.
El Paso Natural Gas
Co., El Paso Products
Co. , subsid.
Poster Grant Co., Inc.
Oulf Oil Corp. -
Carville, La.
Freeport, Tex.
Midland, Mich.
Odessa, Tex.

Baton, Rouge, La.
Welcome, La.
326.9 (720)
846.7 (1865)
158.9 (350)
124.8 (275)

440.4 (970)
256.5 (565)

-------
                                                                                -Table  A-l.  (Continued)
                              Ethyl
                              benzene
                              (oon't)
oo
VO
Ui
                              Ethyl
                              bromide
                              Ethyl
                              cellulose
Usage1


(See previous page)
Organic synthesis;
medicine (anesthetic)i
refrigerant; solvent;
grain & fruit
fumigant
Hot-melt adhesives  &
coatings for cables,
paper, textiles, eta.;
extrusion wire insula-
tion; protective coatt
Ings; pigments-grind*
ing.base; toughening
agent for plastics;
printing inks; molding
powders; proximity
fuses; vitamin prepara-
tion; casing for rocket
propellants; food &•
feed additive
Manufacturer (s)2' 3

Monsanto Co, - Monsanto
Polymers & Petrochems.
Co.
Phillips Petroleum Co.  -
Petrocheffi. & Supply Div.
Standard Oil Coj (Ind.)
Amqco Ghents. Corp.,
subsid.
Sun Oil Co, , Sun Oil
Co. of Pa., subsid. -\
Suntide Refining Co.,
subsid.
Tenneco Ino, -r Tenneco
Oil Co.,- div.
Union Carbide Corp. -
Chems. It Plastics Div.
Dow Chem. U.S.A.
Great Lakes Chem. Corp.
Northwest Indust., Inc. i-
Michigan Chem. Corp.,
subsid.

American Polymers, Inc.
Hercules Inc. - Coatings
4 Specialty Products
Dept.
Location!s)2'3

Chocolate Bayou,
Tex.
Texas City, Tex,
Phillips, Tex.

Texas City, Tex.,
                                                                                                      Corpus  Christ!,
                                                                                                      Tex.
                                                        Chalmette, La.

                                                        Seadrift, Tex.
Midland, Mich.
El Dorado, Ark.
St. Louis, Mich.
                                                        Patterson, N. J.
    1975
  capacity2
MM kg (MM ,l.b)

  667.4 (1170)
                                                                                                                                               Total ""*
                                                                                                                                               production
                                                                                                                                              MM kg (MM Ib)
                                                                                                                                           for year of.estimate
                                                                                                                                                 previous page)
                       «7.7 (106>



                       11.8 (26)

                      151 ,», (3«0)

                        Total *
                     3873.1 (853D
                                                                                                                                               2.9  (6.5)   -1973

-------
                                                                                 Table A-l.  (Continued)
                               Chemical
                               Ethyl
                               chloride
OO
                              Ethyl
                              chloro-
                              acetate
                              Ethyl
                              cyano-
                              acetate

                              Ethylene
Manufacture of tetra-
ethyl lead & ethyl-
cellulose ; anesthetic;
organic  synthesis,
alkylating agent;
refrigeration;; analy-
tical reagent; solvent
for phosphorus, sulfur,
fats, oils, resins &
waxes; insecticides
Solventi organic
synthesis; military
poison gas; vat
dyestuffs
Organic synthesis;
Pharmaceuticals;
dyes

Manufacture of ethyl
alcohol, ethylene
glycols, ethylene
dichloride, aluminum
alkyIs, vinyl chloride,
ethyl chloride, ethy-
lene oxide, ethylene
chlorohydrin, acetalde-
hyde, linear alcohols,
polystyrene, styrene,
polyethylene, poly-
vinyl chloride, SBR,
polyester resins trl-
chloroethylene, etc.;
refrigerant; cryogenic
research; agricultural
chemistry; welding &
cutting of metals;
anesthetic
                                                                          Manufacturer(5)2
                                                                                                      LOGatIpn(sI2 ' 3
                                                                                                   Total1**5
                                                                                 1975              production
                                                                               capacity2          MM kg  (MM Ib)
                                                                             MM kg (MM Ib)     for year of estimate
Dow Chem. U.S.A.
Ethyl Corp.
PPO. Indust., Inc. -
Chem. Div. - Indust.
Chem, Div.
Shell Chem. Co. -
Base Chems .
Stauffer Chem. Co. -
Plastics Div. -
Polymers West
Freeport , Tex.
Baton Rouge, La.
Pasadena, Tex.
Lake Charles, La.
Deer Park, Tex.
Carson, Calif.
31
95.3
68.1
51.5
38.6
50
(75) 299.7 (660.1) -1973
(210)
(150)
(120)
(85)
(110)
Total =
310.5 (750)
Dow Chem. U.S.A.
Kay-Fries Chems. Inc.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Kay-Fries Chems. Inc.
Lonza Inc.
Allied Chem. Corp. -
Union Texas Petroleum
Div.
Midland, Mich.
Stony Point, H. Y.
St. Louis, Mo.
Stony Point, N. Y.
Mapleton, 111.
Geismar, La.
Houston, Tex.
_
-
-
-
-
3^0.5
227
-


-

(750) 10,710.0 (23,590)-1971
(500)
                                                                          ARCO/Polymers,  Inc.  -
                                                                          Atlantic Richfield Co.  -
                                                                          ARCO Chem.  Co., div.

                                                                          Chemplex Co.
                                                                          Cities  Service  Co.,  Inc.
                                                                          North American  Petroleum
                                                                          Group
                                                                          Continental Oil Co.  -
                                                                          Conoco  Chems.

                                                                          Dow Chem. U.S.A.
                                                                          E.  I.  du Pont  de  Ne-
                                                                          mours  &  Co., Inc.  -
                                                                          Plastics Dept.
                                                                          Eastman  Kodak  Co.  -
                                                                          Eastman  Chem.  Products,
                                                                          Inc.,  subsid.  - Texas
                                                                          Eastman  Co., div.
Wilmington, Calif.


Clinton, Iowa
Lake Charles, La.



Westlake, La.

Bay City, Mich.
Freeport, Tex.
Plaquemine, La.
Orange, Tex.


Longview, Tex.
  15.1 (100)


 227   (500)'
 426.8 (910)


 295-1 (650)

  77.2 (170)
1135   resoo)
 499.lt (1100)
 371-5 (825)


 363.2 (800)

-------
                                                                                  Table  A-l.  (Continued)
                                Sthylene
                                 (cont'd)
                                               Usage1

                                               (See previous page)
00
El Paso Natural Gas Co. -
El Paso Products Co.,
subsid.

Exxon Corp.  - Exxon
Chem. Co., dlv. -
Exxon Chem.  Co. U.S.A.
The B. P. Goodrich Co. -
B. P. Goodrich Chem. Co.,
div.
Gulf Oil Corp. - Gulf
Oil Chems. Co., div. -
Petrochems.  Div.

Mobil Oil Corp. - Mobil
Chem. Co., div. -
Petrochems.  Div.

Monsanto Co. - Monsanto
Polymers 6 Petrochems.
Co.

National Distillers &
Chem. Corp.  - Chems.
Div. - U.S.  Indust.
Chems. Co.,  div.
Northern Natural Gas Go.
Northern Petrochem. Co.,
subsid., Polymers Div.
Olin Corp. - Designed
Products Div.
Petro Gas Producing Co.
Phillips Petroleum Co.

Puerto Rico Olefins Co.
Shell Chem.  Co. - Base
Chems.
Standard Oil Co. (Ind.) -
Amoco Chems. Corp.,
subsid.
SunOlin Chem. Co.

Location(s)2'3
Odessa, Tex.
Baton Rouge, La.
Baytown, Tex.


1975
capacity2
MM kg (MM Ib)
231.7
771.8
31.8
(517)
(1700)
(70)
Total4'5
production
MM kg (MM Ib)
for year of estimate
(See previous page)

                                                                                                        Calvert  City,  Ky.
                                                                                                        Cedar Bayou,  Tex.
                                                                                                        Port Arthur,  Tex.

                                                                                                        Beaumont,  Tex.
                                                                                                        Chocolate  Bayou,
                                                                                                        Texas  City,  Tex.


                                                                                                        Tuscola, 111.
                                                                                                     -  Morris,  111.


                                                                                                        Brandenburg,  Ky.

                                                                                                        Groves,  Tex.
                                                                                                        Sweeny,  Tex.
                                                                                                        Penuelas,  P.  R.

                                                                                                        Deer Park, Tex.
                                                                                                        Norco,  La.
                                                                                                        Chocolate  Bayou,



                                                                                                        Claymont,  Del.
                                                                                                                               158.9 (350)
190.7
522.1 (1150)
295.1 (650)
 68.1 (150)

158.9 (350)
363.2 (800)


 5^.5 (120)

  9   (20)
517.6 (1140)
45*   (1000)
681   (1500)
250   (550)
45*   (1000)


102   (225)

-------
                               Ethylene
                               (cont'd)
«£,
vo
00
Ethylene
carbonate
                               Ethylenp
                               chloro-
                               hydrln
                               Ethylene
                               diamlne
               Usage1


               (See pi*evious pafee)
                                                                                 Table A.-1.   (Continued)
                             Mamxfacturer(s)2> 3


                             Texaco  Inc.  -  Jefferson
                             Chem, Co.,  Inc.,  subsid.

                             Union Carbide  Corp.  *.
                             Chems.  S?  Plastics Div.
                                                                          Onion Carbide CaribeA,
                                                                          .Inc.,
Location(s)2'3
Port Neches, Tex.
Seadrift, Tex.
Jaft, La.
Texas City, Tex.
Tbrrance, Calif.
Whiting, In
-------
                                                                                 Table A-l.  (Continued)
                               Chemical
                               Ethylene
                               dibrcmide
 I
00
                               Ethylene
                               dichloride
Scavenger for lead in
gasoline; grain & fruit
f umigant; general sol-
vent ; waterproofing
preparations; organic
synthesis; insecticide;
medicine
Vinyl chloride; chlori-
nated solvent intermedi-
ate; coupling agent in
antiknock gasoline;
paint, varnish & finish
removers; metal degreas-
ing; soaps ft scouring
compounds; wetting &
penetrating agents;
organic synthesis; ore
flotation
                                                                          Manufacturer(s)2 * 3


                                                                          Dow Chem,  U.S.A.
Ethyl Corp. - Brine
Products Dlv.
Great Lakes Chem. Corp.

Northwest Indust.,
Inc. - Michigan Chem.
Corp., subsid.

PPG Indust., Inc. -
Chem. Div. - Houston
Chem. Co., div.

Allied Chem. Corp. -
Indust.  Chems. Div.

Continental Oil Co. -
Conoco Chems.

Diamond Shamrock Corp. -
Diamond Shamrock Chem.
Co., Electro Chems. Div,
Dow Chem. U.S.A.
                                                                          Ethyl Corp.

                                                                          The B. P. Goodrich Co.
                                                                          B. F. Goodrich Chem.
                                                                          Co., div.
                                                                          PPG Indust.
                                                                          Chem.
                                                                          Chem.
                                  Div.
                                  Div.
             Inc. -
           - Indust.
           - PPG
                                                                          PPG Indust..(Caribe)

                                                                          Shell Chem. Co. -
                                                                          Base Chems.
                                                                          Stauffer Chem. Co, -
                                                                          Plastics Div. - Poly-
                                                                          mers West
                                                        Locations)2'3
                            Magnolia, Ark.
                            Midland, Mich.

                            Magnolia, Ark.
                                                                                                      El Dorado, Ark.

                                                                                                      El Dorado, Ark.



                                                                                                      Beaumont, Tex.
Lake Charles, La.



Guayanilla, P. R.
Deer Park, Tex.
Norco, La.
Carson-, Calif.
                                                     1975
                                                   capacity2
                                                 MM kg (MM Ib)
Baton Rouge, La.
West lake, La.
Deer Park, Tex.
Freeport , Tex.
Oyster Creek, Tex.
Plaquemine, La.
Baton Rouge, La.
Pasadena, Tex.
Calvert City, Ky .
295.1
151
118
590.2
199.4
526.6
249. T
118
408.6
(650)
(1000)
(260)
(1300)
(1100)
(1160)
(550)
(260)
(900)
454   (1000)


379.1 (835)
544.8 (1200)
528.9 (1165)
136.2 (300)
                                          Total*'5
                                          production
                                         MM kg (MM  Ib)
                                      for year of estimate


                                        152.1  (335)   -1973
                                                                                                                                             3505   (7,720)-197*

-------
                                                                                        A-l.  (Continued)
                                Chemical


                                Ethylene
                                dichloride
                                (cont'd)
                               Ethylene
                               glyeol
 I
VD
O
O
Usage*


(See previous page)
Coolant & antifreeze;
asphalt-emulsion paints;
heat-transfer agent in
refrigeration & electron
tubes; low-pressure lami-
nates ; brake fluids;
glyeol diacetate; poly-
ester fibers & films;
low-freezing dynamite;
solvent; extractant for
various purposes; sol-
vent mixtures for cel-
lulose esters & ethers,
especially cellophane;
cosmetics £up to 53O;
lacquers; alkyd resins;
printing inks; wood
stains; adhesives;
leather dyeing; tex-
tile processing; tobac-
co; ingredient of
deicing fluid for
airport runways
Manufacturer(s)2 * 3


Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.

Union Carbide Corp. -
Chems. & Plastics Div.

Vulcan Materials Co. -
Chems. Div.
Allied Chem. Corp. -
Specialty Chems. Div.

BASF Wyandotte Corp. -
Indust. Chems. Group

Calcasleu Chem. Corp.

Celanese Corp. - Cela-
nese Chem. Co., div.

Dixie Chem. Co.

Dow Chem. U.S.A.


Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.

ICI United States Inc. -
Specialty Chems. Div.

Northern Natural Gas Co.,
Northern Petrochem. Co.,
subsid, - Polymers Div.

Olin Corp. - Designed
Products Div.

PPG Indust., Inc. -
Chem. Dlv. - Hous ton
Chem. Co., div. -
PPG Indust. (Caribe)

Shell Chem. Co. - Base
Chems.
Location(s)2*3


Port Nechea, Tex.


Taft, La.
Texas City, Tex.

Geismar, La.
Orange, Tex.


Geismar, La.


Lake Charles, La.

Clear Lake, Tex.


Bayport, Tex.

Preeport, Tex.
Plaquemine, La.

Longview, Tex.




New Castle, Del.


Morris, 111.



Brandenburg, Ky.


Beaumont, Tex.


Guayanilla, P. R.

Geismar, La.
                      Total4'5
    1975              production
  capacity2          MM kg (MM  Ib)
MM kg (MM Ib)    for year of estimate
   31.8 (70)


   68.1 (150)
   68.1 (150)

  109   (240)
    Total -
5,579-7 (12,290)

   18.2 (40)

   68.1 (150)

   81.7 (180)
  136.2 (300)
                                                                                                                               65.8 (145)
                                                                                                                              199.8 (440)
                                                                                                                               22.7 (50)
                                                                                                                                4.5 (10)


                                                                                                                              136.2 (300)



                                                                                                                               22.7


                                                                                                                               45.4 (100)


                                                                                                                              181.6 (400)

                                                                                                                               45.4 (100)
                                                                                              (See previous  page)
                                        1,398   (3,080)-1974

-------
                                                                                  Table  A-l.  (Continued)
 I
VO
O
                               Chemical

                               Ethylene
                               glycol
                               (cont'd)
Ethylene
glycol
diacetate
                               Ethylene
                               glycol
                               dlbutyl
                               ether

                               Ethylene
                               glycol
                               diethyl
                               ether

                               Ethylene
                               glycol
                               dimethyl
                               ether

                               Ethylene
                               glycol
                               monoace-
                               tate
               Usage1


                (See previous  page)
Solvent for cellulose
esters & ethers;
resins; lacquers;
printing inks; per-
fume fixative; non-
discoloring plastlci-
zer for ethyl &
benzyl cellulose

High-boiling inert
solvent; specialized
solvent & extraction
applications

Organic synthesis  (reac-
tion medium); solvent &
diluent for detergents
                Solvent
                Solvent  for nitro-
                cellulose,  cellulose
                acetate,  camphor
                            Manufacturers)z *3


                            Texaco Inc. - Jefferson
                            Chem. Co., Inc^,,subsid.

                            Union Camp Corp. -•
                            Chem. Products Div,

                            Union Carbide Corp.  -
                            Chems. & Plastics Div.

                            Union Carbide Caribe,
                            Inc., subsid.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.

Union Carbide Corp. -
Chems. & Plastics Div.
                                            Union  Carbide  Corp.  -
                                            Chems.  &  Plastics  Div.
                                            The  Ansul  Co.  -  Chem.
                                            Div.
Glyco Chems., Inc.
Scher Brothers, Inc.
                            Location(s)
                                                                                                                  2*3
                            Port Neches,  Tex.


                            Dover,  Ohio


                            Seadrift,  Tex.
                            Taft, La.

                            Penuelas,  P.  R.
                                                                                                       Klngsport,  Tenn.
                                                                                                       Institute  &  South
                                                                                                       Charleston,  W.  Va.
                            Institute & South
                            Charleston, W.  Va.
                                                                       Marinefcte, Wise.
                                                        Williamsport, Pa.

                                                        Clifton, N. J.
                                                     1975
                                                   capacity2
                                                 MM kg (MM Ib)
     Total1*'5
     production
    MM kg (MM Ib)
for year of g_stlma_te_
                                                   163.4 (360)     (See previous page)
                                                                                                                              395    (870)
                                                                                                                              136.2  (300)
                                                                                                                              286    (630)
                                                                                                                                Total  -
                                                                                                                            2-009

-------
                                                                                   Table A-l.   (Continued)
                                                                            Manufacturer(s)2 *3
                                                                                                        Location(s)2>
                                                                                                1975
                                                                                              capacity2
                                                                                            MM kg (MM Ib)
                                                                      Total4'5
                                                                      production
                                                                     MM kg  (MM Ib)
                                                                  for year of estimate
 I
VD
O
Ethylene       Solvent for nitrocellu-
glycol         lose resins; spray lac-
mono-          quers; quick-drying
butyl          lacquers; varnishes;
ether          enamels; dry-cleaning
               compounds; varnish
               removers; textile
               (preventing spotting in
               printing or dyeing);
               mutual solvent for
               "soluble" mineral oils
               to hold soap in solution
               & to improve the emulsi-
               fying properties
                                Ethylene        High-boiling solvent for
                                glycol          nitrocellulose lacquers,
                                mono-           epoxy resins, multicolor
                                butyl           lacquers;  film coalescing
                                ether           aid for polyvinyl acetate
                                acetate         latex

                                Ethylene        Solvent for  nitrocellulose;
                                glycol          natural &  synthetic  resins;
                                mono-           mutual  solvent for formula-
                                ethyl           tion of soluble oils;  lac-
                                ether           quers & lacquer thlnners;
                                                dyeing  & printing tex-
                                                tiles;  varnish removersj
                                                cleaning solutions;
                                                leather; anti-icing  addi-
                                                tive for avaltion fuels.

                                Sthylene        Solvent for  nitrocellu-
                                glycol          lose; oils & resins;  re-
                                mono-           tards "blushing"  in  lac-
                                ethyl           quers;  varnish removers;
                                ether           wood stains;  textiles;
                                acetate         leather
Dow Chem. U.S.A.

Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Olin Corp. - Designed
Products Div.
Shell Chem. Co. - Base
Chems.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.

Eastman Kodak Co. - East-
man Chem. Products, Inc.,
subsid. - Tenn.
Eastman Co., div.

Union Carbide Corp. -
Chems. & Plastics Div.

Dow Chem. U.S.A.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.

Olin Corp. - Designed
Products Div.
                                           Shell Chem. Co. - Base
                                           Chems.
                                           Texaco  Inc. - Jefferson
                                           Chem. Co., Inc., subsid.
                                           Union Carbide Corp. -
                                           Chems.  & Plastics Div.
                                                                            Eastman  Kodak  Co.  -
                                                                            Eastman  Chem.  Products,
                                                                            Inc.,  subsid.  -  Texas
                                                                            Eastman  Co., div.
                                                                            Olin Corp.  - Designed
                                                                            Products Div.
                                                                            Union Carbide  Corp.  -
                                                                            Chems. & Plastics  Div.
                                                                                                        Midland, Mioh.
                                                                                                        Longview, Tex.
Brandenburg, Ky,


Geismar, La.


Port Neches, Tex.


Institute & South
Charleston, W. Va.

Kingsport, Tenn.
                                                                       Institute & South
                                                                       Charleston, W.  Va.

                                                                       Midland, Mich.

                                                                       Longview, Tex.
Brandenburg, Ky.




Oeismar,  La.


Port Neches, Tex.


Institute & South
Charleston, W.  Va.
Seadrlft, Tex.
Longview, Tex.



Brandenburg, Ky.

Institute & South
Charleston, W.  Va.
                                                                                                                                                     (120)  -1972
                                         77.2  (170)   -1972

-------
                                                                                 Table A-l.  (Continued)
 I
\D
O
                               Chemical

                               Ethylene
                               glycol
                               mono-
                               he xyl
                               ether

                               Ethylene
                               glycol
                               mono-
                               ethyl
                               ether
                               Ethylene
                               glycol
                               mono-
                               methyl
                               ether
                               acetate

                               Ethylene
                               glycol
                               mono-
                               octyl
                               ether
Usage1

High-boiling solvent
Solvent for nitro-
cellulose, cellulose
acetate, alcohol-
soluble dyes, natural
& synthetic resins;
solvent mixtures;
lacquers; enamels;
varnishes; leather;
perfume fixative;
wood stains; sealing
moixture-proof cello-
phane; jet fuel deicing
additive
Solvent for nitrocellu-
lose, cellulose acetate,
various gums, resins,
waxes, oils; textile
printing; photographic
film; lacquers; dopes

Solvent for cellulose
esters;
plasticiser
                                                                          Manufacturer(s)2 *3
Dow Chem. U.S.A.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.

Olin Corp. - Designed
Products Div,
Pierce Chem. Co.

PPG Indust., Inc. -
Chem. Div. - Houston
Chem. Co., div.

Shell Chem. Co.
Base Chems.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div,
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn..
Eastman Co., div.
Union Carbide Corp. -
Chems. & Plastics Div.
                                                        LocationCs)2'3
Midland, Mich.
Longview, Tex.
Brandenburg, Ky.

Roekford, 111.
Beaumont, Tex.



Geismar, La.


Port Neches, Tex.

Institute & South
Charleston, W. Va.
Taft, La.

Kingsport, Tenn.
Institute & South
Charleston, W. Va.
                                                     1975
                                                   capacity2
                                                 MM kg (MM Ib)
                                           Total1**5
                                           production
                                          MM kg (MM Ib)
                                      for year of e_stJLmatji
                                                                                                        (95) -1972

-------
                                                                                 Table  A-l.   (Continued)
VO
O
                               Chemical

                              Ethylene
                              glycol
                              mono-
                              phenyl
                              ether
                              Ethylene
                              glycol
                              mono-
                              propyl
                              ether

                              Ethylene
                              oxide
Solvent for cellulose
acetate, dyes inks, re-
sins; perfume & soap
fixative; bacterial
agent; organic synthesis
of plasticizers, germi-
cides, perfume materials
& Pharmaceuticals
Manufacture of ethy-
lene glycol & higher
glycols; polyester fi-
ber & film; surfactants;
aerylonitrile; ethanol-
amines; petroleum demulsi-
fier; fumigant; rocket
propellant
                             Manufacturer(s)2'3

                            Dow Chem. U.S.A.
                            Olin Corp. - Designed
                            Products Inc.
Allied Chem. Corp. -
Specialty Chems. Div.
BASF Wyandotte Corp. -
Indust. Chems. Group
Calcasieu Chem. Corp.
Celanese Corp. -
Celanese Chem. Co., div.
Dow Chem. U.S.A.

Eastman Kodak Co.  -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.
Northern Natural Gas -
Co - Northern Petrochem.
Co., subsid. - Poly-
mers Div.
Olin Corp. - Designed
Products Div.
PPG Indust., Inc.  -
Chem. Div. - Houston
Chem. Co., div.
PPG Indust. (Caribe)
Shell Chem. Co. -
Base Chems.
SunOlin Chem. Co.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Union Carbide Caribe,
Inc.» subsid.
                             Locations)2'3

                            Midland, Mich.
                                                        Brandenburg, Ky.
                                                                                                     Longvlew, Tex.



                                                                                                     Morris, 111.



                                                                                                     Brandenburg, Ky.

                                                                                                     Beaumont, Tex.


                                                                                                     Guayanilla, P. R
                                                                                                     Geismar, La.

                                                                                                     Claymont, Del.
                                                                                                     Port Heches, Tex.
                                                                                                     Seadrift, Tex.
                                                                                                     Taft, La.
                                                                                                     Penuelas, P. R.
    1975
  capacity2
MM kg (MM Ib)
Orange , Tex .
Geismar, La.
Lake Charles, La.
Clear Lake, Tex.
Preeport , Tex.
Plaquemine, La.
22.7 (50)
100 (220)
74.9 (165)
136.2 (300)
90.8 (200)
181.6 (400)
                                                                                18.2 (40)



                                                                                90.8 (200)



                                                                                50   (110)

                                                                                38.6 (85)


                                                                               136.2 (300)
                                                                               136.2 (300)

                                                                                1)3.1 (95)
                                                                               227   (500)

                                                                               367.7 (810)
                                                                               201.3 (150)
                                                                               277   (610)

                                                                                 Total  =
                                                                             2,195-1 (1,835)
     Total1"5
     production
    MM kg (MM Ib)
for year of estimate
                                                                                                1,798  (3,960)  -1971

-------
                               Chemical
                                                                                 Table A-l.   (Continued)
                                                                           Mariufacturer(s) 2* 3
                                                                       Location(s)2'3
                                                                                 1975
                                                                               capacity2
                                                                             MM kg (MM ID)
                                           Total1*'5
                                           production
                                          MM kg (MM Ib)
                                      for^yearof estimate
                               Ethyl
                               ether
O
Ui
                               2-
                               Ethyl
                               hexanol
               Manufacture of ethylene
               & other chemical syn-
               thesis; industrial sol-
               vent (smokeless powder);
               analytical chemistry;
               anesthetic; perfumery;
               extractant; alcohol
               denaturant
                               Ethyl
                               ortho-
                               formate

                               Ethyl
                               oxalate
Ethyl
sodium
oxalacetate
               Plasticizer for PVC
               resins; defearning agent;
               wetting agent; organic
               synthesis; solvent
               mixtures for nitrocel-
               lulose, paints, lac-
               quers , baking finishes;
               penetrant for merceriz-
               ing cotton; textile
               finishing compounds;
               plasticizers; inks;
               rubber; paper; lubri-
               cants; photography;
               dry cleaning
                                               Intermediate
Solvent for cellulose
& ethers, many natural
& synthetic resins; radio
tube cathode fixing lac-
quers; dye intermediate;
Pharmaceuticals; perfume
preparations; organic
synthesis

dyes; synthesis
                            Hercules Inc.  -
                            Coatings & Specialty
                            Products Dept.

                            Mallinckrodt,  Inc. -
                            Medicinal Div.

                            National Distillers &
                            Chem. Corp. -  Chenis.
                            Div.
                            Publicker Indust., Inc.

                            Squibb Corp. - E.  R.
                            Squibb & Sons,  Inc.,
                            subsid. - U.S.  Pharma-
                            ceutical Co. -
                            Operations
                            Union Carbide  Corp. -
                            Chems. & Plastics  Div.

                            Dow Badische Co.
                            Eastman Kodak  Co.  -
                            Eastman Chem.  Products,
                            Inc., subsid.  - Texas
                            Eastman Co., div.
                            W. R. Grace &  Co.  -
                            Hatco Group -  Hatco
                            Chem. Div.
                            Oxochem Enterprise
                            Shell Chem. Co. -
                            Base Chems.
                            Union Carbide  Corp. -
                            Chems. & Plastics  Div.
                            Union Carbide  Caribe,
                            Inc., subsid.

                            Kay-Fries Cherns.,  Inc .
                                           PMC Corp.
                                           Chem. Group - Indust.
                                           Chem. Div.
                                                                           PMC  Corp.
                                                                           Chem.  Group  -  indust.
                                                                           Chem.  Div.
                                                        Hopewell, Va.
                                                                                               1   (2)
                                                                                                27.2  (60)  -197*1
St. Louis, Mo.
Tuscola, 111.
Philadelphia, Pa.
New Brunswick,
1
18.2
4.5
1
(2)
(10)
(10)
(2)
Institute It South
Charleston, W. Va.
Texas City, Texas
Freeport, Tex.
Longview, Tex.
Fords, N. J.


Penuelas, P. R.
Deer Park, Tex.

Seadrift, Tex.


Penuelas, P. R.


Stony Point, N. Y.



Baltimore, Md.
                                                                                               6.8 (15)
                                                                                               Total =
                                                                                              32.2 (71)
                                                                                                      Baltimore, Md.

-------
                                                                                 Table A-1-  (Continued)
                               Chemical


                               Formalde-
                               hyde
                               (oontld)
 (See previous page)
 I
vo
O
                               Porma-
                               mide
Solvent, softener,
intermediate in or-
ganic synthesis
                                                                          Manufacturer(s)2 * 3
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. - Hooker
Chems. & Plastics Corp.,
subsid, - Durez Dlv.

Heichhold Chems., Inc.
                            Rohm & Haas Co.
                            Skelly Oil Co. -
                            Chembond Corp.,
                            subsid.
                            Tenneco Inc. - Tenneco
                            Chems., Inc. - Organics
                            & Polymers Dlv.
                            Union Carbide Corp. -
                            Chems. & Plastics Div.
                            Univar Corp. - Pacific
                            Resins & Chems., Inc.,
                            subsid.
                            Wright Chera. Corp.
E. I., du Pont de Ne-
mours & Co., Inc. -
Biochems. Dept.
Location(s)2 ' 3
North Tonawanda,
N. Y.
Hampton, S. C.
Houston, Tex,
Kansas City, Kans.
Malvern, Ark.
Moncure, N. C.
Tacoma, Wash.
Tuscaloosa, Ala.
White City, Ore.
Philadelphia, Pa.
Springfield, Ore.
Winnfield, La.
Fords, N. J.
Garfield, N. J.
Bound Brook, N. J.
Eugene , Ore .
Acme, N. C.
1975
capacity2
MM kg (MM Ib)
61.3
22.7
51.5
22.7
50
51.5
21.8
32.7
113.5
11.3
31.8
31.8
81
45. «
51.5
13.1
36.3
(135)
(50)
(120)
(50)
(110)
(120)
(18)
(72)
(250)
(25)
(70)
(70)
(185)
(100)
(120)
(95)
(80)
Total -
3,808.0 (8,389)
                                                                                                      Belle, W. Va.

-------
                                                                                   Table  A-l.   (Continued)
                                Chemical
                                Formalde-
                                hyde
VO
o
Urea & Melamine resins;
phenolic resins; ethylene
glyeol; pentaerythritol;
hexamethylenetetramine;
fertilizer; acetals; other
chemicals; dyes; medicine
(disinfectant, germicide);
embalming fluids; preser-
vative; hardening agent;
reducing agent, as in
recovery of gold & sil-
ver; corrosion inhibi-
tor in oil wells; durable-
press treatment of tex-
tile fabrics; possible
condensation to sugars
& other carbohydrates
for food use (ex-
perimental)
Manufacturer (s)2 J 3


Allied Chem. Corp. -
Specialty Chems. Div.

Borden Inc.  - Borden
Chem. Div. - Adhesives
& Chems., Div., East
                                                                            Adhesives  & Chems.,  Div.,
                                                                            West
Celanese Corp.  - Cela-
nese Chem. Co., div.


Commercial Solvents
Corp,

E. I. du Pont de Ne-
mours & Co., Inc. -
Biochems. Dept.
Indust. Chems.  Dept.
                                                                            GAP Corp.  - Chem.  Div.

                                                                            Georgia-Pacific Corp. -
                                                                            Chem.  Div.
                                                                            Gulf Oil Corp,  - Gulf
                                                                            Oil Chems.  Co., div.  -
                                                                            Indust.  & Specialty
                                                                            Chems.  Div.

                                                                            Hercules Inc.  -
                                                                            Synthetics  Dept.
                                                                            Monsanto Co.  - Monsanto
                                                                            Polymers &  Petrochems,
                                                                            Co.
1975
capacity2
location(s)2'3
South Point, Ohio
Demopolis , Ala.
Diboll, Tex.
Fayetteville, N. C.
Louisville, Ky.
Sheboygan, Wise.
Fremont, Calif.
Kent, Wash.
La Grande , Ore .
Missoula, Mont.
Springfield, Ore.
Bishop, Tex.
Newark, N. J.
Rock Hill, S. C.
Seiple, Pa.
Belle, W. Va.
La Porte, Tex.
Healing Springs,
N. C.
Linden, N. J.
Toledo, Ohio
Calvert City, Ky .
Albany, Ore.
Columbus, Ohio
Coos Bay, Ore.
Crossett, Ark.
Taylorsville, Miss.
Vienna, Ga.
Vicksburg, Miss.
Louisiana, Mo.
Wilmington, N. C.
Addyston, Ohio
Chocolate Bayou,
Tex.
Eugene , Ore .
Springfield, Mass.
MM kg (MM Ib)
140.7
45.4
36.3
106.7
36.3
59
102.1
36.3
29.5
40.9
109
681
53.1
53.1
29.5
222.5
136.2
90.8

68.1
118
45.1
54.5
54.5
45.4
72.6
54.5
45.4
20.4
77.2
45.4
45.4
88.5

45.4
133.9
(310)
(100)
(80)
(235)
(80)
(130)
(225)
(80)
(65)
(90)
(240)
(1500)
(117)
(117)
(65)
(490)
(300)
(200)

(150)
(260)
(100)
(120)
(120)
(100)
(160)
(130)
(100)
(45)
(170)
(100)
(100)
(195)

(100)
(295)
                                                                                                   Total*'5
                                                                                                   production
                                                                                                  MM kg (MM  Ib)
                                                                                              for year of estimate


                                                                                                976 (2,150)   -1971

-------
                                                                                  Table A-l.  (Continued)
                                Chemical
                               Formic
                               acid
o
00
                               Pumaric
                               acid
Dyeing & finishing of
textiles & paper; leather
    treatment; chemi-
cals  (formates, oxalic
acid, organic esters);
manufacture of fumigants,
insecticides, refriger-
ants ; solvents for
perfumes, lacquers;
electroplating; medi-
cine; brewing (anti-
septic) ; silvering
glass; cellulose for-
mate; natural latex
coagulant; ore flota-
tion; vinyl resin
plasticizers; animal
feed additive

Modifier for polyester,
alkyd, & phenolic res-
ins; paper-size resins;
plasticizers; rosin es-
ters & adducts; upgrading
natural drying oils (es-
pecially tall oil) to
improve drying character-
istics; in foods, to re-
place citric & tartaric
acids as acidulant &
flavoring agent (PDA
approved); mordant;
organic synthesis
Manufacturer(s)2 J 3


Celanese Corp. -
Celanese Chem. Co.,
div.

Middleboro Indust.,
Inc.
Sonoco Products Co.
Union Carbide Corp. -
Chems. & Plastics Dlv.
Allied Chem. Corp. -
Specialty Chems. Div.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsld. - Hooker
Chem. Corp., subsld. -
Hooker Chems. & Plastics
Corp., subsid, - Puerto
Rico Chem. Co., subsid.

Petro-Tex Chem. Corp. -
Fetro-Tex Chem. Co.,
Subsid.
Pfiaer Inc. - Chems. Div,
Tenneeo Inc. - Tenneco
Chems., Inc. - Organics
5 Polymers Div.
U.S. Steel Corp. - USS
Chems., div.
Location(s)2*3

Pampa, Tex.
                                                                                                       Middleboro,
                                                                                                       Mass.
                                                                                                       Hartsville,  S.  C.
                                                                                                       Brownsville,  Tex.
Moundsville, W. Va.

St. Louis, Mo.


Areclbo, P. R.
                                                                                                       Houston,  Tex.



                                                                                                       Terre  Haute, Ind.
                                                                                                       Garfield,  N. J.


                                                                                                       Neville Island,  Pa.
    1975
  capacity2
MM kg (MM Ib)


    4.5 (10)
                         3-2 (7)


                          .5 CD
                        22.7 (50)

                         Total  =
                        30.9 (68)
    6.8 (15)

   13.6 (30)
                                                                                                   Total1*'5-'
                                                                                                   production
                                                                                                  MM kg (MM Ib)
                                                                                              fgjr_yejir of estimate.
19-1 (42)    -1974
                         3.6 (8)


                        11.3 (25)
                         4,5 (10)


                         4.5 (10)

                         Total  •
                        Ml*.5 (98)

-------
                             Chemical
                                                                                Table A-l.   (Continued)
                                                                         Manufacturer^)2'3
                                                                       Location(s)2*3
                                                     1975
                                                   capacity2
                                                 MM kg (MM Ib)
                                                                                                                                               Total1"5
                                                                                                                                               production
                                                                                                                                              MM kg  (MM  Ib)
                                                                                                                                           for year of estimate
 I
vo
O
Glycer-        Biochemical research;
aide-          intermediate; nutrition;
hyde           preparation of polyes-
               ters, adhesives; cellu-
               lose modifier; leather
               tanning

Glycerol       Alkyd resins; eello-
(natural       phane; explosives;
&              ester gums; p-harmaceu-
synthetic)     ticals; perfumery;
               plastieizer for
               regenerated cellulose;
               cosmetics; foodstuffs;
               conditioning tobacco;
               liqueurs; solvent;
               printer's ink rolls;
               polyurethane poly-
               ols; emulsifying
               agent; rubber stamp
               &  copying inks; binder
               for cements & mixes;
               paper coatings  &
               finishes; special
               soaps; lubricant  &
               softener; bacteriostat;
               penetrant; hydraulic
               flui d; h ume c t ant
Natural:
Acme-Hardesty Co., Inc.
Alba Mfg. Co.

Ashland Oil, Inc. -
Ashland Chem. Co., div.,
Chem. Products Div.
Chicago Sanitary Pro-
ducts Co.

Colgate-Palmolive Co,
                                                                         Darling &. Co.
                                                                         Dow Chem. Co.

                                                                         Emery Indust., Inc.  -
                                                                         Western Operations


                                                                         The Greyhound  Corp.  -
                                                                         Armour & Co.,  subsid. -
                                                                         Armour-Dial, Inc., div.
                                                                         The Andrew Jergens Co.
                                                                         H, Kohnstamm & Co.,  Inc.

                                                                         Kraftco Corp.  -
                                                                         Humko Sheffield Chem.
                                                                         Lever Brothers Co.
                                                                         Millmaster Onyx Corp.  -
                                                                         A. Gross & Co., div.
                                                                         Murro Chem. Co.

                                                                         Pacific Soap Co.
                                                                         Pioneer Soap Co., Inc.
Jenkintown, Pa.

Aurora, 111.

Hammond, Ind.
Mapleton, 111.

Chicago, 111.


Berkeley, Calif.
Jeffersonville, Ind.
Jersey City, N. J.
Kansas City, Kans.
Chicago, 111.

Anchorage, Alas.

Cincinnati, Ohio
Santa Fe Springs,
Calif.
Montgomery, 111.
                                                                        Cincinnati, Ohio

                                                                        Clearing,  111.
                                                                        Memphis, Tenn.


                                                                        Baltimore, Md.
                                                                        Edgewater, N. J.
                                                                        Hammond, Ind.
                                                                        Los Angeles, Calif.
                                                                        St. Louis, Mo.

                                                                        Newark, N. J.

                                                                        Portsmouth, Va.
                                                                        Vernon, Calif.

                                                                        San Francisco,
                                                                        Calif.
                                                                                                                                             158.1  (3^8.2) -19&9

-------
                                                                               Table A-l.  (Continued)
                              Chemical


                              Glycerol
                              (contTd)
Usage1


(See previous page)
 I
vO
H1
O
                             Glycerol
                             trlfpoly-
                             oxypropy-
                             lene)
                             ether
Manufacturer (s ) 2 » 3
The Procter & Gamble Co.
The Hewitt Soap Co.,
Inc. , subsid.
Purex Corp., Ltd.
PVO Internat'l. Inc.
Safeway Stores, Inc. -
Newport Products Co.,
dlv.
Stepan Chem. Co. -
Surfactant Dept,
Union Camp Corp, -
Chem. Products Div.
Woburn Chem. Corp.
Synthetic:
Dow Chem. U.S.A.
PMC Corp. - Chem,
Group - Indust. Chem.
Div.
Shell Chem. Co. -
Base Chems .

ICI U.S. Inc. -
Specialty Chems. Div.
Olin Corp. - Designed
Products Div.
Pelron Corp.
Union Carbide Corp. -
Chems. & Plastics Div.
Witco Chem. Corp. -
Organics Div.
Location(s)2'3
Baltimore, Md.
Chicago, 111.
Dallas, Tex.
Ivorydale, Ohio
Kansas City, Kans.
Long Beach, Calif.
Port Ivory, N. Y.
Quincy , Mass.
Sacramento, Calif.
St. Louis, Mo.
Dayton, Ohio
Bristol, Pa.
Omaha, Neb.
Philadelphia, Pa.
Boonton, N, J.
Oakland, Calif.
Anaheim, Calif.
Elwood, 111.
Pleldsboro, N. J.
Dover, Ohio
Kearny, N. J.
Preeport, Tex.
Bayport, Tex.
Deer Park, Tex,
Norco, La.

New Castle, Del,
Brandenburg, Ky .
Lyons, 111.
Institute & South
Charleston, W. Va.
Clearing , 111.
Total4'5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
(See previous page)
-
~
-
~
~
-
-
50 (110)
18.2 (4o)
51.5 (120)
22.7 (50)
Synthetic Total =
145-.3 (320)
-
-
-
-
-

-------
                                                  Table  Ar-1.  (Continued)
Chemical

Glycine
Glyoxal
Guanidine

Heptene
Organic synthesis;
medicine; biochemical
research; buffering
agent; chicken feed
additive; reduces
bitter taste of
saccharin

Mfg. of te-xtile resins
for permanent press
process; dimensional
stabilization of rayon
& other fibers; inaolu—
bilizing agent for com-
pounds containing poly-
hydroxyl groups (poly-
vinyl alcohol, starch,
& celluloslc materialsH
insolubilizing of pro-
teins (casein, gelatin
& animal glue); embalm-
ing fluids; leather
tanning; paper coatings
with hydroxyethylcellu-
lose; reducing agent in
dyeing textiles

Organic synthesis

Organic synthesis; plant
growth retardant; lubri-
cant additive; catalyst
surfactants
Manufacturer(s)2*3

Chattem Drug & Chem.
Co. - Chattem Chems.
Div.
                                           American CyanatnidT Co. •
                                           Organic Chems, Div. —
                                           (Captive Use)

                                           Union  Carbide Corp. -
                                           Chems. & Plastics Div,

                                           Witco  Chem.  Corp. -
                                           0-rganics Div_
Location(s)2*3

Chattanooga* Tenn.
                            Charlotte, N. C.



                            Taft, La.


                            Clearing, 111.
                                                                                                1975
                                                                                              capacity2
                                                                                            MM kg (MM lb)_
                                                                                                   Total1**5
                                                                                                   production
                                                                                                  MM kg (MM Ib)
                                                                                              for year of ._es_tiroatg
American Petrofina Inc.
Cosden Oil & Chem. Co.,
subsid.
Getty Oil Co.
The Humphrey Chem. Co.
Phillips Petroleum Co. -
Petrochem^ It Supply Div.
Standard Oil Co. (Ind.) -
Amoco Chems» Corp.,
subsid.
Big Spring, Tex.


Delaware City, Del.
North Haven, Conn.
Phillips, Tex.

Yorktown, Va.
                                                                    20*1   (450)    -1967

-------
                                                                                   Table A-l.  (Continued)
                                 Chemical
                                                                            Manufacturer(s)2'3
                                                        Location (jO2 *
                                                     1975
                                                   capacity2
                                                 MM kg (MM Ib)
                                          Total1**5
                                          production
                                          MM kg  (MM Ib)
                                      for  year_ of estimate
                                 Hexa-
                                 chloro-
                                 ethane
                                 Hexa-
                                 decyl
                                 alcohol
 r
^o
^_i
to
                                 Hexa-
                                 methy-
                                 lene
                                 glyccl

                                 Hexa-
                                 methy-
                                 lene
                                 tetra-
                                 mine
Organic synthesis; re-
tarding agent in fer-
mentation; camphor sub-
stitute in nitrocellu-
lose; rubber accelera-
tor; pyrotechnics &
smoke devices; solvent;
explosives; medicine

Perfumery; emulsifier;
emollient; foam stabili-
zer in detergent; face
creams; lotions, lip-
sticks; toilet prepara-
tions; chemical inter-
mediate; detergents;
Pharmaceuticals; cosme-
tics; base for making
sulfonated fatty alco-
hols ; to retard evapor-
ation of water, when
spread as a film on
reservoirs, or sprayed
on growing plants

Solvent; resin inter-
mediate ; coupling
agent
Catalyst in phenol-
formaldehyde & resorcinol-
formaldehyde resins; in-
gredient in rubber-to-
textile adhesives; pro-
tein modifier; organic
synthesis; pharmaceuti-
cals; ingredient of high
explosive cyclonite
(q.v.); fuel tablets
                                                                            Hummel Chem. Co., Inc.
Ashland Oil, Inc. -
Ashland Chem. Co.,
dlv. - Chem. Products
Div.

Continental Oil Co. -
Conoco Chems.

Glvaudan Corp. -
Chems. Div,

The Procter & Gamble
Co.

Robinson-Wagner Co.,
Inc.
Guardian Chem. Corp.
Eastern Chem. Div.
Borden Inc.  - Borden
Chem. Div. - Adhesives
& Chems. Div. - East

W. R. Grace  & Co. -
Indust, Chems. Group -
Dewey & Almy Chem. Div.

Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. - Hooker
Chems. & Plastics Corp.
subsid. - Durez Div.

Plastics Engineering Co,

Tenneco Inc- - Tenneco
Chems., Inc. - Organics
Polymers Div.
Union Carbide Corp. -
Chems. & Plastics Dlv,

Wright Chem. Corp,
                            South Plainfield,
                            N. J.
Mapleton, 111.




Westlake, La.


Clifton, N. J.


Ivorydale, Ohio
Sacramento, Calif.

Mamaroneck, N. Y.



Hauppauge, N. ¥.




Demopolis, Ala.
Fayettevllle, N. C.


Nashua, N. H.



North Tonawanda,
                                                                                                        Sheboygan,  Wise.

                                                                                                        Fords, N.  J.



                                                                                                        Bound Brook,  N, J.


                                                                                                        Acme, N.  C.
                                                                                                                                                2.72  (6.0)  «1971
 5.4 (12)       ^5.7 (100.7)  -1973
10.9 (24)
                                                                                                                                12.7 (28)
                                                                                 3.6

                                                                                10   (22)
                                                                                                                                14.1  (3D
                                                                                                                                 Total  •
                                                                                                                                61.3  (135)

-------
                             Chemical
                                                                                Table  A-l.   (Continued)
                                                                         Manufacturer(s)2' 3
                            Location(s)2
    1975
  capacity2
MM kg (MM Ib)
                                                                                                   Total'*'5'
                                                                                                   production
                                                                                                  MM kg (MM Ib)
                                                                                              for year of estimate
                             Hydrogen
                             cyanide
ON

VO
M
U>
                             Hydro-
                             quinone
                             m-
                             hydroxy-
                             benzoic
                             acid
Manufacture of acrylo-
nitrile, acrylates,
adiponitrile, cyanide
salts, dyes; fumigant
for orchards & tree
crops; chelates
Photographic deve-
loper (except color
film); dye intermediate;
medicine; antioxidant;
inhibitor; stabilizer
in paints & varnishes,
motor fuels & oils;
antioxidant for fats
& oils; inhibitor of
polymerization

Intermediate for plas-
ticizers; resins; light
stabilizers; petroleum;
additives; pharmaceuti-
cals; intermediates;
synthetic drugs
American Cyanamid
Co. - Indust. Chems. &
Plastics Div.

Dow Chem. U.S.A.
E. I. du Pont de Ne-
mours & Co., Inc. -
Elastomer Chems, Dept.
Indust. Chems. Dept, >
Plastics Dept.

Hercules Inc . - Coat-
ings & Specialty Products
Dept.

Monsanto Co. - Monsanto
Polymers & Petrochems.
Co,

Rohm & Haas Co. - Rohm
& Haas Texas Inc.,
subsid.

The Standard Oil Co.
(Ohio) - Vistron Corp.,
subsid, - Chems. Dept.
Carus Corp. - Carus
Chem. Co. ., div.

Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.

The Goodyear Tire &
Rubber Co, - Chem. Div.
Mallinckrodt, Inc. -
Washine Div.

Tenneco Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Div.
                            New Orleans, La.
                                                                                                                             12.2  (27)
                                                                                                                                            138.1  (304.3) -1973
Freeport, Tex
Beaumont, Tex
Laplace, La.

Memphis, Tenn.
Victoria, Tex.

Glens Pall
                                                                                                                  N.  1.
                                                        Chocolate Bayou, Tex.
                                                        Texas City, Tex.


                                                        Deer Park, Tex.
Lima, Ohio





La Sails, 111.


Kingsport, Tenn.




Bayport, Tex.



Lodi, N. J.


Garfield, H.  J.
                                                                                                                              2.3
                                                                                                                             13.6
                                                                                                                              9.1
        (5)
        (30)
        (20)
                                                                                                                             57.6  (127)
                                                                                                                             18.2  (40)
                                                                                                                              1.1  (2.4)
   25.4 (56)
   34.1 (75)

   81.7 (180)
   13.6 (30)

    Total =
  269   (592.4)

    3-5 (7.7)

    7-3 (16.0)
                                                                                                                             2.7  (6.0)

                                                                                                                                Total -
                                                                                                                             13.5 (29.7)

-------
                                                                                    Table A-"!,  (continued)
ON

VD
                                  Chemical


                                  Isoamyl
                                  alcohol
                                  Isoamyl
                                  chloride
                                  Isoamylene
                                  Isobutanol
                                  Isobutyl
                                  acetate
                                  Isobutyral-
                                  dehyde
Photographic chemicals;
organic synthesis; phar-
maceutical products;
medicine; solvent; deter-
mination of fat in mi!4c;
microscopy; flavoring

(Mixtures, us-ually also
containing normal amyl
chloride); solvent
(nitrocellulose, var-
nishes, lacquers, neo-
prene); rotogravure
inks? soil fumigation;
organic compounds

Organic synthesis;
dental & surgical
anesthetic; high octane
fuel manufacture

Organic synthesis; la-
tent solvent in paints &
lacquers; intermediate
for amino coating re-
sins; substitute for n-
butyl alcohol, paint re-
movers ; fluororaetrlc
determinations.; liquid
c hromat ography

Solvent for nitrocellu-
lose in thlnners, seal-
ants, & topcoat lacquers;
perfumery; flavoring
agent
Intermediate for rubber
antioxidants & accelera-
tors, for neopentyl
glycol; organic
synthesis
                            Manufacturer(s)2*3


                            Publicker Indust. Inc..
                                                                             Union Carbide Corp.. -
                                                                             Chems. & Plastics Div.
Phillips Petroleum Co.
Petrochem & Supply Div.
                                                                             Bow Badische Co.

                                                                             W. R. £race & Co. -
                                                                             Hatco Group - Hatco
                                                                             Chem. Div.

                                                                             Oxochem Enterprise
Eastman Kodak Co. -
Eastman Chem. Products
Inc., subsid. - Tenn.
Eastman Co., div.

Fritzche Dodge &
Olcott Inc.

Union Carbide Corp. -
Chems. & Plastics Div.
Celanese Corp. -
Celanese Chem, Co., div.

Dow Badische Co.

Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Texas
Eastman Co., div.

Oxochem Enterprise

Union Carbide Corp. -
Chems. & Plastics Div. -
Union Carlbde Caribe,
Inc., subsid.
                            Location(s)2*3


                            Gretna, La.
                            Philadelphia, Pa.

                            Institute & South
                            Charleston, W. Va.
                                                                                                                                  1975
                                                                                                                                capacity2
                                                                                                                              MM kg (MM lb)
                                           Total1**5
                                           production
                                          MM kg (MM  lb)
                                      for year  of  estimate
                                                                                                         Phillips, Tex.
                            Preeport, Tex.

                            Fords, N. J.



                            Penuelas, P, R.
                                                                                                         Kingsport, Tenn.
East Hanover, N. J.


Institute & South
Charleston, W. Va.
Texas City, Tex.

Bishop, Tex.


Preeport, Tex.

Longview, Tex.
                                                                                                         Penuelas, P.  R.

                                                                                                         Texas City,  Tex.

                                                                                                         Penuelas, P.  R.
                                                                                                                                                   5.3 (11.75)  -1972

-------
                                                                                Table A-l.  (Continued)
                               Chemical

                               Iso-
                               butyric
                               acid
                               Iso-
                               decanoic
                               acid
 I
vo
M
Ui
                               Iso-
ol
                               Iso-
                               decyl
                               chloride
                               Iso~
                               octyl
                               alcohol
          Manufacture of esters
          for solvents, flavors,
          & perfume bases; dis-
          infecting agent;
          deliming hides;
          varnish; tanning
          agent

          Intermediate for metal
          salts, ester type
          lubricants, plasticlzers

          Antifoaming agent in
          textile processing
          Solvent for oils, fats,
          greases, resins, gums,
          extractants, cleaning
          compounds; intermediate
          for insecticides, Phar-
          maceuticals , plasticizers,
          polysulfide rubbers,
          resins, & cationic sur-
          factants

          Ingredient of plastici-
          zers ; intermediate for
          non-ionic detergents &
          surfactants; synthetic
          drying oils, cutting &
Manufacturer(s)2 * 3


Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
Union Carbide Corp. -
Chems. & Plastics
Div.

Exxon Corp. -
Exxon Chem. Co., div. -
Exxon Chem. Co. U.S.A.

(Jetty Oil Co.
Union Carbide Corp. -
Chems. & Plastics Div.
U.S. Steel Corp. - USS
Chems., div.
 Exxon Corp. - Exxon
 Chem. Co., div. - Exxon
 Chem. Co. U.S.A.
 Getty Oil Co.
                            Location(s)2*3

                            Kingsport,  Tenn,
                            Texas City, Tex.
                            Baton Rouge, La.



                            Delaware City, Del.
                            Institute & South
                            Charleston, W. Va.
                            Haverhill, Ohio
                                                                                                                               1975
                                                                                                                             capacity2
                                                                                                                           MM kg (MM Ib)
                                                                                                             Total1*'5
                                                                                                             production
                                                                                                            MM kg (MM  Ib)
                                                                                                        for year of estimate
                                                                                                                                               81.7 (180)    -1974
                                                                                                       Baton Rouge,  La.
                                                                                                       Delaware City, Del.
                                                                                                                                                55.Jl  (122)   -196?

-------
                                                                                   Table A-l.  (Continued)
                                 Chemical
                                                                            Manufacturer(s)2 * 3
                                                                                                        Location(s)2'3
                                                                                                                  Total4*5
                                                                                                1975              production
                                                                                              capacity2          MM kg (MM  Ib)
                                                                                            HM_kg (MM Ib)    for year of estimat
                                 Ice-           (See previous page)
                                 octyl           lubricating oils, hydrau-
                                 aleohol        lie fluids; resin sol-
                                 (cont'd)       vent; emulsifier; anti-
                                                fearning agent; Intermed-
                                                iate for insecticides,
                                                Pharmaceuticals, plas-
                                                ticizersj polysulfide
                                                rubbers, resins, &
                                                cationic surfactants
                                            U.S.  Steel  Corp. -
                                            USS  Chems.,  div.
                                                        Delaware City,
                                                        Del.
 I
v£>
l-»
ON
                                 Isophorone
Isqphthalic
acid
                                Isoprene
                                Isopropanol
In solvent mixtures
for finishes; for poly-
vinyl & nitrocellulose
resins; pesticides;
staving lacquers

Polyester, alkyd, poly-
urethane, & other high
polymers; plasticizers
                                                Monomer for manufacture
                                                of polyisoprene;
                                                chemical intermediate
                                               Manufacture  of acetone
                                               6  its  derivatives;  manu-
                                               facture  of glycerol &
                                               isopropyl  acetate;  sol-
                                               vent for essential  &
                                               other  oils,  alkaloids,
                                               gums,  resins,  etc.;
                                               latent solvent for  cel-
                                               lulose derivatives;
                                               coatings  solvent;
                                               deicing  agent  for li-
                                               quid fuels;  Pharmaceu-
                                               ticals;  perfumes;
                                               lacquers;  extraction pro-
                                               cesses ;  dehydrating
                                               agent; preservative
                                                                            Union Carbide Corp. -
                                                                            Chems. & Plastics
                                                                            Div.
Standard Oil Co, (Ind.)
Amoco Chems. Corp.,
subsid.
                                                                        Institute & South
                                                                        Charleston, W. Va,
                                                                       Joliet, 111.
                                           Caribe Isoprene Corp.

                                           Exxon Corp, - Exxon
                                           Chem. Co., div. - Exxon
                                           Chem. Co.  U.S.A.

                                           The Goodyear Tire &
                                           Rubber Co. - Chem. Div.

                                           Neches Butane Products
                                           Co.

                                           Shell Chem. Co. - Base
                                           Chems.
                                           Atlantic Richfield Co. -
                                           ARCO Chem. Co., div.

                                           Eastman Kodak Co. - East-
                                           man Chem. Products, Inc.,
                                           subsid. - Texas Eastman
                                           Co., div.

                                           Exxon Corp. - Exxon Chem.
                                           Co., div. - Exxon Chem.
                                           Co. U.S.A.

                                           Shell Chem. Co. -
                                           Base Chems.

                                           Union Carbide Corp. -
                                           Chems. & Plastics Div.
                                                        Ponce, P, R.

                                                        Baton Rouge, La.



                                                        Beaumont, Tex.


                                                        Port Neches, Tex.


                                                        Deer Park, Tex.
                                                        Wood River, 111.




                                                        Channelview, Tex.


                                                        Longview, Tex.




                                                        Baton Rouge, La.
                                                        Deer Park, Tex.
                                                        Dominguez, Callf.
                                                        Texas City, Tex.
                                                        Whiting, Ind.
                                                                                                    (90)
                                                                                                                                 Total  *
                                                                                                                                I»0.9  (90)
                                                                                                                                30
                                                         (66)
                                                         (10)
            53-6 (118)
                                                                                                                                                151.8  (33*1.3) -1971
                                                                                                                                 76.3  (168)

                                                                                                                                *»5.4  (100)


                                                                                                                                55.8  (123)
                                                                                                                                 Total  *
                                                                                                                               182
                                                                                                                                15.9  (35)
                                                   279-2 (615)
                                                   276.9 (610)
                                                    91*    (207)
                                                    85
                                                    85
(187)
(187)
                                                                                                                                Total -
                                                                                                                               835.8  (18*1)

-------
                                                                                   Table  A-l.   (Continued)
                                Chemical

                                Iso-
                                propyl
                                acetate
VO
                                 Iso-
                                 propyl-
                                 amine
                                 Iso-
                                 prcpyl
                                 chloride
                                 Isopropyl-
                                 phenol
                                 Ketene
Solvent for nitrocellu-
lose, resin gums, etc.;
paints, lacquers, &
printing inks, organic
synthesis
Solvent; intermediate in
synthesis of rubber ac-
celerator, Pharmaceuti-
cals, dyes, insecticides;
bactericides, textile
specialties, & surface-
active agents; dehairing
agent; solubilizer for
2,4-D acid


Solvent; intermediate;
isopropylamine
Intermediate for syn-
thetic resins, plasti-
cizers, surface active
agents, perfumes

Acetylating agent, gen-
erally reacting with com-
pounds having an active
hydrogen atom; reacts
with ammonia to give
acetamide; starting
point for making var-
ious commercially im-
portant products, espe-
cially acetic anhydride
& acetate esters
Manufacturer^)2* 3

Eastman Kodak Co. -
Eastman Chem, Products,
Inc., subsid. - Tenn.
Eastman Co., div.

Union Carbide Corp. -
Chems. & Plastics Div.
Air Products & Chems.,
Inc.

Pennwalt Corp. - Chem.
Div,

Union Carbide Corp. -
Chems. & Plastics Div.

Va. Chems. Inc. -
Indust. Chems. Dept.

Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. -
Hooker Chems. &
Plastics Corp., sub-
sid. , Electrochemical
4 Specialty  Chems. Div.

Ethyl Corp. - Productol
Chem. Co.
                                                                            Monsanto Co.  - Monsanto
                                                                            Indust.  Chems. Co.
                                                        Location(s)2*3


                                                        Kingsport, Tenn.
                                                                                                        Institute &  South
                                                                                                        Charleston,  W.  Va.
                                                                                                        Texas  City,  Tex.
Pensaeola, Pla.


Wyandotte, Mich.


Tart, La.


Portsmouth, Va.


Niagara Palls, N. Y.
Orangeburg, S.  C.
Santa Fe Springs,
Calif.
                                                                                                        Muscatine,  Iowa
                                                                                                                                 1975
                                                                                                                               capacity2
                                                                                                                             MM kg (MM Ib)
                                           Total1"5
                                           production
                                          MM kg (MM Ib)
                                      for year of estimate
                                                                                13-6 (30)

                                                                                 Total -
                                                                                18.1 (40)

-------
                                                                                   Table Ar*l.  (Continued)
                                 Chemical
                                 Maleic
                                 acid
                                 Maleic
                                 anhydride
 I
VO
M
00
                                 Malic
                                 acid
                                 Mesityl
                                 oxide
Organic  synthesis  (malic,
suecinic, aspartic,
tartaric, propionlc,  lac-
tic, malonic , acrylic,
hydraerylic  acids);
dyeing &  finishing of
cotton, wool & silk;
preservative for oils
£ fats

Polyester resins;  alkyd
coating resins; fumaric
acid manufacture;  pesti-
cides ; preservative for
oils S fats; paper;
permanent-press resins
(textiles)
Medicine; manufacture
of various esters &
salts; wine manufacture;
chelating agent; food
acidulant; flavoring

Solvent for cellulose
esters & ethers, oils,
gums, resins, lacquers,
roll-coating inks,
stains, ore flotation;
paint & varnish-removers;
insect repellent
                                                                            Manufacturer(s)2'3
Pfanstiehl Labs.,
Inc.
Allied Chem. Corp. -
Specialty Chems. Div,

Koppers Co., Inc. -
Organic Materials Div.

Monsanto Co. - Monsanto
Indust. Chems. Co.

Petro-Tex Chem. Corp. -
Petro-Tex. Chem, Co.,
subsid.

Reichhold Chems., Inc.


Tenneeo Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Div.

U.S. Steel Corp. - USS
Chems., div.
Allied Chem. Corp. -
Specialty Chems. Div.
Norse Labs. Inc.
Shell Chem. Co. -
Base Chems.

Union Carbide Corp. -
Chems. & Plastics Div.
Location(s)2'3


Waukegan, 111.
                                                                                 1975
                                                                               capacity2
                                                                             MM kg (MM IB)
                                                                      Total1*'5
                                                                      production
                                                                      KM  kg  (MM lb)
                                                                      year of  estimate
Moundsvllle, W. Va.
Brldgevllle, Pa.
St. Louis, Mo.
Houston, Tex.
Elizabeth, N. J.
Morris, 111.
Fords, N. J.
9.1
15.1
^7.7
22. r
13.6
27.2
10
(20)
(34)
(105)
(50)
(30)
(60)
(22)
                                                                    128.5  (283)   -1971
Neville Island,




Moundsvllle, W. Va.

Santa Barbara, Calif.
Deer Park, Tex.
Dominguez, Calif.
Institute & South
Charleston, W. Va.
                                                                                                                                18.2 (»0)

                                                                                                                                 Total =
                                                                                                                               163.9 (361)

-------
                                                  Table A-l.  (Continued)
Chemical

Meth-
acrylic
acid
Meth-
acrylo-
nitrile
Meth-
allyl
alcohol

Meth-
allyl
chloride
Methanol
Monomer for large-vol-
ume resins & polymers;
organic synthesis; many
of the polymers are
based on esters of the
acid, as the methyl,
butyl, or losbutyl
esters (see acrylic
resin)

Vinyl nitrile monomer;
copolymer with styrene,
butadiene, etc.j elasto-
mers , coatings,
plastics

Intermediate
Manufacturer!s)2 * 3

E. I. du Pont de Ne-
mours & Co., Inc. -
Bioehems. Dept.
Hohm & Haas Co.
The Standard Oil
Co. (Ohio); Vistron
Corp., subsid. -
Chems. Dept.
Intermediate for pro-
duction of insecticides,
plastics, Pharmaceuticals,
other organic chemicals;
fumigant for grains,
tobacco, & soil

Manufacture of formalde-
hyde & dimethyl terephtha*
late; chemical synthesis
(methyl amines, methyl
chloride, methyl meth-
acrylate, etc.); avia-
tion fuel (for water
injection); automotive
antifreeze; solvent for
nitrocellulose, ethylcel-
lulose, polyvinyl butyral,
shellac, rosin, manila
resin, dyes; denaturant
for ethyl alcohol; de-
hydrator for natural
gas
FMC Corp. - Ghem. Group
Indust. Chem. Div.

Stauffer Chem. Co. -
Specialty Chem. Div.
                                            Air Products  & Chems.,
                                            Inc.

                                            Borden Inc. - Borden
                                            Chem. Div. -  Petrochems.

                                            Celanese  Corp. -
                                            Celanese  Chem, Co., div.

                                            Commercial Solvents
                                            Corp.

                                            E. I. du  Pont de Ne-
                                            mours & Co.,  Inc. -
                                            Elastomer Chems. Dept,
                                            Plastics  Dept.

                                            Ga.-Pacific Corp. -
                                            Chem. Div,
                            Location(s)2'3

                            Belle,  W.  Va.


                            Bristol, Pa.
                            Lima, Ohio
                                                                                                1975
                                                                                              capacity2
                                                                                            MM kg (MM lb)
                            Baltimore, Md.

                            Edison, N. J.



                            Fensacola, Pla..

                            Gelsmar, La.

                            Bishop, Tex.
                            Clear Lake, Tex.
                            Sterlington, La.
                            Beaumont, Tex
                            Orange, Tex.
                                                                                                   Total14'5
                                                                                                   production
                                                                                                  MM kg (MM lb)
                                                                                              for year of estimate?


                                                                                                 30.9 (68)   -1968
                                                   149.8 (330)

                                                   479.4. (1,056)

                                                   179.8 (396)
                                                   689.2 (1,518)
                                                   149.8 (330)
                                                   599.3 (1,320)
                                                   344.6 (759)
                                                                                                             3,082   (6,790) -1974
                            WJ. 0.11(3 C: ,-LGA.           Jit . U \ ( jy )

                            Plaquemine, La.         299 -6 (660)

-------
                                                                                 Table A-l.  (Continued)
                               Chemicj.1

                               Methanol
                               (cont'd)
 I
VO
ro
o
                              Methyl
                              acetate
                              Methyl
                              aceto-
                              acetate
                              Methyl-
                              amine
Usage1


(See previous page)
Paint remover com-
pounds ; lacquer
solvent; Intermediate
Solvent for cellulose
ethers; ingredient of
solvent mixtures for
cellulose esters;
organic synthesis

Intermediate for acceler-
ators, dyes, Pharmaceuti-
cals; insecticides; fun-
gicides; surface active
agents; tanning; dyeing
of acetate textiles;
fuel additive; polymeri-
zation inhibitor; com-
ponent of paint remov-
ers ; solvent; photo-
graphic developer;
rocket propellant
Manuf a c t ure r (sj 2 * 3


Hercules Inc. -
Synthetics Dept,
Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.

Rohm & Haas Co. - Rohm
& Haas Texas Inc.,
subsid.
Tenneco Inc. - Tenneco
Chems., Inc. - Organics
& Polymers Div.
Borden Inc. - Borden
Chem. Div. - Thermo-
plastic Products
Eastman Kodak Co. -
Eastman Organic Chems.

Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.

Union Carbide Corp. -
Chems. & Plastics Div.

Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. -
Tenn. Eastman Co., div.

Lonza Inc.

Air Products & Chems.,
Inc.
Commercial Solvents
Corp.
E. I, du Pont de Ne-
mours & Co., Inc. -
Biochems. Dept.
GAP Corp. - Chem. Div.
Rohm and Haas Co.
Locatignisl2*3


Hercules, Calif.
Plaquemine, La.

Texas City, Tex.


Deer Park, Tex.


Houston, Tex.
Bainbridge, N. Y.
Compton, Calif.
Demopolis, Ala.
Illiopolis, 111.
Leominster, Mass.
Rochester, N. Y.


Springfield, Mass.
                                                                                                      Institute  &  South
                                                                                                      Charleston,  W.  Va,

                                                                                                      Kingsporfc, Tenn.
Mapleton, 111.

Pensacola, Pla.

Terre Haute, Ind.


Belle, W. Va.
La Porte, Tex.

Calvert City, Ky.
Philadelphia, Pa.
                                                                                                                                                Total4'5
                                                                                                                               1975              production
                                                                                                                             capacity2          MM kg (MM Ib)
                                                                                                                           MM kg  (MM  Ib)    for year of estimate
                                                                                                                             299-6  (660)
                                                                                                                             299.6  (660)


                                                                                                                              65.9  (1,152)


                                                                                                                             239.7  (528)
                                                                                 Total =
                                                                             3,796.3 (8,362)
                                                                                              (See previous page)
 22,7 (50)

  8.2 (18)


 7^.9 (165)
 11.8 (26)


  it.5 (10)
  6.3 (1*0
  Total  =
128.5 (283)
                                                                                                                                              85.1 (187.M -1973

-------
                                                                                Table A-l.  (Continued)
 I
VO
N>
                              Chemical


                              N-methyl-
                              anillne
                              Methyl
                              butynol
                              Methyl
                              chloride
Organic synthesis;
solvent; acid ac-
ceptor
Stabilizer in chlori-
nated solvents; vis-
cosity reducer & stab-
ilizer; electroplating
brightener; inter-
mediate

Catalyst carrier in low-
temperature polymeriza-
tion (butyl rubber);
tetramethyl lead; sill-
cones ; refrigerant; medi-
cine; fluid for thermo-
metric & thermostatic
equipment; methylating
agent in organic syn-
thesis, such as methyl-
cellulose ; extractant &
low-temperature solvent;
propellant in high-
pressure aerosols;
herbicide
                                                                         Manufacturer's )2_J__3
Allied Chem. Corp. -
Specialty Chems.  Div.

American Cyanamid Co. -
Organic Chems. Div.

Air Products & Chems.,
Acetylenic Chems.
Div.

Hoffmann-La Roche Inc.
Location(s)2'3


Buffalo, N. Y.


Bound Brook, "N. J.


Calvert City, Ky.



Nutley, N. J.
                                                                                                                              1975
                                                                                                                            capacity2
                                                                                                                          MM kg (MM Ib)
                                                                                                   Total1**5
                                                                                                   production
                                                                                                  MM kg (MM Ib)
                                                                                              for year__of_ estimate^
Allied Chem. Corp. -
Specialty Chems. Div.
Continental Oil Co. -
Conoco Chems ,
Diamond Shamrock Corp. -
Diamond Shamrock Chem.
Co. - Electro Chems. Div.
Dow Chem. U.S.A.
Dow Corning Corp.
E. I, du Pont de Ne-
mours & Co., Inc. -
Indus t. Chems. Dept .
Ethyl Corp .
Oen. Electric Co. -
Chem, & Metallurgical
Div. - Silicone Pro-
ducts Dept .
Stauffer Chem. Co. -
Indust. Chem. Div.
Union Carbide Corp. -
Chems. & Plastics Div.
Vulcan Materials Co. -
Chems. Div.
Moundsville, W. Va.
Westlake, La.
Belle, W. Va.
Flaquemine, La.
Carrollton, Ky.
Midland, Mich.
Niagara Palls, N. Y.
Baton Rouge, La.
Waterford, N. Y.
Louisville, Ky.
Institute & South
Charleston, W. Va.
Geismar, La.
Newark, N. J.
Wichita, Kans.
11.3
15.4
H.3
68.1
9.1
6.8
36.3
45.4
22.7
6.8
22.7
-
(25)
(100)
(25)
(150)
(20)
(15)
(80)
(100)
(50)
(15)
(50)

                                                                                                                                             201.8 (114.5)  -1973
                                                                                                                              Total
                                                                                                                            286   (630)

-------
                                                  Table A-l.   (Continued)
Chemical


Methyl-
eye lo-
hexane

Methy1-
cyclo-
hexanol

Methyl-
cyclo-
hexanone
Methyl-
dioxo-
lane
Methyl
formate
Methylene
chloride
                Solvent for cellulose
                ethers; organic
                synthesis
                Solvent;  lacquers;
                solvent  for  cellulose
                esters  ft  ethers  for  lac-
                quers;  antioxldant for
                lubricants;  blending
                agent for special
                textile  soaps  &
                detergents

                Extractant & solvent for
                oils, fats,  waxes, dye-
                stuffs,  & cellulose
                derivatives

                Organi c  synthe sis;
                cellulose acetate sol-
                vent; military poison
                gases;  fumigant; lar-
                vlcides
               Paint remover/s; special
               photographic film; fumi-
               gant; solvent degreasing;
               solvent mixtures for
               cellulose esters & ethers;
               textile & leather coat-
               ings; refrigeration; local
               anesthetic; pharmaceutical
               ft food extraction; plas-
               tics processing; spotting
               agent; dewaxing; chemical
               (organic synthesis); as a
               propellant for aerosols;
               blowing agent In foams
Manufacturer(s)2*3


Phillips Petroleum Co. -
Petrochem. & Supply
Div.

Lanza Inc..
Prank Enterprises
Location(s)2^3


Phillips, Tex.



Mapleton, 111.



Columbus, Ohio
                                                                                                1975
                                                                                              capacity2
                                                                                            MM kg (MM Ib)
     Total1"5
     production
    MM kg (MM  Ib)
for year of e^stlmat^e
Celanese Corp. -
Celanese Chem. Co.,
div.

E. I. du Pont de Ne-
mours & Co., Inc, -
Biochems. Dept.

Allied Chem. Corp. -
Specialty Chems. Div.

Diamond Shamrock Corp. -
Diamond Shamrock Chem.
Co. - Electro Chems. Div.

Dow Chem. U.S.A.
                                           E. I. du Pont de Ne-
                                           mours & Co., Inc. -
                                           Indust. Chems. Dept.
                                           Stauffer Chem. Co. -
                                           Indust. Chem. Div.
Pampa, Tex.


Belle, W. Va.
Moundavllle, W. Va.
Belle, W. Va.
Freeport, Tex.
Plaquemine, La.
Niagara Palls,
Louisville, Ky.
22.7
27.2
68.1
10.9
18.2
27.2
(50)
(60)
(150)
(90)
(to)
(60)
                                                                                                               214    (471.3)  -1973

-------
                                                                                Table A—1«  (Continued)
 I
VO
K>
OJ
                              Chemical

                              Methylene
                              chloride
                              (cont'd)
                              Methylene
                              d-lanlllne
Methyl
ethyl
ketone
               Usage1

               (See previous page)
               Determination of tungs-
               ten & sulfates; polymer
               & dye intermediate;
               corrosion inhibitor;
               epoxy resin hardening
               agent
Solvent in nitrocellu-
lose coatings & vinyl
films; "Glyptal" re-
sins; paint removers;
cements & adhesives;
organic synthesis;
manufacture of smoke-
less powder; cleaning
fluids; printing;
catalyst carrier;
Note:  does not dis-
solve cellulose ace-
tate and most waxes
                            Manufacturer(3)2'3


                            Vulcan Materials Co, -
                            Chems, Div.
                            Allied Chem. Corp. -
                            Specialty Chems. Div.

                            Dow Chem. U.S.A.
                                                                                                     Location(s)2*3
                                                                       Geismar, La.
                                                                       Newark, N. J.
                                                                       Wichita, Kans.
                                                                       Moundsville, W. Va.
                                                                                                     Midland, Mich.
                      Total1**5
    1975              production
  capacity2          MM kg (MM Ib)
MM kg (MM Ib)    for year of estimate
                            Eastman Chem. Products,
                            Inc., subsid. - Tenn,
                            Eastman Co., div.
                            Exxon Corp. - Exxon
                            Chem, Co., div. -
                            Exxon Chem. Co. U.S.A.

                            Shell Chem. Co. - Base
                            Chems.


                            Union Carbide Corp. -
                            Chems. & Plastics Div.
                                                                                                     Bayway, N.  J.
                                                                                                     'Deer Park, Tex.
                                                                                                     Martinez, Calif.
                                                                                                     Norco, La.

                                                                                                     Brownsville, Tex.
                                                                                18.2 (40)
                                                                                13.6 (30)
                                                                                 Total =
                                                                               236.1 (520)
                 (See previous  page)
Mobay Chem. Corp, -
Indust . Chems . Div .
Rubicon Chems, Inc.
Atlantic Richfield
Co. - ARCO Chem. Co.,
div.
Celanese Corp. -
Celanese Chem. Co. ,
div.
Dart Indust . , Inc . -
Chem. Group - Chem.
Specialties Sector -
Aztec Chems .
Dixie Chem. Co.
Eastman Kodak Co. -
New Martinsville,
W. Va.
Geismar, La.
Channel view, Tex.
Pampa, Tex.
Elyria, Ohio
Bayport , Tex.
Kingsport, Tex.
_
-
29 (64)
52.2 (115)

1.4 (3)
-
                                                                                                               229.6 (505.8) -1971
                                                                                               90.8 (200)


                                                                                               15.1 (100)

                                                                                               22.7 (50)
                                                                                               27.2 (60)

                                                                                                Total =
                                                                                              268.8 (592)

-------
                                                   Table  A-l.  (Continued)
 Chemical
                                            Manufacturer's)2 * 3
                            Location(s)2'3
                         19T5
                       capacity2
                     MM kg (MM Ib)
     Totalkt5
     production
    MM kg (MM  Ib)
for year of estimate
 Methyl-         Solvent  for dyestuffs;
 isobutyl        oils,  gums, resins,
 carbinol        waxes, nitrocellulose
                &  ethyleellulose;  or-
                ganic  synthesis;  froth
                flotation;  brake  fluids

 Methyl          Solvent  for paints,  var-
 isobutyl        nishes,  nitrocellulose
 ketone          lacquers; manufacture of
                methyl amyl alcohol;
                extraction  processes,
                Including extraction of
                uranium  from fission pro-
                ducts; organic  synthesis;
                denaturant  for  alcohol
Methyl-        Stabilizer  in  chlorinated
pentynol       solvents; viscosity  re-
               ducer i electroplating
               brightening; intermediate
               in  syntheses of  hypnotics
               & isoprenoid chemicals;
               solvent  for polyamide  re-
               sins; acid  inhibitor;
               prevention  of  hydrogen
               embrlttlement; medicine
               (soporific  & anesthetic)

Methyl-        Perfumery;  flavoring;
phenyl-        dyes; laboratory
carbinol       reagent
Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
Exxon Corp. - Exxon
Chem. Co., div. -
Exxon Chem. Co. U.S.A.

Shell Chem. Co. -
Base Chems.
Union Carbide Corp. -
Chems. & Plastics Div.
Air Products & Chems.
Inc. - Acetylenic
Chems. Div.

Hoffman-La Roche Inc.
Union Carbide Corp. -
Chems. & Plastics Div.
Deer Park, Tex.
Dominguez, Calif.
Institute & South
Charleston, W. Va.
                            Kingsport, Tenn.
Bayway, N. J.
                                                                       Deer Park, Tex.
                                                                       Domingue z, Cal1f,
                                                                       Institute & South
                                                                       Charleston, W. Va.
Calvert City, Ky.


Nutley, N. J.
Institute & South
Charleston, W. Va.
                                                    13.6  (30)
                        18.2 (40)
                        36.3 (80)
                        15.9 (35)
                        29.5 (65)
                                                                                                Total =
                                                                                              113.5 (250)
    15-9 (35)    -1973
                                          70.3  (15^.83-1973

-------
                                                 Table A-l.  (Continued)
Chemical

a-methyl-
styrene
Polymerization monomer,
especially for polyester
Manufacturer(s)2 * 3
Allied Chem. Corp. -
Specialty Chems. Div.
Clark Oil & Refining
Corp. - Clark Chem.
Corp., subsid.
Dow Chem. U.S.A.
Ga. -Pacific Corp. -
Chem. Div.
Skelly Oil Co.
Union Carbide Corp. -
Total1"5
1975 production
capacity2 MM kg (MM Ib)
Location(s)2'3 MM kg (MM Ib) for year of estimate
Frankford, Pa.
Blue Island, 111.
Midland, Mich.
Plaquemine, La.
El Dorado, Kans .
Bound Brook, N. J.
6.8
2.3
4.5

-------
                                                   Table  A-l.  (Continued)
 Chemical
                                            Manufacturer (s)2 *3
                                                        Locatlon(s)2'3
                                                     1975
                                                   capacity2
                                                 MM kg  (MM  Ib)
                                           Total^'5-
                                           production
                                          MM kg  (MM Ib)
                                      for, year of estimate
 6-naph-
 thalene
 sulfonic
 acid
a-naphthol


B-naphthol
Neo-
pentanoic
acid

Nitroanisole
Nitro-
benzene
Starting point  in  the
manufacture  of  beta-
naphthol, beta-naph-
tholsulfonic  acid,
beta-naphthylami ne-
sulfonic acid;  etc.

Dyes; organic synthesis;
synthetic perfumes

Dyes; pigments; anti-
oxldants for  rubber,
fats, oils;  insecticide;
synthesis of  fungicides;
Pharmaceuticals, per-
fumes

Intermediate, as a
replacement  for some
natural materials

Organic synthesis;
manufacture of  inter-
mediates for  dyes
& Pharmaceuticals
Manufacture of aniline;
solvent for cellulose
ethers; modifying es-
teriflcation of cellu-
lose acetate; ingredient
of metal polishes & shoe
polishes; manufacture
of benzidine, quino-
line, azobenzene, etc.
American Cyanarnid Co. -
Pine Chems.  Dept.
(See also  a-naph-
thalene sulfonic acid)
Union Carbide Corp. -
Chems.  & Plastics Div.

American Cyanamid Co.
Organic Chems.  Div.
Exxon Corp. - Exxon
Chem. Co., div. -
Exxon Chem. Co. U.S.A1.

E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Dyes & Chems. Div.

Monsanto Co, - Monsanto
Indust. Chems. Co.

Allied Chem. Corp. -
Specialty Chems. Div.

American Cyanamid Co. -
Organic Chems. Div.


E. I. du Pont de Ne-
mours & Co., Inc. -
Elastomer Chems. Dept. -
Indust. Chems. Dept.

First Miss. Corp. -
First Chem. Corp.,
subsid.

Mobay Chem. Corp. -
Indust. Chems. Div.

Monsanto Co. - Monsanto
Indust. Chems. Co.

Rubicon Chems. Inc.
                            Bound Brook,  N.  J.
Institute & South
Charleston, W. Va.

Willow Island,
                                                                        Baton  Rouge, La.
                                                                       Deepwater, N. J.
                                                                        St.  Louis, Mo.
                            Moundsville,  W.  Va.


                            Bound Brook,  N.  J.
                            Willow Island,
                            W.  Va.

                            Beaumont,  Tex.
                            Gibbstown, N. J.
                                                                       Pascagoula, Miss.


                                                                       New Martinsville,
                                                                       W. Va.
                                                                       Sauget, 111.

                                                                       Geismar, La.
                                                                                                                 10.8 (23-8)  -1955
                        25   (55)

                        38.6 (85)
                        27,2 (60)
                        90.8 (200)



                        61.3 (135)


                        61,3 (135)

                         4.5 (10)

                        34   (75)
                         Total »
                       483.5 (1,065)
                                                                                                                250.2 (551.2) -1972

-------
                                                                                Table A-l.   (Continued)
                              Chemical
                                                                         Manufacturer(s)2'3
                                                                        LocatlQH(s)2'3
                                                     1975
                                                   dapaoity2
                                                 MM, Kg (MM lb)
                                           Total"'5
                                           production
                                          MM kg (MB lb)
                                      for ,year Of estimate
vo
                              Hltro-         Organic synthesisj
                              benzole        preparation of  anes-
                              aoid           theties & as  tntermed-
                              (m,o,p)        late in the manufacture
                                             of dyes & s
                                             agents
Nitro-         Propellant!  solvent  for
ethane         nitrocellulose,  cellulose
               acetate, cellu^Qse ae'e-
               topropionate,  e.€flltflose
               acetobutyrate, vinyl,
               alkyd,  & many  other
               resins, waxes, fats  &
               dyestuffs; chemical
               synthesis

Nitro-         Organic synthesis! for
toluene        production of  toluld^ne,
               tolidine, fueh,sin, &
               various synthetic 'dyes
                              Nonene         Organic  synthesis;  wet-r
                                             ting agent;  lube  oil
                                             additive; polymer
                                             gasoline
Bofors Indust., Inc.
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept.
Dyes i Chems. Div.
Salsbury Labs.
Sterling' Drug Inc. -
flhe Hilton-Davis
Chem. Co., div.

Commercial Solvents
Corp,
E. I. du Pont de Ne-
ffiouFs & Co., Inc. -
Orgariio Chems. Dept, T
Dyes & Chems. Div.
First Miss. Corp. r
^irst Chem. Corp.,
subsid.

Atlantic RJehfield Co. -
AI^CO Ch«m, Co., div.
Exxon Corp, - Exxon
Chem. Co., div. -
Exxon Chem. Co, U.S.A.
The, Humphrey Chen. Co.
Sun Oil Co. - Sun Oil
Co. of Fenn., subsid.
Onion Oil Co. of Calif,
                                                                       Linden, N. J.
                                                                       DeepWater, N.  J.
                                                                                                      Charles  City,  Iowa
                                                                                                      Cincinnati, Ohio
                                                                                                     Sterlington,, La.
Deepwater, N. J,



Pascagoula, Hiss.



East Chicago, Ind.

Baton Rouge, La.


North Haven, Conn.
Karcus Hoo^c, Pa.

Beaumont, Tex.

-------
                                                                                 Table  A-l-  (Continued)
                                Chemical


                                Nonyl-
                                phenol
VO
bo
oo
                                Oetyl-
                                phenol
Non-ionic surfactant
(nonbiodegradable); lube
oil additives; stabili-
zers, petroleum demulsi-
fiers, fungicides; bacte-
ricides; dyesj drugs; ad-
he sives; rubber chemicals;
phenolic resins &
plasticizers
Nonionic surfactants;
plasticizers; antioxi-
dants; fuel oil stabi-
lizer; intermediate for
resins, fungicides,
bactericides, dyestuffs
adhesives, rubber
chemicals
Paralde-       Substitute for acetalde-
hyde           hyde; rubber accelera-
               tors; rubber antloxl-
               dants; synthetic or-
               ganic chemicals; dye-
               stuff intermediates;
               medicine; solvent for
               fats, oiIs, waxes,
               gums, resins; leather;
               solvent mixtures for
               cellulose derivatives


Manufacturer(s)2 * 3
Borg-Warner Corp . -
Borg-Warner Chems. -
Weston Div,
Exxon Corp . - Exxon
Chem. Co. , div. -
Exxon Chem. Co. U.S.A.
GAF Corp. - Chem. Div.

Monsanto Co . - Monsanto
Indust . Chems . Co .
Productol Chem. Co .

Rohm & Haas Co. - Rohm
& Haas Texas Inc.,
subsid.
Texaco Inc. - Jefferson
Chem. Co. , Inc. , subsid.
Uniroyal, Inc. - Uni-
royal Chem., div.


GAP Corp. - Chem. Div.
Productol Chem, Co.

Schenectady Chems.,
Inc.
Rohm & Haas Co . - Rohm
& Haas Texas Inc.,
subsid.


Location(s)2'3
Morgantown, W. Va.


Bay way , N . J .


Calvert City, Ky .
Linden, N. J.
Kearny, N. J.

Sante Pe Springs,
Calif.
Philadelphia, Pa.
Deer Park, Tex.

Port Neches, Tex.

Naugat uc k , Conn .



Linden, N. J.
Santa Fe Springs,
Calif.
Rot t er dam June 1 1 on ,
N. Y.
Philadelphia, Pa.
Deer Park, Tex.


1975
capacity2
MM kg (MM Xb)
9-1 (20)


4.1 (9)


2.3 (5)
9.1-(20)
11.3 (25)

1 (2)

9.1 (20)
2.3 (5)

13.6 (30)

4.5 (10)

Total -
66.3 (1^6)
-
-

_

_
-

Total1* >s
production
MM kg (MK lb)
for year of estimate





















_







                                                                           Lonza Inc.

                                                                           Union Carbide  Corp.  -
                                                                           Chems.  & Plastics  Div.
                                                        Mapleton,  111.

                                                        Institute  &  South
                                                        Charleston,  W. Va.

-------
                                                  Table A-l.   (Continued)
Chemical

Penta-
erythritol
Perchloro-
ethylene
Alkyd resins; rosin &
tall oil esters; special
varnishes; pharmaceuti-
cals; plasticizers;
insecticides; synthetic
lubricants;  explosives;
paint swelling agents
Dry cleaning solvent;
vapor-degreasing sol-
vent; drying agent for
metals & certain other
solids; vermifuge; heat-
transfer medium, mfg.
of fluorocarbons
 1-pentene
                Organic  synthesis;
                blending agent  for
                high  octane  motor fuel
Manufacturer(s)2'3


Celanese Corp, - Cela-
nese Chem. Co., div,

Commercial Solvents
Corp.

Hercules Inc.  -
Synthetics Dept.

Pan American Chem.
Corp.
Diamond Shamrock Corp. -
Diamond Shamrock Chem.
Co. - Electro Chems. Div.

Dow Chem. U.S.A.
                                           E.  I. du  Pont de Ne-
                                           mours & Co., Inc. -
                                           Organic Chems. Dept. -
                                           Freon® Products Div.

                                           Ethyl Corp.

                                           Occidental  Petroleum
                                           Corp. - Hooker Chem.
                                           Corp., subsid. -
                                           Hooker Chems. & Plastics
                                           Corp., subsid. -
                                           Electrochemical &
                                           Specialty Chems. Div.

                                           PPG Indust., Inc. -
                                           Chem. Div.  - Indust.
                                           Chem. Div.

                                           Stauffer  Chem. Co. -
                                           Indust. Chem. Div.

                                           Vulcan Materials Co. -
                                           Chems. Div.
                            Phillips Petroleum Co. -
                            Petrochem. & Supply Div.
Location(s)2'3
Bishop, Tex.
Seiple, Pa.
Louisiana, Mo.
Toledo, Ohio
1975
capacity2
MM kg (MM Ib)
34 (75)
11.3 (25)
18.2 (110)
11.3 (25)
Total*'5
production
MM kg (MM Ib)
for year of estimate
46.8 (103.2) -



1973



                                                        Deer Park, Tex.
                                                                       Preeport, Tex.
                                                                       Pittsburg, Calif.
                                                                       Plaquemine, La.

                                                                       Corpus Christ!,
                                                        Baton Rouge, La.
                                                        Taft, La.
                                                        Lake Charles, La.
                                                        Louisville, Ky.

                                                        Geismar, La.
                                                        Wichita, Kans.
                                                                       Phillips, Tex.
                                                                                                Total =
                                                                                               74.9  (165)

                                                                                               72.6  (160)
                                                    54.5 (120)
                                                     9.1 (20)
                                                    68.1 (150)
                                                    72.6 (160)
                                                    22.7 (50)
                                                    22.7 (50)
                                                    90.8 (200)


                                                    31.8 (70)

                                                    68.1 (150)
                                                    22.7 (50)
                                                     Total =
                                                   535-7 (1,180)
                                                                                                332.8 (733)   -1974

-------
                                                                                     Tabl*
                                                                                                  (Continued)
                                                  tfsage*

                                                  Polymerization inhibitor;
                                                  organic synthesis

                                   P-£hene-       Manufacture of tlyes;
                                                  laboratory reagent
 O\
 1
vb
i
               Dyestuffs  intermediates
tidene         Pharmaceuticals; medi-
               cine; laboratory
               reagent

Phenol         Phenolic resins; «poxy
               resins (bisphenol^A);
               nylon-6 Ccaprolactam);
               2,i*i-D; selective solvent
               Tor refining  lubricating
               oils; adtpic  api^i  sali'-
               cyllc acid; phenolphtha*-
               lein; pentachlpt'ophen^l;
               acetophenetidine^ picric
               acidj germlcidal paints;
               Pharmaceuticals; labpra-
               bory reagent ; dyes  &
               indicators ; slimicide
Monsanto Co. - Monsanto
Indust. Chems» Cb.

Monsanto 60. - Monsanto
Indust. Chems. "Co.

Salsbury
       Chem, Corp. -
Specialty Chems. Div.
Clark til 6 Refining
Corp. *- Clark Chem.
Corp., subsid.
Dow Chem. U.S.A.

Georgian-Pacific vCorp. -
Chem. Div.

Kalama Chem. Inc.
Koppers Co,, Inc. -
The Herichem Co.
Monsanto.Co, - Monsanto
Polymers & Petrochems.
Co.

Productol Chem. Co.

Reichhold Chems., Inc.
Skelly Oil Co.
Standard Oil Co. of
Calif. - Chevron Chem.
Co., subsid. - Oronite
Additives ft Indust.
Chems. Div. *- Indust.
Chems.
Stimson Lumber Co. -
Northwest Petrochem.
Corp., div.
Union Carbide Corp. -
Chems. & Plastics Div. -
Onion Carbide Carlbe,
Inc., subsid.
U.S. Steel Corp. - USS
Chems., div.
tioeatlpnta)**,*
                                                                        St.  Louis,  to.
                                                                                                 1975
                                                                                               capacity2
                                                                                             MM kg (MM.Ib)
                                                                       Total1|>6-
                                                                       production
                                                                      MM kg (MM Ib)
                                                                  for. ye.ar .of estimate
                                                                                                          St. Mills, Mo.
                                                                                                          Saugefc,  111.
                                                                                                          Wilnlngtont N. C.

                                                                                                          Frankford, Pak

                                                                                                          Blue  Island,  111.
Midland, Mich.
Oyster Creek^ Tex.
?laquemine. La.

Kalama, Wash*
Follansbee, W. Va,
Houston^ Tex.
Chocolate Bayou,
Tex.

Sante Fe Springs,
Calif.
Tuscaloosa, Ala.
El Dorado, Kans.
Richmond, Calif.
                                                                                                          Anacortes, Wash.
                                                                                                          Bound Brook, N. J.
                                                                                                          Penuelas, P. R.
                                                                                                          Clairton, Pa.
                                                                                                          Haverhlll, Ohio
                       238.3 (525)

                        ltd   (88)
                        45.1 (100)
                       l8l.6 (100)
                       130.3 (28T)

                        25   (55)
                                                                                                                                  201.3  (150)
                                                                                                                                  61.3  (135)
                                                                                                                                  13.1  (95)
                                                                                                                                  25    (55)
                                                                   1,103.2
                                                                                                68.1  (150)
                                                                                                90.8  (200)
                                                                                               127.1  (280)

                                                                                                 Total  =
                                                                                             1,280.3  (2,820)

-------
                                                                                 Table A-l.   (Continued)
SO
CO
                               Chemical

                               Phenol-
                               sulfonic
                               acids
Phenyl
anthra-
nilic
acid

Phenylene-
diamine
               Water analysis; labora-
               tory reagent; electro-
               plated tin coatings
               baths; manufacture of
               intermediates & dyes;
               Pharmaceuticals
Azo dye intermediate;
photographic develop-
ing agent; fur dyes;
photochemical measure-
ments ; intermediate
in manufacture of
antioxidants & ac-
celerators for
rubber; detection of
nitrous acid; textile
developing agent;
organic synthesis;
laboratory reagent
                            Manufacturer(s)2 ' 3


                            Productol Chem. Co.


                            Jim Walter Corp. - U.S.
                            Pipe & Foundry Co.,
                            subsid. - Chem. Div.

                            Witco Chem, Corp. -
                            Ultra Div.

                            Sterling Drug Inc. -
Fairmount Chem. Co.,


The Sherwin-Williams
Co. - Sherwin-Williams
Chems. Div.

Toms River Chem. Corp.

E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Dyes & Chems. Div.

The B. F. Goodrich
Co. - B. F. Goodrich
Chem. Co., div.

Martin Marietta Corp. -
Martin Marietta Chems.
Sodyeco Div.

Ashland Oil, Inc. -
Ashland Chem, Co., div.
Chem. Products Div.

GAP Corp. - Chem. Div.
                            Location(s)2*3


                            Sante Fe Springs,
                            Calif.

                            Birmingham, Ala.



                            Paterson, N. J.


                            Rensselaer, N. Y.
Deepwater, N. J.
Newark, N. J.

St. Bernard, Ohio
                                                                                                      Toms  River,  N.  J,

                                                                                                      Deepwater, N. J.
                                                                                                      Henry,  111.


                                                                                                      Sodyeco,  N.  C.
                                                                                                      Great Meadows,
                                                                                                      N.  J.
                                                                                                      Rensselaer,  N.  Y.
                                                                                                                  Totale*'5'
                                                                                                                  production
                                                                                                                 MM kg (MM Ib)
                                                                                                             for year of _estinmate
                                                                                                                                                29.1
                                                                                                                                                           -1971

-------
                                                                                Table A-l.  (Continued)
                                                                                                                                               Total*' 5-
                                                                                                                              1975              production
                                                                                                                            capacity2          MM kg  (MM Ib)
                                             Organic synthesis, es-
                                             pecially of isocyanates
                                             polyurethane & poly-
                                             carbonate resins, car-
                                             fa antates, organic car-
                                             bonates & chloroform™
                                             ates; pesticides;
                                             herbicides; dye manu-
                                             facture
CO
K)
Manufacturer ( s ) 2 • 3
Allied Chem. Corp. -
Specialty Chems. Div.
BASF Wyandotte Corp. -
Indust. Chems. Group
Chemetron Corp. -
Chems. Group - Organic
Chems. Div.
E. I. du Pont de Ne-
mours & Co . , Inc . -
Elastomer Chenis. Dept.
FMC Corp. - Chem.
Group - Indust. Chem.
Div.
Gen. Electric Co. -
Plastics Business Div. -
Engineering Plastics
Product Dept.
Mobay Chem. Corp. -
Indust. Chems. Div.
Olln Corp. - Agri-
cultural Chems. Div.
Designed Products Div.
PPG Indust., Inc. - Chem.
Div. - Indust. Chem. Div.
Rubicon Chems. Inc.
Stauf f er Chero. Co . -
Agricultural Chem. Div.
Story Chem. Corp. -
Ott Div.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Onion Carbide Corp. -
Chems. 4 Plastics Div.
The Upjohn Co. - Polymer
mer Chems. Div.
Van De Mark Chem. Co.,
Inc.
Location(s)2 » 3
Moundsville, W. Va.
Geismar, La.
La Porte, Tex.
Deepwater Point,
N. J.
Baltimore, Md.
Mount Vernon, Ind.
Cedar Bayou, Tex.
New Martinsville,
W. Va.
Lake Charles, La.
Ashtabula, Ohio
Barberton, Ohio
Geismar, La.
Cold Creek, Ala.
Muskegon, Mich.
Port Neches, Tex.
Institute 4 South
Charleston, W. Va.
La Porte, Tex.
Lookport, N. Y.
MM kg (MM Ib) for year of estimate
44.5
25
9.1
61.3
2.7
27.2
59
111.2
51.5
22.7
2.3
56.7
11.3
1.5
13.6
50
90.8
(98) 330.6 (728.2) -1973
(55)
(20)
(135)
(6)
(60)
(130)
(2»5)
(120)
(50)
(5)
(125)
(25)
(10)
(30)
(110)
(200)
3.6 (8)
Total -
650.1 (1,432)

-------
                                                                                  Table
                                                                                        A-l.
                                                                                              (Continued)
                               Chemj^ca.1

                               Phthalie
                               anhydride
 I
vo
LO
CO
                                Phthali-
                                mide
Alkyd resins; plastici-
zers; hardener for
resins; polyesters; syn-
thesis of phenolphthalein
& other phthaleins, many
other dyes; chlorinated
products; pharmaceutical
Intermediates; insecti-
cides; diethyl phthalate;
dimethyl phthalate;
laboratory reagent
Synthetic indigo, via
anthranilic acid;
fungicide; organic
synthesis; laboratory
reagent
Manufacturer(s)2'3


Allied Chem. Corp. -
Specialty Chems. Div.

BASF Wyandotte Corp. -
Colors & Chems. Group

Exxon Corp. - Exxon
Chem. Co., div. - Exxon
Chem. Co. U.S.A.

Koppers Co., Inc. -
Organic Materials Div.

Monsanto Co. - Monsanto
Indust. Chems. Co.

Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. - Hooker
Chems. & Plastics Corp.,
subsid. - Puerto Rico
Chem. Co., subsid.

Standard Oil Co. of
Calif. - Chevron Chem.
Co .,  subsid. - Oronite
Additives & Indust.
Chems. Div. - Indust.
Chems.
1975
capacity2
Location(s)2'3 MM kg (MM lb)
El Segundo, Calif.
South Kearny, N. J.
Baton Rouge, La.
Bridgeville, Pa.
Cicero, 111.
Bridgeport, N. J.
Texas City, Tex.
Arecibo, P. R.
15.9
59
10.9
1(0.9
59
38.6
59
15.4
(35)
(130)
(90)
(90)
(130)
(85)
(130)
(100)
                                                                                                       Richmond,  Calif.
The Sherwin-Williams
Co. - Sherwin-Williams
Chems. Div.
St. Bernard,
Ohio
                                                                                                   Total'"5-
                                                                                                   production
                                                                                                  MM kg (MM lb)
                                                                                              for year of estimate


                                                                                                1111.5 (979)  -1971
                                                                                                                               22.7  (50)
Stepan Chem. Co. -
Surfactant Dept .
Union Carbide Corp. -
Chems. & Plastics Div.
U.S. Steel Corp. - USS
Anaheim, Calif.
Elwood, 111.
Pieldsboro, N. J.
Institute & South
Charleston, W. Va.
Neville Island,
Pa.
22.7 (50)
22.7 (50)
45. 1 (100)
68.1 (150)
Total =
517.6 (1,140)

-------
                                                  Table  A-l.  (Continued)
 Chemical
Phthalo-
nltrile
Piperazine
Poly-
butenes
Polyethy-
lene
glycol
Intermediate In organic
synthesis, especially
pigments & dyes; base
material for high
temperature lubricants
& coatings; Insecticide

Corrosion inhibitor;
anthelmintic; insecti-
cide; accelerator for
curing polychloroprene
Hot-melt adheslves;
sealing tapes; special
sealants; cable In-
sulation; polymer modi-
fier; viscosity index
improvers; lube oil
additive
Chemical intermediates
(lower molecular weight
varieties); plasticizers;
softeners.& humectants;
lubricants; bases for
cosmetics & Pharmaceu-
ticals; solvents; bin-
ders; metal & rubber
processing; permissible
additives to foods &
animal feed; laboratory
reagent
                                           Manufacturer(s)2*3
                                                                       Locatlon(s)2*3
                                           Calif. - Chevron Chem.
                                           Co., subsid. - Oronlte
                                           Additives  & Indust.
                                           Cheras. Dlv. - Indust.
                                           Chems.

                                           Standard Oil Co. (Ind.)
                                           Amoco Chems, Corp.,
                                           subsid.
Ashland Oil, Inc. - Ash-
land Chem. Co., div. -
Chem. Products Div.

BASF Wyandotte Corp. -
Indust. Chems. Group

Dow Chem. U.S.A.

Hodag Chem. Corp.

Olin Corp, - Designed
Products Div.

Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.

Union Carbide Corp. -
Chems. & Plastics Div.
                                                        Texas City, Tex.
                                                        Wood River, 111.
                                                                       Janesville, Wise.
                                                                       Wyandotte, Mich.


                                                                       Freeport, Tex.

                                                                       Skokie, 111.

                                                                       Brandenburg, Ky.


                                                                       Port Neches, Tex.


                                                                       Institute & South
                                                                       Charleston, W. Va.
                                                                                 1975
                                                                               capacity2
                                                                             MM kg (MM Ib)
                                                                      Total"'5
                                                                      production
                                                                     MM kg (MM Ib)
                                                                 for year of estimate
Fleming Labs., Inc.
Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Dlv.
American Petroflna, Inc. -
Cosden Oil & Chem. Co.,
subsid.
Exxon Corp. - Exxon
Chem. Co., div. - Exxon
Chem. Co. U.S.A.
The Lubrizol Corp.
Standard Oil Co. of
Charlotte, W. C.
Conroe , Tex .
Taft, La.
Texas City, Tex.
Big Spring, Tex.
Bay way , N . J .
Deer Park, Tex.
Richmond, Calif.
-
-
:
9.1 (20)
20.4 (45)
40.9 (90)
20.4 (45)
                                                                    104.H  (230) -1967
                                                    77.2  (170)
                                                    10.9  (90)

                                                    Total =
                                                   208.8  (460)

-------
                                                                                 Table  A-l.  (Continued)
                              Chemical
                                              Usage1
                            Manufacturer(s)2 ' 3
                                                        Locatlon(s)2*3
                                                     1975
                                                   capacity2
                                                 MM kg (MM Ib)
                                                                                                                                                Total1**5-
                                                                                                                                                production
                                                                                                                                               MM kg  (MM Ib)
                                                                                                                                            for year of estimate
                               Poly-
                               ethylene
                               glycol
                               chloride

                               Poly-
                               propylene
                               glycol
 I
vo
u>
Cn
                               Propane
Solvents for cleaning
extracting, '& dewaxing
Hydraulic fluids; rubber
lubricants; antlfcam
agents; intermediates
in urethane foams, ad-
hesives, coatings,
elastomers; plastici-
zers; paint formula-
tions; laboratory
reagent
                                              Organic synthesis;
                                              household & industrial
                                              fuel; manufacture of
                                              ethylene, extractant;
                                              solvent; refrigerant;
                                              gas enrichener; aerosol
                                              propellant; mixture for
                                              bubble chambers
BASF Wyandotte Corp, -
Indus t. Chems. Group

E, R. Carpenter Co.,
Inc. - Choate Chem.
Co., subsid.

Dow Chem. U.S.A.


Hodag Chem. Corp.

ICI United States Inc.
Specialty Chems. Dlv.

Nalco Chem. Co. -
Petroleum & Process
Chem. Div, - Visco
Chems.

Olin Corp. - Designed
Products Div.

Pelron Corp. - Texaco
Inc. - Jefferson Chem.
Co ., Inc., subsid.

Union Carbide Corp. -
Chems. & Plastics Div.

WItco Chem. Corp. -
Organics Div,

Air Products & Chems.
Inc. - Specialty Gas -
Dept. Chemicals -
Intermediates Mktg.

Matheson Gas Products

Phillips Petroleum Co.
Petrochemical & Supply
Div. - Customer Ser-
vice Center

Technical Petroleum Co.
Washington, N. J.
Wyandotte, Mich.

Bayport, Tex.
Freeport, Tex..
Midland, Mich.

Skokie, 111.

New Castle, Del.


Sugar Land, Tex.
                                                                                                      Brandenburg,  Ky,


                                                                                                      Conroe,  Tex.



                                                                                                      Institute & South
                                                                                                      Charleston, W.  Va.

                                                                                                      Clearing, 111.


                                                                                                      Allentown, Pa.
                                                        Lyndhurst, N. J.

                                                        Borger, Tex.
                                                                                                      Chicago,  111.
                                                                                                 38.8 (85.5)  -1973
                                                                                             21,802   (48,022)-1971

-------
                                                                                Table A-l.  (Continued)
                              Chemical


                              Propion-
                              adlehyde
                              Propion3c
                              acid
                              (propanoic
                              acid)
VO
CO
                              Propyl-
                              amine
                              Propyl
                              chloride

                              Propylene
Manufacture of poly-
vinyl acetals & other
plastics; synthesis
of rubber chemicals;
disinfectant;
preservative

Propionates, some of
which are used as mold
inhibitors in bread &
fungicides in general;
emulsifying agents;
solutions for electro-
plating nickel; per-
fume esters; artifical
fruit flavors; Pharma-
ceuticals; solvent mix-
tures for cellulose
derivatives; pretreat-
ment of zinc oxide

Intermediate; laboratory
reagent
Solvent; intermediate
propylamine

Isopropyl alcohol, poly-
propylene , synthetic
glycerol, acrylonitrile,
propylene oxide, heptene,
eumene, polymer gasoline,
anticipated use for
acrylic acid & in vinyl
resins
Manufacturer^) 2*^


Eastman Kodak Co.  -
Eastman Chem. Products,
Inc., subsid.
Union Carbide Corp. -
Chems.  & Plastics  Div.


Celanese Corp.  -
Celanese Chem.  Co., div.

Commercial Solvents Corp.
Eastman Kodak Co.  -
Eastman Chem. Products
Inc., subsid. - Tenn.
Eastman Co., div.

Union Carbide Corp. -
Chems.  & Plastics  Div,
Pennwalt Corp. - Chem.
Div.

Va. Chems.  Inc.  - Indust.
Chems.  Dept.

Publicker Indust. Inc.
                                                                         Amerada Hess Corp.
                                                                         American Petrofina,
                                                                         Inc. - Cosden Oil &
                                                                         Chem. Co., subsid.

                                                                         ARCO/Polymers, Inc.
                                                                         Ashland Oil, Inc. -
                                                                         Ashland Chem. Co., div.,
                                                                         Petrochems. Div.
                                                                         Atlantic Richfield Co. -
                                                                         ARCO Chem. Co., div.


                                                                         BASF Wyandotte Corp. -
                                                                         Indust. Chems. Group
capacity*;
Location(s)2*3 MM kg {MM Ib.)
Longview, Tex.
Seadrift, Tex.
Texas City, Tex.
Pampa, Tex.
Sterlington, La.
Kingsport , Tenn .
Institute & South
Charleston, W. Va.
-
-
5.1
1.4
9.1
11.3


(12)
(3)
(20)
(25)
Total =
27.2 (60)
Wyandotte, Mich.
Portsmouth, Va.
Philadelphia, Pa.
Port Reading, N. J.
Big Spring, Tex.
Eldorado, Tex.
Mount Pleasant, Tex.
Houston, Tex.
Ashland, Ky.
Louisville, Ky.
North Tonawanda
Channel view , Tex .
East Chicago , Ind .
Wilmington, Calif.
Geismar, La.
-
-
-
59
59
15
25
68.1
75
13.6
22.7
6.8
30
45.4
22.7



•(130)
(130)
C33)
(55)
(150)
(165)
(30)
(50)
(15)
(66)
(100)
(50)
                                                                                                                                               Total"'5
                                                                                                                              1975             production
                                                                                                                                               MM kg  (MM Ib)
                                                                                                                                           for  year of estimate
                                                                                                                                              27.1  (60.1)  -1973
                                                                                                                                               7.6  (16.7)   -1972
                                                                  4,5*111  (10,010)  -1974

-------
                                                                                   Table A-l.  (Continued)
                                 Chemical

                                 Prooylene
                                 (cont'd)
Usage V

(See previous page)
ON

VO
co
Manufacturer(s) 2_*3


The Charter Co. -
Charter Oil Co.,
subsid. - Charter
Internat'l Oil Co.,
subsid.
Chemplex Co.

Cities Service Co.,
Inc. - North American
Petroleum Group
Clark Oil & Refining
Corp. - Clark Chem.
Corp., subsid.
Coastal States Gas
Corp. - Coastal
States Marketing,
Inc., subsid.

Continental Oil Co. -
Conoco Chenis.
Dow Chem. U.S.A.
                                                                            E. I. du Pont de Ne-
                                                                            mours & Co., Inc. -
                                                                            Plastics Dept.
                                                                            Eastman Kodak Co. -
                                                                            Eastman Chem. Products,
                                                                            Inc., subsid. - Texas
                                                                            Eastman Co., div.
                                                                            El Paso Natural Gas
                                                                            Co., El Paso Products
                                                                            Co., subsid.
                                                                            Exxon Corp. - Exxon
                                                                            Chem. Co., div. -
                                                                            Exxon Chem. Co. U.S.A.

                                                                            Getty Oil Co.
                                                                            The B. P. Goodrich
                                                                            Co. - B. F. Goodrich
                                                                            Chem. Co., div.
                                                                            Gulf Oil Corp. -
                                                                            Gulf Oil Chems. Co.,
                                                                            div, - Petrochems. Div.

                                                                            Marathon Oil Co.
Location(s) 2) 3
Houston, Tex.
1975
capacity2
MM kg (MM Ib)
34 (75)
Total1**5
production
MM kg (MM Ib)
for year of estimate
(See previous page)
                                                        Clinton,  Iowa
                                                        Lake Charles, La.


                                                        Blue Island, 111.


                                                        Corpus Christ!, Tex.



                                                        Westlake, La.

                                                        Bay City, Mich.
                                                        Freeport, Tex.
                                                        Plaquemlne, La.
                                                        Orange, Tex.


                                                        Longview, Tex.



                                                        Odessa, Tex.
                                                        Baton  Rouge, La.
                                                        Baytown, Tex.
                                                        Bayway, N. J.
                                                        Delaware City,

                                                        Calvert City, Ky.
                                                         Cedar  Bayou, Tex.
                                                         Philadelphia, Pa.
                                                         Port Arthur, Tex.
                                                         Detroit,  Mich.
                                                         Texas  City, Tex.
                                                         Beaumont, Tex.
 61.3 (135)
210.6 (530)


 20.') (45)


 25   (55)



 18.2 (40)

 t5.ll (100)
200   (440)
 72.6 (160)
 68.1 (150)


136.2 (300)



 79.4 (175)


710.5 (1,565)
249.7 (550)
145.3 (320)
 81.7 (180)
 63.6 (140)
                                                    56.7 (125)
                                                    84   (185)
                                                   252   (555)
                                                    45.4 (100)
                                                   129.4 (285)
                                                   220.2 (485)

-------
                                                                                 Table A-l.  (Continued)
                               Propy-
                               lene
                               (cont'd)
                                              Usage1

                                              (See previous page)
OS
00
Manufacturer(s)2'3


Mobil Oil Corp. -
Mobil Chem. Co., div. -
Petrochems. Div.

Monsanto Co. - Monsanto
Polymers & Petrochems.
Co.

Northern Natural Gas
Co. - Northern Petro-
chem., subsid. -
Polymers Div.

Novamont Corp.

The Oil Shale Corp. -
Lion Oil Co., subsid.

Petro Gas Producing Co.

Phillips Petroleum Co.

Puerto Rico Olefins Co.

Shell Chem. Co. -
Base Chems.


Skelly Oil Co.

Standard Oil Co. of
Calif. - Chevron Chem.
Co., subsid. - Oronite
Additives & Indust.
Chems. Div. -
Indust. Chems.

Standard Oil Co. (Ind.)
Amoco Chems. Corp.,
subsid.


The Standard Oil Co.
(Ohio)

Sun Oil Co. - Sun Oil
Co. of Penn., subsid.

Suntide Refining Co.,
subsid.
Location(s)2'3
Beaumont, Tex.
Chocolate Bayou,
Morris, 111.
Kenova, ¥. Va.
El Dorado , Ark .
Groves, Tex.
Sweeny, Tex.
Penuelas, P. R.
Deer Park, Tex.
Dominguez, Calif.
Norco, La.
El Dorado , Kans .
El Segundo, Calif.
Richmond, Calif.
Total1"5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
220.2
250
90.8
81
-
25
68.1
295.1
199.1
79.5
100
11.8
18.2
93.1
(185) (See previous page)
(550)
(200)
(-185)

(55)
(150)
(650)
(1,100)
(175)
(220)
(26)
(10)
(205)
                                                                                                      Chocolate Bayou,
                                                                                                      Tex.
                                                                                                      Texas City, Tex.
                                                                                                      Wood River, 111.
                                                                                                      Lima, Ohio
                                                                                                      Toledo, Ohio
                                                                                                      Duncan, Okla.
                                                                                                      Marcus Hook, Pa.
                                                                                                      Toledo, Ohio
                                                                                                      Corpus Christ!,.
                                                                                                      Tex.
                                                                                                                             179.3 (395)
172.5
 59
 81.7
 88.5
 36.3
151.1
 25
 91
(380)
(130)
(180)
(195)
(80)
(310)
(55)
(200)

-------
                                                                                 Table  A-l.  (Continued)
                               Chemical.

                               Propy-
                               lene
                               (cont'd)
VO
UJ
                               Propylene
                               ehloro-
                               hydrin

                               Propy-
                               lene
                               dichloride
                               Propy-
                               lene
                               oxide
(See previous page)
Organic synthesis
(introducing hydroxy-
propyl group)

Intermediate for per-
chloroethylene &
carbon tetrachloride;
lead scavenger for
antiknock fluids;
solvents for fats,
oils, waxes, gums, &
resins; solvent mix-
tures for cellulose
esters & ethers;
scouring compounds;
spotting agents; metal
degreasing agents;
soil fumigant for
nematodes

Propylene glycol &
other glycols; urethane
foams; surfactants &
detergents; isopropanol
amines; fumigant; syn-
thetic elastomer
(homopolymer)
                            Texaco Inc.

                            Jefferson Chem. Co.,
                            Inc., subsid.
                            Texas City Refining
                            Inc.
                            Union Carbide Corp. -
                            Chems. & Plastics Div.
                                                                           Union Carbide  Caribe,

                                                                           Union Oil Co.  of Calif.
Eastman Kodak Co. -
Eastman Organic Chems.


Dow Chem. U.S.A.


Olin Corp. - Designed
Products Div.

Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.
Union Caribde Corp. -
Chems. & Plastics Div.
BASF Wyandotte Corp. -
Indust.  Chems. Group -
Dow Chem. U.S.A.
                                                                           Olin Corp.  - Designed
                                                                           Products Co.

                                                                           Oxirane Chem.  Co.
                                                                           Texaco Inc.  -  Jefferson
                                                                           Chem.  Co.,  Inc.,  subsid.
                            Locations)2'3


                            Port  Arthur,  Tex.
                            Westville,  N.  J.
                            Port  Neches,  Tex.


                            Texas City, Tex.

                            Seadrift,  Tex.
                            Taft, La.
                            Texas City, Tex.
                            Torrance,  Calif.
                            Whiting, Ind.

                            Penuelas,  P.  R.

                            Beaumont,  Tex.
                                                                                                       Rochester,  N.  Y.
                            Freeport,  Tex.
                            Plaquemine,  La.
                            Brandenburg, Ky.


                            Port Neches, Tex.

                            Institute  &  South
                            Charleston,  W. Va.
Wyandotte, Mich.

Preeport, Tex.
Plaquemine, La.
Brandenburg, Ky.


Bayport, Tex.
Port Neches, Tex.
                         1975
                       capacity2
                     MM kg (MM Ib)


                        11.3 (25)
                        25   (55)
                        59   (130)

                        45.4 (100)

                        50   (110)
                        90.8 (200)
                       109   (240)

                       125   (275)
                       208.8 (1(60)
                        43.1 (95)
                         Total =
                     6,751   (It,870}
                        11.3 (25)
                         4-5 (10)
                                                                                                   Total1* >5
                                                                                                   production
                                                                                                  MM kg (MM Ib)
                                                                                              for year of estimate


                                                                                              (See previous page)
                                                                                                                               11.3  (25)

                                                                                                                               Total =
                                                                                                                              315-5  (695)
                                                    79.^ (175)

                                                   340.5 (750)
                                                   100   (220)
                                                    59   (130)
                                                                               404   (890)
                                                                                68.1 (150)

                                                                                 Total =
                                                                             1,051   (2,315)
                                                                                                                                              808
                                                                                                                                                     (1,780) -1974

-------
                                                                                Table  A-l.  (Continued)
 I
\O
•>
O
                              Chemical


                              Fyridine
                              (natural
                              &
                              synthetic)
Quinone
                             Resorcinol
                             Resor-
                             cylic
                             acid
                             Sali-
                             cylic
                             acid
               Synthesis of vitamins
               & drugs; solvent; water-
               proofing; rubber chemi-
               cals; denaturant for
               alcohol & antifreeze
               mixtures; dyeing assist-
               ant in textiles;
               fumgicides
               Mfg. of dyes & hydro-
               quinone
               Resorcinol-formaldehyde
               resins; dyes; pharma-
               ceuticals; cross-link-
               ing agent for neoprene;
               rubber tackifier; ad-
               hesives for wood veneers
               & rubber-to-textile com-
               posites ; medicine;
               mfg. of styphnic acid

               Dyestuff & pharmaceuti-
               cal intermediate; chemi-
               cal intermediate in
               synthesis of fine or-
               ganic chemicals;
               light stabilizers;
               resins

               Mfg. of aspirin & other
               medlclnals; preserva-
               tive; dyes; perfumes;
               prevulcanization inhib-
               itor; organic Inter-
               mediate; fungicide


Manufacturer(s)2'3
Natural:
Crowley Tar Products,
Inc .
Koppers Co . , Inc . -
Organic Materials Div.
Synthetic :
Reilly Tar & Chem.
Corp.
Warner-Lambert Co . -
Nepera Chem. Co., Inc.,
subsid.



Location(s)2 * 3

Bait imore , Md .
Houston, Tex.
Follansbee, W. Va.


Indianapolis , Ind.

Harriman, N. Y.




1975
capacity2
MM kg (MM lb)

_
-
_


16 C35)

2.3 (5)

Synthetic Total
18.3 (40)
Total1**5
production
MM kg (MM lb)
for year of estimate
3.1} (7.42) -1968









=

Eastman Kodak Co. -
Eastman Chem. Products,
Inc., subsid. - Tenn.
Eastman Co., div.
Prank Enterprises

Koppers Co., Inc. -
Organic Materials Div.
Kingsport, Tenn.




Columbus, Ohio

Petrolia, Pa.
                                                                                                                            11.3 (25)

                                                                                                                             Total =
                                                                                                                            11.3 (25)
                                                                                                                                             11.8 (26)
                                                                                                                                                          -1970
Aldrich Chem. Co., Inc.
Koppers Co., Inc.  -
Organic Materials  Div.
Dow Chem. U.S.A.
Monsanto Co. - Monsanto
Indust. Chems. Co.
Milwaukee, Wise.
Petrolia, Pa.
Midland, Mich.
St. Louis, Mo.
7-7 (17)
9-1 (20)
                                                                                                                                              6.2 (13.6)   -1969

-------
                                                                                 Table A-l.  (Continued)
                              Chemical

                              Sali-
                              cylic
                              acid
                              (cont'd)
                               Sodium
                               acetate
VO
Sodium
carboxy-
methyl
cellulose
(See previous page)
Dye & color intermed-
iate ; Pharmaceuticals;
cinnamic acid; soaps;
photography; purifica-
tion of glucose; meat
preservation; medicine;
electroplating; tanning;
dehydrating agent; buf-
fer in foods; laboratory
reagent
                                              Detergents, soaps, food
                                              products (especially
                                              dietetic foods & ice
                                              cream), where it acts as
                                              water binder, thickener,
                                              suspending agent, & emul-
                                              sion stabilizer; textile
                                              manufacturing (sizing);
                                              coating paper & paper
                                              board to lower porosity;
                                              drilling muds; emulsion
                                              paints; protective
                                              colloid; Pharmaceuticals;
                                              cosmetics
                                           Manufacturer(g)2 *^_


                                           Sterling Drug Inc. -
                                           The Hilton-Davis
                                           Chemical Co., div,

                                           Tenneco Inc. - Tenneco
                                           Chems., Inc. -
                                           Organics & Polymers
                                           Div.
                                           Allied Chem. Corp. -
                                           Specialty Chems. Div.
                                           Dan River, Inc.

                                           Howerton Gowen Chems.,
                                           Inc.
                                           Mallinckrodt, Inc. -
                                           Indust. Chems. Div.
                                           Washine Div.
                                           Hitter Chem, Co., Inc.
                                           Union Carbide Corp. -
                                           Chems. & Plastics Div.
                            BASF Wyandotte Corp. -
                            Indust. Chems. Group
Location(s)2*3


Cincinnati, Ohio



Garfield, N. J.
Marcus Hook, Pa.


Danville, Va.
Roanoke Rapids,
N. C.

St. Louis, Mo.

Lodi, N. J.
Amsterdam, N. Y.
Niagara Palls,
N. Y.

Wyandotte, Mich.
                                                                                 1975
                                                                               capacity2
                                                                             MM kg (MM lb)_

                                                                                 3.2 (7)
                                                                                                                                   (10)
                                                                                                                               Total  =
                                                                                                                              24.5  (54)
                            Co. - The Buckeye Cel-
                            lulose Corp., subsid.

                            United Aircraft Corp. -
                            Essex Internat'l Inc.,
                            subsid.
                                                                                                      Muncle,  Ind.
                                                                                                                               1.8  (4.0)
Brown Co .
Hercules Inc. - Coatings
& Specialty Products
Dept.
H. Kohnstamm & Co.,
Inc.
The Procter & Gamble
Berlin, N. H.
Harbor Beach, Mich.
Hopewell, Va.
Camden, N. J.
Clearing, 111.
Memphis, Tenn,
-
1.5 (10.0)
18 (10.0)
0.9 (2.0)
0.5 (1.0)
3.2 (7.0)
                                                                                                                              1.1  (2.5)
                                                                                                                              Total  =
                                                                                                                              30.2  (66.5)
     Total"5
     production
    MM kg (MM Ib)
for year of estimate

(See previous page)
                                                                                                                                               29.5 (61.9)  -1970

-------
                                                   Table  A-l.  (Continued)
Chemical
                                                                        Locations)2'3
                                                                                 1975
                                                                               capacity2
                                                                             MM kg (MM Ib)
                                                                      Total4'5
                                                                      production
                                                                     MM kg  (MM Ib)
                                                                  for year of estimate
Sodium
formate
Sodium
phenate
Sorbic
acid
Reducing  agent;
medicine; manufacture of
formic acid  & oxalic
acid; organic chemicals;
mordant;  tanning; wall-
paper printing; plating
Antiseptic; salicylic
acid; organic synthesis
Fungicide; food pre-
servative; eopolymeri-
zation; upgrading of
drying oils; cold rub-
ber additive; inter-
mediate for plastici-
zers & lubricants
Commercial Solvents
Corp.

Hercules Inc. -
Synthetics Dept.

Pan American Chem.
Corp.

Tenneco Inc. - Tenneco
Chems., Inc. -
Organics & Polymers Div.

American Petrofina, Inc,
American Petrofina Co.
of Texas, subsld.

Colt Indust., Inc. -
Crucible Stainless Steel
& Alloy Div.

National Steel Corp. -
Great Lakes Steel Div. -
B. F. Div.

Republic Steel Corp. -
Iron & Chem. Div.

Sharon Steel Corp. -
Fairmont Coke Works

Shenango Inc.

Wheeling-Pittsburgh
Steel Corp.

American Hoechst Corp. -
Dyes & Pigments Div.

Pfizer Inc. -
Chems.  Div.
Seiple, Pa.


Louisiana, Mo.


Toledo, Ohio


Fords, N. J.



Port Arthur, Tex.



Midland, Pa.
                                                                        Zug Island
                                                                        (River Rouge),
                                                                        Mich.

                                                                       _Chicagoa 111.
                                                                        Cleveland, Ohio

                                                                        Fairmont, W. Va.
Neville Island, Pa.

Monessen, Pa.


Coventry, R, I.


Groton, Conn.

-------
                                                                                 Table  A-l.   (Continued)
T
                                              Polystyrene  plastics;
                                              SBR,  ABS,  S'SAN res-
                                              ina;  protective coatings
                                              (styrene-butadiene latex;
                                              alkyds);  styrenated poly-
                                              esters ;  rubber-modified
                                              polystyrene; copolymer
                                              resins»  intermediate
                               Suc6inic       ftefticinei organic
                               acid           ^ithesls; mfg. of lac^
                                              quers, dyes, esters for
                                              perfumes, suceinates;
                                              photography^ in fopds
                                              as a sequestrant, buffer,
                                              neutralizing agent
Total1"5
1975 production
capacity2 MM kg (MM Ib)
Manufacturers )2'3
American Petroflna,
Inc. T- Cosden Oil &
Chem. Co., subsid.
ARCO/Polymers, Inc.

Cos-Mar, Inc1.
Dow Chem. U.S.A.

El Paso Natural Gas
Co. - El Paso Co.,
subsid.
Foster Grant Co ,( , Inc .
Gulf OH Corp.. T Gulf
Oil Chems. Co., div. -
Petroehems . Div,
Monsanto Co. - Monsanto
Polymers & Petroehems .
Co.
Standard Oil Co, (Ind.) -
Amoco Chems . Corp . ,
subsid.
Sun Oil Co. - Sun Oil
Co. of Penn., subsid.
Location(s)2'3
Big Spring, Tex.


Beaver Valley, Pa.
Houston, Tex.
Carville, La.
Preeport , Tex .
Midland, Mich..
Odessa, Tex.


Baton Rouge, La.
Welcome, La.


Texas City, Tex.


Texas City, Tex.


Corpus Christ!,
Tex,
MM kg (MM Ib) for year of estimate
51.5


199.8
51.5
272.1
719.1
181.6
51.5


372.3
227


590.2


385.9


36.3

(120) 2,721 (6,000) -1971


(410)
(120)
(600)
(1,650)
(100)
U20)


(820)
(500)


(1,300)


(850)


(80)

                                                                          Suntlde Refining Co.
                                                                          subsid.

                                                                          Union Carbide Corp.  -
                                                                          Chems. & PlastJ.es Dlv.
Allied Chem. Corp. -
Specialty Chems. Div.

Richardson-Merrell,
Inc. - J. T. Bak,er
Chem. Co,, subsid.
Seadrdft, Tex.




Marcus Hook, Pa.

Phillipsburg, N.  J.
                                                   136,2  (300)

                                                    Total *
                                                 3..311.2  (7,300)

-------
                                                                                Table A-l.   (Continued)
                              Succino-
                              nltrlle
                              Sulfo-
                              lane
cr>
 I
Synthesis
gas
                              Tere-
                              phthalic
                              acid
                              Tetra-
                              chloro-
                              ethane
Tetra-
chloro-
phthalic
anhydride
                                             Organic synthesis
                Extraction of  aromatic
                hydrocarbons from oil
                refinery  streams;
                fractionation  of wood
                tars,  tall oil,  & other
                fatty  acids; polymeriza-
                tion solvent;  plastiei-
                ser; component of hydrau-
                lic fluid; textile
                finishing

                Organic synthesis; mfg.
                of alcohols  (Oxo process);
                low-Btu fuel gas

                Production of  linear,
                crystalline polyester
                resins, fibers & films
                by combination with
                glycols,  e.g., "Dacron,1
                "Mylar,"  "Terylene;"
                also used as a reagent
                for alkali in  wool; ad-
                ditive to poultry  feeds
               Solvent; cleansing &
               degreasing metals; paint
               removers, varnishes, lac-
               quers , photographic
               film; resins & waxes;
               extraction of oils &
               fats; alcohol denatu-
               rant; organic synthesis;
               insecticides; weed kil-
               ler; fumigant

               Intermediate in dyes,
               Pharmaceuticals, plasti-
               cizers, & other organic
               materials; flame-
               retardant in epoxy
               resins
                                           Guardian Chem. Corp. -
                                           Eastern Chem. Div.
                                           R.S.A. Corp.

                                           Phillips Petroleum Co.,
                                           Petrochem. & Supply Div.

                                           Shell Chem. Co. -
                                           Base Chems.
Hauppauge, N.  Y.


Ardsley, H. Y.

Phillips, Tex,

Norco, La,
                                           Eastman Kodak Co, -
                                          -Eastman Chem. Products,
                                           Inc., subsid. - Tenn.
                                           Eastman Co., div,
                                           Hercules Inc. -
                                           Synthetics Dept.

                                           Standard Oil Co. (Ind.)
                                           Amoco Chems. Corp.,
                                           subsid.
                                           Occidental Petroleum
                                           Corp. - Hooker Chem.
                                           Corp., subsid. - Hooker
                                           Chems. & Plastics
                                           Corp., subsid. -
                                           Electrochemical &
                                           Specialty Chems. Div.
                                                                         Monsanto Co. - Monsanto
                                                                         Indust. Chems. Co.
                                                                       Kingspcrt,  Tenn.
                                                                                                     Wilmington, N. C.

                                                                                                     Decatur, Ala.
                                                                                                     Joliet, 111.
                                                                                                     Taft, La.
                                      1,557    (3,^30)  -1974
                       113-5

                       363.2  (800)
                        45.if  (100)

                         Total  =
                       522.1  (1,150)
                                                                                                     Bridgeport,  N.  J.

-------
                                                                                 Table A-l.   (Continued)
VO
•C-
Ui
Chemical


Tetra-
ethyl
lead
(TEL)
Tetra-
hydro-
naphtha-
lene
                               Tetra-
                               hydro-
                               phthalic
                               anhydride
                               Tetra-
                               methylene-
                               diamine

                               Toluene
                               -2, II-
                               dlamine
                                              Antiknock gasoline  ad-
                                              ditive;  certain  ethyl-
                                              ation operations
Solvent; chemical
intermediate
               Chemical  intermediate
               for  light-colored  al-
               kyds* polyesters,
               plasticizers  &  ad-
               hesives;  Intermediate
               for  pesticides;
               hardener  for  resins

               Chemical  intermediate
               Dye  intermediate;  direct
               oxidation  black  for  furs
               & hair;  source for
               toluene-2,i}-diisocya~
               nate
                            Manufacturer (s) 2 *_3


                            E. I. du Pont de Ne-
                            mours & Co., Inc. -
                            Oganic Chemicals
                            Dept. - Petroleum
                            Chems. Dlv.

                            Ethyl Corp.


                            Nalco Chem. Co. -
                            Petroleum & Process
                            Chem. Div.

                            PPG Indust., Inc. -
                            Chem, Div. - Houston
                            Chem. Co., div.
E. I. du Pont de Ne-
mours & Co., Inc. -
Dyes & Chems. Div.

Lonza Inc.

Union Carbide Corp. -
Chems. & Plastics Div.

Petro-Tex Chem. Corp.
Petro-Tex Chem. Co.,
subsid.
                                            BASF Wyandotte  Corp.  -
                                            Indust.  Chems.  Group
                            Air Products & Chems.,
                            Inc.

                            American Cyanamid Co. -
                            Organic Chems. Div.

                            E. I. du Pont de Ne-
                            mours & Co., Inc. -
                            Organic Chems. Dept. -
                            Dyes & Chems. Div.

                            GAP Corp. - Chem. Div.

                            Olin Corp. - Agricul-
                            tural Chems. Div. -
                            Designed Products Dlv.
                                                                           Rubicon Chems.  Inc.

                                                                           Union Carbide  Corp.  -
                                                                           Chems.  & Plastics  Div.
Location(s)2'3
Antoich, Calif.
Deepwater, N. J.
1975
capacity2
MM kg (MM Ib)
Kb.* (310)
Total*'5
production
MM kg (MM Ib)
for year of estimate
216.7 (513.1) -1968
                                                                        Baton  Rougei  La.
                                                                        Pasadena,  Tex.

                                                                        Freeport,  Tex.
                                                                                                       Beaumont,  Tex.
                                                                        Deepwater,  N.  J.
                                                                                                       Mapleton,  111.

                                                                                                       Institute  & South
                                                                                                       Charleston, W.  Va.

                                                                                                       Houston, Tex.
                            Wyandotte, Mich.



                            Pasadena, Tex.


                            Bound Brook, N. J.


                            Deepwater, N. J.




                            Rensselaer, N. Y.

                            Lake Charles, La.
                            Ashtabula, Ohio
                            Brande nb urg, Ky.
                            Rochester, N. Y.

                            Geismar, La.

                            Institute & South
                            Charleston, W. Va.
                                                                                                                              158.9 (350)

                                                                                                                               18.2 (40)


                                                                                                                               iJ5.4 (100)
                                                                                                                                Total*=
                                                                                                                              376.8  (830)
                                                                                                                              *  Includes TEL,
                                                                                                                                TML  and mixtures.

-------
                                                                          *Pable A-l.  (Gbntinued)
                       Toluene-
                       sulfonic
                       acids
ON
                       Toluene-
                       sulfon-
                       amide
                       Toluene-
                       sulfonyl
                       chloride

                       Trichloro-
                       benzene
Usage1

Dyes; Organic  synthesis;
acid catalyst
Organic synthesis;
plasticiaers  & resins;
fungicide & mildewcide
in paints & coatings

Organic synthesis;  inter-
mediate in the synthesis
of saccharin  & dyestuffs

Solvent in chemical
mfg.; dyes &  inter-
mediates; dielectric
fluid; synthetic trans-
former oils;  lubricants;
heat-transfer medium;
insecticides
                                                                   Manufacturer^)2*3
American Cyanainid Co. -
Organic Chems . Div.
Cities Service Co.,
Inc. *- North American
Chems . & Metals Group -
Indust . Chems-. Div.
Monsanto Co . - Monsanto
Indust . Chems <. Co .
Wease Chem. Co., Inc.
Jim Walter Corp;. - U.S*
Pipe S Foundry 'Co , ,
subsid. - Chem. Div.

Monsanto Co. •*. Monsanto
Indust . Chems . Co .
Monsanto Co. - Monsanto
Indust-. Chems. Co.
Dow Chem. U.S.A.
Occidental Petroleum
Corp. - Hooker Chem.
Corp., subsid. *• Hooker
Chems. & Plastics
Corp., subsid. -
Electrochemical &
Specialty Chems. Div.
Sobin Cheros., Inc. -
Montrose Chem. Div,
Solvent Chem. Co., Inc.
                                                                   Standard Chlorine
                                                                   Chem.  Co.,  Inc.
Location (s)^.'?


•Bound Brook;, N, J.


Copperhill^ ^Tenn.




St. Louis, Mo.


State College, Pa.

Birmingham, Ala.



St. Louis, Mo.




St. Louis, Mow



Midland, Mich.

Niagara Falls,
N. Y-.
                                                         Newark,  N.  J.

                                                         Maiden,  Mass.
                                                         Niagara  Palls,
                                                         H.  Y.
                                                         Delaware City,
                                                         Del.
                                                         Kearny,  N.  J.
                                                     1975
                                                   capacity2
                                                 MM kg (MM.lto)
     Total1"5
     production
    MM kg {MM lb)
for^year. ,af \e_st i_ma_tg.

-------
                                                  Table A-l.  (Continued)
Trichloro-
ethane
Trichloro-
ethylene
Solvent for cleaning
precision instruments;
aerosol propellant;
metal degreasing;
pesticide; solvent for
fats, oils, waxes,
resins, other products;
organic synthesis
Metal degreasing; ex-
traction solvent for
oils, fats, waxes; sol-
vent dyeing; dry clean-
Ing ; refrigerant &
heat exchange liquid;
organic syntheses;
fumigant; medicine
(anesthetic); clean-
ing & drying electronic
parts
1975
capacity2
Manufacturer(s) 2> 3
Dow Chem. U.S.A.
Ethyl Corp.
PPG Indust. , Inc. -
Chem. Div. - Indust.
Chem. Div.
Vulcan Materials Co. -
Chains, Div.

Location(s)2'3
Freeport, Tex.
Baton Rouge, La.
Lake Charles, La.


Geismar, La.


MM kg
15«.
22.
79.


29.
To
286
(MM Ib)
1 (310)
7 (50)
1 (175)


5 (65)
tal •
(630)
Total1"5
production
MM kg (MM Ib)
for year of estimate
170.1 (371.6) -1971







1,2,3-TTl-
chloro-
propane
Paint & varnish remover;
solvent; degreasing agent
Diamond Shamrock Corp.  -
Diamond Shamrock Chem.
Co. f Electro Chems.
Div.

Dow Chem. U.S.A.

Ethyl Corp.

Occidental Petroleum
Corp. - Hooker Chem Corp.
subsid. - Hooker Chems.
& Plastics Corp.,
subsid. - Electrochemi-
cal & Specialty Chems.
Div.

PPO Indust., Inc. -
Chem. Div. - Indust.
Chem. Div.
Dow Chem. U.S.A.

Shell Chem. Co. -
Base Chems.
                                                                       Deer Park, Tex.
                                                                       Freeport, Tex.

                                                                       Baton Rouge, La.

                                                                       Taft, La.
                                                                       Lake Charles, La.
Freeport, Tex.
Deer Park, Tex.
                                                                                               15.1 (100)
                        68.1 (150)
                        22.7 (50)
                        18.2 (10)
                                                                                              127.1 (280)
                                                                                                Total =
                                                                                              281.5 (620)

-------
                                                                                 Table A-l -  C Cont inued)
 I
VO
•P**
00
                               1,1,2-Tri-
                               chloro-
                               1,2,2-tri-
                               fluoro-
                               ethane
Tri-
ethanol-
amine
                               Triethyl-
                               amlne
                              Trl-
                              ethylene
                              glycol
Dry cleaning solvent;
fire extinguishers; re-
frigerant ; air-condi-
tioning units; to make
chlorotri fluoroethylene;
blowing agent; polymer
intermediate; solvent
drying; drying electro-
nic parts £ precision
equipment

Patty acid soaps used
in drycleaning, cosmet-
ics, household deter-
gents, & emulsions;
wool scouring; textile
antifume agent & water-
repellent ; dispersion
agent; corrosion inhi-
bitor; softening agent,
humectant, & plasticl-
zer; insecticide; che-
lating agent; rubber
accelerator

Catalytic solvent in
chemical synthesis; ac-
celerator activators
for rubber; wetting,
penetrating & water-
proofing agents of
quarternary ammonium
types; curing & harden-
ing of polymers (e.g.,
core-binding resins);
corrosion inhibitor
propellant

Solvent for nitrocellu-
lose; various gums &
resins; lacquers; or-
ganic synthesis; air-
conditioning units;
bactericlde (in vapor
form); humectant in
printing inks; textile
conditioner; fungicide
Manufacturer(s)2»3


Allied Chem. Corp. -
Specialty Chems. Div.
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Preon® Products  Div.


Union Carbide Corp. -
Chems. & Plastics Div.

(See diethanolamlne)
                                           Air Products fr Chems.,
                                           inc.
                                           Pennwalt Corp. -
                                           Chem. Div.
                                           Union Carbide Corp. -
                                           Chems. & Plastics Div.
                                           Va. Chems. Inc. - Indust.
                                           Chems. Dept.
                                           Allied Chem. Corp. -
                                           Specialty Chems. Div.
                                           Celanese Corp. - Cela-
                                           nese Chem. Co., div.
                                           Dixie Chem. Co.
                                           Dow Chem. U.S.A.
                                                                       Location(s)2'3


                                                                       Baton Rouge, La.


                                                                       Antioch, Calif.
                                                                       Deepwater, N. J.
                                                                       East Chicago, Ind.
                                                                       Louisville, Ky.
                                                                       Montague, Mich.
                                                                       Institute & South
                                                                       Charleston, W. Va.
                            Pensacola, Pla,

                            Wyandotte, Mich.


                            Taft, La.

                            Portsmouth, Va.





                            Orange,  Tex.

                            Clear Lake, Tex.


                            Bayport, Tex,
                            Freeport,  Tex.
                            Plaquemine, La.
                                                                                                                               1975
                                                                                                                             capacity^
                                                                                                                           MM kg  (MM lb-)
                                                                                                   Total"'5
                                                                                                   production
                                                                                                  MM  kg  (MM lb)
                                                                                              fgr__yjBar__of^estimate
                                                                                                                                                     (108)  -1974
 1.1 (3)

 1.1 (3)

 0.9 (2)

15.9 (35)
                                                                                                                                               51.3  (113.1) -1973

-------
                                                                                Table A-l.  (Continued)
VO
*>
VO
                              Chemical

                              Tri-
                              ethylene
                              glycol
                              (cent1d)
                              Tri-
                              ethylene
                              glycol
                              dimethyl
                              ether

                              Trl-
                              methyl-
                              amine
Usage1

(See previous page)
Solvent for gases;
coupling immiscible
liquids
Manufacturer(s)z'3


Eastman Kodak Co. -
Eastman Ohem. Products,
Inc., subsid. - Texas
Eastman Co., div.

Olln Corp. - Designed
Products Div.

PPQ Indust., Inc. -
Chem. Div. - Houston
Chem. Co., div. -
PPQ Indust. (Caribe)

Shell Chem. Co. -
Base Chems.

Texaco Inc. - Jefferson
Chem. Co., Inc., subsid.

Union Carbide Corp. -
Chems. & Plastics Div.
                                                                         Union Carbide Caribe,
                                                                         Inc., subsid.
The Ansul Co. -
Chem. Div.
Organic synthesis, es-      Air Products & Chems.,
pecially of chlorine salts; Inc.
warning agent for natu-
ral gas; manufacture of
disinfectants; flota-
tion agent; insect
attractant; quaternary
ammonium compounds;
                                             plastics
Commercial Solvents Corp.
E. I. du Pont de Ne-
mours & Co., Inc. -
Biochems. Dept.
GAF Corp. - Chem. Div.
Rohm & Haas Co.
Locations)2'3

Longview, Tex.



Brandenburg, Ky,

Beaumont, Tex.


Guayanilla, P. R.
Gelsmar, La.

Port Neches, Tex.

Institute & South
Charleston, W. Va.
Seadrlft, Tex.
Taft, La.
Penuelas, P. R.
Marlnette, Wise .





Pensacola, Pla.

Terre Haute, Ind.
Belle, W. Va.
La Porte, Tex.

Calvert City, Ky.
Philadelphia, Pa.
    1975
  capacity2
MM kg (MM Ib)


   <0.5 (
-------
                                                  Table A-l.  (Continued)
Chemical


Tri-
iscbuty-
lene
Urea
Synthesis of resins, &
intermediate organic
compounds; lubricating
oil additive, raw
material for alkyla-
tion in producing
high octane motor fuels

Fertilizer; animal feed;
plastics; chemical inter-
mediate; stabilizer in
explosives; medicine;
adhesives; separation of
hydrocarbons (as urea
adducts); sulfamlc
acid production; flame-
proofing agents; vis-
cosity modifier for
starch or casein-based
paper coatings; re-
ported helpful in treat-
ing sickle-cell anemia
Manufacturer(s)2*3


The B. P. Goodrich
Co. - B. P. Goodrich
Chem. Co,, div.
                                           Agway Inc.

                                           Air Products & Chems.,
                                           Inc.

                                           Allied Chem. Corp. -
                                           Specialty Chems..Div. -
                                           Union Texas Petroleum
                                           Div. - Agricultural Div.

                                           American Cyanamid Co. -
                                           Agricultural Div.

                                           Borden Inc. - Borden
                                           Chem. Div. - Petrochems.

                                           CP Indust., Inc. -
                                           Chattanooga Nitrogen
                                           Complex - Donaldsonvilie
                                           Nitrogen Complex -
                                           Fremont Nitrogen Complex
                                           N. C. Nitrogen Complex

                                           Coastal States Gas
                                           Corp. - Colorado Inter-
                                           state Corp., subsid, -
                                           Wycon Chem. Co., subsid.

                                           Columbia Nitrogen Corp.

                                           Cooperative Farm Chems.
                                           Association

                                           Gardinier Big River, Inc.

                                           Gen. Amer. Oil of Tex. -
                                           Premier Petrochem. Co.,
                                           subsid.

                                           Goodpasture, Inc.

                                           W. R. Grace & Co. -
                                           Agricultural Chems, Group

                                           Hercules Inc. - Synthe-
                                           tics Dept.
Location(s)2'3


Port Neches, Tex.
                            Clean, N.  Y.

                            Pensacola, Fla.


                            South Point,  Ohio

                            Geismar, La.
                            Omaha, Neb.

                            New Orleans,  La.


                            Geismar, La.
                                                        Tyner, Tenn.
                                                        Donaldsonvllle,
                                                        La.
                                                        Fremont, Neb.
                                                        Tunis, N. C.

                                                        Cheyenne, Wyo.
                                                        Augusta, Ga.

                                                        Lawrence, Kans.


                                                        Helena, Ark.

                                                        Pasadena, Tex.



                                                        Dimmitt, Tex.

                                                        Memphis, Tenn.


                                                        Hercules, Calif.
                                                        Louisiana, Mo.
                                                                                                1975
                                                                                              capacity2
                                                                                            MM kg (MM Ib)
                                                                                                   Total4'5
                                                                                                   production
                                                                                                  MM  kg  (MM  Ib)
                                                                                              for year of  estimate
                        51.5 (120)

                        22.7 (50)


                        63.6 (140)

                       201.3 (450)
                       127.1 (280)

                       131.7 (290)


                       177.1 (390)
                                                    36.3 (80)
                                                   331.4 (730)

                                                    18.2 (40)
                                                   154.4 (340)
                                                    45.4 (100)
                                                    27.2 (60)
                                                   181.6 (400)

                                                    59   (130)
                                                    95.3 (210)


                                                    22.7 (50)
                                                   122.6 (270)

                                                    36.3 (80)
                                                    86.3 (190)
                                                                                                             3,350   (7,38o)-1974

-------
                                                                                Table A-l.   (Continued)
                              Chemical

                              Urea
                              (cont1d)
Usage1

(See previous page)
Ui
Manuf acturer(s)2!>3


Kaiser Aluminum & Chem.
Corp. - Kaiser Agri-
cultural Chems. Div.

Lone Star Gas Co. -
Nipak, Inc., subsid.
Miss. Chem. Corp.

Mobil Oil Corp. -
Mobil Chem, Co., div. -
Petrochems. Div.
N-Ren Corp. - Cherokee
Nitrogen Div. - High
Plains Div.
Olin Corp. - Agricul-
tural Chems. Div.

Phillips Pacific Chem.
Co.
Phillips Petroleum Co. -
Fertilizer Div.

Reichhold Chems., Inc.
St. Paul Ammonia Pro-
ducts, Inc.
J. R. Simplot Co. -
Minerals & Chem. Div.

Skelly Oil Co. - Hawk-
eye  Chem. Co., subsid.
The Standard Oil Co.
(Ohio) - Vistron Corp.,
subsid. - Chems.. Dept.
Tenn. Valley Authority
Terra Chems. Internat'l,
Inc.
Triad Chem.
Loeatlon(s)2'3
Savannah , Ga .
Kerens, Tex.
Pryor, Okla.
Yazoo City, Miss.
Beaumont, Tex.
Pryor, Okla.
Plainview, Tex.
Lake Charles, La.
Kennewick, Wash.
Beatrice, Net).
St. Helens, Ore.
East Dubuque, 111.
Pocatello, Idaho
Clinton, Iowa
Lima , Ohio
Muscle Shoals, Ala.
Port Neal, Iowa
Total1"5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
72.6
77.2
122.6
168
45.4
18.2
51.5
115-3
10.9
50
50
72.6
-
54.5
217.9
63.6
154.4
(160) (See previous page)
(170)
(270)
(370)
(100)
(40)
(120)
(320)
(90)
(110)
(110)
(160)

(120)
(180)
(140)
(340)
                                                                                                      Donaldsonville,  La.
                                                                                                                                   (970)

-------
                                                  Table  A-l.  (Continued)
Chemical

Urea
(con'd)
Vinyl
acetate
Usage1


(See previous page)
Polyvinyl acetate,
polyvinyl alcohol, poly-
vinyl butyral, & poly-
vinyl chloride-acetate
resins (q.v.); these are
used particularly In
latex paints; paper
coating; adhesives;
textile finishing;
safety glass inter-
layers
Manufacturer(s) 2 ' 3

Tyler Corp. - Atlas
Powder Co., subsld.
Union Oil Co. of Calif.
Collier Carbon & Chem.
Corp., subsid.
U.S. Steel Corp. -
USS Agri-Chems. div.
Valley Nitrogen Pro-
ducers, Inc.
The Williams Companies
Agrlco Chem. Co.,
subsid.
Borden Inc. - Borden
Chem. Div. - Petrochems.
Celanese Corp. - Cela-
nese Chem. Co., div.


E. I. du Pont de Ne-
mours & Co,, Inc. -
Plastics Dept.

National Distillers &
Chem. Corp. - Chems.
Div. - U.S. Indust.
Chems. Co., div.
National Starch 4 Chem.
Corp.
Reichhold Chems., Inc. -
Reichhold Chem. Del
Caribe, Inc., subsid.
Union Carbide Corp. -
Chems. & Plastics Div.
Location(s)2'3
Joplin, Mo.
Brea, Calif.
Kenai, Alas.
1975
capacity2
MM kg (MM Ib)
59 (130)
50 (110)
308. T (680)
Total1*'5
production
MM kg (MM Ib)
for year of estimate
(See previous page)
                                                                       Cherokee, Ala.
                                                                                               22.7' (50)
El Centre, Calif.
Helm, Calif.
Blythevllle, Ark.
Donaldsonville, La.
110.7
31.8
299.6
299.6
(310)
(70)
(660)
(660)
Total -
5,057.6 (11,1*0)
Geismar, La.
Bay City, Tex.
Clear Lake, Tex.
Pampa, Tex.
La Porte, Tex.
68.1
136.2
158.9
29.5
158.9
(150)
(300)
(350)
(65)
(350)
                                                                       Deer Park, Tex.



                                                                       Long Mott, Tex.

                                                                       Rio Piedras, P. R.


                                                                       Texas  City, Tex.
170.2 (375)



 31.8 (70)

  6.8 (15)


120.3 (265)

  Total -
880.8 (1,910)
                                                                                                               635-6 (1,100) -1971

-------
                                                                                 Tab le A-l.  (Cont Inued)
                              Chemical
                              Vinyl
                              chloride
Polyvinyl chloride (q,
ft copolymers; organic
synthesis j adhesives
for plastics
VO
Ln
CO
      Manufacturer(s)2 *3


v.)   Allied Chem. Corp. -
      Indust. Chems. Dl v.

      Borden Inc. - Borden
      Chem. Div. - Petrochems.

      Continental Oil Co.  -
      Conoo.o Chems.

      Dow Chem. U.S.A.
                            Ethyl Corp.


                            The B. F. Goodrich Co. -
                            B. P. Goodrich Chem.,
                            Co., subsid.

                            Monochem, Inc.

                            PPG Indust., Inc. -
                            Chem. Div.  - Indust.
                            Chem. Div.  - PPG Indust.
                            (Caribe)

                            Shell Chem. Co. - Base
                            Chems.

                            Stauffer Chem, Co. -
                            Plastics Div. - Poly-
                            mers West

                            Tenneco Inc. - Tenneco
                            Chertis., Inc.. - Organic s
                            & Polymers  Div.

                            Union Carbide Corp. -
                            Chems. & Plastics Div.
Locatlon(s)2'3
Baton Rouge, La.
Geismar, La.
Westlake, La.
Freeport , Tex.
Oyster Creek, Tex.
Plaquemlne, La.
Baton Rouge, La.
Pasadena, Tex.
Calvert City, Ky.
Geismar, La.
Lake Charles, La.
Quayanilla, P. R.
Deer Park, Tex.
Norco, La.
Carson, Calif.
Total1"5
1975 production
capacity2 MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
136.2
-
295.1
90.8
317.8
177.1
136.2
68.1
151
136.2
181.6
227
381.1
317.8
79.5
(300) 2,512 (5,600) -1971

(650)
(200)
(700)
(390)
(300)
(150)
(1,000)
(300)
(loo)
(500)
(810)
(700)
(175)
                                                                                                      Houston, Tex.



                                                                                                      Texas City, Tex.
                                                                                                                             102.1 (225)
                                                          68.1 (150)

                                                           Total =
                                                       3,169   (6,980)

-------
                                                                                 Table A-l.  (Continued)
CT»

V0
Ui
                              Ch_emlc_ajl


                              Vinyli-
                              dene
                              chloride
                              Vinyl
                              toluene
in-xylene
                              o-xylene
               Copolymerized  with  vinyl
               chloride  or  acryloni-
               trile  to  form  various
               kinds  of  saran;  other
               copolymers are also made;
               adhesives; component of
               synthetic fibers

               Solvent;  Intermediate
               Solvent;  intermediate for
               dyes  & organic  synthesis,
               especially  isophthalic
               acid; insecticides;
               aviation  fuel

               Mfg.  of phthalic  an-
               hydride;  vitamin  &
               pharmaceutical  synthesis;
               dyes; insecticides; motor
               fuels
Manufacturer(s)2 *3


Dow Chem. U.S.A.


PPG Indust., Inc. -
Chem. Div. - Indust.
Chem. Divf.



Dow Chem.' U.S.A.

Foster Grant Co., Inc.

Atlantic Richfield
Co. - ARCO Chem. Co.,
div.
                                                                          American Petrofina,
                                                                          Inc.  - Cosden Oil &
                                                                          Chem. Co._, subsid.

                                                                          Atlantic Richfield Co.  -
                                                                          ARCO Chem. Co., div.

                                                                          Cities Service Co.,
                                                                          Inc.  - North American
                                                                          Petroleum Group

                                                                          Coastal States Gas
                                                                          Corp. - Coastal States
                                                                          Marketing, Inc., subsid.

                                                                          Commonwealth Oil Refin-
                                                                          ing Co., Inc. - Common-
                                                                          wealth Petrochems.,
                                                                          Inc., subsid.

                                                                          Crown Central Petroleum
                                                                          Corp.

                                                                          Exxon Corp,  - Exxon
                                                                          Chem. Co., div. -
                                                                          Exxon Chem.  Co. U.S.A.

                                                                          Kerr-MeGee Corp. - South-
                                                                          western Refining Co.,
                                                                          Inc., subsid.
Locatlon(s)2'3
Freeport, Tex.
Plaquemine, La.
1975
capacity2
MM JCK (MM Ib)
-
Total"'5'
production
MM kg (MM Ib)
for year of estimate
77.2 (170) -1971
                                                                                                      Lake Charles,  La.
                                                                        Midland,  Mich.

                                                                        Baton  Rouge,  La.

                                                                        Channelview,  Tex.
                            Big Spring, Tex.



                            Houston, Tex.


                            Lake Charles, La.



                            Corpus Christ!,



                            Penuelas, P. R.




                            Pasadena, Tex.


                            Baytown, Tex.



                            Corpus Christ!, Tx.
 15.9 (35)





  8.2 (18)



 95.3 (210)


 51.5 (120)



 18.2 do)



 63.6 (110)




 31   (75)


222,5 (190)



 ")5.1 (100)
                                                                                                                      (78)
                                                                                                                             -1970
                                                                                                                                                    (824.8)  -1970

-------
                                                                                            Table  A-l.  (Continued)
                                          Chemical
                                          o-xylene
                                          (cont'd)
Ln
Ln
                                          p-xylene
                                                         Usage1

                                                         (See previous page)
Synthesis of tere-
phthalic acid for
polyester resins &
fibers ("Dacron,"
"Mylar," "Terylene");
vitamin & pharmaceu-
tical syntheses;
insecticides
                            Manufacturer(s)2 J 3


                            Monsanto Co. - Monsanto
                            Polymers & Petrochems.
                            Co.
                            Phillips Petroleum Co.  -
                            Phillips Puerto Rico
                            Core,  Inc., subsid.
                            Shell Chem. Co. - Base
                            Chems.

                            Standard Oil Co. of
                            Calif. - Chevron Chem.
                            Co., subsid. - Oronlte
                            Additives & Indust.
                            Chems. Div. - Indust.
                            Chems.
                            Sun Oil Co. - Sun Oil
                            Co. of Penn,, subsid. -
                            Suntide Refining Co.,
                            subsid.
                            Tenneco Inc. - Tenneco
                            Oil Co., div.
Atlantic Richfield Co. -
ARCO Chem. Co.s  div.
The Charter Co.  -
Charter Oil Co., subsid.,
Charter Internat'l Co.,
subsid.
Cities Service Co.,
Inc, - North American
Petroleum Group
Exxon Corp. - Exxon
Chem, Co., div.  -
Exxon Chem. Co.  U.S.A.

Hercor Chem. Corp.
Phillips Petroleum Co. -
Phillips Puerto Rico
Core Inc., subsid.
LooatiQn(s)2*
Chocolate Bayou,
Tex.
                                                                                                                  Guayama,  P.  R.


                                                                                                                  Deer  Park,  Tex.


                                                                                                                  Richmond, Calif.
                                                                                                                  Corpus  Christ!,
                                                                                                                  Tex.
Chalmette, La.




Houston, Tex.

Houston, Tex.




Lake Charles, La.


Baytown, Tex.



Penuelas, P. R.
Guayama, P. R.
    1975
  capacity2
MM kg (MM Ib)
                                                                       Total1*1*
                                                                       production
                                                                      MM kg (MM Ib)
                                                                  for year_ _p_f^estimat_e_
   13.6 (30)     (See previous page)



   59   (130)


   90.8 (200)


   67.2
   72.6 (160)



   70.4 (155)

    Total =
  915-3 (2,016)

  181.6 (iioo)    1,216.7 (2,680) -1974

    6.8 (15)



   15.9 (35)


  181.6 (Hoo)


  238.3 (525)
   34   (75)

-------
                                                                                  Table A-l.  (Continued)
                                                                                                                                                 Total '•
 I
vo
Ui
Chemical Usage1
p-xylene (See previous page)
( cont ' d)


Manufacturer(s)2' 3
Shell Chem. Co. -
Base Chems.
Standard Oil Co. of
Calif. - Chevron Chem.
Co., subsid. - Oronite
Additives 8 Indust.
Chems. Div. - Indust.
Chems .
Standard Oil Co. (Ind.) -
Amoco Chems . Corp . ,
Location(s)2'3
Deer Park, Tex.
El Segundo, Calif.
Pascagoula, Miss.
Richmond, Calif.
Decautur, Ala.
Texas City, Tex.
1975 production
capacity2' MM kg (MM Ib)
MM kg (MM Ib) for year of estimate
45.1
HO. 7
50
121.8
121.8
(100) (See previous page)
(310)
(110)
(275)
(275)
Xylenol
(mixed 2,
4~; 2,5-;
3, it-;
3,5-)
Xylidlne
(mixed 2,3-;
2 , if- ; 2,5-;
2,6-)
                                               Disinfectants; solvents,
                                               Pharmaceuticals, insect-
                                               icides ft fungicides;
                                               plasticizers; rubber
                                               chemicals; additives to
                                               lubricants & gasoline;
                                               manufacture of poly-
                                               phenylene oxide
                                               (2,6-isomer only);
                                               wetting agents;
                                               dye stuffs

                                               Dye intermediates;
                                               organic syntheses;
                                               Pharmaceuticals
                                            subsid.

                                            Sun  Oil  Co.  -  Sun Oil
                                            Co.  of Penn.,  subsid.
                                            Suntide  Refining Co.,
                                            subsid.

                                            Tenneco  Inc. - Tenneco
                                            Oil  Co.,  div.
Koppers Co., Inc. -
Organic Materials Div.
Productol Chem, Co.
                                           Stimson Lumber Co. -
E. I. du Pont de Ne-
mours & Co., Inc. -
Organic Chems. Dept. -
Dyes & Chems. Div.
                                                                                                       Corpus Christi,
                                                                                                       Chalmette, La.
                                                                                                       Follansbee, W. Va.
                            Santa Pe Springs,
                            Calif.
                            Anacortes,  Wash.
                                                                       Deepwater, N. J.
                                                                                                                              136.2  (300)
                                                    15.l| (100)

                                                     Total =
                                                 1,325.7 (2,920)

-------
 APPENDIX B






RAW MATERIALS
 6-957

-------
                            Table B-l.  RAW MATERIALS FOR THE
                           INDUSTRIAL ORGANIC CHEMICALS INDUSTRY
*Acetaldehyde
*Acetaldol
*Acetam"lide
*Acetic acid
*Acetic anhydride
*Acetone
*Acetone cyanohydrin
*AGetonitrile
 Acetyl chloride
*Acetylene
*Acrolein
*Acrylic acid
*Acrylonitrile
 Air
 Alkyl amines   -^
 Alkyl benzenes -I group
 ...  ,  .,  .,   I names
 Alkyl chloridesj
*Allyl alcohols
*Allyl chlorides
 Alumina gel
 Aluminum chloride
 Ammonia
 Ammonium salts
  (e.g., carbonate)
*Amyl alcohols
*Amyl chlorides
*Aniline
*Aniline hydrochloride
 Aniline sulfate
 Antimony (III) fluoride
 Aromatics, C8-groups
*Benzaldehyde
*Benzene
*m-Benzene disulfonic acid
*p-Benzene disulfonic acid
*Benzene sulfonic acid
*Benzil
*Benzoic acid
*Benzoin
*p-Benzoquinone
*Benzotrichloride
*Benzoyl chloride
*Benzyl chloride
 Bromine
*Bromobenzene
*1,3-Butadiene
*n-Butane
 2-Butanone
*l-Butene
*2-Butene
*n-Butenes
*n-Butyraldehyde
*n-Butyl alcohol
*sec-Butyl alcohol
*tert-Butyl alcohol
*tert-Butyl toluene
*Butyric acid

 Calcium carbonate
 Calcium hydroxide
 Calcium oxide
 Carbon
 Carbon dioxide                      •
 Carbon monoxide                     ,1
*Carbon disulfide
*Carbon tetrachloride
 Catalytic gas oils
 a-Cellulose
 Charcoal
 Chlorine (dry)
*Chloracetic acid
*Chlorobenzene
*Chloroform
*Chlorotoluene
 Coal tars
 Cobalt toluate
*Crotonaldehyde
*Cumene
*Cumene hydroperoxide
*Cyanogen chloride
*Cyclohexane
*Cyclohexanol
*Cyclohexanone

*Diacetone alcohol
 Diallyl ether - group name
*o-Di chlorobenzene
*m-Di chlorobenzene
*Dichlorohydrin
*Diethylene glycol dibutyl ether
 Diethylene glycol monoethers - group
._..  .,  ,   .,                    name
*Diethyl ether
                                         6-958

-------
                       Table B-l  (Continued).   RAW MATERIALS FOR THE
                           INDUSTRIAL  ORGANIC  CHEMICALS INDUSTRY
 Diethyl  oxalate
*1,1-Di f1uoroethane
*Diisobutylene
 Dimethyl acetal
*Dimethyl sulfate
*Dimethyl sulfide
*Dinitrobenzenes
*Dinitrobenzoic acid
*Dinitrotoluene
*Diphenyl oxide
*Dodecene
 Drip oils

*Epichlorohydrin
*Ethane
*Ether
*Ethyl acetate
*Ethyl alcohol
*Ethyl benzene
*Ethyl chloroacetate
*Ethyl chloride
 Ethyl formate
 Ethyl sulfate
 Ethyl toluene
 Ethylene
*Ethylene chlorohydrin
*Ethylene diamine
*Ethylene dibromide
*Ethylene dichloride
*Ethylene glycol
*Ethylene oxide
 Flue gas
*Formaldehyde
*Formic acid
*Fumaric acid
 Furfural

*Glyceraldehyde
*Glycerol

*Heptene
 Hexyl alcohol
 Hydrochloric acid
 Hydrofluoric acid
 Hydrogen
 Hydrogen bromide
 Hydrogen chloride
*Hydrogen cyanide
 Hydrogen fluoride
 Hydrogen peroxide
*Hydroquinone
 Hypochlofous acid

 Iron sulfate
*Isoamylenes
 Isobutane
 Isobutene
*Isobutyl alcohol
 Isobutylene
*Isobutyraldehyde
 Isopentane
*Isopropyl alcohol
*Isopropyl chloride

*Ketene

 Lead
 Lead amalgam
 Light cycle oils

*Maleic acid
*Maleic anhydride
 Manganese dioxide
*Mesityl oxide
*Methallyl chloride
 Methane
*Methyl acetate
*Methyl alcohol
*Methyl chloride
*Methyl cyclohexane
*Methyl ethyl ketone
*Methyl formate
 Methyl iodide
*Methyl isobutyl ketone
 Methyl propene
*Methylene chloride
 Monoethylene glycol monoether
  group name
*Naphthalene
*l-Naphthalene sulfonic acid
*2-Naphthalene sulfonic acid
 Natural gas
 Nitric acid
                                         6-959

-------
                       Table B-l (Continued).   RAW MATERIALS FOR THE
                           INDUSTRIAL ORGANIC  CHEMICALS INDUSTRY
*Nitrobenzene
 m-Ni trochlorobenzene
 Nitrogen
 Nitrogen dioxide
   (dinitrogen tetraoxide)
*o-Nitroanisole
*p-Nitroanisole
*o-Nitrophenol
*p-Nitrophenol
 Nitrosylsulfuric acid
*Nitrotoluene
*Nonene

 Octyl alcohol
 "Olefins"
 Oxalic acid (dihydrate)
 Oxygen

*Pentane
 Peracetic acid
*Perchloroethylene
*Phenol
*Phosgene
 Phosphorous tribromide
*Phthalic anhydride
*Phthalimide
 Polychloroaromatics
 Potassium t-butoxide
 Potassium cyanide
 Potassium hydrosulfide
 Potassium hydroxide
 Potassium permanganate
 Potassium sulfide
*Propane, liquid
*n-Propyl alcohol
*n-Propyl chloride
 Propylene
*Propylene chlorohydrin
 Propylene glycol
*Propylene oxide
*Pyridine

 Refinery gas caustic
   extract
 Reformer bottoms

 Silica gel
 Sodium
*Sodium acetate
 Sodium bicarbonate
 Sodium bisulfite
 Sodium carbonate
 Sodium carbonate
   emulsifier
*Sodium chloroacetate
 Sodium chloride
 Sodium cyanide
 Sodium dichromate
 Sodium ethoxide
*Sodium formate
 Sodium hydrosulfide
 Sodium hydrosulfite
 Sodium hydroxide
 Sodium perborate
*Sodium phenate
 Sodium "salt"
 Sodium stearate
 Sodium sulfide
 Sodium sulfite
 Sulfur, organic derivatives
 Sulfur dioxide
 Sulfur dioxide, liquid
 Sulfur trioxide
 Sulfuric acid
   Oleum
 Sulfuric acid, monohydrate
 Synthesis gas
*1,1,2,2-Tetrachloroethane
 Tetrahydrofuran
*Trichloroaniline
*1,1,2-Trichloroethane
*Tri chloroethylene
 2,4,6-Trichlorophenol
 Toluene
*Toluene sulfonyl chloride
*Toluidine
 Tolunitrile

*Urea

 Water
 Water, demineralized
 Water, distilled
 Water, steam
                                         6-960

-------
                       Table B-l (Continued).  RAW MATERIALS FOR THE
                           INDUSTRIAL ORGANIC CHEMICALS INDUSTRY
*m-Xylene
*o-Xylene
*p-Xylene
 Zeolite,  synthetic
 Zinc
* Indicates  chemical  is also a product of this industry.
                                          6-961

-------
APPENQIX C




CATALYSTS
6-962

-------
                       Table C-l.   CATALYSTS USED IN THE PRODUCTION
                              OF INDUSTRIAL ORGANIC CHEMICALS
Acetic acid
Alkali metals
Alumi na
Alumina,  modified anhydrous Gamma
Alumina,  gel
Alumina-chromia
Aluminum  turnings
Aluminum  alkoxides
Aluminum  chloride
Amine bases
Ammonium  chloride
Ammonium  metavanadate
Ammonium  persulfate-ammonium bromide
Aniline hydrochloride
Antimony, partially fluorinated
Antimony  (III) chloride
Antimony  (V)  chloride
Antimony  (V)  fluoride

Barium chloride on carbon
Barium hydroxide
Bauxi te
Bismuth-molybdenum
Boric acid
Boron trifluoride
Brass
Bromine

Calcium carbide
Calcium chloride
Calcium nickel phosphate stabilized
 with 2%  Chromium oxide
Calcium oxide
Carbon
Carbon, activated
Carboxyl salts of divalent transition
 metals, e.g., zinc isovalerate
Chromic acid
Cobalt acetate
Cobalt carbonyl compounds
Cobalt carbonyl compounds, phosphorus
 promoted
Cobalt compounds
Cobalt-manganese activated by bromine
Cobalt-manganese activated by acetaldehyde
Cobalt-manganese activated by methyl
 ethyl ketone
Cobalt naphthenate
Cobalt oxides
Cobalt "salts"
Cobalt "salts" activated by bromine
Cobalt stearate
Copper
Copper, solid, promoted by cobalt or
 chromium on asbestos
Copper-silica
Copper acetate
Copper chromite
Cuprammonium nitrate
Cupric chloride
Cupric chloride impregnated on a fluid -
 or fixed-bed support
Cupric oxide
Cupric sulfate
Cuprous oxide

Diatomaceous earth
Dichlorohydrin
Disul fides
Dowex 50 ion exchange resin
                                        6-963

-------
                     Table C-l.  (Continued).  CATALYSTS USED IN THE
                        PRODUCTION OF INDUSTRIAL ORGANIC CHEMICALS
Ethyl acetate

Ferric acetate
Ferric bromide
Ferric chloride
Ferric oxide-chromium oxide-potassium oxide
Friedel-Crafts reagents
Fuller's earth

Gamma radiation from Cobalt-60
Nickel
Nickel, activated
Nickel, activated, on asbestos carrier
Nickel-chromium catalyst, reduced
Nickel acetate
Nickel oxide in refractory cement
Nickel chromite
Nickel chromate
Nickel, Raney
Nickel sulfide
Heavy metal salts
Hydrochloric acid

Ion exchange resins
Iron turnings
Iron-molybdenum oxide

Lewis acid catalyst
Light
Lithium arsenate
Lithium phosphate
Lithium "salt"

Magnesium
Magnesium oxide
Manganese acetate
Manganese butyrate
Manganese oxide
Mercaptans
Metaboric acid
Molybdenum chloride
Molybdenum oxides
Molybdenum sulfide
Oleic acid

Palladium
Palladium catalyst, supported
Palladium chloride promoted for metal
 oxidation by cooper chloride
Phosphoric acid, solid
Phosphoric acid, on kieselguhr
Phosphorus, red
Phosphorous trichloride
Phosphorous pentachloride
Platinum
Platinum-rhodium mesh
Platinum oxide
Potassium carbonate
Potassium cyanide
Potassium hydroxide
Potassium sulfate

Rhodium-carbonyl complex

Silica-alumina
Silica gel catalyst
                                        6-964

-------
                     Table C-l. (Continued).   CATALYSTS  USED IN THE
                        PRODUCTION OF INDUSTRIAL ORGANIC CHEMICALS
Silica-zerconia
Sodamine
Sodium
Sodium hydroxide
Silver
Silver, crystalline
Silver oxide
Sulfuric acid

Tin
p-Toluene sulfonic acid
Triethyl phosphate
Tungsten
Tungsten sulfide
Tungstic acid

UV light from mercury vapor lamps
Uranium oxide

Vanadium
Vanadium pentoxide

Water

Zinc chloride
Zinc compounds
Zmc oxide promoted with alumina and chromates
Zmc oxide on pumice
Zirconium chloride
                                        6-965

-------
         APPENDIX D



INDUSTRIAL ORGANIC CHEMICALS
        6-966

-------
            Table  D-l.   INDUSTRIAL ORGANIC CHEMICALS

                        NAME
ACETAL
ACETALOEHYDE
ACETAMIDE
ACETANILIDE
ACETIC ACID
ACETIC ANHYDRIDE
ACETONE
ACETONE CYANQHYORIN
ACETONITRILE
ACETOPHENONE
ACETYL CHLORIDE
ACETYLENE
ACROLEIN
ACRYLAMIDE
ACRYLIC ACID AND ACRYLATE ESTERS
ACRYLQNITRILE
AOXPIC ACID
ADIPQNITRILE
ALKYLNAPHTHALENES (METHYL
AUYL ALCOHOL
ALLYL CHLORIDE
AHINOBENZOIC ACID (M,P)
AM1NOETHYLETHANOLAMINE
P»AMINOPHENOL
AMYL ACETATES
ANYL ALCOHOLS (8 ISOMERS)
AMYL CHLORIDE
AMYL MERCAPTANS
AMYL PHENOL
ANILINE
AMILINE HYDROCHLORIOE
ANISIOINE
ANXSOLE
ANTHRANILIC ACID
AMTHRAQUINONE
BENZALDEHYDE
                            6-967

-------
      Table D-l.   (Continued).  INDUSTRIAL ORGANIC CHEMICALS

                       NAME

BENZAMIDE
BENZENE
BENZENEDISULFQNIC  ACID
BENZENESULFONIC ACID
BENZ!l
BENZILIC ACID
BENZOIC ACID
BENZOIN
BENZONITRILE
BENZOPHENONE
BENZQTRICHLORIDE
BENZOYL CHLORIDE
BENZYL ALCOHOL
BENZYLAMINE
BENZYL BENZOATE
BENZYL CHLORIDE
BENZYL DICHLORIDE
BIPHENYL
BI8PHENOL A
BROMQBENZENE
BROMQNAPHTHALENE
BUTADIENE
U6UTENE
N-BUTYLACETATE
N*BUTYLACRYLATE
N»BUTYL ALCOHOL
SEC-BUTYL ALCOHOL
TERT*BUTYL ALCOHOL
N«BUTYLAMINE
8EC»BUTYLAMINE
TERT»BUTYLAMINE
P.TERT.BUTYLBENZOIC AGIO
1,3 BUTYLENE SLYCQL
TERT«8UTYLPHENOL
N.BUTYRALDEHYDE
N«BUTYRIC ACID
N.BUTYRIC ANHYDRIDE
N.BUTYRONITRILE
                            6-968

-------
     Table D-l.  (Continued).  INDUSTRIAL ORGANIC CHEMICALS

                       NAME

CAPRQLACTAM
CARBON DISULFIDE
CARBON TETRA8RQMIOE
CARBON TETRACHLQRIDE
CELLULOSE ACETATE
CHLOROACETIC ACID
M*CHLQRQANILINg
0-CHLORQANILINE
P«CHLORQANILINE
CHLORQBENZALDEHYDE
CHLOR08ENZENE
CHLOROBENZOIC  ACID
CHLOROBENZOTRICHLORIDE (D,P)
CHLQRQBENZOYL  CHLORIDE
CHLORODIFLUOROETHANE
CHLQRQQIFLUQRQMETHANE
CHLOROFORM
CHLORONAPHTHALENE
O.CHLORONJTR08EN2ENE
P«CHLORONITR08ENZENE
CHLOROPHENOLS
CHLOR03ULFONIC ACID
M*CHLOROTOLUENE
0«CHLOROTOLUENE
P-CHLORQTQLUENE
CMLOROTRIFLUOROMETHANE
CROTONALDEHYOE
CROTONIC ACID
CjMENE
CUMENE HYDROPEROXIDE
CfANOACETIC ACID
CYANOGEN CHLORIDE
CYANURIC ACID
CYANURIC CHLORIDE
CYCLOHEXANE
CYCLOHEXANOL
CYCLOHEXA^ONE
CYCLOHEXENE
                            6-969

-------
      Table D-l.  (Continued).  INDUSTRIAL ORGANIC CHEMICALS

                        NAME

CYCLQHEXYLAMINE
CYCLOQCTADIENE
OECANQL
DIACETQNE ALCOHOL
DIAMINQBENZQIC ACID
DICHLOROANILINE
M»DICHLORQ8ENZENE
0»OICHLORQBENZENE
P*DICHLQROBENZENE
OICHLQKODIFLUORQMETHANE
1,2-OXCHLQRQETHANE
DICHLQROETHYL ETHER
OZCHl,OROHYORIN
DICHIOROPROPENE
OICYCIOHEXYI.AM1NE
DIITHYLAMINE
OIITHYUENE GLYCOL
OIETHYIENE GUYCOL DIETHYt, ETHER
OXITHYLENE GlYCOL DIMETHYL ETHER
OIITHYLENE GUYCOL MONOBUTYU ETHER
OI6THYIENE GLYCOU MONOIUTYl. ETHER ACETATE
OIETHYLENE GUYCOL MQNOETHYU ETHER
OIETHYUENE GLYCOL MONOETHYL ETHER ACETATE
OIETHYLENE GLYCOL MQNQMgfHYL ETHER
OIETHYL SULFATE
OIPLUOROETHANE
OIISQ8UTYLENE
OIKETENE
DIMETHYLAMINE
N,N»OIMETHYLANILINE
DIMETHYL ETHER
N,N»-OIMETHYLFORMAMIOE
DIMETHYL HYORAZINE
DIMETHYL SULFATE
DIMETHYL SiJLFXDE
DIMETHYL SULFOXIDE
DIMETHYL TEREPHTHALATE
3,5*DINITRQBENZOIC ACID
                            6-970

-------
     Table D-l.   (Continued).  INDUSTRIAL ORGANIC CHEMICALS

                       MAME

2,4*DINITROPHENOL
OJNITRQTQLUENE
OJQXANE
OlOXQLANE
DIPHENYLAMINE
DIPHENYL OXIDE
OIPHENYITHIOUREA
OIPRQPYLENE SLYCOL
OODECENE
DQDECYLANIL1NE
QODECYLPHENQL
EPICHLQRQHYDRIN
ETHANOL
EHTANOI.AMINE
ETHYL ACETATE
ETHYL ACETOACETATE
ETHYL ACRYLATE
ETHYLAMINE
ETHYLBENZENE
ETHYL BROMIDE
ETHYL CELLULOSE
ETHYL CHLORIDE
ETHYL CHLOROACETATE
ETHVLCYANOACETATE
ETHYLENE CARBONATE
ITHYLENE CHLOROHYDRIN
ETHYLENE DIAMINE
ITHYLENE DIBROMJDE
fTHYLENE SLYCOL
ETHYLENE SLYCOL OIACETATE
ETHYLENE SLYCOL DIMETHYL ETHER
ETHYLENE SLYCOL MONQBUTYl ETHER
ITHYLENE SLYCOL MQNOBUTYL ETHER ACETATE
ITHYLENE SLYCOL MONOETHYL4 ETHER
ETHYLENE SLYCOL MONOETHYLS ETHER ACETATE
ETHYLENE SLYCOL MONQMETHYL ETHER
ITHYLENE SLYCOL MQNQMETHYL ETHER ACETATE
ETHYLENE SLYCOL MONOPHEMYL ETHER
                            6-971

-------
      Table D-l.  (Continued).  INDUSTRIAL ORGANIC CHEMICALS
ETHYLENE 6LYCQL MQNQPROPYL ETHER
ETHYLENE OXIDE
ETHYL ETHER
2»ETHYL HEXANQL
ETHYL ORTHOFORMATE
ETHYL OXALATE
ETHYL SODIUM OXALACETATE
FORMALDEHYDE
FQRMAMIDE
FORMIC ACID
FUMARIC ACID
6LflrCEROL(NATURAL&3YNTHETIC)
SLYCEROL DICHLOROHYDRIN
BLYCEROL TRHPOLYOXYPROPYLENE) ETHER
G^YCINE
5LYOXAL
HEPTENE
HEXACHLOROBENZENE
HEXACHLOROETHANE
HEXAOECYL ALCOHOL
HEXAMETHYLENEDIAMINE
HEXAMETHYLENE GLYCOL
HEXAMETHYLENE TETRAMINE
HYDROGEN CYANIDE
HYDROQUINONE
PwHYOROXYBENZOIC ACID
ISOAMYLENE
X808UTANOL
I80BUTYL ACETATE
I30BUTYLENE
I80BUTYLRALDEHYDE
I80BUTYRIC ACID
I80DECANDL
isoocTYL ALCOHOL
XSOPENTANE
X80PHORONE
J80PHTHALIC ACID
I30PRENE
                            6-972

-------
     Table D-l.  (Continued).  INDUSTRIAL ORGANIC CHEMICALS


                       MAME

IS0PRQPANQL
ISOPRQPYL ACETATC
I80PRQPYLAMINECMQNQ)
ISQPRQPYL CHLORIDE
ISOPROPYLPHENQL
KETENE
MALEIC AGIO
MALEIC ANHYDRIDE
MALIC ACID
ME3ITYI OXIDE
METANII.IC ACID
METHACWYUC ACID
NETHALLYU CHLORIDE
HEfHANOL
METHYL ACETATE
METHYL ACETOACETATE
METHYLAMINE
N.METNYLANILINE  '
METHYL BUTYNOL
MITHYL CHLORIDE
METHYLCYCLOHEXANE
MITHYLCYCLOHEXANONE
METHYLENE CHLORIDE
METHYLENE OIANILINE
METHYL ETHYL KETONE
METHYL FORMATE
METHYLISOBUTYL CARBINOL
METHYLIS08UTYL KETONE
METHYL METHACRYLATE
METHYLPENTYNOL
A»METHYLSTYRENE
MORPHOLINE
A«NAPHTHALENE SULFONIC ACID
B-NAPHTHALENE SULFONIC ACID
A»NAPHTHQL
8»NAPHTHOL
NEOPENTANOIC ACID
Q»NITROANILINE
                             6-973

-------
     Table D-l.   (Continued).   INDUSTRIAL ORGANIC  CHEMICALS

                       NAME

P*NITRQANILINE
0*NITRQANISQLE
P«NITRQANXSQLE
NITROBENZENE
NITRQBENZQIC ACID (M,0,P)
NITROETHANE
NJTRQMETHANE
NITRQPHENOL
NITROPROPANE
NITROTQLUENE
NONENE
NQNYLPHENOL
OCTYLPHENOL
PARAIDEHYDE
PINTAERYTHRITOL
NsPENTANE
J.PENTENE
PERCHUQROETHYLENE
PIRCHUOROMfTHYI. MERCAPTAN
OePHENETIOINE
P«PMENETIOINE
PHENOU
PHCNOtSULFONJC ACIDS
PHCNYU ANTHRANIUC ACID
PHSNYI.ENEOIAMINE
PHOSGENE
PHTHA^IC ANHYDRIDE
PMTHAUIMIDE
S*PICQUINE
PIPERAZXNE
POLY8UTENES
POLYETHYLENE GLYCQL
POLYPROPYLENE SLYCOL
P^OPIONALOEHYDE
PROPIONIC ACID
N-PROPYL ALCOHOL
PROPYLAMINE
PROPYL CHLORIDE
                             6-974

-------
     Table D-l.  (Continued).  INDUSTRIAL ORGANIC CHEMICALS


                       SAME

PRQPYLENE
PRQPYLENE CHLQRQHYDRIN
PRQPYLENE DICHLORIDE
PRQPYLENE GLYCQL
PRDPYLENE OXIDE
PYRIOINE (NATURAL ft SYNTHETIC)
OU7NONE
RESORCINOL
RESQRCYLIC ACID
SALICYLIC ACID
SODIUM ACETATE
SODIUM BENZOATE
SODIUM CARBOXYMETHYL CELLULOSE
SODIUM CHLOROACETATE
SODIUM FORMATE
SODIUM PHEMATE
3QRBIC ACID
STYRENE
9UCCINIC ACID
8UCCINONITRILE
SULFANILIC ACID
SULFOLANE
TANNIC ACID
TEREPHTHALIC ACID
TETRACHLOROETHANE
TETRACHLOROPHTHALIC ANHYDRIDE
TITRAETHYL LEAD
TEfRAHYDRONAPHTHALENE
TITRAHYOROPHTHALIC ANHYDRIDE
TlfRAMETHYLENEDIAMlNE
TITRAMETHYLETHYLENEDIAMINE
TOLUENE
TOLUENE»2,4«DIAMINE
2,4-TOLUENE DIISOCYANATE
TOLUENE DIISOCYANATES(MIXTURE)
TOLUENESULFONAMIDE
TOLUENESULFQNXC ACIDS
TOLUENESULFONYL CHLORIDE
                           6-975

-------
    Table D-l.   (Continued).   INDUSTRIAL ORGANIC CHEMICALS


                       NAME

TOLUIOINES
mCHLOROBENZENE
l,i,l*TRICHLORQETHANE
TRICHLQRQETHYLENE
TRICHLORQFLUQRQMETHANE
t,2,3«TRICHLOROPRQPANE
i,t,2»TRIC*LORQ«l,2,2»TRIFLUROETHANE
TRJETHYUM1NE
TRJETHYLENE 6LYCOU
TRIETHYLENE GUYCOl DIMETHYL ETHER
TRIISOBUTYUENE
TRIMETHYLAMINE
UREA
VINYI ACETATE
VINYU CHLORIDE
VINYLIOENE CHLORIDE
VINYL TOLUENE
XYLENES, MIXED
O-XYLENE
XYLENOL
XYLIDINE
                            6-976

-------
             APPENDIX E



INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
            6-977

-------
               Table E-l.  INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME

A380TT LABORATORIES
ACETO CHEMICAL CO, INC,
ACME«HAROESTY CO, INC,
ADO PROCESSING CORP,
ASWAY, INC
AIRCO CHEMICALS AND PLASTICS
AIR PRODUCTS AND CHEMICALS INC,
AIR PRODUCTS AND CHEHICALS INC,
AIR PRODUCTS AND CHEMICALS INC,
AIR PRODUCTS AND CHEMICALS INC,
AKZONA INC,
ALBA MANUFACTURING CO,
ALCO STANDARD CORP,
ALDRICH CHEMICAL co,
ALLIED CHEMICAL CORP.
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
-LLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP.
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP,
ALLIED CHEMICAL CORP.
AMERICAN ANILINE AND EXTRACT CO,
AMERICAN COLOR AND CHEMICAL CORP.
AMERICAN CYANAMID CO.
AMERICAN CYANAMIO CO,
AMERICAN CYANAMID CO,
AMERICAN CYANAMID CO,
AMERICAN CYANAMID CO,
AMERICAN CYANAMID CO,
AMERICAN HOECHST CORP,
AMERICAN PETROFINA INC.
      CITY

NORTH CHICAGO
CARLSTAOT
JENKINTOWN
ABBEVILLE
CLEAN
LOUISVILLE
CALVERT CITY
HOMETOWN
PASADENA
PENSACOLA
LOWLAND
AURORA
EODYSTONE
MILWAUKEE
BATON ROUGE
BUFFALO
DANVILLE
ELIZABETH
EL SEGUNDO
FRANKFORD
GEISMAR
KQPEWELL
MARCUS HOOK
MOUNOSVILLE
OMAHA
ORANGE
SOUTH POINT
SYRACUSE
PHILADELPHIA
LOCK HAVEN
BOUNDBROOK
CHARLOTTE
LINDEN
MARIETTA
NEW ORLEANS
WILLOW ISLAND
COVENTRY
BIG SPRING
STATE

 IL
 NJ
 PA
 LA
 NY
 KY
 KY
 PA
 TX
 FL
 TN
 IL
 PA
 WI
 LA
 NY
 IL
 NJ
 CA
 PA
 LA
 VA
 PA
 WV
 NE
 TX
 OH
 NY
 PA
 PA
 NJ
 NC
 NJ
 OH
 LA
 WV
 RI
 TX
                                   6-978

-------
       Table E.I.  (Continued).  INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME

AMERICAN POLYMERS INC,
AMES LABORATORIES IMC,
ANSUL CO,
ARCO CHEMICAL CO,
ARCO CHEMICAL CO,
ARCO CHEMICAL CO,
ARCO CHEMICAL CO,
ARCO CHEMICAL CO,
ARCO CHEMICAL CO,
ARCO/POLYMERS INC,
ARMOUR AND COMPANY
ASHLAND CHEMICAL CO,
ASHLAND CHEMICAL CO,
ASHLAND CHEMICAL CO,
A$HLANO CHEMICAL co,
ASHLAND CHEMICAL CO.
BASF XYANDQTTE CORP,
BASF WYANDOTTE CORP,
BASF WYANDOTTE CORP,
BASF WYANOOTTE CORP,
8ECKMAN INSTRUMENTS, INC,
BEKER INDUSTRIES CORP,
BETHLEHEM STEEL CORP,
BIQ^RAD LABORATORIES
BLUE SPRUCE CO,
BQFQRS INDUSTRIES INC,
BOROEN CHEMICAL
BORDEN CHEMICAL
BORDEN CHEMICAL
BORDEN CHEMICAL
BORDEN CHEMICAL
BOROEN CHEMICAL
BORDEN CHEMICAL
BOROEN CHEMICAL
BORDEN CHEMICAL
BOROEN CHEMICAL
BORDEN CHEMICAL
BORDEN CHEMICAL
      CITY

PATTERSON
MILFORO
MARINETTE
BEAVER VALLEY
CHANNELVIEW
EAST CHICAGO
HOUSTON
PORT ARTHUR
WILMINGTON
HOUSTON
MONTGOMERY
ASHLAND
GREAT MEADOWS
HAMMOND
JANESVILLE
MAPLETON
GEISMAR
KEARNY
WASHINGTON
WYANOOTTE
PALO ALTO
CARLSbAO
SPARROWS POINT
RICHMOND
EDISON
LINDEN
BAINBRIDGE
COMPTON
DEMOPOLIS
OIBOLL
FAYETTEVILLE
FREMONT
GEISMAR
ILLIOPOL2S
KENT
LA GRANDE
LEOMINSTER
LOUISVILLE
STATE
     i
 NJ
 CT
 WI
 PA
 TX
 IN
 TX
 TX
 CA
 TX
 IL
 KY
 NJ
 IN
 WI
 IL
 LA
 NJ
 NJ
 MI
 CA
 NM
 MD
 CA
 NJ
 NJ
 NY
 CA
 AL
 TX
 NC
 CA
 LA
 IL
 WA
 OR
 MA
 KY
                                 6-979

-------
      Table E.I.   (Continued).  INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME

BORDEN CHEMICAL
BORDEN CHEMICAL
BORDEN CHEMICAL
80RG*WARNER CORP,
BROWN CO,
BUCKMAN'LABORATORIES INC.
BUCKMAN LABORATORIES INC,
CALCASIEU CHEMICAL CORP,
CARI8E ISOPRENE CORP,
CARUS CORP,
CELANESE CHEMICAL CO,
CELANESE CHEMICAL CO,
CELANESE CHEMICAL CO,
CELANESE CHEMICAL CO,
CELANESE CHEMICAL CO.
CELANESE CHEMICAL CO,
C5LANESE CHEMICAL CO,
CELANESE CHEMICAL CO,
CF INDUSTRIES
CF INDUSTRIES
CF INDUSTRIES
CF INDUSTRIES
CHARTER CHEMICALS
CHATTEM DRUG AND CHEMICAL CO,
CHATTEM DRUG AND CHEMICAL CO,
CHEMETRON CHEMICALS
CHEMICAL FORMULATORS INE,
CHEMICAL & POLLUTION SCIENCES, INC,
CHEMICAL PRODUCTS CORP,
CHEMOL INC,
CHEMPLEX CO,
CHEVRON CHEMICAL CO,
RICHMOND CHEMICAL CO,
CHICAGO SANITARY PRODUCTS CO,
CI8A*G£IGY CORP
CI8A*GEIGY CORP
CITIES SERVICE CO INC
CITIES SERVICE CO INC
      CITY

MISSOULA
SHEBOYGAN
SPRINGFIELD
MORGANTOWN
BERLIN
CADET
MEMPHIS
LAKE CHARLES
PONCE
LASALLE
BAY CITY
BISHOP
CLEAR LAKE
NARROWS
NEWARK
PAMPA
ROCK HILL
ROME
DONALDSONVILLE
FREEMONT
TUNIS
TYNER
HOUSTON
CHATTANOOGA
LONG BEACH
LAPQRTE
NITRO
OLD BRIDGE
CARTERSVILLE
GREENSBORO
CLINTON
EL SEGUNDO
RICHMOND
CHICAGO
MCINTOSH
ST. GABRIEL
COPPERHILL
LAKE CHARLES
STATE

 MT
 HI
 OR
 WV
 NH
 MO
 TN
 LA
 PR
 IL
 TX
 TX
 TX
 VA
 NJ
 TX
 SC
 GA
 LA
 NE
 NC
 TN
 TX
 TN
 CA
 TX
 WV
 NJ
 GA
 NC
 IA
 CA
 CA
 IL
 AL
 LA
 TN
 LA
                                   6-980

-------
    Table E.I.   (Continued).  INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME

CLARK CHEMICAL CO.
CLORAY NJ CORP,
COASTAL STATES GAS CO,
COASTAL STATES GAS CO,
COLGATE PALMOLIVE co,
COLGATE PALMOLIVE CO,
COLGATE PALMOLIVE CO,
COLGATE PALMOLIVE co,
COLT INDUSTRIES INC,
COLUMBIA NITROGEN CORP.
COMMERCIAL SOLVENTS CORP,
COMMERCIAL SOLVENTS CORP.
COMMERCIAL SOLVENTS CORP,
COMMONWEALTH OIL REFINING CO.
CONTINENTAL OIL COMPANY
CONTINENTAL OIL COMPANY
COOPERATIVE FARM CHEMICAL ASSOC.
COPOLYMER RUBBER AND CHEMICAL CORP,
C03*MAR INC
CRQMPTQN & KNOHLES CORP,
CRQMPTON 4 KNOWLES CORP,
CRQWLEY HYDROCARBON CHEMICALS INC,
CROWLEY HYDROCARBON CHEMICALS INC,
CRQWLEY HYDROCARBON CHEMICALS INC,
CSOWLEY TAR PRODUCTS
CRQWLEY TAR PRODUCTS
CRQKN ZELLERBACH CORP,
CROWN ZELLERBACH CORP,
DAN RIVgR INC,
DARLING AND CO.
DART INDUSTRIES INC,
DIAMOND SHAMROCK CORP,
DIAMOND SHAMROCK CORP,
DIAMOND SHAMROCK CORP,
DIXIE CHEMICAL CO
DON CHEMICAL CO,
DOM BADISCHE CO.
DOM CHEMICAL CO,
      CITY

BLUE ISLAND
NEWARK
CHEYENNE
CORPUS CHRISTI
BERKELY
JEFFERSONVILLE
JERSEY CITY
KANSAS CITY
MIDLAND
AUGUSTA
SEIPLE
STERLINGTON
TERRE HAUTE
PENUELAS
NEWARK
WESTLAKE
LAWRENCE
BATON ROUGE
CARVILLE
GIBRALTAR
READING
HOUSTON
KENT
OKLAHOMA CITY
BALTIMORE
HOUSTON
BOGALUSA
CAMAS
DANVILLE
CHICAGO
ELYRIA
BELLE
CEDARTOWN
DEER PARK
BAYPQRT
ANCHORAGE
FREEPORT
BAY CITY
STATE

 IL
 NJ
 WY
 TX
 CA
 IN
 NJ
 KA
 PA
 GA
 PA
 LA
 IN
 PR
 NJ
 LA
 KA
 LA
 LA
 PA
 PA
 TX
 OH
 OK
 MD
 TX
 LA
 WA
 VA
 IL
 OH
 WV
 GA
 TX
 TX
 AK
 TX
 MI
                                   6-981

-------
     Table E.I.   (Continued).   INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME

DOW CHEMICAL CO,
DOW CHEMICAL CO,
DOW CHEMICAL CO,
OOW CHEMICAL CO,
DOW CHEMICAL CO.
DOW CHEMICAL CO,
DON CORNING
DOW CORNING
El DU PONT OE  NEMOURS  &  CO
El DU PONT OE  NEMOURS  &  CO
II DU PONT DE  NEMOURS  &  CO
El DU PONT DE  NEMOURS  &  CO
El DU PONT DE  NEMOURS  &  CO
El DU PONT DE  NEMOURS  &  CO
61 OU PONT DE  NEMOURS  &  CO
El DU PONT DE  NEMOURS  &  CO
El OU PONT DE  NEMOURS  ft  CO
EZ DU PONT DE  NEMOURS  &  CO
El OU PONT OE  NEMOURS  &  CO
El DU PONT DE  NEMOURS  &  CO
El OU PONT DE  NEMOURS    CO
El DU PONT DE  NEMOURS    CO
El DU PONT DE  NEMOURS    CO
El DU PONT DE  NEMOURS    CO
El DU PONT DE  NEMOURS    CO
El DU PONT DE  NEMOURS    CO
El DU PONT DE  NEMOURS    CO
El DU PONT DE  NEMOURS  &  CO
DYE SPECIALTIES INC
EASTERN COLOR  AND CHEMICAL co
EASTMAN KODAK  co,
EASTMAN KODAK  CO,
EASTMAN KODAK  CO.
EL. PASO NATURAL GAS CO.
EMERY INDUSTRIES INC.
EMERY INDUSTRIES INC,
EMKAY CHEMICAL CO,
ENSERCH CORP,
      CITY

FREEPORT
MAGNOLIA
MIDLAND
OYSTER CREEK
PITTS8URG
PLAQUEMINE
CARROLLTON
MIDLAND
ANTIOCH
BEAUMONT
BELLE
CAPE FEAR
CORPUS CHRISTI
DEEPWATER POINT
EAST CHICAGO
GIBBSTQUM
HEALING SPRINGS
LAPLACE
LAPORTE
LINDEN
LOUISVILLE
MEMPHIS
MONTAGUE
NIAGARA FALLS
ORANGE
TOLEDO
VICTORIA
WAYNESBORQ
JERSEY CITY
PROVIDENCE
KIN6SPORT
LQNGVIEM
ROCHESTER
ODESSA
CINCINNATI
CITY OF COMMERCE
ELIZABETH
KERENS
STATE

 TX
 AR
 MI
 TX
 CA
 LA
 KY
 MI
 CA
 TX
 WV
 NC
 TX
 NJ
 IN
 NJ
 NC
 LA
 TX
 NJ
 KY
 TN
 MI
 NY
 TX
 OH
 TX
 VA
 NJ
 RI
 TN
 TX
 NY
 TX
 OH
 CA
 NJ
 TX
                                  6-982

-------
      Table E.I.   (Continued).   INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME

ENSERCH CORP,
ESNARK, INC,
ESMARK, INC,
ETHYL. CORP.
ETHYL CORP,
ETHYL CORP,
ETHYL CORP,
EXXON CHEMICAL CO,
EXXON CHEMICAL CO,
EXXON CHEMICAL CO,
FAIRMONT CHEMICAL CO,
FERRQ CORP,
FERRO CORP,
FIRESTONE TIRE AND RUBBER CO,
FIRST MISSISSIPPI CORP,
FLEMING LABORATORIES INC,
FMC CORP,
FHC CORP,
FMC CORP,
FMC CORP,
FOSTER«GRANT CO, INC,
FRANK ENTERPRISES
FRITZCHE DOOSE 4 OLCOTT INC,
5AF CORP,
5AF CORP,
GAF CORP,
GAROINIER 9IG RIVER, INC.
GENERAL AMERICAN OIL OF TEXAS
GENERAL ELECTRIC CO,
GENERAL ELECTRIC CO,
GENERAL ELECTRIC co,
THE GENERAL TIRE & RUBBER CO,
GEORGIA PACIFIC CORP,
GEORGIA PACIFIC CORP,
GEORGIA PACIFIC CORP,
GEORGIA PACIFIC CORP.
GEORGIA PACIFIC CORP,
GEORGIA PACIFIC CORP.
      CITY

PRYOR
BEAUMONT
WINCHESTER
BATON ROUGE
MAGNOLIA
ORANGEBURG
PASADENA
BATON ROUGE
BAYTOHN
BAYWAY
NEWARK
BATON ROUGE
SANTA FE SPRINGS
ORANGE
PASCAGOJLA
CHAROLTTE
BALTIMORE
BAYPORT
MEAOVILLE
SOUTH CHARLESTON
BATON ROUGE
COLUMBUS
EAST HANOVER
CALVERT CITY
LINDEN
RENNSELEAR
HELENA
PASADENA
MOUNT VERNON
SELKIRK
WATERFORD
ASHTABULA
ALBANY
BELLINGHAM
COLUMBUS
COOS BAY
CROSSETT
PLAQUEMINE
STATE

 OK
 TX
 MA
 LA
 AR
 SC
 TX
 LA
 TX
 NJ
 NJ
 LA
 CA
 TX
 MS
 NC
 MD
 TX
 PA
 MV
 LA
 OH
 NJ
 KY
 NJ
 NY
 AR
 TX
 IN
 NY
 NY
 OH
 OR
 MA
 OH
 OR
 AR
 LA
                                  6-983

-------
     Table E.I.   (Continued).  INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME

GEORGIA PACIFIC CORP,
GEORGIA PACIFIC CORP,
GEORGIA' PACIFIC CORP,
GETTY OIL CO,
GIVAUDAN CORP,
GOOOPASTUREi INC,
9F GOODRICH CHEMICAL, CO,
BF GOODRICH CHEMICAL CO,
BF GOODRICH CHEMICAL CO,
GOODYEAR TIRE AND RUBBER CO,
GOODYEAR TIRE AND RUBBER CO,
W, R, GRACE AND CO,
W, R, GRACE AND CO,
W, R, GRACE AND CO.
GRAIN PROCESSING CORP,
GREAT LAKES CHEMICAL CORP,
GUARDIAN CHEMICAL CORP,
GULF OIL CO,
GULP OIL CO,
GULF OIL CO,
GULF OIL CO,
GULF OIL CO,
GULF OIL CO,
HARDWICKE CHEMICAL CO,
HEICO, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HERCULES, INC,
HOOAG CHEMICAL CORP,
HOWERTQWN GQWEN CHEMICALS, INC.
HUMMEL CHEMICAL CO,
HUMPHREY CHEMICAL CO,
      CITY

RUSSELLVILLE
TAYLORSVILLE
VIENNA
DELAWARE CITY
CLIFTON
OIMMITT
CALVERT CITY
HENRY
PORT NECHES
BAYPORT
BEAUMONT
FORDS
MEMPHIS
NASHUA
MUSCATINE
EL DORADO
HAUPPAUSE
ALLIANCE
CEDAR BAYOU
PHILADELPHIA
PORT ARTHUR
VICKS3URG
WELCOME
ELGIN
DELAWARE MATER GAP
BURLINGTON
GIB8STOHN
GLENN FALLS
HARBOR 8EACH
HERCULES
HOPEWELL
LOUISIANA
PLAQUEMINE
WILMINGTON
SKOKIE
ROANOKE RAPIDS
SOUTH PLAINFIELD
NORTH HAVEN
STATE

 SC
 MS
 GA
 DE
 NJ
 TX
 KY
 IL
 TX
 TX
 TX
 NJ
 TN
 NH
 IA
 AR
 NY
 LA
 TX
 PA
 TX
 MS
 LA
 SC
 PA
 NJ
 NJ
 NY
 MI
 CA
 VA
 MO
 LA
 NC
 IL
 NC
 NJ
 CT
                                  6-984

-------
     Table E.I.  (Continued).  INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME
ICC INDUSTRIES, INC,
ICC INDUSTRIES, INC,
ICI UNITED STATES
INLAND CHEMICAL CORP,
INLAND CHEMICAL CORP,
JEFFERSON CHEMICAL CO.,
JEFFERSON CHEMICAL CO,,
JOC OIL, INC,
ANDREW JERGENS CO,
KAISER CHEMICALS
KALAMA CHEMICALS, INC,
KAY-FRIES CHEMICALS, INC,
KEWANEE INDUSTRIES, INC,
H, KOHNSTAMM AND CO,, INC,
1.1  L4A*lklAV«L4k* A L • M «* A   « L 1 M
                        INC,
                        INC,
   unite, irnuua I rc*t
H, KOHNSTAMM AND CO,,
H, KOHNSTAMM AND CO,, INC,
KQPPERS CO., INC,
KOPPERS CO,, INC,
K3PPERS CO,, INC,
KOPPERS CO,, INC,
KKAFTCQ CORP,
LACAT CHEMICALS  INC,
LEVER BROTHERS CO,
LEVER BROTHERS CO,
LEVER BROTHERS CO,
LEVER BROTHERS CO,
LEVER BROTHERS CO,
ELI LILLY AND CO,
LONZA, INC,
LUBRIZOL CORP,
LUBRIZOL CORP,
MALLINCKROOT, INC,
MALLINCKROOT, INC,
MALLINCKROOT, INC,
MARATHON OIL CO,
MARATHON OIL CO,
MARTIN MARIETTA CORP,
MERCK AND COMPANY INC,
MERICHEM CO,
      CITY

DOVER
NIAGARA FALLS
NEW CASTLE
JUNEAU
MANATI
CONROE
PORT NECHES
HOUSTON
CINCINNATI
SAVANNAH
KALAMA
STONY POINT
GLOUCESTER CITY
CAMDEN
CLEARING
BRIDGEVILLE
CICERO
FOLLANSBEE
PETROLIA
MEMPHIS
CHICAGO HEIGHTS
BALTIMORE
EOGEWATER
HAMMOND
LOS ANGELES
ST, LOUIS
LAFAYETTE
MAPLETON
DEER PARK
DEER PARK
LODI
RALEIGH
ST. LOUIS
ROBINSON
TEXAS CITY
SODYECO
ALBANY
HOUSTON
STATE

 OH
 NY
 OE
 NX
 PR
 TX
 TX
 TX
 OH
 GA
 WA
 NY
 NJ
 NJ
 IL
 PA
 IL
 WV
 PA
 TN
 IL
 MO
 NJ
 IN
 CA
 MO
 IN
 IL
 TX
 TX
 NJ
 NC
 MO
 IL
 TX
 NC
 GA
 TX
                                  6-985

-------
      Table  E.I.   (Continued).   INDUSTRIAL  ORGANIC  CHEMICAL PRODUCERS
                 NAME

 MIDDLEBORO  INDUSTRIES,  i^c,
 MILES LABORATORIES, INC,
 MILLMASTER  ONYX  CORP.
 MISSISSIPPI  CHEMICAL CORP.
 MOBAY CHEMICAL co,
 MQBAY CHEMICAL CO,
 MQ8JL OIL CORP,
 MONOCHEM, INC,
 MONSANTO CO,
 MONSANTO CO,
 MONSANTO co,
 MONSANTO CO,
 MONSANTO CO,
 MONSANTO co,
 MONSANTO co,
 MONSANTO co,
 MONSANTO co,
 MONSANTO co,
 MONSANTO co,
 MONSANTO co.
 MONSANTO co,
 MONSANTO co,
 MONSANTO co,
 MONSANTO co,
 MONTROSE CHEMICAL CORP. OF CALIFORNIA
 MURRO CHEMICAL co.
 NALCO CHEMICAL CO.
 NALCO CHEMICAL CO,
 NAPP CHEMICALS,  INC,
 NATIONAL DISTILLERS AND CHEMICAL CORP,
 NATIONAL DISTILLERS AND CHEMICAL CORP,
 NATIONAL STARCH  AND CHEMICAL CORP,
 NATIONAL STEEL CORP,
 NEASE CHEMICAL CO,, INC,
 NEASE CHEMICAL CO,, INC,
 NECHES BUTANE PRODUCTS CO,
 NIPRO, INC,
NORDA, INC,
      CITY

MIDDLE3QRO
ZEELAND
NEWARK
YAZOO
CEDAR BAYOU
NEW MARTlNSVlLLt
BEAUMONT
GEISMAR
ADOYSTON
ANNISTON
BRIDGEPORT
CHOCOLATE BAYOU
OECATUR
EUGENE
EVERETT
KEARNY
LULING
NITRO
PENSACOLA
ST. LOUIS
SAUGET
SPRINGFIELD
TEXAS CITY
TRENTON
HENDERSON
PORTSMOUTH
FREEPORT
SUGARLAND
LODI
DEER PARK
TUSCULA
LONG MQTT
ZUG ISLAND
FERNALD
STATE COLLEGE
PORT NECHES
AUGUSTA
BOONTON
STATE

 MA
 MI
 NJ
 MS
 TX
 HV
 TX
 LA
 OH
 AL
 NJ
 TX
 AL
 OR
 MA
 NJ
 LA
 WV
 FL
 MO
 IL
 MA
 TX
 MI
 NV
 VA
 TX
 TX
 NJ
 TX
 IL
 TX
 MI
 OH
 PA
 TX
 GA
 NJ
                                  6-986

-------
    Table E.I.   (Continued).   INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME

NORSE LABS, INC,
NORTHERN FINE CHEMICALS
NORTHERN NATURAL GAS CO,
NORTHWEST INDUSTRIES INC,
NORTHWEST INDUSTRIES INC,
NORTHWEST INDUSTRIES INC.
NORTHWEST INDUSTRIES INC,
N«REN CORP,
N«REN CORP,
OCCIDENTAL PETROLEUM
OCCIDENTAL PETROLEUM
OCCIDENTAL PETROLEUM
OCCIDENTAL PETROLEUM
OLIN CORP,
OLIN CORP,
OLIN CORP,
OL2N CORP,
QRBIS PRODUCTS CORP,
OXIRANE CHEMICAL CO,
QXQCHEM ENTERPRISE
PACIFIC SOAP CO,
PAN AMERICAN CHEMICAL CORP,
PARKE'DAVIS & CO,
PELRON CORP,
PENNWALT CORP,
PENNWALT CORP,
PENNWALT CORP^
PENNWALT CORP,
PENNWALT CORP,
PENNWALT CORP,
PETRO*TEX CHEMICAL CORP,
PFANSTIEHL LABROATQRIES, INC
CHAS, PFIZER & CO,i INC
CHAS, PFIZER & CO,, INC
CHAS, PFIZER 4 CO., INC
PHILLIPS PACIFIC CHEMICAL CO,
PHILLIPS PETROLEUM CO,
PHILLIPS PETROLEUM CO,
      CITY

SANTA BARBARA
FRANKLIN
MORRIS
BEAUMONT
CHATTANOOGA
EL DORADO
ST, LOUIS
PLAINVIEW
PRYOR
ARECIBO
NIAGARA FALLS
NORTH TANAWANOA
TAFT
ASHTABULA
BRANDENBURG
LAKE CHARLES
ROCHESTER
NEWARK
8AYPORT
PENUELAS
VERNON
TOLEDO
HOLLAND
LYONS
BEAUMONT
CALVERT CITY
GENESEO
GREENS BAYOU
THOROFARE
WYANDOTTE
HOUSTON
WAUKEGAN
GREENSBORO
GROTON
TERRE HAUTE
KENNENECK
BEATRICE
BQRGCR
STATE

 CA
 NJ
 IL
 TX
 TN
 AR
 MI
 TX
 OK
 PR
 NY
 NY
 LA
 OH
 KY
 LA
 NY
 NJ
 TX
 PR
 CA
 OH
 MI
 IL
 TX
 KY
 NY
 TX
 NJ
 MI
 TX
 IL
 NC
 CT
 IN
 WA
 NE
 TX
                                 6-987

-------
      Table E.I.   (Continued).   INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME

PHILLIPS PETROLEUM CO,
PHILLIPS PETROLEUM CO,
PHILLIPS PETROLEUM co,
PIERCE CHEMICAL co,
PILOT CHEMICAL co,
PIONEER SOAP co,
PLASTICS ENGINEERING CORP,
PPG INDUSTRIES, INC,
PPG INDUSTRIES, INC,
PPG INDUSTRIES, INC,
PPG INDUSTRIES, INC,
PPG INDUSTRIES, INC,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PROCTOR & GAMBLE CO,
PUBLICKER INDUSTRIES INC,
PUBLICKER INDUSTRIES INC,
PUERTO RICO OLEFINS co,
PUREX CORP,
PURE* CORP,
PYO INTERNATIONAL, INC,
REICHGLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICAL INC,
REICHOLD CHEMICALS, INC,
REICHOLD CHEMICALS, INC,
      CITY

GUAYAMA
PHILLIPS
SWEENEY
RQCKFQRO
HOUSTON
SAN FRANCISCO
SHEBOYGAN
BARBERTON
BEAUMONT
GUAYANILLA
LAKE CHARLES
NATRIUM
BALTIMORE
CHICAGO
DALLAS
DAYTON
IVORYOALE
KANSAS CITY
LONG BEACH
MEMPHIS
SACRAMENTO
GRETNA
PHILADELPHIA
PENUELAS
BRISTOL
OMAHA
BQONTON
AUSTIN
ELIZABETH
HAMPTON
HOUSTON
KANSAS CITY
MALVERN
MQNCURE
MORRIS
ST. HELENS
TACOMA
TUSCALOOSA
STATE

 PR
 TX
 TX
 IL
 TX
 CA
 WI
 OH
 TX
 PR
 LA
 WV
 MO
 IL
 TX
 OH
 OH
 KA
 CA
 TN
 CA
 LA
 PA
 PR
 PA
 NE
 NJ
 TX
 NJ
 SC
 TX
 KA
 AR
 NC
 IL
 OR
 WA
 AL
                                  6-988

-------
      Table E.I.   (Continued).  INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME

RE1CHOLO CHEMICALS, INC.
REILY TAR 8, CHEMICAL CORP,
REPUBLIC STEEL CORP,
REPUBLIC STEEL CORP,
RICHARDSON*MERRELL INC.
RITTER CHEMICAL CO,
RQBINSON-WAGNER INC,
ROHM & HAAS CO,
ROHM & HAAS CO,
ROHM & HAAS CO,
ROHM & HAAS CO.
ROHM & HAAS CO,
R.S.A, CORP,
RUBICON CHEMICALS INC,
SALISBURY LABS
SALISBURY LABS
SCHENECTAOY CHEM., INC,
G.O.SEARLE & CO,
SHARON STEEL CORP,
SHELL OIL CO,
SHELL OIL CO,
SHELL OIL CO,
SHELL OIL CO,
SHELL OIL CO,
SHELL OIL CO.
SHENAN60 INC,
SNfRWIN WILLIAMS CO
J, R, SIMPLOT CO,
SKELLY OIL CO,
SKELLY OIL CO,
SKELLY OIL CO,
SKELLY OIL CO,
SOLVENT CHEMICAL CO,
SOLVENT CHEMICAL CO.
SQNOCO PRODUCTS CO,
SOUTH HAMPTON CO,
SPECIALTY ORGANICS, INC.
SQUIBB CORP,
      CITY

WHITE CITY
INOIANOPOLIS
CHICAGO
CLEVELAND
PHILLIPSBURG
AMSTERDAM
MAMARONECK
BRISTOL
DEER PARK
KNOXVILLE
LOUISVILLE
PHILADELPHIA
AROSLEY
GEISMAR
CHARLES CITY
WILMINGTON
ROTTERDAM JUNCTION
NORWOOD
FAIRMONT
DEER PARK
DOMINGUEZ
GEISMAR
MARTINEZ
NORCO
HOOD RIVER
NEVILLE ISLAND
ST. BERNARD
POCATELLO
CLINTON
EL DORADO
SPRINGFIELD
WINNFIELD
MALDEN
NIAGRA FALLS
HARTSVILLE
SILSBEE
IRWINDALE
NEW BRUNSWICK
STATE

 OR
 IN
 IL
 OH
 NJ
 NY
 NY
 PA
 TX
 TN
 KY
 PA
 NY
 LA
 IA
 NC
 NJ
 OH
 WV
 TX
 CA
 LA
 CA
 LA
 IL
 PA
 OH
 ID
 IA
 KA
 OR
 LA
 MA
 NY
 SC
 TX
 CA
 NJ
                                  6-989

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    Table E.I.   (Continued).  INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME

STANDARD CHLORINE CHEMICAL CO,
STANDARD CHLORINE CHEMICAL CO,
STANDARD OF INDIANA
STANDARD OF INDIANA
STANDARD OF INDIANA
STANDARD OF INDIANA
STANDARD OF INDIANA
STANDARD OF INDIANA
STANDARD OF OHIO
STAUFFER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STAUFPER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STAUFFER CHEMICAL CO,
STEFAN CHEMICAL CO,
STEFAN CHEMICAL CO,
STEPAN CHEMICAL CO,
STERLING DRUG, INC,
STERLING DRUG, INC.
STERLING DRUG, INC,
STIMSON LUMBER COMPANY
ST. PAUL AMMONIA PRODUCTS, INC,
STORY CHEMICAL CORP,
SUNOCO
SjNOCQ
SUNOCO
SJNOCO
SUNOLIN CHEM, CO.
SYBRON CORP,
SYNTEX CORP,
TENNECO CHEMICALS, INC.
TENNECO CHEMICALS, INC.
TENNECO CHEMICALS, INC.
TENNECO CHEMICALS, INC.
      CITY

DELAWARE CITY
KEARNY
CHOCOLATE BAYOU
DECATURE
JOLIET
TEXAS CITY
WOOD RIVER
YORKTOWN
LIMA
CARSON
COLD CREEK
DELAWARE CITY
EDISON
HENDERSON
LE MOYNE
LOUISVILLE
NIAGARA FALLS
PERRY
ANAHEIM
ELWOQO
FIELDSBORO
CINCINATTI
MEMPHIS
RENSSELAER
ANACORTES
EAST DU3UQUE
MUSKEGON
CORPUS CHRISTI
DUNCAN
MARCUS HOOK
TOLEDO
CLAYMONT
LYNDHURST
NEWPORT
CHALMETTE
FORDS
GARFIELD
HOUSTON
STATE

 DE
 NJ
 TX
 AL
 IL
 TX
 IL
 VA
 OH
 CA
 AL
 DE
 NJ
 NV
 AL
 KY
 NY
 OH
 CA
 IL
 NJ
 OH
 TN
 NY
 WA
 IL
 MI
 TX
 OK
 PA
 OH
 DE
 NJ
 TN
 LA
 NJ
 NJ
 TX
                                  6-990

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     Table  E.I.   (Continued).   INDUSTRIAL ORGANIC CHEMICAL PRODUCERS
                NAME

TENNESSEE VALLEY AUTHORITY
TERRA CMEM INTERNATIONAL, INC.
TIXACO, INC,
TEXACO, INC,
TEXAS-U.S, CHEMICAL CO,
TOMS RIVER CHEMICAL CORP.
TRIAD CHEMICAL
TYLER CORP.
UNION CAMP CORP,
UNION CAR8IOE CORP,
UNION CARBIDE CORP.
UNION CARBIDE CORP,
UNION CARBIDE CORP,
UNION CARBIDE CORP.
UNION CARBIDE CORP,
UNION CARBIDE CORP,
UNION CARBIDE CORP.
UNION CARBIDE CORP,
UNION CARBIDE CORP,
UNION OIL OF CALIFORNIA
UNION OIL OF CALIFORNIA
UNION OIL OF CALIFORNIA
UNION PACIFIC CORP, CHAPLIN
UNIRQYAL, INC,
UNITED AIRCRAFT
UNITED STATES STEEL CORP,
UNITED STATES STEEL CORP,
UNITED STATES STEEL CORP,
UNITED STATES STEEL CORP,
UNIVAR CORP,
UNIVERSAL OIL PRODUCTS CO,
UNIVERSAL OIL PRODUCTS CO,
UPJOHN CO,
VALLEY NITROGEN PRODUCERS, INC,
VALLEY NITROGEN PRODUCERS, INC,
VAN OE MARK CHEM, CO,
VIRGINIA CHEMICALS, INC,
VULCAN MATERIALS CO,
      CITY

MUSCLE SHOALS
PORT NEAL
PORT ARTHUR
NESTVILLE
PORT NECHES
TOMS RIVER
OONALDSONVILLE
JOPLIN
DOVER
ASHTABULA
BOUND BROOK
BROWNSVILLE
INSTITUTE AND SOUTH
MARIETTA
NIAGRA FALLS
PENUELAS
SEADRIFT
TAFT
TEXAS CITY
BEAUMONT
BREA
KENAI
CORPUS CHRISTI
NAUGATUCK
MUNCIE
CHEROKEE
CLAIRETON
HAVERHILL
NEVILLE ISLAND
EUGENE
EAST RUTHERFORD
MCCOOK
LAPORTE
EL CENTRO
HELM
LOCKPORT
PORTSMOUTH
GEISMAR
         STATE
          AL
          IA
          TX
          NJ
          TX
          NJ
          LA
          MO
          OH
          OH
          NJ
          TX
CHARLESTONWV
          OH
          NY
          PR
          TX
          LA
          TX
          TX
          CA
          AL
          TX
          CT
          IN
          AL
          PA
          OH
          PA
          OR
          NJ
          IL
          TX
          CA
          CA
          NY
          VA
          LA
                                  6-991

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     Table  E.I.   (Continued).   INDUSTRIAL ORGANIC  CHEMICAL PRODUCERS
                NAME                              CITY                   STATE

VULCAN MATERIALS CO,                        WICHITA                       KA
JIM WALTER CORP,                            BIRMINGHAM                    AL
WARNER LAMBERT CO,                          HARRIMAN                      NY
WHEELING PITTS8URG STEEL; CORP,              MQNESSEM                      PA
WHITE CHEMICAL CORP,                        BAYONNE                       NJ
WILLIAMS COMPANIES                          BLYTHEVILLE                   AR
WILLIAMS COMPANIES                          CATQOSA                       OK
WILLIAMS COMPANIES                          DONALDSONVILLE                LA
WITCO CHEMICAL CORP,                        CLEARING                      IL
WITCO CHEMICAL CORP,                        PATERSQN                      NJ
WOBURN CHEMICAL co,                         KEARNY                        NJ
WOONSOCKET COLOR AND CHEMICAL CO.           WOONSOCKET                    RI
WRIGHT CHEMICAL CO,                         ACME                          NC
                                   6-992

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7.AUTHORIS)               "
 P.airjond Liepins and  Forest Mixon (RTl), Charles Hudak
 anaJTerry B. Parsons (Radian)
9. PEHFORMsNG ORGANIZATION'rMAME AND ADDRESS
 Research Triangle Institute
 P.O. Box 1219U
 Ressa.rch Triangle Park, HC   27709
1. REPORT NO.
                                   TECHNICAL REPORT DATA
                            (PicBfe rcaiJ Jiatrnctions on trie reverse before completing)
                                                           3. RECIPIENT'S ACCESSION-NO
I. T;TUE AND SUBTITLE
 Industrial Process  Profiles for Environmental User
 Chapter 6.  The  Industrial Organic Chemicals Industry
 12. SPONSORING AGENCY NAME-AMD ADDRESS
 Industrial Environmental Research Laboratory
 Office  of Research and Development
 U.S. ENVIRONMENTAL PROTECTION AGEMCY
 Cincinnati,  Ohio
                                                           5 REPORT DATE
                                                             February 1977J	
                                                           6. PERFORMING ORGANIZATION CODE
                                                           8. PERFORMING ORGANIZATION REPORT NO.
                                                           10. PROGRAM ELEMENT NO.

                                                            1AB015:  ROAP 21AFH-025L
                                                           11. CONTRACT/GRANT NO.

                                                            68-02-1325/T.ask  70
                                                           13. TYPE OF REPORT ANH PERIOD i
                                                            Initial:
                                                           14. SPONSORING AGENCY CODE
                                                             EPA/600/12
 15. SUPPLEMENTARY NOTES
 10. ABSTRACT
 The catalog of Industrial Process Profiles  for Environmental Use was  developed as an
 aid in  defining the environmental impacts  of industrial activity in the  United Stages,
 Entries for each industry arc in consistent format and form separate  chapters of the
 study.   Industrial organic chemicals  are the product of at least one  chemical reactior
 in this industry and will undergo at  least  one additional treatment step in a down-
 stream  processing industry.  These  compounds are intermediate materials  in the manu-
 facture of  such products as plastics,  synthetic fibers, Pharmaceuticals  and sxir-
 factants among others.  The industry  is discussed in terms of ten feedstock groups:
 "benzene, butylenes, sources of cresylic acids, ethylene, methane, naphthalene,
 paraffins5  propyiene, toulene and xylenes.   Ten chemical trees, ten process flow
 sheets  and  36.5 process descriptions have been prepared to characterise the Industry.
 Within  each process description available  data have been presented on function, input
 materials,  operating parameters, utilities, waste streams, EPA Source Classification
 Code arid references.   Data related to  the  subject matter, including company, product
 and raw material data, are included as appendices.
                                KEY WORDS *ND DOCUMENT ANALYSIS
 Pollution
                  DESCRIPTORS
 Industrial Processes
I Chemical Engineering,
 Organic Compounds
 Organic Chemistry
IP. DtST-l;3UTION S TA I'tMfcN T

      Uulimit3d
                                              b. IDENTIFIERS/OPEN ENDED Tt«Mf
                                              Process Assessment
                                              Environmental Impact
                                              Industrial Organic
                                                Chemicals
                                              19. SECURITY CLASS (This Report)
                                               Unclassified
                                               Unclassified
:. COSATi Fiold/C.roup

 13E
 13H
 OTA
 11C
 07C
                                                                         2i. NO. C»; PAGHS
                                            6-993
                                                                      ft U.S. GOVERNMENT PRINTING OFFICfc 1978 -659-5IO/Z1

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