KP*
GRI    	


        Development Document for

Interim Final Effluent Limitations Guidelines

  and New Source Performance Standards

                 for the
    SIGNIFICANT ORGANIC PRODUCTS
             Segment of the
  ORGANIC CHEMICAL MANUFACTURING
          Point Source Category
 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

             NOVEMBER 1975

-------

-------
          DEVELOPMENT  DOCUMENT

                  for

   INTERIM FINAL EFFLUENT LIMITATIONS

                  and

    NEW SOURCE PERFORMANCE STANDARDS

                for the

  SIGNIFICANT ORGANIC  PRODUCTS SEGMENT

                 Of the

    ORGANIC CHEMICALS  MANUFACTURING

         POINT SOURCE  CATEGORY
            Russell E. Train
             Administrator

      Andrew W. Breidenbach, Ph.D.
     Acting Assistant Administrator
   for Water and Hazardous Materials

                  y"!*'4**
         Allen Cywin, Director
      Effluent Guidelines Division

   John A. Nardella, Project Officer
      Effluent Guidelines Division
             November, 1975

      Effluent Guidelines Division
Offj.ce of Water and Hazardous Materials
  U.S. Environmental Protection Agency
        Washington, D.C.  20460

-------

-------
                          ABSTRACT
A study of the significant organic products segment  of  the
organic  chemicals  manufacturing  industry was conducted by
Roy F. weston. Inc.  for  the  United  States  Environmental
Protection  Agency.   The  purpose  of  this  study  was  to
establish  effluent  limitations  guidelines  for   existing
point-source  discharges  and  standards  of performance and
pretreatment standards for  new  sources.   This  study  and
proposed  regulations  were  undertaken  in  fulfillment  of
Sections 301, 304, 306, and 307  of  the  Federal  Pollution
Control Act Amendments of 1972.

For  the purposes of this study, 55 product/process segments
of the industry  were  investigated.   Effluent  limitations
guidelines  were  developed  for 27 of these product/process
segments.  Other 28 product/processes  are  currently  being
reviewed  to determine the possible economic impact and will
be published at a later date.  This  study  was  the  second
part of a two phase effort.  In the first phase, process raw
waste   loads   and  effluent  limitations  guidelines  were
established for 40 product/process groups.  Coverage of  the
industry has now been extended to include 67 product/process
segments.

In  this studies, product/process groups were subcategorized
into four major  subcategories.   Effluent  limitations  and
guidelines  were then determined for each product/process by
multiplying the raw waste load by an  appropriate  reduction
factor  or concentration.  The resultant limit is considered
a long term or design limit.  In order to convert the design
limit to the daily maximum and 30 day  maximum  average  the
design  limit  is  multiplied  by an appropriate variability
factor.

Supportive data and the rationale  for  development  of  the
proposed  effluent  limitations  guidelines and standards of
performance are contained in this report.

-------
                           CONTENTS


Section                                                  Page

I        CONCLUSIONS                                      1

II       RECOMMENDATIONS                                 5

III      INTRODUCTION                                    21

IV       INDUSTRY  CATEGORIZATION                        41

V        WASTE CHARACTERIZATION                         255

VI       SELECTION OF  POLLUTANT PARAMETERS              261

VII      CONTROL AND TREATMENT TECHNOLOGIES             291

VIII     COST, ENERGY  AND NONWATER QUALITY ASPECTS      341

IX       BEST PRACTICABLE CONTROL TECHNOLOGY            345
         CURRENTLY AVAILABLE (BPCTCA)

X        BEST AVAILABLE TECHNOLOGY ECONOMICALLY         355
         ACHIEVABLE (BATEA)

XI       NEW SOURCE PERFORMANCE STANDARDS-BEST          359
         AVAILABLE DEMONSTRATED CONTROL TECHNOLOGY
          (BADCT)

XII      PRETREATMENT  GUIDELINES                        363

XIII     VARIABILITY IN TREATMENT                       367
         PLANT PERFORMANCE

XIV      ACKNOWLEDGMENTS                                371

XV       BIBLIOGRAPHY                                    373

XVI      GLOSSARY  AND  ABBREVIATIONS                     385
                                11

-------
FIGURES
figure

4-1
4-2
4-3
4-4
4-5
4-6
4-7
4-8
4-9
4-10
4-11
4-12
4-13
4-14
4-15
4-16
4-17
4-18
4-19
4-20
4-21
4-22
Title
Flow Diagrams
Cumene
p-Xylene
Chlor obenz en e
Chlorobenzene (incl. dichlorobenzene)
Chlorinated Methanes
Chlor otoluene
Dipheny 1 amine
Perchloroethylene
Phthalic Anhydride (o-Xylene)
Phtnalic Anhydride (Naphthalene)
Hexamethylenediamine (Adiponitrile)
Hexamethylenediamine (Hexanediol)
Methyl Ethyl Ketone
Tricresyl Phosphate
Adiponitrile
Benzoic Acid and Benzaldehyde
Methyl Chloride
Maleic Anhydride
Acetic Esters
Propylene Glycol
Caprolactam (DSM)
Cyclohexanone Oxime
Page

48
50
54
55
59
62
65
69
73
77
81
85
89
92
96
101
105
108
113
118
121
125
    111

-------
        Figures                                            Page



4-23     Formic Acid                                       131



4-24     Isopropanol                                       134



4-25     Oxalic Acid                                       138



4-26     Calcium Stearate                                  141



4-27     Hexamethylene Tetramine  (Plant  1)                 144



4-28     Hexamethylene Tetramine  (Plant  2)                 145



4-2-9     Hydrazinfi                                         149



4-30     Isobutylene                                       152



4-31     Sec-Butyl Alcohol                                 155



4-32     Acrylonitrile                                     158



4-33     Cresol                                            161



4-34     p-Aminophenol                                     165



4-35     Propylene Oxide                                   169



4-36     Pentaerythritol                                   173



4-37     Saccharin                                         176



4-38     o-Nitroaniline                                    179



4-39     p-Nitroaniline                                    182



4-40     Pentachlorophenol                                 185



4-41     Fatty Acids and Primary  Derivatives              192



4-42     lonone and Methylionone                           207



4-43     Methyl Salicylate                                 210



4-44     Citroneilol and Geraniol                         214



4-45     Plasticizers                                      217



4-46     Pigments                                          231



4-47     Citric Acid                                       234
                               IV

-------
           Figures                                      Page



4-48     Naphthenic Acid                                239



4-49     Monosodium Glutamate                           242



4-50     Tannic Acid                                    247



4-51     Vanillin                                       251



7-1      BPCTCA Waste Treatment Model                   335



7-2      BATEA Waste Treatment Model                   336
                              v

-------
                           TABLES
Table                       Title                      Page

2-1      Subcategories of the Secondary Organic          7
         Products Segmentof tlie Organic Chemicals
         Manufacturing Industry

2-2      Effluent Limitations for Best                  10
         Practicable Control Technology
         Currently Available (BPCTCA)

2-3      Effluent Limitations for Best                  13
         Available Technology Economically
         Achievable (BATEA)

2-4      Standards of Performance for New               17
         Organic Chemicals Manufacturing
         Sources

3-1      Chemicals Listed under SIC Code 2865           24

3-2      Chemicals Listed under SIC Code 2869           27

4-1      Process Raw Waste Load Based on DSM           128
         Process

4-2      Process Raw Waste Load Based on DSM           129
         Process

4-3      Some Examples of Commercial Fatty             189
         Acids Showing Typical Percentage
         of Constituent Acids

4-4      Chemical Conversions and Unit Opera-          202
         tions Contributing to Process Raw
         Waste Loads for the Manufacture of
         Fatty Acids and Primary Derivatives

4-5      Process RWL Associated with Manu-             204
         facture of Fatty Acids

4-6      Process RWL Associated with Manu-             205
         facture of Primary Derivatives from
         Fatty Acids

4-7      RWL Data for Batch Chemical Complex           212

4-8      Usage Classification of Dyes                  221
                                VI

-------
              Tables                                      Page

4-9      Chemical Classification of Dyes                   223

4-10     U.S. Production of Dyes by Classes                224
         of Application, 1965

4-11     U.S. Production and Sales of Dyes                 225
         by Chemical Classification, 1964
5-1      Subcategory A - Product-Process                   257
         Raw waste Loads

5-2      Subcategory B - Product-Process                   257
         Raw Waste Loads

5-3      Subcategory C - Product-Process                   258
         Raw Waste Loads

5-4      Subcategory D - Product-Process                   259
         Raw Waste Loads

6-1      List of Pollutants Analyzed for the Organic       262
         Chemicals Industry

6-2      Miscellaneous RWL for Subcategory A               269

6-3      Miscellaneous RWL for Subcategory B               270

6-4      Miscellaneous RWL for Subcategory C               273

6-5      Miscellaneous RWL for Subcategory D               275

7-1      Organic Chemicals Study Treatment                 299
         Technology Survey

7-2      Historic Treatment Plant Performance              321
         50 Percent Probability of Occurrence

7-3      Treatment Plant Survey Data                       322

7-4      Effectiveness of Filtration Test on               328
         Biological Treatment Effluent

7-5      Organic Chemical Plants Using Activated           330
         Carbon to Treat Raw Wastewaters
7-6      Summary COD Carbon isotherm Data                  331
                              vn

-------
              Tables                                           Page

7-7      Summary TOC Carbon Isotherm Data                      332

7-8      Summary TOC and COD Carbon Exhaustion Rates           333

8-1      Summary of  Waste Treatment Costs for                 342
         BPCTCA, BATEA, and BADCT

9-1      Development of Effluent Limitations for the           353
         Secondary Organic Products Segment of  the Organic
         Chemicals Point Source Category by Application
         of the Best Practicable control Technology
         Currently Available (BPCTCA)

10-1     Development of Effluent Limitations for the           358
         Secondary Organic Products Segment of the Organic
         Chemicals Point Source Category by Application of
         tne Best Available Technology Economically
         Achievable  (BATEA)

11-1     Development of Standards of Performance for           361
         the Secondary Organic Products Segment of the
         Organic Chemicals Point source Category by
         Application of the Best Available Demonstrated
         Control Technology

12-1     Pretreatment Unit Operations for the                  365
         Organic Chemicals Industry
                                Vlll

-------
                         SECTION I

                        CONCLUSIONS
The  complex  task  of  establishing   effluent   guidelines
limitations for the organic chemicals industry required that
the  industry  be divided into a two-phase study.  The final
Phase I development document was issued in April 1974.  That
document  recommended  the  use  of  process-oriented   sub-
categories which were developed as follows:

Continuous Nonagueous Processes {Phase I Subcategory A)

Contact  between water and reactants or products is minimal.
Water is not required as either reactant or diluent, and  is
not  formed  as  a  reaction  product.  The only water usage
stems from periodic washes or catalyst hydration.

Continuous Vapor Phase Processes Where  Contact Process
Water is used as Diluent, Quench or Vent Gas Absorbent
(Phase I Subcateqory B)

Process water is generated through the use of diluent steam,
product quench or vent gas  absorption.   Process  reactions
are  all  vapor-phase  over solid catalysts.  Most processes
use a vent gas absorber, coupled  with  steam  stripping  of
chemicals  for  purification  and  recycle  of  the absorber
water.

Continuous Aqueous Liquid-Phase Reaction Systems
(Phase I Subcategory C)

Process reactions are liquid-phase, with the catalyst in the
aqueous medium.  Continuous  regeneration  of  the  catalyst
requires  extensive  water usage, and substantial removal of
spent catalyst and inorganic by-products  may  be  required.
Additional - process  water is involved in final purification
and/or neutralization of products.

Batch and Semi-Continuous Processes (Deleted from Phase I
but covered under Phase II)

Many reactants are in the liquid-phase with aqueous catalyst
systems.   Requirement  for  very  rapid   process   cooling
necessitates  provisions  for the direct addition of contact
quench water or ice.  Reactants and products are transferred
from one piece of equipment  to  another  by  gravity  flow,
pumping,  or pressurization.  Much of the materials handling
is manual, and  there  is  only  limited  use  of  automatic

-------
process   control.    Filter  presses  and  centrifuges  are
commonly used  for  solid-liquid  separations,  and  air  or
vacuum   ovens  are  used  for  drying.   Cleaning  of  non-
continuous production equipment constitutes a  major  source
of waste water.

The   criteria   established   for   these   four   industry
subcategories was also used in the Phase II study.   The  40
product/process  segments  covered in the Phase I study were
further subcategorized into seven subgroups: A, Bl, B2,  Cl,
C2t  C3,  and C4.  Effluent limitations were then calculated
on the basis of the mean subcategory group raw  waste  load.
In  the  Phase  II  study,  the  effluent  limitations  were
established on the individual product/process raw waste load
rather than on the mean for the subcategory group.   Twenty-
seven   product/process segments of the 55 product/processes
investigated were selected  for  establishment  of  effluent
limitations.  A preliminary economic analysis indicated that
there   may   be   a   possible   adverse   impact   for  19
product/processes.   More  detailed  analysis  is  currently
underway  to  firmly  establish  the  extent of any possible
impact  and  the  possibility   of   establishing   effluent
limitations    in    the    future.     For    seven   other
product/processes,  the  data  base   was   not   considered
satisfactory to support effluent limitations at this time.

Many  RWL  parameters  were considered during the study, and
specific   pollutants   which   might   be   inhibitory   or
incompatible with biological treatment systems were cited in
Section  VI.  Effluent limitations and standards for cyanide
were established for hexamethylenediamine, adiponitrile  and
acrylonitrile  product/processes.   Total copper limitations
were also established for the plasticizers segment.

End-of-process treatment for the 1977 standard is defined as
equivalent to biological treatment as  typified  by  current
exemplary  processes  such  as  activated  sludge, trickling
filters, aerated  lagoons,  and  anaerobic  lagoons.   These
systems  may require pH control and equalization in order to
control variable waste loads, and  also  will  require  good
clarification  with  the  addition  of  chemicals  to aid in
removing suspended solids.  These systems  do  not  preclude
the  use  of  equivalent  chemical-physical  systems such as
activated   carbon.    Additionally,   suitable   in-process
controls  may  be needed for the control of those pollutants
which may be inhibitory to the  biological  waste  treatment
system and for possible reduction of raw waste loads.

Best  available  technology  economically achievable, BATEA,
(1983 Standard) is based on the addition of activated carbon

-------
treatment following biological treatment.   This  technology
permits   substantial   reductions   of   dissolved  organic
pollutants which are biorefractory as well as many which are
biodegradable.   The  application  of  exemplary  in-process
systems   is  also  considered  to  be  applicable  to  this
technology.  End-of-process activated carbon treatment  does
not  preclude  the  use  of  such treatment as an in-process
technology.

End-of-process technology for new sources utilizing the best
available demonstrated control technology (BADCT) is defined
as equivalent to biological treatment with suspended  solids
removal  via  clarification,  sedimentation,  sand, or dual-
media filtration.  In addition, the  use  of  exemplary  in-
process  controls are assumed to be applicable, particularly
where  biotoxic  pollutants  must   be   controlled.    This
technology does not preclude the use of equivalent chemical-
physical  systems  such as activated carbon as either an in-
process or end-of-process treatment.  The use  of  chemical-
physical  systems  may  be  necessary  in  areas  where land
availability is limited.

Time based effluent limitations were derived as the  maximum
parameter  value  for any one day and the maximum average of
daily values for any period of thirty consecutive days.  The
factors used in deriving these -time-based  limitations  were
determined  from long-term performance (i.e.  daily, weekly,
monthly) from the best treatment  systems  evaluated.   Time
based   limitations   consider   the  normal  variations  of
exemplary designed and operated waste treatment systems  and
include allowances for expected variation by use of suitable
variability factors.

-------

-------
                         SECTION II

                      RECOMMENDATIONS
Effluent   limitations  defining  best  practicable  control
technology  currently  available  are  presented  for   each
industrial    subcategory    of    the   organic   chemicals
manufacturing industry.   Product-process  segments  of  the
industry  which  were  covered  in  this study are listed in
Table  2-1.   Those  product/process  segments   for   which
effluent  limitations  and  guidelines  are  recommended are
indicated in Table 2-1 as well as the  28  product/processes
for  which  effluent  limitations  and  guidelines  are  not
proposed at this time.  Effluent limitations  for  the  1977
Standards  (BPCTCA)  are  shown  in  Table  2-2  for  the 27
designated product/processes.  Process waste waters  subject
to  these  limitations include all contact process water but
do not include noncontact sources such as boiler and cooling
water blowdown, and other similar sources.

Implicit in BPCTCA RWL data is the segregation of noncontact
waste waters from  process  waste  waters  and  the  maximum
utilization   of  applicable  in-plant  pollution  abatement
technology in order to  minimize  capital  expenditures  for
end-of-pipe waste water treatment facilities.

End-of-process    technology   for   BPCTCA   involves   the
application of the equivalent  of  biological  treatment  as
typified  by  activated  sludge,  trickling filters, aerated
lagoons, or anaerobic lagoons.  Equalization with pH control
and oil separation may  be  required  in  order  to  provide
optimal  as  well as a uniform level of treatment.  Chemical
flocculation aids, when necessary, should be  added  to  the
clarification  system  in  order to control suspended solids
levels.

Effluent limitations to be attained by  the  application  of
the  best  available  technology economically achievable are
presented in Table 2-3 for the 27 designated product/process
segments listed in Table 2-1.  End-of- process treatment for
BATEA includes the addition of activated carbon  systems  to
biological  waste treatment processes.  Exemplary in-process
controls,  as  discussed  in  the  later  sections  of  this
document,  are  also  included  in  this  technology.  It is
emphasized that the model treatment system does not preclude
the use of activated carbon  or  other  suitable  in-process
control   systems   within  the  plant.   Such  systems  are
frequently employed for recovery of  products,  by-products,
and catalysts.

-------
The  best  available demonstrated control technology for new
sources includes the most  exemplary  process  controls,  as
previously  enumerated,  with biological waste treatment and
systems for the removal of  suspended  solids.   New  source
standards for the 27 designated product/process segments are
presented in Table 2-4.

-------
                         TABLE 2-1

Subcategories   of   the   Organic  Chemicals  Manufacturing
Industry  (Phase II - Significant Product-Processes)
              Nonagueous Processes Subcategory
  Products	
BTX aromatics1
Cumene1

p-Xylene1
  Process Descriptions
Fractional distillation
Alkylation of benzene with
  propylene
Isomerization, crystalli-
  zation and filtration of
  mixed xylenes
                Processes With Process Water
               Contact only as Steam Diluent
                 Product Quench or Vent Gas
                   Absorbent Subcategory
Cnlorobenz ene2
Chloromethanes*

Chlorotoluene2
Diphenylaminel
Perchloroethylene2

Phthalic anhydride2
Phthalic anhydride1

Hexamethylenediamine 4
Hexamethylenediamine *
Methyl ethyl Ketone1

Tricresyl phosphate2
Adiponitrile1
Benzoic acid and1
  benzaldehyde
Methyl chloride2
Maleic anhydride1
Chlorination of benzene
Chlorination of methyl chloride
  and methane mixture
Chlorination of toluene
Deamination of aniline
Chlorination of chlorinated
  hydrocarbons
Oxidation of naphthalene
Oxidation of o-xylene

Hydrogenation of adiponitrile
Ammonolysis of 1, 6 hexanediol
Dehydrogenation of sec-butyl-
  alcohol
Condensation of cresol and
  phosphorus oxychloride

Chlorination of butadiene
Catalytic oxidation of
  toluene with air
Esterification of methanol
  with hydrochloric acid

Oxidation of benzene
               Aqueous Liquid Phase Reaction
                     Systems Subcategory

-------
Ethyl acetate1

Propyl acetate2

Propylene glycol2

Cyciohexanone oxime2
Formic acid2
Isopropanol1
Oxalic acid2


Calcium stearate1

Hexamethylenetetramine 2
Hydrazine solutions1
Isobutylene1

Sec-butyl alcohol1


Acrylonitrile1
Synthetic cresol2
Caprolactam2
p-Aminophenoll

Propylene oxide2

Pentaerythritol2
Saccharin2
 Esteritication of ethyl alcohol
     with acetic acid
 Esterification of propyl alcohol
    with acetic acid
 Hydrolysis of propylene oxide

 Hydroxylamine process
 Hydrolysis of formaldehyde
 Hydrolysis of propylene
 Nitric acid oxidation of
   carbohydrates

 Neutralization of stearic
   acid
 Ammonia systhesis
 Raschig process
 Extraction from C± BTX
   hydrocarbon mixture
 Sulfonation and hydrolysis
   of mixed butylenes

 Ammoxidation of propylene
 Methylation of phenol
 DSM process
 Catalytic reduction of
   nitrobenzene
 Chlorohydrin process

 Aldehyde condensation

 Synthesis from phthalic
   anhydride derivatives
            Batch and Semi-Continuous Processes
o-Nitroaniline1

p-Nitr oaniline *•
Ammonolysis of o-nitro-
  chlorobenzene
 Ammonolysis of p-nitro-
    chlorobenz en e
Pentachlorophenol2
 Chlorination of phenol
Fatty acids2
 Hydrolysis of tall oil,
   animal tallow and grease,
   vegetable oils and soap stocks

-------
Fatty acid derivatives2
                      Esterification, ammination
                        of fatty acids
lonone and methyl-1
 ionone
Methyl salicylate1
                      Condensation and cyclization
                        of Citral
                      Esterification of salicylic
                        acid with methanol
Miscellaneous batch2
 chemicals
                      Numerous batch processes in
                        an organic chemical
                        complex
Citronelloi and Geraniol1  Citronella oil distillation

Plasticizers1              Condensation of phthalic
                             anhydride
Dyes and dye inter-2
  mediates
                      Numerous batch processes
Pigments, Toners2
                      Diazotization and coupling
                        of amine, sulfuric acid
                        etc.
Pigments, Lakes2
                      Diazotization and coupling
                        of amine, sulfuric acid,
Citric Acid2
Napthenic acid2
                      Fermentation of molasses
                      Extraction and acidulation
                        of caustic sludge from
                        petroleum refinery
Monosodium glutamate2
                      Fermentation of beet sugar
                        molasses
Tannic acid1
                      Extraction of natural vege-
                        table matter
Vanillin2
                      Alkaline oxylation of spent
                        sulfite liquor
 1
 2
•Effluent limitations proposed.
Effluent limitations not proposed pending further
analysis of technical and/or economic data.

-------
                             Table 2-2

     Effluent Limitations for the Best Practicable Control
         Technology Currently Available (BPCTCA)  Organic
            Chemicals Manufacturing Industry - Phase II,
                  Significant Organic Products Segment
Efficient                            Effluent
Characteristic                      Limitations
                                kg/kkg production or
                                 lb/1,000 Ib production

                       Maximum for       Average of daily
                       any one day       values for thirty
                                         consecutive days
                       	       shall  not exceed

            Subcategory A - Nonaqueous Processes

BTX Aromatics (Fractional distillation)
   BOD5                  0.0039             0.0021
   TSS~                  0.0055             0.0029

Cumene
            No discharge of process waste water pollutants

p-Xylene
   BOD5                  0.0035             0.0019
   TSS                   0.0052             0.0028

    Subcategory B - Processes with Process Water Contact
    only as Steam Diluent, Quench or Vent Gas Absorbent

Chloromethanes
   BOD5_                  0.22               0.12
   TSS                   0.33               0.18

Diphenylamine
   BOD5                  0.041              0.021
   TSS~                  0.062              0.033

Phthalic Anhydride (oxidation of o-xylene)
   BOD5                  0.046              0.025
   TSS"                  0.069              0.038
                            10

-------
                              Table 2-2 (continued)
Hexamethylenediamine  (adiponitrile process)
   BOD5.                  0.16               0.084
   TSS                   0.12               0.063
   Cyanide               0.0010             0.00050

Hexamethylenediamine  (hexanediol process)
   BOD5_                  0.16               0.084
   TSS                   0.13               0.069
   Cyanide               0.0011             0.00055

Methyl ethyl ketone
   BOD5_                  0.16               0.082
   TSS                   0.16               0.082

Adiponitrile
   BOD£                  1.1                0.61
   TSS                   1.1                0.61
   Cyanide               0.0098             0.0049

Benzoic Acid & Benzaldehyde
   BOD5.                  1.0                0.55
   TSS                   0.33               0.18

Maleic Anhydride
   BOD5.                  4.2                2.3
   TSS                   0.27               0.15

               Subcategory C - Aqueous Liquid
                   Phase Reaction Systems

Ethyl Acetate
   BOD5.                  0.10               0.055
   TSS                   0.16               0.082

Isopropanol
   BOD5_                  0.27               0.15
   TSS                   0.29               0.16

Calcium Stearate
   BOD5.                  4.2                2.3
   TSS                   6.3                3.4

Hydrazine
   BOD5.                  0.37               0.20
   TSS                   0.37               0.20

Isobutylene
   BOD5.                  2.4                1.3
   TSS                   2.4                1.3
                               11

-------
                           Table 2-2 (continued)
Sec Butyl Alcohol
   BOD5.                  0.55               0.29
   TSS                   0.074              0.040

Acrylonitrile
   BOD5_                  1.6                0.82
   TSS                   0.51               0.27
   Cyanide               0.0045             0.0022

p-Aminophenol
   BOD5_                  1.6                0.88
   TSS                   1.5                0.80

    Subcategory D - Batch and Semi-Continuous Processes

o-Nitroaniline
   BOD5_                 21                 12
   TSS                  31                 17

p-Nitroaniline
   BOM                  3.0                1.7
   TSS                   4.6                2.5

lonone and Methylionone
   BOD5_                  1.1                0.59
   TSS                   1.1                0.59

Methyl Sal icy!ate
   BOD5_                  0.87               0.46
   TSS                   0.19               0.11

Citronellol and Geraniol
   BOD5.                  2.2                1.3
   TSS                   1.2                0.63

Plasticizers
   BOD5>                  2.1                1.2
   TSS                   0.076              0.041
   Total Copper          0.00065            0.00032

Tannic Acid
   BOD5.                  6.0                3.2
   TSS                   1.2                0.63

   pH for all subcategories between 6.0 - 9.0.
                               12

-------
                         Table 2-3

    Effluent Limitations for the Best Available Technology
               Economically Achievable (BATEA) Organic
            Chemicals Manufacturing Industry - Phase II,
                  Significant Organic Products Segment
Effluent                            Effluent
Characteristic                      Limitations
                                 kg/kkg production or
                                 lb/1000 Ib production

                       Maximum for       Average of daily
                       any one day       values for thirty
                                         consecutive days
                       	       shall not exceed

            Subcategory A - Nonaqueous Processes

BTX Aromatics (Fractional distillation)
   COD                   0.016              0.0089
   BOD5.                  0.0018             0.00099
   TSS                   0.0026             0.0015

Cumene
            No discharge of process waste water pollutants

p-Xylene
   COD                   0.0086             0.0047
   BOD5_                  0.0018             0.00093
   TSS                   0.0026             0.0014

    Subcategory B - Processes with Process Water Contact
    only as Steam Diluent, Quench or Vent Gas Absorbent

Chloromethanes
   COD                   0.55               0.29
   BOD5.                  0.11               0.059
   TSS                   0.17               0.086

Diphenylamine
   COD                   0.10               0.055
   BOD5.                  0.021              0.011
   TSS                   0.031              0.017
                              13

-------
                              Table 2-3 (continued)
Phthalic Anhydride (oxidation of o-xylene)
   COD                   0.22
   BOD5_                  0.023
   TSS                   0.035

Hexamethy1enediamine (adiponitrile process)
   COD                   6.6
   BOD5_                  0.039
   TSS
   Cyanide
 0.058
 0.00050
Hexamethylenediamine (hexanediol process)
   COD                   3.7
   BOD5_                  0.043
   TSS                   0.062
   Cyanide               0.00055

Methyl ethyl ketone
   COD                   0.67
   BOD5_                  0.051
   TSS                   0.078

Adiponitrile
   COD                  42
   BOD5_                  0.39
   TSS                   0.55
   Cyanide               0.0049

Benzoic Acid & Benzaldehyde
   COD                  16
   BOD5_                  0.11
   TSS                   0.17
Maleic Anhydride
   COD
   BOD5_
   TSS
90
 0.47
 0.13
                    0.11
                    0.012
                    0.018
 3.5
 0.021
 0.032
 0.00025
                    2.0
                    0.023
                    0.033
                    0.00022
                    0.36
                    0.027
                    0.042
                   22
                    0.21
                    0.30
                    0.0024
                    8.5
                    0.059
                    0.086
48
 0.25
 0.074
               Subcategory C - Aqueous Liquid
                   Phase Reaction Systems
Ethyl Acetate
   COD
   BOD5_
   TSS

Isopropanol
   COD
   BOD5_
   TSS
 0.25
 0.051
 0.078
 0.94
 0.098
 0.14
 0.14
 0.027
 0.042
 0.50
 0.052
 0.080
                              14

-------
                       Table  2-3  (continued)
Calcium Stearate
   COD                  11                  5.7
   BOD5_                  2.1                1.1
   TSS                   3.1                1.7

Hydrazine
   COD                  36                 19
   BOD5_                  1.2                0.63
   TSS                   1.8                0.94

Isobutylene
   COD                  20                 11
   BOD5_                  0.78               0.42
   TSS                   1.2               0.63

Sec Butyl Alcohol
   COD                  12                  6.5
   BOD5_                  0.062              0.034
   TSS                   0.038              0.020

Acrylonitrile
   COD                  42                 22
   BOD5_                  0.18               0.095
   TSS                   0.26               0.14
   Cyanide               0.0022             0.0011

p-Aminophenol
   COD                  23                 13
   BOD5_                  0.51               0.27
   TSS                   0.74               0.40

    Subcategory D - Batch and Semi-Continuous Processes

o-Nitroaniline
   COD                  50                 27
   BOD5_                 11                   5.7
   TSS                  16                  8.5

p-Nitroaniline
   COD                  25                 13
   BOD5.                  1.6                0.82
   TSS                   2.3                1.2

lonone and Methylionone
   COD                  30                 16
   BOD5_                  0.36               0.20
   TSS                   0.55               0.30
                              15

-------
                         Table 2-3 (continued)
Methyl Salicylate
   COD                  30                 16
   BOD5                  0.094              0.050
   TSS                   0.10               0.054

Citronellol and Geraniol
   COD                  34                 16
   BOD                   0.39               0.21
   TSS                   0.59               0.32

Plasticizers
   COD                  27                 14
   BOD5                  0.21               0.11
   TSS"                  0.038              0.021
   Total Copper

Tannic Acid
   COD                 335                180
   BOD5                  0.66               0.36
   TSS                   0.60               0.32

   pH for all subcategories between 6.0 to 9.0.
                              16

-------
                         Table 2-4

          Standards of Performance for New Organic
            Chemicals Manufacturing - Phase II,
            Significant Organic Products Segment
Effluent                            Effluent
Characteristic                      Limitations
                                  kg/kkg production or
                                   lb/1000 Ib production

                       Maximum for       Average of daily
                       any one day       values for thirty
                                         consecutive days
                       	       shall not exceed

            Subcategory A - Nonaqueous Processes

BTX Aromatics (Fractional distillation)
   BOD5_                  0.0032             0.0018
   TSS                   0.0028             0.0015

Cumene
            No discharge of process waste water pollutants

p-Xylene
   BOD5_                  0.0029             0.0016
   TSS                   0.0026             0.0015

    Subcategory B - Processes with Process Water Contact
    only as Steam Diluent, Quench or Vent Gas Absorbent
Chloromethanes
   BOD5_                  0.18               0.098
   TSS                   0.16               0.089

Diphenylamine
   BOD5_                  0.033              0.018
   TSS                   0.031              0.017

Phthalic Anhydride (oxidation of o-xylene)
   BOD5_                  0.039              0.021
   TSS                   0.035              0.019
                            17

-------
                         Table 2-4 (continued)
Hexamethylenediamine (adiponitrile process)
   BOD5_
   TSS
   Cyanide
0.13
0.059
0.0010
Hexamethylenediamine (hexanediol process)
   BOD5_                  0.13
   TSS                   0.065
   Cyanide               0.0011

Methyl ethyl ketone
   BOD5.                  0.12
   TSS                   0.078

Adiponitrile
   BOD5.                  0.95
   TSS                   0.55
   Cyanide               0.0098

Benzoic Acid & Benzaldehyde
   BOD5                  0.87
   TSS                   0.16
Maleic Anhydride
   BOD5_
   TSS
3.5
0.14
0.069
0.032
0.00050
                   0.069
                   0.034
                   0.00055
                   0.068
                   0.042
                   0.50
                   0.29
                   0.0049
                   0.46
                   0.089
1.9
0.074
               Subcategory C - Aqueous Liquid
                   Phase Reaction Systems
Ethyl Acetate
   BOD5
   TSS

Isopropanol
   BOD5
   TSS"

Calcium Stearate
   BOD5_
   TSS

Hydrazine
   BOD5_
   TSS

Isobutylene
   BOD5
   TSS"
0.087
0.078
0.22
0.15
3.5
3.1
2,1
1.8
2.0
1.2
0.046
0.042
0.12
0.08
1.9
1.7
1.1
0.94
1.1
0.63
                             18

-------
                        Table  2-4  (continued)
Sec Butyl Alcohol
   BOD5_                  0.47                0.25
   TSS                   0.037               0.020

Acrylonitrile
   BOD5.                  1.2                 0.67
   TSS                   0.26                0.14
   Cyanide               0.0045              0.0022

p-Aminophenol
   BOD5.                  1.4                 0.74
   TSS                   0.74                0.38

    Subcategory D - Batch and Semi-Continuous  Processes

o-Nitroaniline
   BOD5_                 17                   9.4
   TSS                  16                   8.4

p-Nitroaniline
   BOD5_                  2.5                 1.4
   TSS                   2.2                 1.3

lonone and Methylionone
   BOD5_                  0.87                0.48
   TSS                   0.55                0.29

Methyl Salicylate
   BOD5_                  0.71                0.39
   TSS                   0.10                0.055

Citronellol and Geraniol
   BOD5_                  1.9                 1.0
   TSS                   0.59                0.32

Plasticizers
   BOD5^                  1.7                 0.94
   TSS                   0.038               0.021
   Total  Copper          0.00065             0.00032

Tannic Acid
   BOD^                  4.9                 2.6
   TSS                   0.59                0.32

   pH for all subcategories between 6.0 - 9.0.
                            19

-------

-------
                        SECTION III

                        INTRODUCTION
Purpose and Authority

Section 301(b) of the Act requires the achievement,  by  not
later  than  July 1, 1977, of effluent limitations for point
sources, other than publicly-owned  treatment  works,  which
are based on the application of the best practicable control
technology   currently   available   as   defined   by   the
Administrator  pursuant  to  Section  304(b)  of  the   Act.
Section  301(b)  also requires the achievement, by not later
than  July  1,  1983,  of  effluent  limitations  for  point
sources,  other  than  publicly-owned treatment works, which
are  based  on  the  application  of  the   best   available
technology  economically  achievable  which  will  result in
reasonable futher  progress  toward  the  national  goal  of
eliminating  the  discharge of all pollutants, as determined
in accordance with regulations issued by  the  Administrator
pursuant  to  Section 304(b) to the Act.  Section 306 of the
Act requires the achievement, by new sources, of  a  Federal
standard  of  performance  providing  for the control of the
discharge of pollutants which reflects the  greatest  degree
of  effluent reduction which the Administrator determines to
be achievable through the application of the best  available
demonstrated   control   technology,   processes,  operating
methods,   or   other   alternatives,    including,    where
practicable,   a   standard   permitting   no  discharge  of
pollutants.

Section 304(b) of the  Act  requires  the  Administrator  to
publish,   within   one   year  of  enactment  of  the  Act,
regulations providing guidelines  for  effluent  limitations
setting  forth  tne  degree of effluent reduction attainable
through the application  of  the  best  practicable  control
technology  currently  available  and the degree of effluent
reduction attainable including treatment techniques, process
and procedure  innovations,  operation  methods,  and  other
alternatives.   The  regulations  proposed  herein set forth
effluent limitation guidelines pursuant to Section 304(b) of
the Act for the organic chemicals industry.

Section 306 of the Act requires  the  Administrator,  within
one  year  after a category of sources is included in a list
published pursuant to Section 306 (b) (1) (A) of the  Act,  to
propose   regulations   establishing  Federal  standards  of
performances  for  new  sources  within   such   categories.
Section 307(c) of the Act also requires the Administrator to
                              21

-------
propose  pretreatment standards for new sources discharge to
publicly owned waste treatment  plants.   The  Administrator
published,  in  the Federal Register of January 16, 1973 (38
F.jR. 1624) , a list of 27 source categories.  Publication  of
the  list  constituted  announcement  of the Administrator1s
intention of establishing, under Section 306,  standards  of
performance  applicable  to  new  sources within the organic
chemicals industry, which was included in the list published
January  16,  1973.   This  document  is   published   under
authority  of  Section 304 (c) of the Act which requires that
information be made available in the  form  of  a  technical
report  on  alternate treatment models to implement effluent
limitation and standards of performance for new sources.

Implementation of the Act  regarding  fulfillment  of  these
requirements  as  outlined  above  was accomplished in a two
pnase  effort.   On  April  25,  1974,   the   Environmental
Protection   Agency   published   effluent  limitations  and
standards for 40  product/process  segments  (40  CFR  414).
These   segments   generally  constitute  the  large  volume
products and were designated  the  "Major  Organic  Products
Segment  of the Organic Chemicals Point Source Category".  A
technical report for Phase I effluent limitations  was  also
published  in  April  1974,  (EPA 440/1-73/009) in which the
rationale and  technical  basis  for  the  regulations  were
presented.   The  data  and  information  presented  in this
document  provides   technical   description   of   the   55
product/process  segments investigated in the Phase II study
of   the   Organic   Chemicals    Manufacturing    Industry.
Additionally   the   rationale   and   basis   for  effluent
limitations for the selected 29 product/processes  are  also
presented.

Scope of^the Study

The  Organic Chemicals Industry was defined to include those
commodities  listed  under  SIC  2865   (Cyclic  Crudes   and
Intermediates)  and  SIC  2869  (Industrial Organic Chemicals
Not Elsewhere Classified).

Tables 3-1 and 3-2 show 260 materials listed under SIC  2865
and 2869.  It was noted that many specific commodities  (e.g.
ethylene,   adiponitrile,   hydrazine,  synthetic  vanillin,
sodium sulfoxalate formaldehyde, etc.) are in the same  list
with  references  to  very  large families of products  (e.g.
synthetic  organic  dyes,  coal  tar  distillates,   organic
pigments, alcohols, flavors, enzymes, etc.).

These lists are developed by the United States Department of
Commerce  and are oriented toward the collection of economic
                                22

-------
data related to gross production,  sales,  and  unit  costs.
They  are not related to the true nature of this industry in
terms   of   actual   plant   operations,   production,   or
considerations  associated with water pollution control.  It
should also be noted that all the major producers of organic
chemicals  are  not  included  in  the  286  group.    Major
companies  not  in  group  286  are  covered in such diverse
classifications  as  petroleum  refining,  meat  and   dairy
products, and photographic and optical equipment.

The  exact  nature  of  the  manufacturing operations at any
specific facility is characteristic only of  that  facility.
There  are  very few, if any, organic chemicals plants which
manufacture one  product  by  a  single  process.   Instead,
almost  all  plants  are  multi-product facilities where the
final mix of products shipped from each plant is unique.  In
some cases, the actual number of commodities produced can be
in the thousands (such as a batch chemicals complex),  while
other  facilities  manufacture only two or three high volume
products.
                               23

-------
                         Table 3-1
            Chemicals Listed Under SIC Code 2865

  Cyclic Intermediates, Dyes, Organic Pigments  (Lakes and
           Toners), and Cyclic (Coal Tar) Crudes


Acid dyes, synthetic
Acids, coal tar:  derived from
    coal tar distillation
Alkylated diphenylamines, mixed
Alkylated phenol, mixed
Aminoanthr aquinone
Aminoazobenzene
Aminoazotoluene
Aminophenol
Aniline
Aniline oil
Anthracene
Anthraquinone dyes
Azine dyes
Azobenzene
Azo dyes
Azoic dyes
Benzaldehyde
Benzene, product of coal tar
    distillation
Benzoic acid
Benzol, product of coal tar
    distillation
Biological stains
Chemical indicators
Naphthalene, chips and flakes
Chlorobenz ene
Chloronaphthalene
Chlorophenol
Chlorotoluene
Coal tar acids, derived from
    coal tar distillation
Coal tar crudes, derived from
    coal tar distillation
Coal tar distillates
Coal tar intermediates
Color lakes and toners
Color pigments, organic:  ex-
    cept animal black and bone
    black
Colors, dry:  lax.es, toners, or
    full strength organic colors
Colors, extended  (color lakes)
                               24

-------
Cosmetic dyes, synthetic
Cresols, product of coal tar
    distillation
Creosote oil, product of coal tar
    distillation
Cresylic acid, product of coal tar
    distillation
Cyclic crudes, coal tar:  product
    of coal tar distillation
Cyclic intermediates
Cyclohexane
Diphenylamine
Drug dyes, synthetic
Dyes, synthetic organic
Eosine toners
Ethylbenzene
Food dyes and colors, synthetic
Hydroquinone
isocyanates
Lake red C toners
Lithol rubine lakes and toners
Maleic anhydride
Methyl violet toners
Naphtha, solvent:  product of
    coal tar distillation
Naphthalene, product of coal tar
    distillation
Naphthol, alpha and beta
Naphtholsulfonic acids
Nitroaniline
Nitrobenzene
Nitro dyes
Nitrophenol
Nitroso dyes
Oils.:  light, medium/ and heavy—
    product of coal tar distillation
Orthodichlorobenzene
Paint pigments, organic
Peacock blue lake
Pentachlorophenol
Persian orange lake
Phenol
Phloxine toners
Phosphomolybdic acid lakes and
    toners
                              25

-------
                         Table 3-1
                        (continued)
Phosphotungstic acid lakes and
    toners
Phthalic anhydride
Phthalocyanine toners
Pigment scarlet lake
Pigments, organic:  except
    animal £>lack and bone black
Pitch, product of coal tar
    distillation
Pulp colors, organic
Quinoline dyes
Resorcinol
Scarlet 2 R lake
Stilbene dyes
Styrene
Styrene monomer
Tar, product of coal tar dis-
    tillation
Toluene, product of coal tar
    distillation
Toluol, product of coal tar
    distillation
Toiuidines
Toners  (reduced or full strength
    organic colors)
Vat dyes, synthetic
Xylene, product of coal tar
    distillation
Xylol, product of coal tar
    distillation
                              26

-------
                         Table 3-2
            Chemicals Listed Under SIC Code 2869
   Industrial Organic Chemicals, Not Elsewhere Classified
Accelerators, rubber processing:
    cyclic and acyclic
Acetaldehyde
Acetates, except natural acetate
    of clime
Acetic acid, synthetic
Acetic anhydride
Acetin
Acetone, synthetic
Acids, organic
Acrolein
Acrylonitrile
Adipic acid
Adiponitrile
Alcohol, aromatic
Alcohol, fatty: powdered
Alcohols, industrial:  de-
    natured  (nonbeverage)
Algin products
Amines of polyhydric alcohols,
    and of fatty and other acids
Amyl acetate and alcohol
Antioxidants, rubber processing:
    cyclic and acyclic
Bromochloromethane
Butadiene, from alcohol
Butyl acetate, alcohol, and
    propionate
Butyl ester solution of 2, 4-D
Calcium oxalate
Camphor, synthetic
Carbon bisulfide (disulfide)
Carbon tetrachloride
Casing fluids, for curing fruits,
    spices, tobacco, etc.
Cellulose acetate, unplasticized
Chemical warfare gases
Chloral
Chlorinated solvents
Chloroacetic acid and metallic
    salts
Chloroform
Chloropicrin
Citral
                              27

-------
                              Table 3-2
                           (continued)

Citrates
Citric acid
Citronellol
Coumarin
Cream of tartar
Cyclopropane
DDT, technical
Decahydronaphthalene
Dichlorodiflouromethane
Diethylcyclohexane  (mixed isomers)
Diethylene glycol ether
Dimethyl divinyl acetylene (di-
    isopropenyl acetylene)
Dimethylhydrazine, unsymmetrical
Enzymes
Esters of phthalic anhydride:  and
    of phosphoric, adipic, lauric,
    oleic, sebacic, and stearic
    acids
Esters of polyhydric alcohols
Ethanol, industrial
Ether
Ethyl acetate, synthetic
Etnyl alcohol, industrial (non-
    beverage)
Ethyl butyrate
Ethyl cellulose, unplasticized
Ethyl chloride
Ethyl ether
Ethyl formate
Ethyl nitrite
Ethyl perhydrophenanthrene
Ethylene
Ethylene glycol
Ethyiene glycol ether
Ethylene glycol, inhibited
EthyJLene oxide
Ferric ammonium oxalate
Flavors and flavoring materials,
    synthetic
Fluorinated hydrocarbon gases
Formaldehyde  (formalin)
Formic acid and metallic  salts
Freon
                              28

-------
                         Table 3-2
                         (continued)
Fuel propellants, solid organic
Fuels, high energy, organic
Gases, fluorinated hydrocarbon
Geraniol, synthetic
Glycerin, except from fats
     (synthetic)
Grain alcohol, industrial
Hexamethylenediamine
H examethy1enet etramine
High purity grade chemicals,
    organic:  refined from
    technical grades
Hydraulic fluids, synthetic base
Hydrazine
Industrial organic cyclic compounds
lonone
Isopropyl alcohol
Ketone, methyl ethyl
Ketone, methyl isobutyl
Laboratory chemicals, organic
Laurie acid esters
Lime citrate
Malononitrile, technical grade
Metallic salts of acyclic organic
    chemicals
Metallic stearate
Methanol, synthetic  (methyl alco-
    hol)
Methyl chloride
Methyl perhydrofluorine
Methyl salicylate
Methylamine
Methylene chloride
Monochlorodifluoromethane
Monomethylparaminophenol sulfate
Monosodium glutamate
Mustard gas
Nitrous ether
Normal hexyl decalin
Nuclear fuels, organic
Oleic acid esters
Organic acids, except cyclic
Organic chemicals, acyclic
Oxalates
Oxalic acid and metallic salts
Pentaerythritol
                              29

-------
                              Table 3-2
                            (continued)
Per ciilor oe thy len e
Perfume materials, synthetic
Phosgene
Phthalates
Plasticizers, organic:  cyclic
    and acyclic
Polyhydric alcohols
Potassium bitartrate
Propellants for missiles, solid,
    organic
Propylene
Propylene glycol
Quinuclidinol ester of benzylic
    acid
Reagent grade chemicals, organic:
    refined from technical grades
Rocket engine fuel, organic
Rubber processing chemicals, or-
    ganic:  accelerators and anti-
    oxidants—cyclic and acyclic
Saccharin
Sebacic acid
Silicones
Soaps, naphthenic acid
Sodium acetate
Sodium alginate
Sodium benzoate
Sodium glutamate
Sodium pentachlorophenate
Sodium sulfoxalate formaldehyde
Solvents, organic
Sorbitol
Stearic acid esters
Stearic acid salts
Sulfonated naphthalene
Tackifiers, organic
Tannic acid
Tanning agents, synthetic organic
Tartaric acid and metallic salts
Tartrates
Tear gas
Terpineol
Tert-butylated bis  (p-phenoxy-
    phenyl) ether fluid
                               30

-------
                         Table 3-2
                        (continued)
Tetr a ch lor oethylene
Tetraethyl lead
Thioglycolic acid, for permanent
    wave lotions
Trichloroethylene
Trichloroethylene stabilized,
    degreasing
Trichlorophenoxyacetic acid
Trichlorotrifluoroethane tetrachloro-
    dixluoroethane isopropyl alcohol
Tricresyl phosphate
Tridecyl alcohol
Trimethyltrithiophosphite  (rocket
    propellants)
Triphenyl phosphate
Urea
Vanillin, Synthetic
Vinyl acetate
                               31

-------
Methods Used for Development o£ the Effluent
Limitations and Standards of Performance

The  effluent  limitations  guidelines  and   standards   of
performance  proposed herein were developed in the following
manner.  The point-source category was first  subcategorized
for  the purpose of determining whether separate limitations
and standards are appropriate for different segments  within
a  point-source  category.  Such subcategorization was based
upon raw  material  used,  product  produced,  manufacturing
process   employed,   and  other  factors.   The  raw  waste
characteristics for each subcategory were  then  identified.
This  included  an  analysis of: 1) the source and volume of
water used in the process employed and the sources of  waste
and  waste  waters  in  the  plant;  and 2)  the constituents
(including thermal) of all  waste  waters  (including  toxic
constituents  and other constituents)  which result in taste,
odor,  and  color   in   the   receiving   waterbody.    The
constituents  of  waste  waters  which  should be subject to
effluent limitations guidelines and standards of performance
were identified.

The  full  range  of  control  and  treatment   technologies
existing  within  each  subcategory  was  identified.   This
included an identification  of  each  distinct  control  and
treatment  technology,  including  both in-plant and end-of-
pipe technologies, which are existent or  capable  of  being
designed   for   each  subcategory.   It  also  included  an
identification of the  effluent  level  resulting  from  the
application  of  the  treatment and control technologies, in
terms of the amount of constituents (including thermal)  and
of the chemical, physical, and biological characteristics of
pollutants.   The  problems, limitations, and reliability of
each treatment  and  control  technology  and  the  required
implementation  time were also identified.  In addition, the
nonwater quality environmental impact  (such as  the  effects
of the application of such technologies upon other pollution
problems,  including air, solid waste, noise, and radiation)
was also identified.  The energy requirements of each of the
control and treatment technologies were identified, as  well
as the cost of the application of  such technologies.

The  information,  as  outlined above, was then evaluated in
order to determine what levels of technology constituted the
"best practicable control technology  currently  available",
"best available technology economically achievable", and the
"nest  available demonstrated control technology, processes,
operating methods, or other  alternatives."  In  identifying
such  technologies,  various factors were considered.  These
included the total cost  of  application  of  technology  in
                              32

-------
relation  to  the effluent reduction benefits to be achieved
from such application, the age of equipment  and  facilities
involved,  the  process employed, the engineering aspects of
the application of  various  types  of  control  techniques,
process   changes,  nonwater  quality  environmental  impact
(including energy requirements), and other factors.

During the initial phases of the study,  an  assessment  was
made  of  the  availability, adequacy, and usefulness of all
existing data sources.  Data on the identity and performance
of waste water treatment systems were known to  be  included
in:

    1.   Letter  surveys  conducted  by  the   Manufacturing
         Chemists' Association (MCA).

    2.   NPDES Permit Applications.

    3.   Self-reporting discharge data from various states.

Limited data on process raw waste loads were also  known  to
be included in previous MCA survey returns.

A  preliminary  analysis  of these data indicated an obvious
need for additional information.

NPDES permit applications data are limited to identification
of  the  treatment  system  used  and  reporting  of   final
concentrations  (which  were  diluted with cooling waters in
many cases); consequently, operating performance  could  not
be determined.

Texas,  where  there  is  a  high  concentration  of organic
chemical plants,  has  a  self-reporting  discharge  system.
These  reports again show only final effluent concentrations
and  identify  the  system  used;  only  rarely   is   there
production  information  available  which  would  permit the
essential determination of unit waste loads.

Additional  data  in  the  following  areas  were  therefore
required:  1)   process  RWL  (Raw  Waste  Load)   related  to
production; 2) currently practiced or  potential  in-process
waste   control   techniques;   and   3)   the  identity  and
effectiveness of end-of-pipe treatment  systems.   The  best
source   of   information  was  the  chemical  manufacturers
themselves.  This additional data was obtained  from  direct
interviews  and  from  inspection  and  sampling  of organic
chemical manufacturing and waste water treatment facilities.
                              33

-------
Collection of the data necessary for development of RWL  and
effluent treatment requirements within dependable confidence
limits  required  analysis  of both production and treatment
operations.  In number  of  cases,  the  plant  visits  were
planned  so that the production operations of a single plant
could be  studied  in  association  with  an  end-of-process
treatment  system  which  receives only the wastes from that
production.   The  RWL  for  such  a  plant  and  associated
treatment  technology  would  fall within a single category.
However,  the  unique   feedstock   and   product   position
applicable  to  individual manufacturers made this idealized
situation rare.

In  the  majority  of  cases,  it  was  necessary  to  visit
individual  facilities  where the products manufactured fell
into several subcategories.   The  end-of-process  treatment
facilities  received  combined  waste waters associated with
several subcategories (several products).  It was  necessary
to  analyze  separately  the  production  (waste generating)
facilities and the effluent  (waste  treatment)  facilities.
This required establishment of a common basis, the Raw Waste
Load   (RWL),  for  common levels of treatment technology for
the products within a subcategory and for the translation of
treatment technology between categories.

The selection of process plants as candidates to be  visited
was  guided  by the trial subcategorization, which was based
on anticipated differences in  RWL.   Process  plants  which
manufacture only products within one subcategory, as well as
those  which cover several subcategories, were scheduled for
inspection and sampling  to  insure  the  development  of  a
dependable data base.

The   selection   of  treatment  plants  as  candidates  for
visitation  and  sampling  was  developed  from  information
available  in  tne  MCA  survey  returns. Corps of Engineers
Permit Applications, state  self-reporting  discharge  data,
and  contacts within the industry.  Every effort was made to
choose  facilities  where  meaningful  information  on  both
treatment  facilities  and  manufacturing processes could be
obtained.

The selection of  plants  visited  was  based  upon  several
factors.   First,  since most plants in this industry do not
have biological treatment facilities, every effort was  made
to  visit those plants which do have such facilities.  Other
plants were selected  on  the  basis  of  accessibility  and
engineering  judgement  on  the part of the contractor as to
which plants were representative  of  the  product/processes
studied.
                              34

-------
Survey  teams  composed  of project engineers and scientists
conducted actual plant visits.  Information on the  identity
and  performance  of  waste  water  treatment  systems  were
obtained through:

    1.   Interviews  with  plant  water  pollution   control
         personnel.

    2.   Examination   of   treatment   plant   design   and
         historical  operating data (flow rates and analyses
         of influent and effluent).

    3.   Treatment plant influent and effluent sampling.

The data base obtained in this manner was then  utilized  by
the  methodology previously described to develop recommended
effluent limitations and standards of  performance  for  the
organic chemical industry.  References utilized are included
in  Section XV of this report.  The data obtained during the
field data collection program are included in Supplement  B.
Due  to  the large volume of information in Supplement B, it
was not practical to be included in this report.

A copy of Supplement B  is  on  file  at  the  Environmental
Protection  Agency's  Freedom  of  Information Office, 401 M
Street, S.W. Washington, D.C. and can be inspected  at  that
location.

Water Usage Associated  with Different Segments of a
Chemical Plant

The  production  quantities  associated with the product mix
snipped from a plant are not necessarily a  true  indication
of  the  extent  or type of manufacturing activities carried
out within that plant.  In many cases, several products  are
produced   captively   within  the  plant  and  subsequently
utilized as feedstocks in the production of  those  products
ultimately shipped from the plant.

These  factors are worthy of consideration in that the water
usage and subsequent water pollution caused by  the  Organic
Cnemicals  industry  are  directly  related  to the specific
nature of its diverse manufacturing processes.  Analysis  of
these  manufacturing  processes  is,  therefore, the logical
starting  point  for  any  study  whose  objective  is   the
development   of   production-based   effluent   limitations
guidelines.

In  order  to   develop   such   production-based   effluent
limitations  guidelines,  it  was  necessary to utilize some
                                 35

-------
"common denominator" which would relate  diverse  production
activities   (waste   generating   activities)    with  water
pollution control technologies (waste treatment activities).
Process raw waste load (RWL)  was considered as the best tool
for accomplishing this objective.  Other waste water sources
of a nonprocess origin such as rain water  runoff  and  from
utilities, laboratories,  storage and transfer facilities may
also   contain  significant  raw  waste  loads  and  require
treatment  together  with   process   waste   waters.    The
quantities  of  nonprocess waste water loads is not normally
related to the quantities of production.   These  nonprocess
waste waters were therefore not considered in addition to or
as  part  of  the  process raw waste loads except in certain
cases such as in batch  process  as  noted  in  Section  IV.
Nonprocess  waste  waters  which are significant and require
treatment may be  provided  effluent  allocations  for  such
sources under Section 402 (NPDES) for permit issuance.

For  purposes  of  this study, the process RWL is defined as
the  quantity  of  waste  and  pollutants  generated  by   a
manufacturing  process,  divided by the quantity of chemical
product derived from the  process.   In  this  context,  the
process  represents a unique set of chemical conversions and
unit operations by which a specific feedstock is transformed
into a  specific  set  of  products,  co-products,  and  by-
products.   The  quantities  of  water  and  pollutants  are
measured prior  to  treatment  for  removal  of  pollutants.
These  quantities include all water which contacts chemicals
within the process battery limits and  excludes  non-contact
water  associated  with  heating  and  cooling  surface heat
exchangers.  This differentiation was  drawn  on  the  basis
that   oxygen-demanding   parameters    (for  which  effluent
limitations  guidelines  are  subsequently  developed)   are
associated  primarily  with  such  contact  wastes.   It  is
appreciated that surface run-off, tank drainage,  and  other
sources  outside  the  battery limits may also contribute to
this type of pollution, but very little data  are  available
to  indicate  the  significance of these sources compared to
actual process wastes.

A detailed  discussion  of  the  process  RWL,  contact  and
noncontact  water usage, and the interactions of feedstocks,
products,  and  associated  chemical  conversions  and  unit
operations  within  the  manufacturing plant complex is also
given in the Development Document for Phase I of this  study
(EPA440/1-73/009).    Phase  II  of  the  organic  chemicals
industry  study  includes  29   additional   product/process
segments  for  which effluent limitations and guidelines are
presently established and  26  other  product/processes  for
which  effluent  limitation and guidelines are not presently
                              36

-------
established.  It is expected that limitations and guidelines
for these will be established at a later date.

Waste Water Control Technology

The development of waste water reduction factors is  another
item  requiring  preliminary  comment.   It  was  originally
anticipated that these  factors  (relating  to  demonstrated
treatment  technologies   defining BPCTCA, BATEA, and BADCT)
could be obtained from performance data  on  many  operating
treatment  plants in the organic chemicals industry.  It was
known that this industry did not have numerous  waste  water
treatment  facilities;  however,  the  original  assumptions
proved to be  overly  optimistic.   Relatively  few  organic
chemical manufacturers were able to provide substantial data
on the treatment of their waste water.

Information  from  an  industry  survey conducted in 1972 by
members of  the  Manufacturing  Chemists  Association  which
consisted of 100 organic chemicals plants had indicated that
approximately   10   percent  of  the  plants  surveyed  had
biological treatment systems installed.  This was  confirmed
from  plant  visits  by  the  contractor and review of NPDES
permit  applications.   For  these  sources  of   data   and
information,   the  following  approximately  describes  the
industry's waste treatment  practices:  80  percent  of  the
industry's 674 production facilities  (Dept. of Commerce 1972
Census  of  Manufacturers)   were found to provide no on-site
treatment other than neutralization of  their  waste  water.
Many of these (approximately 50 percent) presently discharge
to  municipal  treatment  systems.   Of  the  remainder, ap-
proximately  10  percent  provide   miscellaneous   physical
treatment  such  as  sedimentation,  while  approximately 10
percent  provide  biological   treatment   of   some   type.
According  to  the  1967  Department  of  Commerce Census of
Manufacturing - Water Use (latest data available) there  are
174  plants treating wastewaters.  This is 26 percent of the
674 plants.  Of these, 77 plants  have  pH  control  and  an
estimated 40 plants have pH control only.  Thus, 134 plants,
20  percent  of  the  total,  have  treatment  other than pH
control.

Biological  treatment  typified . by  the  activated   sludge
process  was  defined  as BPCTCA.  The addition of activated
carbon with  suspended  solids  removal  by  filtration  was
defined as BATEA.  The addition  of a filtration step to the
BPCTCA activated sludge process was defined as BADCT.

Reduction  factors  based  upon  the performance of existing
biological systems, in this and other similar industries  as
                             37

-------
established.  It is expected that limitations and guidelines
tor these will be established at a later date.

Waste Water Control Technology

The development of waste water reduction factors is  another
item  requiring  preliminary  comment.   It  was  originally
anticipated that these  factors  (relating  to  demonstrated
treatment  technologies   defining BPCTCA, BATEA, and BADCT)
could be obtained from performance data  on  many  operating
treatment  plants in the organic chemicals industry.  It was
known that this industry did not have numerous  waste  water
treatment  facilities;  however,  the  original  assumptions
proved to be  overly  optimistic.   Relatively  few  organic
chemical manufacturers were able to provide substantial data
on the treatment of their waste water.

Information     from     an industry     survey conducted in
1972 by members of the  Manufacturing  Chemists  Association
which   consisted   of  100  organic  chemicals  plants  had
indicated  that  approximately  10  percent  of  the  plants
surveyed  had  biological treatment systems installed.  This
was confirmed from plant visits by the contractor and review
of NPDES permit applications.   For these sources of data and
information,  the  following  approximately  describes   the
industry's  waste  treatment  practices:  80  percent of the
industry's 674 production facilities  (Dept. of Commerce 1972
Census of Manufacturers) were found to  provide  no  on-site
treatment  other  than  neutralization of their waste water.
Many of these (approximately 50 percent) presently discharge
to municipal  treatment  systems.   Of  the  remainder,  ap-
proximately   10   percent  provide  miscellaneous  physical
treatment such  as  sedimentation,  while  approximately  10
percent   provide   biological   treatment   of  some  type.
According to the  1967  Department  of  Commerce  Census  of
Manufacturing  -  Water Use        data available) the   are
174 plants treating wastewaters.  This is 26 percent of  the
674  plants.   Of  these  77  plants  have pH control and an
estimated 40 plants have pH control only.  Thus, 134 plants,
20 percent of  the  total,  have  treatment  other  than  pH
control.

Biological   treatment  typified  by  the  activated  sludge
process was defined as BPCTCA.  The  addition  of  activated
carbon  with  suspended  solids  removal  by  filtration was
defined as BATEA.  The addition  of a filtration step to the
       activated sludge process was defined as BADCT.
Reduction factors based upon  the  performance  of  existing
biological  systems, in this and other similar industries as
                               38

-------
well as in-process control, and information available in the
literature were tne bases used to  develop  each  technology
level  effluent  limitation.  These factors were  applied to
each of the raw waste  loads  determined  for  each  of  the
product/process segments.
                                39

-------

-------
                         SECTION IV

                  INDUSTRY CATEGORIZATION


Discussion of the Rationale of categorization

A major goal of this effort was to broaden the RWL data base
and  to  further substantiate the Phase I subcategorization.
The  following  is  a  synopsis  of  the   subcategorization
rationale  which  was  thoroughly  discussed  in the Phase I
study.

The diverse range of products and manufacturing processes to
be covered suggested that separate effluent  limitations  be
designated  for  different segments within the industry.  To
this end,  a  subcategorization  of  the  organic  chemicals
industry was developed.

Manufacturing  processes  have been examined for the type of
contact process water usage associated with  each.   Contact
process  water  is  defined  to  be all water which comes in
contact with chemicals within the process and includes:

    1.   Water  required  or  produced  (in   stoichiometric
         quantities) in the chemical reaction.

    2.   Water used as a solvent or as an aqueous medium for
         the reactions.

    3.   Water which enters the  process  with  any  of  the
         reactants  or which is used as a diluent (including
         steam).

    4.   Water associated with mechanical  devices  such  as
         steam-jet  ejectors  for  drawing  a  vacuum on the
         process.

    5.   Water used as a quench  or  direct-contact  coolant
         such as in a barometric condenser.

Noncontact  flows  not  included in the RWL data include the
following:

    1.   Sanitary waste water.

    2.   Boiler and cooling tower blowdown  or  once-through
         cooling water.
                             41

-------
    3.   Chemical  regenerants  from   boiler   feed   water
         preparation.

    4.   Storm water runoff  from  nonprocess  plant  areas,
         e.g., tank farms.

The  type  and  quantity  of contact process water usage are
related  to  the  specific  unit  operations  and   chemical
conversions within a process.  The term "unit operations" is
defined  to  mean  specific  physical  separations  such  as
distillation,    solvent    extraction,     crystallization,
adsorption,  etc.  The term "chemical conversion" is defined
to mean specific reactions such as oxidation,  halogenation,
neutralization, etc.

Description of Subcategories

Four  process  subcategories  have  been established and are
discussed in the following text.  Subcategories A, B, and  C
relate  to continuous processes, while Subcategory D relates
to batch and semi-continuous  processes.   In  the  Phase  I
study, subcategories A, B, and C were developed to represent
product/process  segments  that  are  continuously operated.
The following subcategories with  accompanying  descriptions
also apply to Phase II product/process segments.

Subcategory A;  Continuous Nonaqueous Processes

This  group  involves  minimal  contact  between  water  and
reactants or products within  the  process.   Water  is  not
required  as  a  reactant or diluent, and is not formed as a
reacrion product.  The only water usage stems from  periodic
wasnes of working fluids or catalyst hydration.  Heating and
cooling   are   done   indirectly   or   through  nonaqueous
(hydrocarbon)  working  fluids.   Process  raw  waste  loads
should  approach zero, with variations caused only by spills
or  process  upsets,  which  can  be   minimized   by   good
housexeeping, equipment maintenance and process controls.

Subcategory B: Continuous Vapor-Phase Processes Where Contact,
Water is Used Only as Diluent, Quench or Vent Gas Absorbent

In  this  Subcategory, process water usage is in the form of
dilution steam, a direct contact quench, or as an  absorbent
for  reactor  effluent gases.  Reactions are all vapor-*phase
and are carried out over solid  catalysts.   Most  processes
have  an  absorber coupled with steam stripping of chemicals
for purification  and  recycle.   Steam  is  also  used  for
catalyst  decoking.   It  is feasible to reduce some process
                            42

-------
raw waste loads almost to  zero  through  increased  recycle
and/or reuse of contact water in this subcategory.

Subcateqory C;  Continuous Liquid-Phase Reaction Systems

Liquid-phase  reaction  systems  involve  a  catalyst  in an
aqueous medium such as dissolved or emulsified mineral salt,
or acid/caustic solution.  Continuous  regeneration  of  the
catalyst system requires extensive water usage.  Substantial
removal of spent catalyst and inorganic salt by-products may
also  be required.  The working aqueous catalyst solution is
normally corrosive.  Additional water may  be  required  for
final    purification   or   neutralization   of   products.
Requirements for purging waste  materials  from  the  system
prevent process raw waste load from approaching zero.

Subcateqory D:  Batch and Semi-Continous Processes

This  subcategory  is  characterized  by processes which are
carried out in reaction  kettles  equipped  with  agitators,
scrapers,  reflux  condensers, etc., depending on the nature
of the operation.   Many  reactions  are  liquid-phase  with
aqueous   catalyst  systems.   Reactants  and  products  are
transferred from  one  piece  of  equipment  to  another  by
gravity  flow,  pumping, or pressurization with air or inert
gas.  Much of the material handling is manual, with  limited
use  of  automatic  process  control.   Filter  presses  and
centrifuges are commonly used  to  separate  solid  products
from  liquid.  Where drying is required, air or vacuum ovens
are used.  Cleaning of  noncontinuous  production  equipment
constitutes a major source of waste water.

Basis for Assignment to Subcategories

The  subcategorization  system  assigns specific products to
specific subcategories  according  to  the  water  usage  in
manufacturing  as  previously  defined.  Where more than one
process is commercially used to produce a specific chemical,
it is possible that the chemical may be listed in more  than
one  subcategory  since  the  unit  operations  and chemical
conversions associated with different feedstocks may  differ
drastically  in regard to process water usage and associated
RWL.

It is noted that the field sampling  in  Subcategory  D  for
fatty  acids,  dyes,  pigments and plasticizers was based on
end-of-pipe sampling.  Therefore, the  associated  RWL  flow
data contains minimal amounts of noncontact waters.  This is
in  contrast  to other products where noncontact waters were
able to be excluded.
                             43

-------
Product:  BTX Aromatics

Process:  Fractional Distillation

Process RWL Subcategory:  A

Chemical Reactions:  None

The  product  obtained  here  is  a  mixture  consisting  of
benzene, • toluene,  and  xylenes  which  are  separated from
paraifinic,  olefinics,  and  mixed  high  boiling  aromatic
organics   (over   150°C).    Some  ethyl  benzene  is  also
recovered.  The process involves a series  of  fractionating
columns.  There is no direct contact water; consequently raw
waste loads are very low.

                PROCESS FLOW
                   liters/kkg          46.7
                   gals/M Ibs           5.6

                BOD5 RWL
                   mg/liter1            320
                   kg/kkg*              0.015

                COD RWL
                   mg/liter1             1150
                   kg/kkg*              0.053

                TOC RWL
                   mg/literi            328
                   kg/kkgz              0.015

i   Raw  waste  concentrations  are  based on unit weight of
pollutant per unit volume of process waste waters.
2  Raw waste loadings are based on unit weight of  pollutant
per 1000 unit weights of product.
                              44

-------
Product;  Cumene

Process;  Alkylation of Benzene  with  Propylene

Process RWLSubcategory;  A

Chemical Reactions:
                           HjPOj,
               CH3CH - CH2
          Benzene + Propylene             Cumene
                                    (I sopropy1 Benzene;
Typical Material Requirements;

1000 Kg Cumene

                                     1000  Kg Cumene

Benzene                                720 kg
Propylene                              389 kg
Phosphoric Acid  (SPA)                  666 kg
Cumene  is  an  intermediate  in  the  production  of  phenol.
(Acetone and Acetophenone are co-products.)  Cumene is   also
an excellent blending ingredient of high-octane  gasoline.

Although  cumene  is a naturally occurring chemical,  present
in many crude oils, the commercial product is synthesized  by
the catalytic  alkylation  of  benzene  by  propylene.   The
principal  side  reactions, depending on the catalyst system
employed,  include  polyalkylation  to  form  di-  and   tri-
isopropyl-benzene,   polymerization  of  a  portion   of  the
propylene,  and  the  production   of   n-propylbenzene    by
isomerization.

Catalyst  systems  that  have  been  used  to produce cumene
include such materials as sulfuric acid, hydrofluoric acid,
boron  trifluoride,  silica,  zinc  chloride on  alumina, and
others.  However, the two  catalyst  systems  most commonly
used  for  commercial  production  are aluminum  chloride and
solid phosphoric acid (SPA).  The catalyst  system used   at
the  process  plant visited during the field data  collection
program employed the SPA catalyst.
                                45

-------
A typical .flow diagram for the solid phosphoric acid process
of producing cumene is illustrated in Figure 4-1.  As shown,
this process  requires  a  reactor  and  three  distillation
columns  - one for rejection of propane, one for the recycle
of unreacted benzene, and the  third  to  rerun  the  cumene
product  so  as  to reject a minor quantity of polyalkylated
materials (mainly diisopropylbenzene).  Yields  obtained  by
this  process  are over 90% of stoichiometric values on both
benzene and olefin.

The aluminum chloride process is similar to that illustrated
for solid phosphoric acid but requires additional  equipment
for  the drying of recycle streams and neutralization of the
reaction products.

A mixture of propylene and  propane  is  blended  with  both
fresh  and  recycled  benzene  in a raw materials feed tank.
Water (as steam condensate) at 100-150 ppm is injected  into
the  reaction  mixture.  The reaction mixture is feed to the
top of a fixed-bed reactor, where the liquid  trickles  down
through  the  catalyst  bed.   Steam  (noncontact) is used to
preheat the reaction mixture.  The process is carried out in
a continuous manner.

The reaction product  (effluent from  the  reactor)   is  then
filtered.   The water phase  ( 1.0 liter/day) is removed to a
water drain.  A  depropanizer  still  receives  the  organic
phase.   Propane is separated out and can be recycled to the
reactor.  Waste water from the propane  accumulator  amounts
to about 0.3 kg/1000 kg of product.

Unreacted  benzene  is  removed  in  a  benzene distillation
column.  The benzene is recycled with fresh benzene  to  the
raw  materials  mix or feed tank.  Bottoms from the "benzene
column" contain cumene and higher alkylaromatics.

Cumene is removed as  a  product  in  the  finishing  still.
Diisopropylbenzene  is the major by-product removed as still
bottoms.

The only continuous waste water streams are from the benzene
storage  area,  the  waste  water  following   the   propane
accumulator   (  0.3  liter/1,000 kg of cumene produced), and
the water phase from the filter following the reactor.  This
latter stream is an intermittent flow (< 1.0 liter/day).

In newer processing plants, a combination air/water  cooling
system  can greatly reduce the noncontact water requirement.
This is illustrated as follows:
                              46

-------
                  Cooling Water Circulation_Requirement

          With air cooling      24,200 liters/kkg product
          Without air cooling   82,600 liters/kkg product

Steam required to heat the distillation towers is  7,590  kg
per 1000 kg of product.

Process  RWL based on waste water flows are indicated in the
tabulation below:

                     PROCESS FLOW
                       liters/kkg            0.334
                       gal/M Ibs             0.04

                     BOD5 RWL
                       mg/liter*              180
                       kg/kkg*              0.0001

                     COD RWL
                       mg/liter1              490
                       kg/kkg*              0.0003

                     TOC RWL
                       mg/liter1              180
                       kg/kkg*              0.0001

1 Raw waste concentrations  are  based  on  unit  weight  of
pollutants per unit volume of process waste waters.
2  Raw waste loadings are based on unit weight of pollutants
per 1000 unit weights of product.

The raw waste load from cumene is minimal when expressed  on
a  production basis.  It is recommended that the process raw
waste load for  the  cumene  process  be  considered  as  no
dishcarge   since   the  quantity  of  the  actual  load  is
insignificant.
                              47

-------
F
i«
                   TTTTfi?
                    REACTOR

                      1
                  DEPROPAN1ZER


                  BENZENE STRIPPER
             n
CUMENE FINISHING
                             I
                                n

                                i
                                rn
                                Z
                                                 -<
                                                 r-

                                                 ;H

                                                 O  -p

                                                 Z  O
                                                 Z
                                                 M
                                                 m
                                                 Z
                                                 -o
                                                 70

                                                 O
                                                 •o
           CO

           CO

-------
Product:  p-Xylene

Process:  Isomerization, Crystallization, and Filtration  of
         mixed Xylenes.

Process RWL Subcategory:  A

Because  of  the  rapidly increasing demand for aromatic di-
functional acids, interest in pure xylene isomers  has  been
growing.   The  C8  aromatics  found  in catalytic reformate
consist roughly of 45 percent m-xylene, 20 percent  each  o-
and  p-xylene,  and  15 percent ethylbenzene.  There is much
less demand for m-xylene than for either of  the  other  two
xylene  isomers.   An  isomerization  unit, which is used to
shift  methyl  groups,  converting  m-   and   o-xylene   to
additional  p-xylene,  is  frequently  built  onto  existing
xylene-isomer separation facilities.

All  p-xylene  processes  currently  in  operation   use   a
combination   of   crystallization   and  centrifugation  to
separate and purify p-xylene.  The crystallization  step  is
usually in concert with o-xylene and/or ethylbenzene removal
and isomerization.

Figure  4-2  illustrates a typical two-stage crystallization
process with an isomerization unit.
                                                   *
Crystallization processes generally have the following steps
in common, although the techniques may vary:

     Feedstock drying
     First-stage crystallization (to about -27°C to 32°C)
     Second-stage crystallization  (to about -18°C to -4°C)
     Recovery and melting of crystals from first stage
     Recovery and melting of crystals from second stage.

It is necessary to lower the water content in the  feedstock
to  about  10  ppm because water introduced into the process
will freeze and cause plugging of the centrifuges and rotary
filters.  All processes utilize similar  drying  techniques,
which usually consist of passing the feed through alumina or
silica-gel  beds.   One bed is on-stream while the other bed
is being regenerated either  by  electric  heaters  or  with
jacketed steam.

The  major differences in the processes are the mechanics of
the  crystallization  and   separation   facilities.     Most
processes  use  direct refrigeration.  The feed is precooled
to about -40°C using propane and ethylene, and  the  chilled
feed  is  then  sent  to  the first-stage crystallizer at an
                            49

-------
                                          FIGURE 4-2
   PARA-XYLENE, ISOMERIZATION; CRYSTALLIZATION, AND FILTRATION OF MIXED-XYLENE
      MIXED Cg

      AROMATICS
                                          REFRIGERATION
                                          SYSTEM
FIRST STAGE
CRYSTAL-
LIZER
ui
o
            H2MAKF,UP
Ll
SECOND  STAGE
CRYSTAL-
LIZER
                                                                              ROMATICS

-------
operating temperature of -62°C  to  66°C.   The  first-stage
crystallizers are usually scraped-surface tubular exchangers
or  tank  crystallizers.   In  each  of  these  devices,  an
agitator with spring-loaded blades is used to scrape the  p-
xylene crystals from the walls.

The crystals formed in the first stage are relatively small.
Therefore,  strict  control  of crystal size is necessary to
insure  that  the  centrifuges  or  filters  used  in  their
recovery will be of adequate size.

Considerable  advances  have  been  made in the last several
years  in  development  of   more   efficient   solid-liquid
separation  devices.   Most  modern  domestic plants utilize
continuous solid-bowl centrifuges in the first  stage.   Two
bowls  rotating  horizontally  at  different  speeds cause a
helical screw motion on the outer surface of the inner bowl.
The helical motion moves the solids from the settling slurry
pool through a draining section emitting a nearly dry  cake.
The  centrifuges can be regulated to control bowl revolution
speeds, bowl differential, and slurry pool depth.  This  can
achieve p-xylene first-stage purity of 85%.  The centrifuges
can  be  fitted for backwash, but the benefits are doubtful.
Crystals grown in the first stage tend to be long  and  thin
monoclinic needles that drain with difficulty.  As a result,
a  sizable portion of mother liquor tends to remain occluded
in the interstices between the p-xylene crystals.

Crystals from the  first  stage  are  melted  (or  partially
melted) and recrystallized at about -32°C.  The second-stage
crystallizers  are  similar  to  the first-stage units.  The
second-stage crystals  tend  to  be  cylindrical  in  shape,
approximately  200  X  360  microns,  and drain more easily.
Furthermore, the viscosity  of  the  mother  liquor  in  the
second  stage  is  about 1 cp* compared to 5 cp in the first
stage.  This difference in viscosity enhances  the  drainage
rate.   Also,  a  pusher-plate mechanism is available in the
second stage crystallizer to increase the drainage  rate  in
the  exit  section.   About  99.5% pure p-xylene is obtained
from this type of two stage operation.

The filtrates from the first- and the  second-stage  liquid-
solid separation are sent to the isomerization reactor after
mixing  with  hydrogen  gas.   In  the  reactor, m-xylene is
isomerized over a  platinum  catalyst  into  an  equilibrium
mixture of the three isomers, which is then recycled through
                               51

-------
the   p-xylene  crystallization  steps.   The  isomerization
reaction is run to extinction, that is, only the para isomer
of xylene is withdrawn  from  the  manufacturing  operation.
The  hydrogen  gas  is  required  to  provide  the  hydrogen
atmosphere necessary for conducting the xylene isomerization
process   and   is   generally   produced   on   the   site.
Consequently,  the isomerization and the hydrogen facilities
are an integral part of the p-xylene process.

The major sources of waste water are the regeneration  water
used  during  decoking  of  catalyst beds and the steam drum
washdown from the hydrogen plant.  These streams are  inter-
mittent,   and   the   amounts   are   insignificant.    The
monoethanolamine (MEA)  contaminated  waste  water  from  the
hydrogen plant may be difficult to treat biologically.  Deep
well  disposal  has been practiced in the past in some cases
on these wastes.

The averages of four sets of composite samples for the plant
which was surveyed are presented in the tabulation below:

                     PROCESS FLOW
                      liters/kkg         44.3
                      gals/M Ib           5.3

                     BOD5 RWL
                      mg/literi             238
                      kg/kkg *             0.01

                     COD RWL
                      mg/literi             580
                      kg/kkg2             0.025

                     TOC RWL
                      mg/liter1             159
                      kg/kkg              0.007

1. Raw waste concentrations are based on unit weight of
pollutants per unit volume of process waste waters.
2. Raw waste loadings are based on unit weight of pollutants
per 1000 unit weights of product.

The p-xylene process produces very small raw waste loads  on
the basis of unit production.
                               52

-------
Product;  Chlorobenzene

Process; Chlorination of Benzene

Process RWL Subcategory;  B

Chemical Reaction;

            C6H6 + C12 	> C6H5C1 + HC1

             Benzene             Chlorobenzene


Chiorobenzene,  an important intermediate in the manufacture
of  dyes  and   insecticides,   is   manufactured   by   the
chlorination  of  benzene.   Two  faciilities  were  visited
during  the  field-data  collection   program,   one   which
manufactured  Chlorobenzene  exclusively, and one which also
produced diChlorobenzene.  Figures 4-3 and 4-4  are  process
flow diagrams of these two facilities, respectively.

At  the  first  facility  (Chlorobenzene  only), benzene and
chlorine are fed to the reactor, and the  hydrochloric  acid
produced  by  the  reaction  is  absorbed  in  water to make
aqueous hydrochloric acid.  The Chlorobenzene formed by  the
reaction is neutralized with sodium hydroxide and then puri-
fied   by   distillation.    The  brine  formed  during  the
neutralization step  goes  to  the  sewer,  and  a  tar-like
residue from the Chlorobenzene distillation is incinerated.

The  second  facility (chlorobenzene-dichlorobenzene) uses a
very smilar processing strategy, with a few additions.   The
hydrochloric   acid  coming  from  the  absorption  step  is
purified by carbon adsorption, and the tail gas which passes
through the absorber is scrubbed with water prior to exhaust
to the atmosphere.   Another  difference  in  the  procssing
strategy  at  this  facility  is  in the purification of the
Chlorobenzene reaction products.  The products proceed to  a
distillation  column,  where  any unreacted benzene is taken
overhead and recycled  to  the  chlorinator.   The  products
proceed  from  the  bottom  of this distillation column to a
second distillation column,  where Chlorobenzene  product  is
taken  overhead  while  the  bottoms  from  the distillation
column proceed to dichlorobenzene refining.

In the survey period, waste water samples from each facility
were collected for analysis.   The  following  is  the  mean
value of waste water analyses from the two plants:
                             53

-------
                                    FIGURE 4-3
                CHLOROBENZENE—CHLORINATION  OF BENZENE
                        WATER
en
          BENZENE
           CHLORINE
                                                                CHLOROBENZENE
                                                              HEAVY ENDS
                                                              TO  INCINERATION

-------
                                        FIGURE 4-4
                    DICHLOROBENZENE—CHLORINATION OF BENZENE
                                                                      »TO  ATMOSPHERE
                                   WATER
BENZENE
                                                    RECYCLE TO
                                                    CHLORINATOR
                                                                                               HCI
                                                                                            WASTEWATER

                                                                                        CHLOROBENZENE
                                                                                           TO DICHLORO-
                                                                                           BENZENE
                                                                                           REFINING

-------
PROCESS FLOW
   liter/kkg
   gal/1000/lb

BODji
   ing/liter
   kg/kkg
COD
   n
   J

TOC




1.

2.
mg/1
kg/kkg
mg/1
kg/kkg
                    50
                     6
                   300
                 0.015
  7700
0.38
  4780
0.239
 Raw waste concentrations are based on unit weight of
 pollutant per unit volume of process waste waters.
 Raw waste loadings are based on unit weight of
 pollutant per 1000 unit weights of product.
                                  56

-------
Product:   Cnlorinated Methanes  (Methylene Dichloride,
           Chloroform, and Carbon  Tetrachloride)

Process;   Chlorination of Methyl  Chloride and Methane
           Mixture

Process RWL Subcategory:  B

Chemical  Reactions:
                                     -> CH^Cl + HC1
                   Methane
                     CH Cl + 2C12


               Methyl Chloride

                     CH.C1 + 2C12

               Methyl Chloride
               Methyl Chloride
                                      Methyl    Hydrogen
                                      Chloride  Chloride
                                           CH2C12 + HCl

                                          Methylene
                                          Dichloride r
                                          CHC1- + 2HC1

                                          Chloroform
                                          'C
                                                + 3HC1
                     CH2C12 + C1
                               2
               Methylene Dichloride
    Carbon
 Tetrachloride
- > CHC13 + HCl

    Chloroform
                     CHC1
                            C1
                        i3 -  v,,2

                  Chloroform


Typical Material  Requirements:
                                               + HCl
                                          Carbon
                                      Tetrachloride
The   material   requirements   depend  upon  which  of  the
chlorinated  products is desired.  In  general,  the  chlorine
consumption   is  7%  beyond  theoretical  needs,  but may be
lowered depending on the chloromethanes  products  mix.   The
methyl  chloride  requirement also is approximately 1% above
theoretical  needs.

Chloromethanes find their widest  application  as  solvents.
Methylsne  dichloride  is  used  in   the plastics field as a
solvent  for  polycarbonates,  isocyanates,    and   cellouse
diacetate.    As  a urethane-foam blowing agent in Europe, it
is important as the spinning solvent  for cellulose  acetate.
Chloroform   is  used as a solvent for textile degreasing and
                                57

-------
an extractant for food flavors, steroids,  and  antibiotics.
Carbon  tetrachloride  is  used as a solvent in nonflammable
cleaning agents.

In addition  to  their  wide  use  as  solvents,  there  are
numerous  other  applications  of chloromethanes.   Methylene
dichloride is used as a nonflammable paint remover, and also
in purification of steroids as a reaction medium,   e.g.,  in
the  manufacture  of phosphates, insecticides, and vegetable
oil  extracts.   Two   developments   of   great   potential
importance   are  the  use  of  methylene  dichloride  as  a
polyurethane-foam blowing agent and in aerosal hair sprays.

Chloroform  finds  wide  use  as  an  intermediate  in   the
production  of  other materials.  In addition, chloroform is
used in certain pharmaceutical formulations  such  as  cough
medicines, rubbing liniments, and anesthetics.

Carbon tetrachloride is used primarily in the manufacture of
methylene chloride and chloroform.  However, it is also used
as a fluid in certain fire extinguishers.

Chlorinated  methanes  can  be  produced  from methane, from
methyl chloride, or from a mixture of both  materials.   The
reactions  may  be  carried  out  by either thermal or photo
activation.  The former, which  requires  a  temperature  of
approximately  700°F,  is preferred commercially,  because it
requires lower investment and maintenance costs, and  allows
more complete conversion of chlorine.

A  typical process flow diagram for producing chloromethanes
starting with a mixture of methane and  methyl  chloride  is
shown in Figure 4-5.

The   feed   methane  is  first  purified  and  dried  in  a
purification unit, and  then  is  fed  to  the  chlorination
reactor  along  with  fresh and recycled methyl chloride and
chlorine gas.  Following the reaction step, the  chlorinated
products are quenched and absorbed in a refrigerated mixture
of recycle carbon tetrachloride and chloroform.  Methane and
HCl  are  taken  overhead  from  the  quench  column and are
absorbed in weak hydrochloric acid, which removes  the  HCl.
The  remaining  methane  is  then  passed  through a caustic
scrubber before being returned to the chlorination reactor.

The bottoms stream from the quench tower is stripped of  its
light  constituents.   These are absorbed in water to remove
the remaining HCl, and are  then  neutralized  with  caustic
solution.   This light-product stream is then passed through
a series of distillation towers from which methyl  chloride,
                               58

-------
                                        FIGURE  4-5
                        CHLORINATED METHANES-  CHLORINATION
                       OF METHYLCHLORIDE AND METHANE MIXTURE
    METHANE
METHANE
PURIF.
                     n
            fWASTEWATER
    METHYLCHLORIDE

  CHLORINE 	
Ul
          CHLORINATION
          REACTOR
                                              _ CO
                                              C_3 CO
                                 HCI ACID
                                                        «X CJ
                                                        CJ> CO
                                                                CAUSTIC  SOLUTION
                                          WASTEWATER
                                                        — CO
                                                        CO CO
                                                               WATER
                                                                      CAUSTIC SOLUTION
                         1
                                     .CHLOROFORM
                                                                    CARBON
                                                                    TETRACHLORIDE
                                                   RESIDUE
                      »»METHYL
                        CHLORIDE
                        METHLENE
                         DICHLORIDE

-------
methylene  dichloride,  chloroform, and carbon tetrachloride
are in turn obtained as final products for sale or  recycled
back to the process as raw material or as absorbent.

The  major  water  pollution  sources of the process are the
waste streams discharged  from  the  HCl  absorber  and  the
caustic  scrubber.   Process  RWL  calculated  from the flow
measurements and analyses of water samples obtained  in  the
survey  period  are  presented  in the following tabulation.
The analytical results also indicate that,  in  addition  to
the  parameters  shown in the tabulation, parameters such as
pH and chloride may be at levels  potentially  hazardous  to
biological  treatment  processes unless acclimated to accept
these wastes.
                          Plant 1
PROCESS FLOW
   liter/kkg
   gal/M Ib

BOD5 RWL
   mg/liter1
   kg/kkg2

COD RWL
   mg/liter1
   kg/kkg2

TOC RWL
   mg/liter1
   kg/kkg2
                Sample
               Period #1
                598
                 72
                  7
                  0.004
                113
                  0.07
                420
                  0.25
                                   Sample
                                  Period #2
598
 72
 18
  0.011
385
  0.23
 42
  0.25
                    Plant 2
                   Sample
                  Period #1
2800
 335
  77
   0.22
 335
   0.94
 132
   0.37
                                                          of
1  Raw waste concentrations are  based  on  unit  weight
pollutant per unit volume of process waste waters.
2   Raw waste loadings are based on unit weight of pollutant
per 1,000 unit weights of product.

The data shown for Plant 2 was selected for BPCTCA raw waste
load.  These waste  waters  are  presently  neutralized  and
discharged to surface waters.
                                 60

-------
Product;  Chlorotoluene

Process:  Chlorination of  Toluene

Process RWL Subcategory:   B

Chemical Reaction:


          C6H5CH3 * Cl2 	>C6^ (CH3)  Cl + HC1
          Toluene  Chlorine      Chlorotoluene Hydrogen Chloride
A  simplified  process  flow  diagram  for the  manufacture of
chlorotoleune is shown in Figure  4-6.   The chlorine  gas  is
reacted  with  liquid toluene in  the presence  of a catalyst.
The unreacted chlorine  gas  is   removed  in  an  absorption
tower, and sent to the muriatic acid plant for reprocessing.
The  crude  product  mixture  is  then  purified  by passing
through a series of distillation  stills.   The  light ends and
residues  are  disposed  of  by   incineration,   while   the
unreacted toluene is recyled back to the reactor.

Vacuum  distillation  is  employed  in  purifying  the crude
product.  The steam jets  (with barometric  condensers)   used
to pull the vacuum constitute the only waste water pollution
source of the process.  The process RWL calculated from flow
determinations  and  the  analyses  of  the waste stream are
indicated in the tabulation below:

    PROCESS FLOW
      liter/kkg               121,000
      gal/M Ib                 14,500

    BOD5 RWL
      mg/liter1                     2
      kg/kkg*                       0.24

    COD RWL
      mg/liter1                     15
      kg/kkg2                       1.82

    TOC RWL
      mg/literi                     2
      kg/kkg2                       0.24

*  Raw waste concentrations are   based  on  unit  weight  of
pollutant per unit volume of contact process waste waters.
                                 61

-------
                   FIGURE 4-6
CHLOROTOLUENE  - CHLORINATION OF TOLUENE
 CHLORINE
             REACTOR
                                 •WATER
                          ABSORBER
AQUEOUS HCL  TO  oTr,H  ,FT
MURIATIC ACID  ."""  JET
PLANT        |
                                         AI7
                                     TOLUENE
                          RESIDUE TO
                          INCINERATION
                                          STEAM JET
                                          CONDENSATE
                          62

-------
2   Raw waste loadings are based on unit weight of pollutant
per thousand unit weights of product.
The only waste water from this process is the large quantity
of  steam  jet  condensate  from  the  vacuum  still.    The
contaminant  concentrations  in  these streams are, however,
quite low.  In the near future, the process will be modified
from vacuum distillation to atmospheric distillation.   This
modification  should  substantially  reduce  the  wastewater
volume and pollutants.  At the  present  time,  all  process
waste water is discharged to the local municipal waste water
treatment plant.
                                63

-------
Product;  Diphenylamine

Process:  Deamination of aniline

Process RWL Subcategory;  B

Chemical Reaction;
          2 C6H5NH2
              line          Diphenylamine  Ammonia
Diphenylamine   (DPA)  is  used  extensively  in  the  rubber
cnemicals  field,  generally  as   a   retarder,   and   its
derivatives are employed as antioxidants.

Production  of  diphenylamine may proceed by various routes;
however, the plant visited during the field survey  utilized
a  vapor-phase  catalytic reaction involving the deamination
of aniline.  A simplified process flow diagram is  shown  in
Figure 4-7.

As  shown  in  the  diagram,  liquid  aniline is pumped at a
uniform rate from storage tanks  into  an  externally-heated
vessel  which  serves  as  preheater and vaporizer.  In this
vessel, aniline is vaporized, and the vapors are heated to a
temperature of approximately 400°C to  500°C.   Hot  aniline
vapors   pass   through   the  catalyst  chamber,  which  is
maintained at approximately 400°C to 550°C.  The exit  gases
of  the DPA converter then pass into an aniline stripper, in
which aniline  and  other  volatile  constituents   (such  as
ammonia,  small  amounts  of  water,  and other volatile by-
products) remain in the vapor  state,  while  DPA  condenses
with  some aniline and is drawn off as crude DPA.  The crude
product  is  then  purified  in  a  series  of  distillation
columns.

The  gases  leaving  the  aniline  stripper are cooled in an
aniline condenser and a portion recycled to the aniline feed
line.  The vapors  (containing mostly ammonia, small  amounts
of water, and other volatiles) pass to an ammonia scrubber.
                                 64

-------
DPA

DISTILLATION

                                                  m


                                                  O  30
                                                  m  rn
                                                  O



                                                  O
                                                  -n

                                                  >

-------
DPA  converters  will  not operate indefinitely,  because the
reaction  causes  a  certain  amount  of  decomposition   of
aniline,   which   deposits  carbonaceous  residues  on  the
catalyst.  These  residues  reduce  the  efficiency  of  the
catalyst, and it is necessary to regenerate periodically. As
a  result,  in  a  normal  plant  there is more than one DPA
converter. Some converters are on a regeneration cycle while
the remaining ones  are  on  a  production  cycle.    On  the
average, each production cycle lasts 50 hours.

Regeneration is affected by the following procedures:

    1.   Steam is introduced to  vaporize  the   aniline  and
         DPA.

    2.   Steam  and  air  are   introduced   to   burn   the
         carbonaceous  impurities  deposited on the catalyst
         surface.

    3.   Steam is then introduced to purge the  reactor.

    4.   An aniline purge is used to remove water vapor.

The  off-gases  resulting  from  the  burning  of  tars  are
exhausted, and aniline and DPA are recycled.

The major waste water source in this process is the effluent
from  the ammonia scrubbing tower. The waste waters from the
catalyst regeneration process are  usually  disposed  of  by
incineration  and  are  not  included  in the raw waste load
calculations. The total process RWL from  flow  measurements
and  the  analyses  of the waste streams during the sampling
survey are presented in the following tabulation:

                    Sample Period #1        Sample Period #2

PROCESS FLOW
  liter/kkg               526                     526
  gal/M Ib                 63.0                    63.0

BOD RWL
  mg/liter1               220                     108
  xg/kkg*                   0.116                   0.057

COD RWL
  mg/literi               550                     650
  kg/kkg*                   0.287                   0.339

TOC RWL
  mg/literi               450                     420
                               66

-------
  kg/kkg                    0.237                   0.218

1  Raw waste concentrations are  based  on  unit  weight  of
pollutant per unit volume of process waste waters.
2   Raw waste loadings are based on unit weight of pollutant
per 1000 unit weights of product.

The arithmetic  average  of  the  values  presented  in  the
foregoing tabulation are for BPCTCA.

All   cooling   water   used   during   the   production  of
diphenylamine is indirect; tube  and  shell  exchangers  are
employed.  Steam usage is 1.15 Ibs per Ib product (including
the   steam  employed  during  catalyst  regeneration),  and
approximately 7531 of the condensates are  collected.   Steam
used  in  the regeneration cycle is live steam, and the rest
is reboiler steam.

Diphenylamine can also be produced by catalytic liquid-phase
process in which a mixture of primary arylamine and catalyst
is mixed with reactant aniline in a stainless steel reaction
chamber.  The temperature of the reaction mixture is  raised
to 175°C to 450°C, and the pressure is permitted to build up
to  Jceep the reaction mixture in a liquid state.  During the
course of the reaction, ammonia is split and vaporized.  The
ammonia vapor pressure maintains the reaction mixture  in  a
liquid  state.   After  holding the reaction mixture for the
requisite time at the desired temperature and pressure,  the
hot  mixture  is  permitted  to  flow into a receiver.  Upon
cooling  the  mixture  to  about  275°C,  the  catalyst   is
substantially  crystallized  from  the  mixture.   The crude
reaction mixture can be filtered and then  purified  to  the
final product.
                               67

-------
Product:  Perchloroethylene

Process:  Chlorination of chlorinated hydrocarbons

Process RWL Subcategory;  B

Chemical Reactions:

          Chlorinated  +  cl      _^   cl  c = c cl
          Hydrocarbons
                      Chlorine        Perchloroethylene
Perchloroethylene  is used largely in dry-cleaning and vapor
degreasing.  Dry-cleaning consumes approximately 85  percent
of  the  total;  the rest goes into general solvent services
and as intermediate for fluorocarbons.

A   process   flow   diagram   for   the   manufacture    of
perchloroethylene is shown in Figure 4-8.

The  chlorinated  hydrocarbons  and chlorine gas are reacted
thermally  (rather than catalytically) at temperatures in the
range of 500-700°C.  The reactions  are  highly  exothermic,
and  control  of  heat  transfer  is  a  key  to  smooth and
efficient reactor performance.

The reaction mechanism may be  visualized  in  terms  of  an
initial,   very  rapid,  thermally  activated,  free-radical
Chlorination   to   transient    compounds    having    high
chlorine/carbon  ratios.   These  transient  compounds decay
quickly,  primarily  to  the  low  free-energy  forms.   The
perchloroethylene-carbon  tetrachloride  mixture then shifts
toward equilibrium in the rate-controlling step.

The reactor effluent is quenched, and the gas stream leaving
the quench vessel is absorbed with recycled HCl solution  in
an  absorption tower.  The remaining unabsorbed chlorine gas
is then dehydrated and recycled back to the reactor.

The liquid reaction product  stream  goes  from  the  quench
vessel to the separator, where the aqueous stream is removed
as  HCl solution.  The product mixture  (carbon tetrachloride
and perchloroethylene) is separated  by  distillation.   The
perchloroethylene-carbon tetrachloride mixture is controlled
by   suitable   recycle  and  by  provision  of  appropriate
residence time in the reactor.
                               68

-------
                                         FIGURE 4-8

       PERCHLOROETHYLENE-CHLORINATION OF CHLORINATED  HYDROCARBONS
o
vo
            CHLORINE
CHLORINATED
HYDROCARBONS
                          CHLORINE  RECYCLE
QUENCH
VESSEL
                               HEAVY
                               ENDS
                               STILL
                                T

T
Cl
R s n D .
•—
WJTFD
Cl 2
DEHYD-
DRATOR
                                                                       + PURGE  TO OTHER
                                                                         SCRUBBING SYSTEM

I
1 I
H
L



HCI
ABSOR-

^
I


*



uf« T r D
nA 1 1 n


SEPARATOR


CCI,
STILL
                                          HEAVY BY-PRODUCTS
                                                                        »HCI SOLUTION


                                                                           ^CARBON TETRACHLORIDE
                                                                                   |    »PERCHLORO-
                                                                                        ETHYLENE
                                                                         STILL
                            HEAVY WASTE
                            TO LANDFILL

-------
The waste water pollution sources of this process are  pump-
seal  leakages and miscellaneous reactor washdowns.  Process
RWL calculated from flow measurements and  analyses  of  the
waste water streams are shown in the following tabulation.


                       Sample Period »1      Sample Period t2

  PROCESS FLOW
    liter/kkg             5,400                 5,400
     gal/M Ib                643                   643

  BOD5_ RWL
     mg/liter1              84                    80
     kg/kkgV                   0.449                 0.427

  COD RWL
    mg/literi               357                   695
    kg/kkg*                   1.92                  3.73

  TOC RWL
    mg/liter»                30                    31
    kg/kkg*                   0.164                 0.169


1   Raw  waste  concentrations  are  based on unit weight of
pollutant per unit volume of process waste waters.
2  Raw waste loadings are based on unit weight of  pollutant
per 1000 unit weaghts of product.

An  average  of the foregoing values was selected for BPCTCA
RWL.  The wastes from this process are currently disposed of
by deep-well injection.

An   alternative   method    for    the    manufacture    of
perchloroethylene  is by the Detrex-SD process, in which the
feedstocks (ethylene  and  chlorine)  enter  a  liquid-phase
chlorination  reactor.   Temperature and pressure are moder-
ate, and concentrations are carefully controlled by  recycle
quantity   and  composition  to  give  the  desired  product
distribution at optimum economics.

In the classical route, perchloroethylene is  prepared  from
acetylene,  via trichloroethylene.  The chemical reaction is
shown as follows:
                               70

-------
The chlorine and aceytlene are  brought  into  contact  with
each other in a reactor at a temperature of 250-300°C in the
presence of barium chloride deposited on carbon as catalyst.
The  product,  tetrachloroethane, is then dehydrochlorinated
in a catalytic reactor to produce  trichloroethylene,  which
is  chlorinated  at  80-90°C over a catalyst containing 0.2-
0.3X    FeC13    to    yield     pentachloroethene.      The
perchloroethylene     is     then     obtained     by    the
dehydrochlorination of pentachloroethane by milk of lime  at
110°C and 200 mm Hg.
                                71

-------
Product;  Phthalic Anhydride

Process:  Oxidation of o-Xylene

Process RWL Subcategory;  B

Chemical Reactions;
          o-xylene
    (C0)20
phthalic
anhydride
                                                3H20
Phthalic  anhydride  is  commonly  produced by either of two
methods:    oxidation   of   o-xylene,   or   oxidation   of
naphthalene.   in  the  U.S.,  about  80% of the capacity is
still based on napthalene,  although  there  is  a  definite
trend  in  favor  of  the vapor-phase oxidation of o-xylene.
This  trend  is  based  primarily  on  economics    (o-xylene
feedstock  is  cheaper  than naphthalene).  A description of
the production of phthalic  anhydride  using  a  naphthalene
feedstock is found in the following section.

Phthalic  anhydride  has  become  one  of our most important
intermediates.  It is commonly used during the production of
plasticizers.   The  less  volatile  phthalates   are   used
principally  in wire and cable coatings which are subject to
higher temperatures.   Phthalic  anhydride  derivatives  are
also  used  in the production of alkyl resins.  These resins
are  in  turn  used  in  coatings,  such  as  latex  paints,
thermosetting   acrylic   finishes,   and   epoxy  coatings.
Phthalic anhydride is used directly in making  a  number  of
dyes  such  as eosin, quinoline yellow, phenolphthalein, and
copper  phthalocyanine.   It  is  also   used   during   the
production of anthraquinone and anthraquinone derivatives by
condensation  (Friedel Crafts) procedures.

Production of phthalic anhydride by oxidation of o-xylene is
based   on   vapor-phase,   fixed-bed  technology.   Typical.
operating conditions are 5 psig and-188°C.  The process uses
a  carrier  supported  vanadium  pentoxide  catalyst,  which
normally  lasts  from  3  to 5 years.  The crude product ob-
tained is 99-99.536 phthalic  anhydride,  with  some  maleic,
benzoic, and other acids.

An  ortho-xylene  oxidation process flow diagram is shown in
Figure 4-9.  Filtered air is first compressed and  preheated
in  a  heat  exchanger.   The  o-xylene  feedstock  is  also
preheated  and  vaporized  by  injection  into  the  hot-air
                               72

-------
                                              FIGURE 4-9


                             PHTHALIC ANHYDRIDE—OXIDATION OF O-XYLENE
OJ
            O-XYLENE  	

                 STEAM
        AIR
                  1
STEAM   WATER

   t_J
REACTOR



^—
1
MOLTEN
SALT
HEAT
iXCHANGER
              ADDITIVES



r-

WASTE-
HEAT
BOI LER
                        •+STEAM
HEAT
TRANSFER
OIL


 I   t
                             S.WITCH

                              CONDENSER
                                                                    I
                                                                                03

                                                                                CO
               T
WATER
                      STACK
                                                                 STORAGE
                                            WASTEWATER

                                                  STEAM
                                                                                     1


r \STEAM /
^^^M 1 1" T P /
I
PRE-
TREATMENT
VESSEL

— ^
T
cc.
UJ
Q_
Q_
CC.
1 —
CO




T
ce
LU
I —
CJ)
LU
oc
ANHYDRIDE WATER
INCINEF

                                                             HEAVY ENDS TO

                                                             INCINERATION

-------
stream;  unevaporated  o-xylene is trapped before the stream
enters the reactor.

During the reaction step, a considerable quantity of heat is
generated.  The heat is removed by molten  salt  circulating
on  the shell side of the reactor.  The molten-salt solution
is passed from the top of the  reactor  to  a  heat-exchange
system,  where process steam is produced.  Gases leaving the
reactor at 375°C are passed through a waste-heat boiler  for
additional  steam  generation.  Cooled gases enter a bank of
automatically controlled switch condensers.

When a condenser  is  on  the  crystallization  cycle,  cold
mineral  oil  is  circulated  through  the coils to cool and
crystallize phthalic anhydride from the gaseous phase.  When
the condenser is switched to  phthalic  anhydride  recovery,
hot  oil is circulated through the coils to remelt the crude
product.   The  crude  product  is  then  drawn  off  to  an
intermediate   storage   tank.    Residual  gases  from  the
condensers are  scrubbed  to  reduce  the  volatile  organic
content.   The scrubbed gas passes through a demister and is
vented to the atmosphere.

Crude product from the storage tank is then passed through a
heater  and  into  the  continuous   pretreatment   section.
Dissolved  phthalic acid is dehydrated under a slight vacuum
to the anhydride.  Additives may be introduced at this point
to remove impurities produced by polycondensation  of  heat-
sensitive  compounds.   The crude phthalic anhydride is then
pumped through a pre-cooler  to  a  continuous  distillation
section.   Two  columns  are  employed, both operating under
vacuums created by two-stage steam ejectors.   Waste  waters
from  these  ejectors  are  sent  to an incinerator.  In the
first-stage stripper column, maleic  anhydride  and  benzoic
acid  are  separated  as overheads.  Bottoms from the first-
stage column are passed to a second-stage rectifier  column.
Final  product   (99.99%  phthalic anhydride) is withdrawn as
distillate overhead.

Since  waters  from  stream  ejectors  are  disposed  of  by
incineration, the only water pollution source of the process
is  the  waste  stream withdrawn from the vent gas scrubber.
Process  RWL  calculated  from  the  flow  measurements  and
analyses  of water samples obtained during the survey period
are snown in the following tabulation:

                     PROCESS FLOW
                        liter/kkg           593
                         (gal/M Ib)           71.2
                               74

-------
                     BOD5 RWL
                        mg/liter*           215
                        kg/kkgz               0.128

                     COD RWL
                        mg/liter1         1,080
                        kg/kkg*               0.642

                     TOC RWL
                        mg/liter*            34
                        kg/kkg*               0.02

1  Raw waste concentrations are  based  on  unit  weight  of
pollutant per unit volume of process waste waters.
2   Raw waste loadings are based on unit weight of pollutant
per 1000 unit weights of product.

These waste loads are considered as the  basis  for  BPCTCA.
They  are  combined  with  other  wastes  in  this plant and
treated in a biological system prior to discharge.
                                75

-------
Product;  Phthalic Anhydride

Process:  Oxidation of Naphthalene

Process RWL Subcategory:  B

Chemical Reactions;



                          V20r
          C10H8 +  ^02	> CgH^'(CO)20  +  2C02 + 2H20

      Naphthalene                PhthalIc Anhydride
In the United  States,  approximately  80*  of  the  present
phthalic  anhydride  capacity is based upon the oxidation of
naphthalene.  However, there is a trend  toward  the  vapor-
phase oxidation of o-xylene, which has been discussed in the
previous  section.   Phthalic anhydride may be produced from
naphthalene using either a fixed or fluid catalyst bed.   In
addition  to  process  variations,  the  purity of the final
product is a function of the reactor type,  in  that  maleic
anhydride is formed as a by-product in the fixed-bed reactor
but it is not formed in the fluidized-bed reactor.

During  the  sampling  period,  an  installation employing a
fluidized-bed  reactor  was  visited.   The  fluid  catalyst
consisted of a finely powdered vanadium catalyst.

A process flow diagram for the naphthalene oxidation process
is  shown  in  Figure  4-10.   The  reactor  containing  the
catalyst  is  heated  to   an   operating   temperature   of
approximately  480°C.  Molten naphthalene is then introduced
into the reactor and vaporized by direct  contact  with  the
catalyst  charge.   The  vapors  become  admixed immediately
because of the agitated nature of  the  catalyst  bed.   The
air-naphthalene vapor mixture passes upward through the bed,
and  the  naphthalene  is  converted  to phthalic anhydride,
carbon dioxide,  carbon  monoxide,  and  water  vapor.   The
product  gases, after leaving the dense catalyst phase, pass
through a settling  zone  and  into  a  cyclone  system  for
removal  of  the  catalyst.   Recovery  of  the  catalyst is
reported to be 100X; thus, make-up catalyst is not required.
Following removal of the catalyst, the  product  gases  pass
through  a  condensing  system.   Aqueous  products are then
purified, using a series of distillation columns.
                               76

-------
        LL
PURI FICATI
STILLS

                              >
                              ^
                              n
                           8S
                           2 m
                           £<-

                           I5
                           O
CO   Z
    C3
X>   <»
                     CO
                     m
                     CO
   m    C3

-------
There are two major discharges from the  phthalic  anhydride
process area.  The most significant of these discharges is a
gaseous  waste  stream vented during the reaction step.  The
gas  contains  a  high  concentration  of  organics  and  is
discharged to an incinerator.

The  second discharge is primarily steam vapor from a vacuum
jet in the distillation section.  The stream is contaminated
with a low concentration of phthalic anhydride.  This stream
is aJ.so discharged to the incinerator.

A portion of  the  material  sent  to  the  incinerator  was
condensed  and  analyzed.  These data were used to calculate
the RWL shown in the following tabulation:

         PROCESS FLOW
            liters/kkg                    2,290
            gal/M Ib                        275

         BOD5 RWL
            mg/literi                    46,700
            kg/kkg2                         107

         COD RWL
            Dig/liter*                   125,300
            kg/kkg2                         287

         TOC RWL
            mg/liter1                    52,400
            kg/kkg*                         120

*  Raw waste concentrations are  based  on  unit  weight  of
pollutant per unit volume of process waste waters.
2   Raw waste loadings are based on unit weight of pollutant
per 1000 unit weights of product.

This waste loading is not discharged to any sewer but rather
burned in a liquid waste incinerator.

Since the only source of waste  water  is  periodic  process
washings,  the  raw waste load approaches zero.  Although it
is recognized that  pollutant  loadings  from  the  washings
contribute  to  the  raw  waste  load, it is not possible to
obtain representative samples of the  waste  waters.   Thus,
equipment  washings  have not been included in the raw waste
evaluations.

Noncontact waste waters associated with  phthalic  anhydride
include  an  involuntary blowdown from the internal tempered
water system in the crude-product condensing step.   In  the
                               78

-------
condensing  step,  there is a swing between the use of steam
and tempered water.  During the swing,  the  tempered  water
condenses  the  trapped  steam  and is discharged.  The only
pollutants are corrosion inhibitors which are in the initial
water.
                              79

-------
Product;  Hexamethylenediamine (HMDA)

Process:  Hydrogenation of Adiponitrile  (ADN)

Process RWL Subcategpry:  B

Chemical ^Reactions:

                          NH_
         NC(CH2)lfCN + /»H2

          AdlponltrMe          Hexamethylened famine
Hexamethylenediamine (HMDA)  is  used  in  combination  with
adipic  acid  to  form polyhexamethylene adipamide, commonly
known as nylon.  The demand for HMDA is estimated to be  900
million pounds by 1975, and 1,250 million pounds by 1980.

Figure   4-11   presents   a   process   flow   diagram   of
hexamethylenediamine production  via  the  hydrogenation  of
adiponitrile.

The   hydrogenation   of  adiponitrile  is  carried  out  by
contacting  hydrogen  with  an  ammonia-solvent-ADN   liquid
mixture  in a fixed-bed reactor containing 8-14 mesh cobalt-
oxide catalyst at 100-250°C and 200-700  atmospheres.   This
transformation  is  characterized by its high selectivity to
HMDA at almost complete conversion of ADN.

Fresh adiponitrile and the  recycle  solvent  (toluene)  are
mixed  at  32°C  before  being  pumped  to  about 4,400 psia
pressure and heated to 88°C.  This stream is then mixed with
fresh  and  recycled  hydrogen  and  ammonia.   The  gaseous
effluent   is   recycled,   while  the  liquid  effluent  is
depressurized from the reactor to 3,000 psia and  heated  to
400°F.   This  stream  goes  to  a  separator  followed by a
flasher for ammonia removal.  A portion of  the  ammonia  is
compressed  and  recycled  to the reactor, and the remainder
proceeds to an  absorber.   Water  is  used  to  absorb  the
ammonia,  which  then  proceeds to an ammonia stripper.  The
stripped ammonia is  recycled  to  the  reactor,  while  the
bottoms from the column go to the sewer.

The  liquid  product  stream  from  the flasher is sent to a
toluene stripper.   Overhead  toluene  is  recycled  to  the
reactor,   and   the   bottoms  are  recovered  for  further
purification.
                               80

-------
                          18
.	 IMINE
                         m  era
                            5-
                             HYDROGENATION
                             REACTOR
I
PER
i
— 1


1 '
TRATI




	 1
3D
CT

CO
^
-n
ON _ m
v
I
CO
-H
— t
C=»
I —
m
rn








=o
rn
n
C~3
m
r
i



r~
TOLUENE
STRIPPER
                                               o

rs
1


i i
= J
ER
CO
— 1
m
3= a
<>_
1
EPARATOR

~1
-n
i—
i-
CO
rn
=0
* 1
* =0

™ I- N"3 -1
33 1 ABSORBERS
1 '
NH3
1!
                                        COLUMN
X
>
O

X  2
J  O

"71  »
i  m

St
71  _-
o
o
m
Z
>
^
O
Z
>
o
•o
O
Z

-------
The first step in  refining  consists  of  removal  of  HMDA
(water  azeotrope) as bottoms from the first column which is
operated at 18 psia.  The overhead  water-amine  mixture  is
discarded  for  fuel, and the bottoms are sent to the medium
boiler stills (concentrators)  to recover HMDA.  The  bottoms
stream  from  the medium boiler column is then discharged to
the HMDA refining column.  Refined HMDA  is  taken  overhead
under vacuum.

The  major  water  pollution sources of this process are the
bottoms from the ammonia recovery column, water withdrawn as
overhead from the medium boiler stills, and  the  steam  jet
condensate  from  the  HMDA  refining  column.   Process RWL
calculated from flow data and the analyses  of  waste  water
samples  collected in the survey period are presented in the
following tabulation.

                      Plant 1                     Plant 2
                  Sampling Period            Sampling Period
                   11       #2           JLL       12      £3

PROCESS FLOW
  liter/kkg      1,695   1,695       1,010  '  1,010    1,010
  gal/M Ibs        203     203         121      121      121

BOD5> RWL
  mg/literi     58,850  12,800       5,500    4,500    1,800
  kg/kkg2         99.8    21.7        5.55     4.54     1.82

COD RWL
  mg/literi     71,850  62,400      20,200   22,200   20,300
  kg/kkg*          122     106        20.4     22.4     20.5

TOC RWL
  mg/literi     17,800  31,400       4,600    5,700    5,000
  kg/kkg*         30.2    53.2        4.65     5.76     5.05


1  Raw waste concentrations are  based  on  unit  weight  of
pollutant per unit volume of process waste waters.
2   Raw waste loadings are based on unit weight of pollutant
per 1000 unit weights of product.

The data shown in the above tabulation reveal that there are
significant differences in RWL  from  the  plants  surveyed.
There  are three major reasons for these differences.  Plant
2 partially recycles the bottoms from the  ammonia  recovery
column  to the HMDA refining section and incinerates all the
light-end organic wastes from the refining  portion  of  the
                                 82

-------
operation.   Plant  1  is  equipped  with a stack which uses
water to quench the unabsorbed vapors.

An average value from the data  collected  at  Plant  2  was
derived.   It  is  noted  that  the process wastes from both
Plant 1 and Plant 2 are currently disposed of  by  deep-well
injection.

The  following  paragraphs  describe the pretreatment system
used at Plant 2.  It should be noted that this  system  also
handles wastes from adiponitrile manufacture.

Aqueous  waste from the hexamethylene diamine  (HMDA) process
is  fed  along  with  by-product  brine  from  other   plant
operations  into  a settling tank; HMDA-waste comprises less
than 10% of the total flow.  Sludge  which  settles  out  is
pumped  to a pit for further settling, while the main stream
goes through primary filtration  in  precoated,  horizontal,
leaf  filters.   After a second filtration, the waste stream
is pumped into injection wells for disposal.  Backwash  from
both filtration steps is pumped to the sludge pits.

The primary purpose of the waste treatment area is to remove
all  solids  which  might  cause  plugging  of the injection
wells.

Noncontact cooling water usage for both plants is  tabulated
below:

              Plant 1  -  453,000 liters/kkg of product
              Plant 2  -   31,500 liters/kkg of product

HMDA  can  also  be  produced  by  the  ammonolysis  of  1,6
hexanediol,  a  process  which  will  be  described  in  the
following sub-section.
                                83

-------
Product:  Hexamethylenediamine  (HMDA)

Process:  Ammonolysis of 1,6 - Hexanediol

Process RWL Subcategory:  B

Chemical Reaction:

                              H.
         HO(CH2)6OH  *  2 NH3  	> H2N(CH2)6NH2 + 2 H20

               Hexanediol             Hexamethylenediamine


A  typical  process  flow  diagram  of  hexamethylenediamine
production via the ammonolysis of 1,6 - Hexanediol is  shown
in Figure 4-12.

The  ammonolysis  reactor is a flooded, fixed-bed, catalytic
reactor.  The fresh and recycled hydrogen and liquid ammonia
are pumped to the reactor at a pressure of 3,000 psig.   The
liquid  ammonia is preheated to a temperature of 180 - 220°C
and fed to the reactor bottom.   At  this  temperature,  the
ammonia  is  above  its  critical  temperature (132°C).  The
organic    feed    stream,     consisting     of     recycle
hexamethyleneimine   (HMI)   (30  wt X) plus fresh and recycle
hexanediol is also pumped as a liquid into the reactor.   By
means  of two heat exchangers  (one a product-feed exchanger,
and the second a preheater), the  organic  liquid  phase  is
raised to the reaction temperature of 180 - 220°C.  Positive
displacement pumps are necessary to transfer both the liquid
NH^  and  the liquid organic feed at the 3,000-psig pressure
level.

Within the reactor, the  liquid  organic  phase  floods  the
fixed-bed  catalyst, and the liquid product stream overflows
through a discharge line at the top of the bed.  Both E2 and
NH3 enter the bottom of the fixed bed as gases, but  because
of  the high pressure and the solvent action of the HMI, the
NH3 gas is absorbed in the HMI  and  subsequently  reacts  in
the  liquid  phase  with the 1,6-hexanediol to produce HMDA.
Since the concentration  of  HMI  in  the  liquid  phase  is
already  at its equilibrium value, further conversion of the
diol and NH3 to the imine is negligible.  A reflux condenser
is situated at  the  top  of  the  reactor  and  the  liquid
condensate  is  returned  to  the top of the fixed bed.  The
vapor stream leaving this condenser is used to pre-cool  the
hydrogen  gas  prior  to  recycle  to the compressor, and to
condense NH3 vapor carryover from the reactor.  This ammonia
condensate is returned to the reactor ammonia feed.
                              84

-------
                                             FIGURE  4-12
                   HEXAMETHYLENEDIAMINE-  AMMONOLYSIS OF 1,6-HEXANEDIOL
 HYDROGEN
oo
Ul
      H2  RECYCLE
      COMPRESSOR
  AMMONIA-

I ,6 HEXANEDIOL

HMI RECYCLE
                                                                                        STEAM
                                                                                        JETS
                                                                                         WASTEWATER
                                                                                    HEAVY ENDS TO
                                                                                    INCINERATION

-------
Catalysts suitable for the ammonolysis  step  include  Raney
cobalt,  Raney  nickel,  reduced  copper,  Raney copper, and
nickel on kieselguhr.  The preferred catalyst is  pelletized
Raney  nickel.   At  reaction  conditions,  an  ammonia feed
stream of 19 moles NH3 per mole  of  diol  (2.73  kg  NH3/kg
diol)  and  a  hydrogen supply of 0.125 moles H2 per mole of
NH3  (0.0147 kg H2/kg NH3)   have  been  found  to  give  high
yields.   A  yield of 93 mole X HMDA on a diol-reacted basis
is practical, and conversions of 70 mole % per reactor  pass
are used for design.  A residence time of 1 hour is typical.

The   liquid   reactor  product  consisting  of  HMDA,  HMI,
dissolved NH3 and H2, unreacted diol,  by-product  H2_O,  and
high  boilers  is  heat exchanged with the incoming HMI-diol
feed stream and then fed to a series of three  flash  drums.
The  flashing  operation  provides  a stagewise reduction in
pressure and recovers the dissolved hydrogen as a vapor  for
refeeding  to  the  compressor.   A  small  portion  of  the
dissolved NH3 is also vaporized, and this  is  recovered  in
the  knockout  drums  of the compressor facility.  The major
part of the dissolved ammonia is recovered  in  the  ammonia
stripper  column.  Ammonia is liquefied overhead by a water-
cooled condenser, from which it is pumped back  to  the  NH3
feed tank.

The  ammonia  stripper column operates at about 200 psig, to
condense  the  ammonia  overhead  at  55°C.    The   bottoms
temperature  averages  about  200°C.   The  bottoms  product
(containing HMDA, HMI, diol, H20 and high boilers)  is fed to
a drying column and then to the water stripper column.   The
water  stripper  operates  as  an  azeotropic  column  using
cyclohexane  as  the  entraining  agent  to  promote   water
separation.    The   use   of  cyclohexane  counteracts  the
formation of the H20/HMI  azeotrope.   (This  azeotrope  has
been  reported  as  a  means  of separating the HMI from the
HMDA.) The overhead stream from this  tower  consists  of  a
heterogeneous  cyclohexane-water  azeotrope, which condenses
as  a  two-phase  liquid  in  the  overhead  decanter.   The
cyclohexane  upper  layer  is  returned  to  the column as a
reflux, and the lower layer, mostly water, is sent to waste.
This column normally operates at atmospheric pressure,  with
an   overhead  temperature  of  about  74°C  and  a  bottoms
temperature of 100°C - 107°C.

The bottoms from this tower, essentially anhydrous, are  fed
to  tne  HMI  stripper  column  to remove HMI for recycling.
This stripper column is operated under a vacuum of about 200
mm Hg. such that reboiler temperatures in the range of  310-
330°F  are  not  exceeded.  Temperatures of 390°F and higher
tend to promote reactions between the HMDA and the unreacted
                               86

-------
diol to produce high boilers.  The HMI stripper bottoms  are
then fed to the HMDA product column, where the HMDA is taken
overhead  at  99.9456  purity.   The bottoms, consisting of a
small percentage of HMDA and the unreacted  diol  plus  high
boilers,  are  recycled  to  the  diol  feed tank.  Periodic
buildup of. the high-boiler concentration will necessitate an
intermittent purge of the bottoms.   Alternatively,  a  1,6-
hexanediol  polishing  still  may  be  added  to provide for
continuous separation of the diol from the high boilers.  In
actual operation, the reactor  conditions  may  possibly  be
adjusted  so  that  the  high-boiler content is minimized to
some equilibrium value.

The major waste water pollution sources for this process are
waste waters from the drying column, the decanter associated
with the azeotropic column, and the  steam  jet  condensate.
The analytical results obtained from the sampling survey are
shown in the following tabulation.

                      PROCESS FLOW
                         liter/kkg          1,100
                         gal/M Ib             132

                      BOD5 RWL
                         mg/liter1          3,630
                         kg/kkg*                4.0

                      COD RWL
                         mg/liter*         10,600
                         kg/kkgz               11.7

                      TOC RWL
                         ing/liter*          2,260
                         kg/kkgz                2.5


1   Raw  waste  concentrations  are  based on unit weight of
pollutant per unit volume of process waste waters.
2  Raw waste loadings are based on unit weight of  pollutant
per 1000 unit weights of product.

It  is  noted  that  most  of the waste water upon which the
previous RWL calculations are based is currently disposed of
via deep-well injection.  Only wastes such as slab  washdown
water and storm runoff are treated in an aerated lagoon.
                              87

-------
Product:  Methyl Ethyl Ketone  (MEK)

Process:  Dehydrogenation of Secondary Butyl Alcohol  (SBOH)

Process RWL Subcategorv;  B

Chemical Reactions:
            CH3CH(OH)CH2CH3   — *  CH3COCH2CH3  + H2

            Sec-butyl  Alcohol    methyl ethyl ketone
A  flow  diagram  for  this process is  shown in Figure  4-13.
Methyl ethyl ketone  (MEK) is obtained by the dehydrogenation
of secondary butyl alcohol in a  process  analogous   to  the
production of acetone from isopropyl alcohol.

Preheated  vapors  of  secondary  butyl alcohol   are passed
through a reactor, containing a catalytic bed of  zinc  oxide
or  brass  (zinc  copper  alloy) maintained at 400 to 550°C.
The reaction takes place at atmospheric pressure.

The reaction gases are condensed by passage through  a brine-
cooled condenser.  The uncondensed gas  may be scrubbed   with
water or a nonaqueous solvent to remove any entrained ketone
or alcohol from the  hydrogen-containing gas.

The  condensed product is run into a distillation column and
fractionated.  The   main  fraction   (methyl  ethyl  ketone),
boiling  between  78°C  and 81°C, is obtained in  an  85  to 90
percent yield based  on the weight of secondary butyl alcohol
charged.

The following tabulation summarizes the raw waste load   data
obtained  from  the  two  plants sampled.  The RWL shown for
Plant  2  is  much   higher  because  some   of    the   light
hydrocarbons  purged  (used  elsewhere  or burned)  in Plant 1
are discharged in the waste water from  Plant 2.

                            Plant 1           Plant  2

         PROCESS FLOW
           liters/kkg        1,310                795
           gal/M Ib             157                 95

         BODS RWL
                                88

-------
                                         FIGURE 4-13
    METHYL  ETHYL  KETONE (MEKj-DEHYDROGENATION OF SEC-BUTYL ALCOHOL (SBOH.
     SEC-BUTYL
     ALCOHOL
                    PREHEATER
                                    REACTOR
co
                                                              SOLVENT
CONDENSER
                                                                             -^HYDROGEN
                                                                         0£
                                                                         CJ
                                                                \
                                                                             METHYL
                                                                             ETHYL
                                                                             KETONE
                                                            ALCOHOL
                                                            TO RECOVERY

-------
mg/literl
kg/kkg2
COD RWL
mg/ liter1
kg/kkg2
TOG RWL
mg/liter1
kg/kkg 2
3,000
3.

1,627
2.

521
0.
92

13

68
91,000
72.1

260,000
206

102,000
80.9
i  Raw waste concentrations are  based  on  unit  weight  of
pollutant per unit volume of process waste waters.
2  Raw waste loadings are based on unit weight of pollutants
per 1000 unit weights of product.

The RWL from Plant 1 was chosen as BPCTCA basis.
                              90

-------
Product::  Trier esyl Phosphate  (TCP)

Process:  Condensation  of Cresol and Phosphorus  Oxychloride

Process RWL Subcategory:  B

Chemical Reaction:
                                        (C6Hj,(CH3)0)3PO  +   3HC1
  cresol (mixture of o-,   phosphorus            trlcresyl
  m-, and p-!somers)      oxychloride           phosphate
TCP  has the property of reducing  the  flammability of films.
This property has led  to  its   use  as   a  plasticizer  for
nitrocellulose    and   vinyl    chloride   plastics.     This
flammability-reducing property  qualifies it for  use   as  an
additive  in  hydraulic  fluids and  lubricants.  TCP  is also
used as a gasoline additive.

Figure 4-14 presents a simplified  process  flow  diagram  of
trieresyl  phosphate  production.  Basically,  the processing
involves purification  and  then  condensation  of the  raw
materials,  preliminary purification,  and final purification
of the product.

Cresol  supply  has  been  a  problem  to  manufacturers  of
tricresyl  phosphate  for  a  number  of  years,   both as to
availability and quality.  Until the post-war  period, almost
all cresol for tricresyl phosphate manufacture  was  derived
from  coal tar acids.  Most recently,  improved processing of
carbolate liquids from petroleum  sources  has  resulted  in
cresols  essentially  equivalent to  those produced from coal
tar acids.  Furthermore, the shortage  of cresols  which  has
long   plagued  tricresyl  phosphate  producers  and   which,
probably  more  than  any   other    factor,    had  led   to
commercialization  of cresyl diphenyl  phosphate in the post-
war period, appears to  have  been  eliminated.   Since  the
ortho  form  of  tri-cresyl  phosphate  is considerably more
toxic than those derived from m- and p-cresols,  the   cresol
used  for  the  production  of   plasticizer grade tricresyl
phosphate  is  primarily  a  mixture  of  m-   and  p-cresol.
Although the xylenol content may be  allowed to reach  as high
as  30  or  4OX,  the  o-cresol content  is   held below 3X.
Because of the random distribution of  the three  isomers  in
the  resulting  phosphate  ester,  the  tri o-cresyl phosphate
content of the product is quite low.   The cresols  used  for
                                91

-------
          C-3
    DISTILLATION
    COLUMN
      STRIPPING
      COLUMN
     T
3>  3;


11
CO —| 30
rn 30
































CO •= 3D "II
— i o <= — < 1 1
1-co m
i
rn
CO















ESTER
n r r 11 y n
n t r N Nu
COLUMN




r
I 4
n CD m
3C 3D m
^ O C~3
m x — l
z m «=
CO _| 3D
=o — a»
c? ^
a
=C co
f •»• — i
f —t m
csi m »
i i i
—i
rn


«-i
r
CO OO |T1
3E ^O m

rn ~&
=o — ^
C'J 3E
m
CO
                                                 TO —
                                                 m O
                                                 O I  2

                                                 is  2
                                                 O '   m
                                                 TO n  ^
                                                 O O  t

                                                 ^ D
                                                 o 5
                                                 5 CO
                                                 o  z
                                                 o  o
                                                 m  ~"

-------
production  of  tricresyl phosphate for addition to gasoline
may contain a slightly higher o-cresol content and a  higher
percentage of xylenols,

Cresols  react rather readily with phosphorus oxychloride at
a temperature of approximately 100°C to form  a  mixture  of
aryl  and  diaryl  phosphoryl  chlorides,  with  only  small
amounts  of  triaryl  phosphate.   The   diaryl   phosphoryl
chloride  being  the least reactive, more drastic conditions
are required to obtain complete reaction.  The  presence  of
significant quantities of aryl phosphoryl chlorides not only
reduces yield but leads to difficulty in subsequent refining
operations.   Therefore,  the condensation of cresol and the
oxychloride is carried out at elevated  temperatures  (150°C
to  300°C)  depending  upon  the  catalyst, and purification
schemes employed.  A slight excess of cresol favors complete
esterification.  The time required for the condensation will
vary with the catalyst and temperature of reaction.  Loss of
oxychloride in the hydrogen chloride off-gas is minimized by
operating under moderate pressure and/or venting  through  a
condenser.  Many catalysts have been reported, but the metal
halides   appear   to  be  preferred,  because  they  permit
condensation  times  of  6-9  hours   at   temperatures   of
approximately 200°C.  Because the reaction mixture is highly
corrosive,  glass-lined  or  alloy  kettles  are  used.   The
condensation  reaction  may  be  operated  continuously,  by
permitting  the reaction mixture to pass through a series of
reactors at successively higher temperatures.

The purification techniques employed appear to  have  become
rather  well  standardized.   Variation  lies  rather in the
oequence of application, the use of classical batch  washing
in   lieu   of  the  use  of  columns,  and  the  extent  of
purification  required  for  product  end-use.   Preliminary
purification  may  involve  direct flash distillation of the
crude reaction mixture.  The crude reaction product  may  be
first  be  washed  with  dilute  caustic  to  neutralize any
hydrogen chloride and to hydrolyze  and  extract  traces  of
partial   esterification  products  and  unreacted  cresylic
compounds.  The addition of lime  to  the  reaction  mixture
prior  to  distillation,  to  minimize  corrosion,  has been
reported.  Final purification of plasticizer grade  products
employs  wasning  with  dilute  caustic and water  (to remove
traces  of   organic   acidity),   treatment   with   dilute
permanganate   solution  (to  improve  color  and  oxidation
stability of the product, a widely accepted quality factor) ,
dehydration by heating  under  reduced  pressure,  bleaching
with activated carbon and finally filtration.  The use of an
ampnoteric  metal  in  conjunction with an alkaline wash has
also been claimed as a color-improvement refining step.    In
                              93

-------
production  of  tricresyl  phosphate as a gasoline additive,
some or all of the final purification steps may be  omitted;
low  acidity  is required, but color and oxidation stability
are not critical.

As indicated in the process flow diagram, each step  of  the
process  is performed under vacuum conditions, and each step
is equipped with steam jets and barometric condensers.   The
major  pollution  sources  are  the waste streams from these
barometric condensers.   The  analytical  results  from  the
sampling program are presented in the following tabulation.

                     PROCESS FLOW
                        liter/kkg         28,000
                        gal/M Ibs          3,355

                     BOD
                        mg/literl             40
                        kg/kkg*                1.12

                     COD
                        mg/literi            408
                        kg/kkg*               11.4

                     TOG
                        mg/literi             70
                        kg/kkg2                1.96

1   Raw  waste  concentrations  are  based on unit weight of
pollutant per unit volume of process waste waters.
2  Raw waste loadings are based on unit weight of  pollutant
per one thousand unit weights of product.

By  using surface condensers it is possible to substantially
reduce the  process  flow  requirements.   Noncontact  waste
waters include cooling water flows and steam condensate; the
cooling  water  usage  is  approximately  740  kg per kkg of
product, while condensate flow to the sewer is at  the  rate
of 0.96 kg per kkg of product.

The  process  RWL  shown  above  are  considered  for BPCTCA
determination.  All wastes  from  the  plant  are  currently
discharged to the municipal sewer system.
                               94

-------
Product;  Adiponitrile

Process:  Chlor ination of Butadiene

Process RWL Subcategory:  B

Chemical Reactions

 CH2CH CH CH2 + C12 - > Mixture of  fsomeric dichlorobutenes
 Butadiene + Chlorine
      NCCH2CH = CH CH2CN - * - > NC

       Dicyanobutene                 Adiponitrile
Adiponitrile   (ADN)  is commonly  used  during the manufacture
of hexamethylene diamine  (HMDA) .  H.examethylene  diamine  is
in  turn  used  as  a  raw material  during the production of
Nylon 6/6.

A schematic flow diagram  of the process  is given  in  Figure
4-15,  and  the  general  process  information is described in
the following paragraphs:

The first step in the manufacture of ADN  via  butadiene  is
tne  vapor-phase chlorination  of  butadiene.   The reaction is
carried  out  at  250°C   and   at  pressures   slightly  above
atmospheric.   The  inlet section of the reactor is  designed
to insure complete and rapid mixing  of  the   reactants,   and
the  rest  of  the vessel constructed  to guarantee plug-flow
conditions,  which  favor the high  degree   of   chlorine
conversion  desired.   By-product formation is minimized if
the molar ratio of butadiene to chlorine is  kept around  6.5
to  1 and if the vapor phase is diluted  with nitrogen gas to
keep a 10#  (volume) of inerts  in  the  reactor  feed   stream.
The ratio of fresh to recycle  butadiene  is approximately 0.2
to  1.   When  the chlorine conversion is close to 10056, the
molar yield of chlorine to chlorinated butenes is 95%.    The
relative amount of the 1,4 and 3,4 dichlorobutene isomers is
of  no  importance  since in  subsequent reaction steps both
isomers are  converted  to  the  same  final  product.    The
composition  of the chlorinated butenes  is as follows:   93.4
wt % dichlorobutenes, 1.6 wt % low boilers and 4.9 wt % high
boilers.   The vapor-phase reaction   is  carried  out  in  an
empty  reactor.  The reactants enter at  120°C and are heated
up to the reaction temperature (250°c) by the  heat   evolved
during the reaction, which is  39  kilocalories per mole.
                              95

-------
                  FIGURE  4-15
ADIPONITRILE-CHLORINATION OF  BUTADIENE
AQ.  CAUSTIC
BUTADIENE
CHLORINE
IOPANE 	 J,
PROCESS
COMPRES-
SION
UJ-,
^DICHLOROBUTENE
HHANUFACTURE
L
1 1 1
_ i --» r

NaCN I


/ENT SCRUBBERS
IT CONDENSATE
IUSTIC SCRUBBER
^

HC1
^WASTES
S
DICYANO-
BUTENE
MANUFACTURE
J It
ATER 1 	 »
1 	 »4I
WASTE
STORAGE
                                              HYBROGEN
                                                     CATALYST
                                    kBRINE

                                    * \ ET  CONDENSATE
                                    HCN  VENT SCRUBBEF

                                     '  VFNT
                                       WASTEWATER
                                                                DIPQNITR1LE
                                                                                   JET  CONDENSATE 1WASTE-

                                                                                                R/WATER
^PROCESS SCRUBBEF
                                                                                         BOILER
                                                                                         FUEL

                           BOILER
                           FUEL

-------
The  effluent stream from the reactor is cooled down to room
temperature, and  condensed.   The  unreacted  butadiene  is
separated   from   the  liquid  phase,  which  contains  the
chlorinated products, and recycled back to the reactor.  The
liquid phase is sent  to  the  cyanization  section  of  the
plant.    This   liquid   is   composed   of  a  mixture  of
dichlorobutenes,  chlorobutenes,  chlorinated  butanes,  and
heavy materials such as tar and polymeric compounds.

The  cyanization reaction is carried out in the liquid phase
at 100°C and under atmospheric pressure in the  presence  of
an inert gas such as nitrogen.  The reaction is catalyzed by
an  aqueous  mixture of cuprous chloride, copper powder, and
cuprous cyanide.  The molar ratio  of  hydrogen  cyanide  to
dichlorobutenes  is  close  to 2.3 to 1.  The composition of
the liquid feed to the reactor is given below  on  a  weight
percent basis.

                     cuprous cyanide            0.93
                     calcium carbonate         15.6
                     water                     54.6
                     hydrogen cyanide           9.6
                     dichlorobutenes           19.5

The  reaction  time  to  achieve a 92.5 mole % conversion to
1,4-dicyanobutenes is approximately 40 minutes.

The  next  steps  in  the  production   of   ADN   are   the
isomerization  and  purification  of  the cyanobutenes.  The
purpose of isomerization is the conversion of  some  of  the
1,4-dicyanobutene-2 to its isomer, 1,4-dicyanobutene-1.  The
purpose of purification is to render the crude dicyanobutene
mixture non-corrosive.

The  liquid  reaction product stream leaving the cyanization
reactor is cooled to 25°C.  The cyanobutenes and organic by-
products are extracted with benzene and  diluted  until  the
benzene  concentration is approximately 66X by weight.  This
organic mixture is  sent  to  an  agitated  tank  where  the
temperature  is  raised to 60°C and the pH adjusted with 10%
sodium hydroxide to 11.5.  The two liquid phases that result
are separated in  a  liquid-liquid  separator;  the  aqueous
phase  is  sent  to  the  waste  treatment  plant, while the
organic phase, after  being  heated  to  70°C,  is  sent  to
another  agitated  tank where more (10SS) sodium hydroxide is
added until its weight percent in the second  aqueous  phase
formed  is  around 15.  These two liquid phases are agitated
vigorously in the tank which has an average  residence  time
of  25 minutes.   The two-phase effluent stream is sent to a
decanter where the organic and aqueous phases are separated.
                               97

-------
This  second  aqueous  phase  is  also  sent  to  the  waste
treatment   tank  and  the  organic  phase  (containing  the
isomeric  mixture  of  1,4-cyanobutenes)   is  sent  to   the
adiponitrile plant.

The benzene-cyanobutene mixture is then diluted with benzene
until  the  cyanobutene  concentration is 20% by weight, and
then fed to the hydrogenation reactor.  This reaction vessel
contains a packed bed of activated charcoal promoted with 2%
(by  weight)   palladium.   The  hydrogenation  reaction   is
carried  out  under  a  hydrogen  pressure  of 400 psig at a
temperature between 100 and 120°C.  The hydrogen is  bubbled
concurrently  with  the  liquid  at  a  ratio of 35 moles of
hydrogen  per  mole  of  dicyanobutene.   The  liquid  space
velocity in the reactor is approximately 0.4 reactor volumes
of  liquid  per  hour  per  volume  of  catalyst.  The molar
conversion of cyanobutene is  95%,  with  a  selectivity  to
adiponitrile   of   99X.    Since   the  reaction  is  quite
exothermic, the reactor must be equipped with  an  efficient
heat  removal  system.  For example, the reaction is carried
out inside of tubes packed with catalyst while cooling water
runs through shell side of the reactor.  The catalyst has an
active  life  of  about  500  hours.   It  can   be   easily
regenerated  by  passing hydrogen at 500°C over the catalyst
until no more sulfur is evolved from the reactor tubes.

The reactor effluent is cooled down to room temperature  and
the  hydrogen  separated  from  the  liquid  organic  phase,
recycled water and vacuum jet condensates.  The  latter  two
waste  streams  are  typical  of a Subcategory B vapor-phase
manufacturing operation.  Process raw waste loads calculated
from flow measurements and analyses  of  these  streams  are
shown in the following tabulation:
              Sample
            Period f1
 Sample
Period t2
Adiponitrile

   Sample
  Period #3
Average
PROCESS FLOW

  liter/kkg     9766      9766
  (gal/M Ib)    1170      1170

BOD5 RWL

  ing/liter*     1250      2850
  kg/kkg2        12.2      27.8
             9766
             1170
             1800
              17.6
                9766
                1170
                1970
                 19.2
                               98

-------
COD RWL

  mg/literi     15,000    14,400     12,000   .    13,800
  kg/kkgz          146       141        118          135

TOC RWL

  ing/liter*      4600       4500       4450         4500
  kg/kkg*        44.9       43.8       43.4         44.0
1   Raw  waste  concentrations  are  based on unit weight of
pollutant per unit volume of process waste waters.
2  Raw waste loadings are based on unit weight of  pollutant
per 1000 unit weights of product.

The  analytical  results  (shown in Section V) indicate that
the  pollutants  in  the  waste  waters  (such  as   ammonia
nitrogen,  sulfate,  cyanide,  chloride,  and copper) are at
levels which may  be  potentially  hazardous  to  biological
treatment  processes.   It  should  be  noted  that although
biological treatment  was  chosen  as  the  model  treatment
system  most generally applicable for BPCTCA, several of the
process plants surveyed currently  utilize  other  means  of
disposal,  such  as  deep-well injection.  This was the case
with the adiponitrile plant sampled.  The  raw  waste  loads
shown  previously  are  all  treated  by filtration prior to
disposal by deep-well injection.  In this regard, it  should
be noted that the adiponitrile plant also sampled noncontact
cooling  water  on  a  once-through  basis.   The  volume of
cooling water amounts to 424,000 liters/kkg of adiponitrile.
When it becomes necessary to  treat  the  wastes  from  this
adiponitrile  plant  in  a  biological system, a multi-stage
biological system combined with in-plant controls to  lessen
the discharge of inhibitory compounds may be required.
                              99

-------
Product:  Benzole Acid and Benzaldehyde

Process:  Catalytic Oxidation of Toluene with Air

Process RWL Sujbcategory;  B

Chemical Reactions:
            2C6H5CH3 + 302

             Tol uene
             •Toluene
2C6H5COOH + 2H20

  Benzoic acid

CgH5CHO + H20

 Benzaldehyde
A  simplified  flow  diagram  for  this oxidation process  is
shown in Figure 4-16.  Toluene and air, with  a  mixture   of
recycle  gas  and  toluene,  are  combined  in  the reactor.
Reaction temperatures may range from  150°C to 500°C, with   a
corresponding   pressure  range  of   10  to  1  atmospheres.
Specific  manufacturers  operate  at  different  conditions.
Depending upon the operating conditions, the material  in the
reactor  may  be  in  the  liquid  or vapor phase.  Reaction
conditions may be varied to give different selectivities   to
benzole  acid  or benzaldehyde.  The process RWL's have been
calculated on the basis of the total production  of  benzole
acid and benzaldehyde during the sampling period.

The  catalysts  most  frequently  used  consist of oxides  of
metals belonging  to  the  fifth  or  sixth  groups  of  the
periodic  table.   A  mixture  of  uranium   (93 percent) and
molybdenum oxides (7 percent), impregnated on  a  pumice   or
asbestos  carrier, is claimed to give relatively high  yields
of benzaldehyde with low percentages  of  toluene  loss  via
complete  combustion.   The  addition  of  small  amounts  of
copper oxide to the catalyst  mixture  reduces  by-  product
maleic  anhydride  formation.   A cobalt acetate catalyst  in
aqueous solution has also been used successfully.

As shown in Figure 4-16, the reactor effluent is sent  to   a
decant  tank.  A three-phase mixture of gas, organic liquid,
and aqueous liquid usually exists in this vessel.   The  gas
                                100

-------
                                          FIGURE  4-16
                             BENZOIC ACID AND BENZALDEHYDE
TOLUENE
                              RECYCLE TOLUENE
                                 WATER  OF
                                 REACTION
                                      .FRESH NaOH
                                      SOLUTION
                                 RECYCLE
                                 NaOH
                                 SOLUTION
                        SCRUBBER
                        RECYCLE
                        TANK
                             SPENT
                             SCRUBBER
                             SOLUTION
                                                                       AQUEOUS
                                                                       NaC03
                                                                       SOLUTION
                                                                       AQUEOUS
                                                                       DRAIN
                  L
                         CO-PRODUCT
                         BENZALDEHYDE
            FRESH NaOH
            SOLUTION
                           •STILL BOTTOM
                            RESIDUE AND WASH
                            TO SEWER
        RECYCLE
        NaOH
        SOLUTION
SCRUBBER
RECYCLE
TANK
          SPENT
          SCRUBBER
PRODUCT    SOLUTION
BENZOIC
ACID
                            -^RECYCLE
                              TO  PROCESS
                      TAR

-------
(mainly  inert  nitrogen)   is vented under pressure control,
with a portion recycled to the reactor  to  maintain  proper
dilution.   The  aqueous  liquid  phase (containing water of
reaction)  is  decanted  off  using  an  interfacial   level
controller.   The  aqueous  layer  is  discharged  to  waste
treatment.

The organic layer is sent to  the  toluene  stripper,  where
toluene is taken overhead and recycled to the reactor, which
normally  operates  at  30-35%  toluene conversion per pass.
The bottoms from the main stripper are  crude  benzoic  acid
and by-products such as maleic anhydride, anthraquinone, and
complex  high-boiling aromatics of unknown composition.  The
crude  acid  is  sent  to   the   product   (benzoic   acid)
purification section of the process.

A side-stream containing some benzaldehyde is washed with an
aqueous  solution  of sodium carbonate in a wash tank.  This
step is necessary to,  neutralize  organic  acid  by-products
(and  some benzoic acid) present with the benzaldehyde.  The
aqueous layer from the wash tank is drained and  discharged.
The  organic  layer  from  the  wash  tank  is  sent  to the
benzaldehyde still, where  purified  benzaldehyde  is  taken
overhead.   The  benzaldehyde  still  operates  under vacuum
drawn by a  vacuum  pump.    Seal  water  from  the  pump  is
continuously  discharged.   An organic residue, which must be
removed periodically by water washing, forms in  the  bottom
of   the   benzaldehyde   still.    This  material  is  also
discharged.  The benzoic acid purification section  consists
of two rectifying columns and a batch tar stripper.  Each of
these  distillation  columns  operates under vacuum drawn by
steam jet ejectors.  The steam is not condensed, but  rather
is  discharged  directly into the atmosphere.   Consequently,
this  steam  was  not  considered   in   the   process   RWL
calculations.   Jt  be  noted  that the gases drawn into the
jets are scrubbed; and little carryover of organic matter is
anticipated.

The crude benzoic acid from the main strippers  is  sent  to
the  middles  column, where partially rectified benzoic acid
is drawn off as bottoms.  The overhead gases  are  drawn  by
vacuum  through  the middles column scrubber,  where they are
scrubbed with an aqueous caustic solution prior to discharge
through the steam jets.  The caustic solution is recycled by
means of the scrubber recycle tank; fresh caustic  is  added
periodically  to  the  circulating  solution,  with a portion
drawn off to maintain a high pH.

The bottoms from the middles column are sent to the  product
column,  where  product  benzoic  acid  is  drawn  off.  The
                             102

-------
overhead vapors from the product, column  are  scrubbed  with
caustic  in a recirculating system similar to that used with
the middles column (see  Figure  4-16).   Bottoms  from  the
product   column   are  sent  to  the  tar  stripper,  where
additional benzoic  acid  is  stripped  batchwise  from  by-
product tar.

The  major  RWL's  for  this  process  are summarized in the
following tabulation;
  Waste System
Water of Reaction
1/kkg

  247
Aqueous Drain from
  Benzaldehyde Wash Tank  52.2
Benzaldehyde Still
  Residue
   5.0
Vacuum Pump Seal Water   2,200

Middles Column Scrubber
    Blowdown               209

Product Column Scrubber
  Blowdown                 122

TOTAL                    2,840
kg/kkg

  8.74


 11.9
           0.91


           1.31


           2.74

            25.6
 COD
kg/kkg

 15.0
                    16.1
            1.61


            1.71
 TOC
kg/kkg

  6.52
            8.34
            0.73
            1.04
The major source of waste loadings in  the  process  is  the
aqueous drain from the benzaldehyde wash tank, where organic
concentrations  are  greater  than  100,000 mg/1.  Materials
present include sodium benzoate and other aromatics such  as
biphenyls.   it is questionable whether this stream could be
incinerated, because of its high alkalinity.  However,  some
removal  of  organic wastes may be possible by acidification
of the waste water  followed  by  gravity  separation.   The
organic wastes removed could then be burned.
                                103

-------
Product;  Methyl Chloride

Process:  Esterification of Methanol with Hydrochloric Acid

Process RVIL Subcategory:  B

Chemical Reactions;


     CH3OH   +  HC1       Hetal  Catalyst>  ^    +    ^

   Methanol Hydrochloric Acfd          Methyl Chloride
Methyl  chloride is used primarily as an intermediate during
the production of  other  chemicals.   Primary  end-products
include  silicones, tetra methyl lead, and cellulose ethers.
Chlorinated solvents such as carbon tetrachloride  can  also
be  manufactured  using  methyl chloride as a raw feedstock.
Methyl chloride is also used as a catalyst  solvent  in  the
production of butyl rubber.

A process flow diagram for the production of methyl chloride
by  esterification  of  methanol  with  hydrochloric acid is
shown in figure 4-17.

Methanol and hydrochloric acid are heated and then  combined
in  the presence of ZnC12 in the reactor.  The crude product
is discharged into a fractionator from  which  the  catalyst
stream  is  recycled  bacJc  to the reactor.  The vapor phase
from the fractionator is then passed  through  a  series  of
scurbbing  units.   Water  and  caustic solution are used to
scrub the product vapor, which is then sent to a  condenser.
Finally,  the  product  is  treated with highly concentrated
sulfuric acid to remove the water from the product stream.

The major pollution sources of this process are  the  waters
discharged from various scrubbing units and the concentrated
sulfuric  acid  stream  from  the  drying unit.  Process RWL
calculated from the flow measurements and  the  analyses  of
waste  water  samples  obtained  in  the  survey periods are
presented in the following tabulation:
                               104

-------
                                              FIGURE 4-17
          METHYL CHLORIDE- ESTERIFICATION OF METHANOL WITH  HYDROCHLORIC ACID
o
en

METHANOL





PRE-
HEATER





i


MI


i





r>




REACTOR


t_

            HYDROCHLORIC
ACID
             PRE-
             HEATER
SOLVENT
                                     SULFURIC
                                     ACID
                                    DRYER
                                   WASTEWATER
                                                                SCRUBBING
                                                                SYSTEMS
                                                                CONDENSER
WASTEWATER
                                     ^.METHYLCHLORIDE

-------
                     Plant 1
                                         Plant 2
                          Plant 3
PROCESS FLOW
  liter/kkg
  (gal/M Ib)

BOD5 RWL
  mg/liter1
  kg/Jckg2

COD RWL
 mg/liter1
 kg/kxg2

TOC RWL
  mg/liter1
  kg/kkg2
              Sample
             Period t1
                583
                 69.9
              1,210
                  0.703
            119,700
                 69.8
             29,000
                 16.9
                              Sample
                             Period #2
    583
     69.9
  1,940
      1.13
112,800
     65.8
 31,600
     18.4
             Sample
             Period #1
12,000
 1,430
 1,480
    17.7
 5,240
    62.7
 1,070
    12.8
             Sample
             Period #1
 842
 101
 371
   0.314
4,090
    3.45
1,080
    0.908
                                                          of
1  Raw waste concentrations are  based  on  unit  weight
pollutant per unit volume of process waste waters.
2   Raw waste loadings are based on unit weight of pollutant
per 1000 unit weights of product.

In the foregoing examples, considerable differences in  flow
are  avident.   This  may be explained partially by the fact
tnat Plants  1  and  2  utilize  scrubbers  for  removal  of
hydrochloric  acid  while  Plant  3 employs a freezing step.
Waste waters  common  to  both  installations  include  pump
leakages and washdowns.

The  analytical  results  also indicate that, in addition to
the parameters shown  in  the  tabulation,  water  pollution
parameters such as pH, sulfate, chloride, and zinc may be at
levels  potentially  hazardous  to biological treatment pro-
cesses.  The low BOD 5 values shown in  the  tabulation  for
Plant  3  may  be  the result of biological inhibition.  The
differences in pollutant  loadings  among  three  facilities
visited  in  the survey period are attributed to differences
in operating efficiencies in the scrubbing and drying units.
Plant 1 data was selected for BPCTCA RWL.  The median values
for Plant 1 are 0.92 kg/kkg  BOD5,  68  kg/kkg  COD  and  18
kg/kkg TOC.

An  alternative  method  for producing methyl chloride is by
direct  chlorination  of   methane.    Despite   the   ample
availability  of  cheaper  methane, approximately 65% of all
methyl chloride is produced in the  U.S.  is  produced  from
methanol.   Part  of  the  reason  lies  in the economics of
chlorine utilization.
                              106

-------
Product.;  Maleic Anhydride

Process:  Oxidation of Benzene

Process RWL Subcategory:  B

Chemical Reactions;
                      V,0r
                  02 - L  *  > (CH)2-(CO)2-0 + 2 C02
            Benzene             Maleic
                             Anhydride
The market for maleic anhydride is currently  growing  at  a
rate  of  about  15  percent  per year after having remained
static for several  years;  the  growing  use  of  polyester
resins is the main reason for this rapid increase in demand.
Additional uses of maleic anhydride include pesticides, sur-
face  coatings,  plasticizers, and lubricants.  Also, maleic
anhydride is used as a raw material for  the  production  of
fumeric  and  maleic acid.  Fumeric acid finds wide use as a
food acidulant;  additional  applications  of  fumeric  acid
resemble  those  of  maleic  anhydride.  Maleic acid is used
solely as a food acidulant.

Essentially all maleic anhydride in the U.S. is based on the
oxidation of  benzene.   A  process  flow  diagram  of  this
oxidation  process is shown in Figure 4-18.  As shown in the
process flow diagram, the production of maleic anhydride  is
achieved by a process consisting of;

    1.   A reaction section, where benzene is oxidized  with
         air to form maleic anhydride.

    2.   A recovery section, in which  maleic  anhydride  is
         separated from noncondensibles.

    3.   A dehydration section,  in  which  maleic  acid  is
         dehydrated to maleic anhydride,

    4.   A  fractionation  section,  in  which  pure  maleic
         anhydride is produced.

Benzene  is  vaporized  and  fed  to a fixed-bed reactor, to
which  compressed  air  is  also  fed.   Typical   operating
                               107

-------
                                                   FIGURE 4-18
                                MALEIC ANHYDRIDE-OXIDATION  OF BENZENE
                                                       VENT GASES
                                                       TO STACK
o
oo
           BENZENE
           COMPRESSER
           AIR 	
CRUDE
MALEIC
ANHYDRIDE
TANK
                                                I
REFINED
MALEIC
ANHYDRIDE
                                                                                   HEAVY
                                                                                   ENDS
                                                                        WASHING
                                                                        WASTEWATER
                                                                                                    WATER
                                                    WASTE-
                                                    WATER

-------
conditions  are 25 psig and 400°C.  Conversion of benzene is
essentially complete on a once-through  basis.   Temperature
control  is  achieved by circulation of a heat-transfer salt
tnrough the shell side of the reactor, with  indirect  steam
generation.  Vanadium pentoxide is used as the catalyst.


Reactor  off-gas  is cooled in a precondenser to condense as
much of the maleic anhydride as  possible  from  the  vapor.
Condensed  maleic  anhydride is piped to crude storage tanks
prior to fractionation.  The remainder of  maleic  anhydride
is  recovered  by scrubbing with water, forming maleic acid.
The acid is then dehydrated, thus forming maleic  anhydride.
Xylene  is  added  to  the  dehydrator to form an azeotropic
mixture,  thus  facilitating  dehydration..   The  xylene  is
recovered from the excess water by decantation.

The   recovered   maleic  anhydride  in  the  separator  and
dehydrator is fed  to  a  fractionator,  where  pure  maleic
anhydride  is  produced.   The  light  and  heavy  ends  are
withdrawn from the  dehydration  and  fractionation  columns
respectively, and are disposed of by incineration.

The  major  water  pollution sources of this process are the
excess water withdrawn from the decanter  and  the  periodic
washings  from  the  dehydrator,  fractionator,  and storage
tanks.  Process RWL calculated from  the  flow  measurements
and  analyses  of waste water samples obtained in the survey
periods are presented in the following tabulation:

                                  Plant 1           Plant 2

         PROCESS FLOW
           liter/kkg               6,600             2,300
           (gal/M Ib)                 788               274

         BOD5 RWL
           mg/literi              63,500            47,000
           kg/kkgz                   418               108

         COD RWL
           mg/liter*              90,000           126,000
           kg/kkgz                   592               287

         TOC RWL
           mg/literi              23,500            52,500
           kg/kkg2                   155               120

1  Raw waste concentrations are  based  on  unit  weight  of
pollutant per unit volume of process waste waters.
                              109

-------
2   Raw waste loadings are based on unit weight of pollutant
per 1000 unit weight of product.

Based on the previous process description, the flow and  raw
waste  loadings for Plant 1 appear extremely high.  This may
be partially explained by the fact that  waste  waters  from
the dehydrator are presently discharged rather than recycled
to  the  scrubber.   This  flow  is approximately 2/3 of the
total flow.  These waste waters contain high  concentrations
of  fumeric  acid, thus contributing to a high BOD, COD, and
TOC.  It is anticipated that this stream will be recycled in
the near future.  At the Plant 2  facility,  the  dehydrator
water is recycled, and both the flow and pollutant level are
lower  than  that  of  Plant  1.   The  RWL from Plant 2 was
considered  as  BPCTCA  because  of  the   waste   reduction
accomplished through in-process controls.

Waste  water  from  Plant  1  is combined with other process
wastes from the facility and is  treated  by  the  activated
sludge  process.   The  waste water is fed to the biological
system at a  slow,  controlled  rate  because  of  its  high
concentrations.   The  waste water from Plant 2 is currently
hauled away by a contract disposal service.
                                  110

-------
Product: Acetic Esters  (Ethyl Acetate,  Propyl  Acetate)

Process: Esterification of  Alcohol  with  Acetic  Acid  and
         Catalyzed by Aqueous Sulfuric  Acid

Process RWL Subcategory:  C

Chemical Reactions:
                      H ~

                          >

alcohol       acetic acid    acetic ester
                              CHjCOOH  - > CH3COOR
    where
          R is Ethyl  (CH3CH2-),
              Propyl (CH3CH2CH2-),
            or Butyl  (CH3CH2CH2CH2-)
Typical Material Requirements:
   Basis         1QQO kg Ethyl Acetate     1000  kg Butyl Acetate

Ethyl Alcohol  (95X)       620 kg
Butyl Alcohol               —                       713 kg
Acetic Acid  (100*)         688 kg                     550 kg
Sulfuric Acid  (66°Be')    15 to  150 kg             2,708 kg

Acetic  acid esters are used mainly as  solvents;  the shorter
the alcohol, the lower boiling the solvent.   Ethyl  acetate
xs  a  low-boiling  solvent  for  lacquers,   and  the various
propyl  and  butyl  acetates  are  popular  medium-  boiling
solvents  used  mainly  in  surface coatings.   In all cases,
acetic acid is  esterified  with  ethyl,   propyl,  or  butyl
alcohol in the presence of aqueous sulfuric  acid  to form the
respective  acetate.   When  the  reaction  is  carried  out
continuously in aqueous solution, it  is considered to be  in
Subcategory  C, while batch type processes are  considered to
be in Subcategory D.

The process plant visited during the  field  data   collection
program included manufacturing facilities  for ethyl, propyl,
and  butyl  acetate.   The acetates were produced in a semi-
continuous manner in two independent  systems.   Since  there
were  only two systems, only two different acetates could be
manufactured simultaneously.  At  the  time   of  the  visit,
ethyl  acetate  was  being produced in  one system and propyl
acetate in the second.
                               Ill

-------
The facilities normally  are  operated  continuously  for  a
period  of  from 1 to 6 weeks.  When it is desired to change
production  (turnaround, e.g. from  ethyl  acetate  to  butyl
acetate),  the  reaction  stills  are washed.  Production is
then resumed.  Thus, all three acetates are manufactured  in
two  independent facilities by alternating production within
each facility.

Ethyl acetate is produced by the  esterification  of  acetic
acid and ethyl alcohol in the presence of a catalyst such as
sulfuric  acid.   A flow diagram for the process is shown in
Figure 4-19.  The  reaction  is  reversible  and  eventually
reaches  an  equilibrium at about a 67 percent conversion to
ethyl acetate,  in order to obtain high yields, the reaction
must be forced to completion by removing  the  water  formed
and  employing  one  reactant  in  excess.   There  are many
modifications of the process, but all operate  on  the  same
general  principle;  that is, acetic acid is reacted with an
excess of ethyl alcohol in the presence of catalytic amounts
of sulfuric acid.

The process is carried out either batch by  batch  or  in  a
continuous  manner,  depending  on  the  nature  of  the raw
materials and the size of operation.  The main  variable  is
acetic  acid concentration, which may range from very dilute
(about 8  percent)   to  concentrated  (about  100  percent).
Generally,  95  percent  ethyl  alcohol  and  50  to 66° Be1
sulfuric acid are  used.   The  ratio  of  reactants  varies
according  to  the  process  used  and the type of equipment
available.  For a batch process, the reactants may be  mixed
in  the  following  proportions:   10  parts  by weight of 8
percent acetic acid, 10 parts by weight of 95 percent,  ethyl
alcohol,  and  0.33  part by weight of 50 to 66°Be* sulfuric
acid.

Toe  continuous  process  may   be   used   for   any   acid
concentration,  but  it  is  particularly  applicable to the
utilization of dilute acetic acid,  such  as  that  obtained
from  ethyl alcohol by fermentation.  Acetic acid, excess 95
percent  ethyl  alcohol,  and  about  1  percent  of  66°Be'
sulfuric  acid  are  mixed and continuously passed through a
preheater to an esterifying column.  The  column  and  other
equipment  are generally constructed of copper.  The mixture
is allowed to reflux, and a suitable amount of distillate is
withdrawn from the top of the column, which is held at about
80°C.

The distillate, containing  about  70  percent  alcohol,  20
percent  ester,  and  10  percent  water  (the acetic acid is
consumed in the esterifying column) is run to  a  separating
                                112

-------
                                                FIGURE  4-19

                                  ETHYL ACETATE VIA  ESTERIFICATION  OF
                                        ACETIC  ACID AND ETHANOL
             SULFURIC
             ACID
 ETHYL

 ALCHOL
ACETIC
ACID
                                                          SURFACE
                                                          CONDENSER
                                                                       WATER
   RECYCLED TO
                                                                                                   SEPARATING
                                                                                                    COLUMN
                                                 CONTINUOUS  WASTEWATER
                                                 DISCHARGE
                                PERIODIC DISCHARGE
                                OF WASTE ORGANICS
   1
ETHYL
ACETATE

-------
column.   Here  the  mixture  is  refluxed,  and  a  ternary
azeotrope  <83  percent  ethyl  acetate,  9  percent   ethyl
alcohol, and 8 percent water)  is removed from the top of the
separating column at approximately 70°C.

This  homogeneous  mixture  is  run to a proportional mixer,
where it is blended with (approximately) an equal volume  of
water.   The  mixture  is  allowed  to settle in a decanter,
where the two layers that form are  separated.   The  bottom
aqueous  layer,  containing  small  amounts  of  alcohol and
ester, is recycled to  the  lower  part  of  the  separating
column,  where  the  ester  and  alcohol  are removed in the
constant-boiling ternary mixture taken  overhead.   A  waste
water  stream  is continuously drawn off as bottoms from the
separating column.  This stream is necessary  to  provide  a
route  for  removal  of water from the process,  it includes
stoichiometric  water  from  the  esterification  reactions,
dilution  water  which  may  be  present  in the feedstocks,
decanter water, and condensed stripping steam  used  in  all
three distillation columns.

The  top  layer  in  the  decanter contains about 93 percent
ethyl acetate, 5 percent water, and 2 percent ethyl alcohol.
This layer overflows to a drying column, where a  sufficient
amount of the ester is distilled to carry over all the water
and  alcohol present.  This overhead material is returned to
the separating column for recovery of the ester and reuse of
the alcohol.

Ethyl acetate is withdrawn as bottoms from the drying column
and then is 'either  run  to  storage  or  redistilled.   The
latter  is generally necessary to remove copper salts formed
in the copper columns.  Other  impurities  such  as  higher-
boiling  esters may also be present, depending on the purity
of tne raw materials.  The yield of ethyl acetate is  90  to
100  percent based on acetic acid.  Batch process yields are
about 95 percent.

During the sampling visit, propyl acetate was being produced
in a manner analogous to that described in detail for  ethyl
acetate.   During  the  actual  production  runs,  the  only
continuous process waste water stream from either  unit  was
the aqueous bottoms from the separating column.  Process RWL
calculated  from flow measurements and the analysis of these
streams are indicated in the following tabulation:

                         Ethyl Acetate        Propyl Acetate

            PROCESS FLOW
               liter/kkg     1,290                1,190
                               114

-------
               gal/M Ib       155                  142

            BOD5 RWL
               mg/liter*        38                    7
               kg/kkg2          0.049                0.008

            COD RWL
               mg/liter*        79                   10
               kg/kkg*           0.102                0.012

            TOC RWL
               mg/liter1        26                    4
               kg/kkg*           0.034                0.005

i  Raw waste concentrations are  based  on  unit  weight  of
pollutant per unit volume of process waste waters.
2   Raw waste loadings are based on unit weight of pollutant
per 1000 unit weights of product.

Based on the previous process  description,  the  raw  waste
concentrations and subsequent loadings appear reasonable low
for   Subcategory   C  processes.   This  may  be  partially
explained by the fact that each of  the  three  distillation
columns  in  the  process  utilizes direct steam sparging to
volatilize organic materials and drive them overhead.

Although the recycle of decanter water  and  overheads  from
the  drying  column  for  recovery  of unreacted alcohol and
product esters is considered good operating practice, it  is
questionable whether such low organics concentrations in the
separating  column  bottoms  can  be maintained on a steady-
state basis.  It should be also noted that  both  the  ethyl
and  propyl  units  were operating respectively at 87.5X and
90.5% of original design capacity.  Under  such  conditions,
each  unit may be able to provide sufficient hold-up so that
a bottoms stream which is relatively free of organics may be
withdrawn for limited periods of time.

There are also noncontinuous waste streams  associated  with
process turnarounds when production shifts from one ester to
another.   organic  residues from the esterifying column may
amount to approximately 3  kg/kkg  of  ester  product  on  a
cumulative  basis.   These  organic  residues contain no ap-
preciable water and are burned in an incinerator.

In addition, the esterifying  columns  are  normally  washed
with   a  detergent  or  cleaning  agent  during  production
turnarounds.  This waste water  is  highly  concentrated  in
organics  and amounts to an additional 3 liter/kkg of esters
on a cumulative basis.
                             115

-------
Although it is clear that these concentrated organic streams
would add to the process RWL, it is not possible to  specify
quantitative  values  for pollution parameters such as BOD5,
COD, etc. The RWL values shown were used in the  development
of effluent limitations for ethyl and propyl acetate.

Noncontact   waste   waters  include  cooling  water  flows.
Cooling  water  is  circulated  throughout   the   reaction,
refining,  and stripping stills.  A loop system is employed.
MaJce-up water for the entire plant is  approximately  78,000
liters/kkg  of  esters (20,000 gal/M Ib).  Most of this loss
results from evaporation in the  cooling  towers.   A  small
flow  is  bled  from  the esters units to prevent a chloride
build-up.  This waste water flows to the dilute  stream  and
eventually to the waste water treatment faciliites.

Condensate  from  the  entire  plant  is  piped  back  to  a
condensate return system for boiler feed water.   The  total
quantity  of  condensate  is  approximately  2,000 kg/kkg of
ester.  Condensate from  the  various  processes  cannot  be
segregated,  but  it is estimated that condensate from ester
production is less than 1 percent of the pollution abatement
systems.
                               116

-------
product.;  Propylene glycol

Process:  Hydrolysis of propylene oxide

Process RWL Subcategory;  C

Chenucal Reactions:
                                H 0    	>    CH CHOHCH2OH
   Propylene                     water           propylene glycol
    oxi de
Propylene glycol is by far the most widely used difunctional
alcohol for the manufacture of unsaturated polyesters.  This
end use consumes nearly one-half  of  the  propylene  glycol
produced in the United States.

Propylene  glycol  is also used as a cellophane plasticizer.
This market is relatively new, since propylene glycol  is  a
substitute  for  ethylene  glycol,  which  has recently been
deemed toxic.  Toxicity regulations also dictate the use  of
propylene  glycol  in  tobacco.  Miscellaneous  outlets  for
propylene glycol include uses as a binder  for  cork  bottle
caps,  as  a  humectant in cosmetics, and as an intermediate
for propylene carbonate.

Production of propylene glycol is based on the  liquid-phase
hydrolysis  of  propylene  oxide,  and  is  shown  as a flow
diagram in Figure 4-20.  The hydrolysis reaction  occurs  at
elevated  temperature  and  pressure  in  the  presence of a
sulturic acid catalyst..

By selection of the ratio of feedstock  propylene  oxide  to
water, it is possible to control the production of the mono-
, di-, and higher glycols produced. Excess water is required
for   temperature   control  and  to  prevent  formation  of
undesirable by-products.

Reaction products are passed from the reactor to a series of
evaporation and drying towers to remove excess  water.  This
excess vapor is often discharged to the atmosphere, although
it could be recycled to the reactor.

After  passing  through  the  drying  operation,  the  crude
propylene glycol is sent to a series of  fractionators.  The
first  tower  removes  water  and  traces of the light ends.
                             117

-------
                                     FIGURE 4-20
             PROPYLENE GLYCOL-HYDROLYSIS OF  PROPYLENE  OXIDE
00
        PROPYLENE
        OXIDE
        CATALYST-

        WATER 	
         PROPYLENE
         GLYCOL «—
   REACTOR
                     LU  CD
>- O CO
a. co —
                                STEAM JETS
                                   AND
                                BAROMETRIC
                                CONDENSERS
                                 WASTEWATER
                                      CRUDE
                                      DI-PROPYLENE
                                      GLYCOL
                                      STORAGE
                                                                      STEAM
                                                                        i
                                                TO ATMOSPHERE
                                              LIGHT ENDS
                                              TO  INCINERATION
                                                                -»FOOD GRADES
                                                                  DI-PROPYLENE GLYCOL
                                                    HEAVY ENDS
                                                    TO INCINERATION

-------
Mono-propylene glycol  is  then  separated,  condensed,  and
stored  as an industrial grade product. The bottoms from the
mono-propylene glycol  tower  are  sent  to  the  crude  di-
propylene glycol storage facilities.

Crude di-propylene glycol is then vacuum-distilled. The tops
are  recycled to the reactor hydrolyzer to dry the materials
further and to recover glycol product. Bottoms leaving  this
first column are further distilled.  Food-grade di-propylene
glycol  is  obtained as bottoms from the second distillation
step.  The tops  are  then  further  distilled  to  separate
additional  mono-propylene glycol. Both light and heavy ends
are waste products.

Waste waters from the production  of  propylene  glycol  are
generated  during  the  evaporation-drying operation and the
distillation  processes.  Steam  ejectors   and   barometric
condensers are employed in most of the distillation columns.
During  the  plant  visit,  samples of these contact process
waste  waters  were  obtained.  Process  raw   waste   loads
calculated  from  flow  measurements  and  analyses of these
streams are indicated in the tabulation below:

               PROCESS FLOW

                     liter/kkg          5,500
                     gal/M Ib             660

               BOD5 RWL
                      mg/liter1             3
                      kg/kkg*                .016

               COD    RWL
                      mg/literi            10
                      kg/kkg2                .055

               TOG    RWL
                      mg/liter1             1
                      kg/kkg*                .006

         iRaw waste concentrations are based on unit  weight
         of  pollutant  per  unit  volume  of  process waste
         waters.

         2 Raw waste loadings are based  on  unit  weight  of
         pollutant per 1000 unit weights of product.

These RWL values were used as the basis for BPCTCA.
                              119

-------
Product;  Caprolactam

Process;  DSM Caprolactam Process

Process RWL Subcategory;  C
Caprolactam  is manufactured by a second process referred to
as the Dutch States Mines (DSM)  process which  differs  from
the  UBE  Jnventa  process  which was covered in Phase I.  A
schematic flow diagram for this process is shown  in  Figure
4-21.    Cyclohexanone   is  prepared  in  two  stages;   1)
oxidation  of  cyclohexane  to  cyclohexanol;  2)   catalytic
dehydrogenation of cyclohexanol to cyclohexanone.

Cyclohexane  is first oxidized with air in the presence of a
cobalt   catalyst.    The   major   oxidation   product   is
cyclohexanol,  with  some  cyclohexanone  produced  as a co-
product.  Oxidation by-products such as acetic acid,  adipic
acid, and cyclohexanol esters are also formed.

Off  gases  from  the  oxidizers  are scrubbed with kerosene
prior to venting.   Unreacted  cyclohexane  is  subsequently
recovered  for  recycle in a stripper.  The process operates
at a cyclohexane single pass  conversion  of  less  than  10
percent,  so  that  recovery  of unreacted cyclohexane is an
important part of the process.

The liquid effluent from the reactor is sent to  a  decanter
where  the  aqueous  phase  is  removed as waste water.  The
organic phase is  combined  with  the  cyclohexane  stripper
overhead.

This mixture is then combined with aqueous saponified liquor
(containing free caustic) and sent to a neutralization tank.
The  effluent  from  this  tank  is decanted.  A heavy layer
containing saponified acids, and esters are  drawn  off  and
sold.  This stream is similar in nature to the combined acid
water  and caustic water from the Inventa process.  Its only
value is for recovery of dibasic acids such as adipic  acid.
This  can  be  done  by  lowering  the pH and extracting the
organic acids with a solvent such as methanol.

The light layer from the decanter is sent to the cyclohexane
recovery column.   The  column  overhead  is  condensed  and
separated  into  aqueous  and  organic  layers.  The organic
layer is cyclohexane, which is recycled to the reactor;  the
aqueous layer is discharged.
                              120

-------
                     FIGURE 4-21
CAPROLACTAM-DUTCH STATE MINES CAPtOlACTAM PROCESS
                                                                         HYDROGEN VENT
OFF-GAS
r T
00 - Q.
	 » |*1 i , 	 .
SIS
1 &^ 1 ts,


—
mr.ir.it ° ( j~~|
CYCLOHEXANt "f T | ,
j COUP. | *
*IR DECANT
HATER
AMMONIUM HYDROXIDE
• fc l^~~^~~l
LIGHT ENDS
TO FLARE
NEUT. Ill
TANK ' " 1
	 1 	 ^ 1 I 	 1 1
»= REFLUX 111 ^
1,1 = «»T£R s L- 1 — lrl =
rr is = — 1 ^V" i =
1 1 	 ^ ^ = S * UJ ^™ UJ
' SS =: C»USTIC ^S S»
^ ' — i — 1 ^^ **TER S3 S3
SAPONIFIED £3 _>S ut>
ACIDS AND FSTFRS 	 * *™
SOLD ' 	 ' 1 	 ' ' 	
CVCLOHEXANONE
SAPONIFIFD

LIQUOR REFINED
UNE IANK *
CYCLUHEXANUNt ^
^

. OXIME ' 1 •* ""
	 • RIAC10R III '
HVIUniVI AHINF ShlFITF ' - , • (• » HYDROXIDE ... .
PRODUCED BY NH, OXIDATION 1 * 	 • £ 1 1 — > 1 * 	 »
J 1 	 X CK 1 1 A W
IE o * ^WATER
CYCLOHEXANONE OX 1 ME PRODUCED BY °* ~ KFIITRAL = = *-

DE
RE
p»
^ SFI
POT


*— WATER

* WATER
HYDROGENATION
ACTOR
T
CVCLOHEXANONE
COLUMN
—1 1

M^H
1 SOLVENT
RECOVERY
HIGH BO
BURNED
Tf
EXTRACT
HATER
NtW U.S.M. PROCESS (ALItRNAIt) l-T,j "..;.L 'I1 - ' J

AQUEOUS LACTAM SOLUTION
• "•• ^ "P1 ts ^j
RECYCLE WATER f
A r^
|

REGENERATION 1
WATER AND ACID SLOWDOWN
i HYDROGEN

^

( * » _• HYDROGENATION , , -
' S5 ' REACTOR ' =
= S "
fc AQUEOUS BACKWASH 1
FROM ION EXCHANGE t 	 .
STOOGE TO FLAKING AND TRUCK LOADING




LERS
N BOI LER
AMMONIUM
SULFATE
RECOVERY
AMMONIUM
SULFATE
CRYSTALS

-------
The  bottoms  from  the  cyclohexane  column are sent to the
saponification column, where an excess of caustic and  water
are  needed.  The effluent from the saponification column is
decanted into heavy saponified liquor, which  is  sent  back
and  mixed  with  the  reactor effluent, and a light organic
layer.  The light layer is sent to a series of  distillation
columns,   which   remove   light   ends,  cyclohexane,  and
cylcohexanol respectively.  The cyclohexanol is  sent  to  a
catalytic  dehydrogenation reactor to produce cyclohexanone.
The reactor effluent is sent back to the light-ends column.

The overhead from the  light-ends  column  is  burned  in  a
flare.   Hydrogen from the dehydrogenation reactor is passed
through a seal pot containing water and  is  vented.   Water
from the seal pot is discharged to the sewer.

Refined  cyclohexanone  is  combined with ammonium hydroxide
and hydroxylamine sulfate in the oxime  reactor  to  produce
cyclohexanone  oxime.  The hydroxylamine sulfate is produced
by ammonia oxidation similar to the Inventa process.

It is noted that  DSM  has  also  developed  an  alternative
process  to  produce cyclohexanone oxime which minimizes the
amount  of  by-product  ammonium  sulfate.    This   process
utilizes hydroxylamine phosphate oxime  (HPO) and produces an
amine  which  may  be  fed  directly  to  the  rearrangement
reactor.  The process has been  integrated  into  the  total
manufacturing  scheme so that the rearrangement reaction can
utilize  oxime  feed  from  either  the  conventional  oxime
reactor or HPO.

Excess  sulfuric acid in the effluent from the rearrangement
reactor  is  neutralized  with  ammonium  hydroxide  in  the
neutralization  reactor.   The reaction mixture is then sent
to a benzene solvent reactor, in which the crude  lactam  is
absorbed  in  benzene  and  separated  from aqueous ammonium
sulfate.  The aqueous salt solution is  combined  with  that
from  the  oxime  reactor  and  sent  to a recovery plant to
produce crystals for use in fertilizer.

The lac-cam/benzene extract is mixed with water and sent to a
solvent recovery column.  The overhead  mixture  of  benzene
and   water  is  decanted,  with  benzene  recycled  to  the
extractor and extract water discharged.

An aqueous lactam solution is drawn off as bottoms from  the
solvent  recovery  column.   The  lactam is then purified by
cation exchange followed by hydrogenation.  The ion exchange
resin beds are regenerated by  backwashing  with  water  and
acid.  The backwash waste water is discharged.
                            122

-------
The  purified  lactam  is dried in a vacuum evaporator, with
the water recycled to the neutralization  reactor.   Product
caprolactam is withdrawn from the bottom of the evaporator.

Process  RWLgs for the DSM caprolactam process are presented
and discussed at the conclusion of  the  following  section,
which   describes   the   DSM   process   for  manufacturing
cyclohexanone oxime.
                             123

-------
Product;  Cyclohexanone Oxime

Process;  DSM Cyclohexanone Oxime Process

Process RWL Subcateqory;  C

Dutch  States  Mines  has  developed  a  new   process   for
manufacturing   Cyclohexanone   oxime   without   by-product
ammonium sulfate.  This process has been integrated into the
overall   caprolactam   production   scheme    to    provide
Cyclohexanone  oxime  feed  directly  to  the  rearrangement
reactor as shown by the dashed line in Figure 4-21.

The basic chemistry for the new  process  is  shown  in  the
reactions listed below:
                   + 5 02 —> 4 NO  + 6 H20

           2.  2 NO  + 02 —> 2 N02

           3.  3 N02  + H20 —> 2 HN03  +  NO
           5.  NH^OH*

           6.  H* +
A  simplified  flow sheet for the process is shown in Figure
4-22.  The first processing step is the oxidation of ammonia
with air to nitrogen dioxide (equations 1 and 2).  The gases
from the  oxidizer  are  then  absorbed  in  a  recirculated
aqueous  process  solution  in  the  nitrogen  gas absorber.
Nitrogen is vented as off-gas from the absorber.

The liquid effluent from the absorber is a buffered  aqueous
solution  of  nitric acid (equation 3), phosphoric acid, and
ammonium  nitrate.   This  mixture  is  passed  to  the  HPO
reactor, where hydroxylamine is produced (equation 4).

The HPO reactor is a column sparged with compressed hydrogen
gas.   Unused  hydrogen  gas  is separated from the catalyst
suspension  (palladium metal  on  carbon),  and  recycled  by
means of a compressor.

The  aqueous  hydroxylamine solution from the HPO reactor is
sent to a series of stirred tank oximation  reactors,  where
it  countercurrently  contacts Cyclohexanone in the presence
                                124

-------
SZT -
30
3» -O -X. 
^° ^ >
z
a NITROUS G
*^ ABSORBER
'
I

:= :so ^ ^
-< c^ m ~o -n
=0 i , X  - ca ^
m =o co
_fi *
— ^ -* e=»
1"^ -^ < 	 CD ^
^ =D rn
£ OXIME 25
m« 	 EXTRACTOR -*l ,T
*• = x 1 r! • 1
~ ^T L15 ,J
=s 1 j
i- IQ- . -1-
^ _. ,„ 	 i = \ o i
1 z A x m
1 " J , = =
-T-1 	 *— *• m

RECTI Fl ER , z °
°° « _,_ 2,1
— !• ^ -e -n "^ n 1 .-. -_,
S^n »m = d " S

=0 <= » 1 GO
X S 1 ' ' -H
^ fi : ^
' 	 '" |f 	 ^
1 i
1 1
1
. PRnCFSSLIQUID ' '
* EXTRACTOR
|
i
ppnrFSS i i nill I) 	
STRIPPER
o. r
™ J ??<
•• •x.<= "
z am
IS -*? z
|— C3 fj^
GO
O
X
^
rn
b
C
-«
n
i
C/> ~n
>l
m »
£ m
m ^- ^
„ = "T
22
slES CYCLOHEXANONE OXIME PROCESS
RCULATED AQUEOUS PROCESS SOLUTION

-------
of toluene.  Cyclohexanone oxime is  produced  as  shown  in
equation  5.   Hydrogen  ions  liberated  by  the  oximation
reaction are accepted by the phosphoric acid  buffer  system
(phosphate  ions  in equation 6).  The oximation occurs at a
pH of 1 to  2.   Due  to  the  countercurrent  flow,  nearly
quantitative conversion of cyclohexanone is obtained.

Product  cyclohexanone  oxime  is  drawn  from the oximation
cascade (lefthand side of Figure  4-22),  as  a  mixture  of
oxime,   water,   and  toluene.   This  product  mixture  is
contacted with additional toluene in  the  oxime  extractor.
The aqueous bottoms from the oxime extractor is drawn off as
waste water.

Tne  oxime-toluene solution from the oxime extractor is sent
to the oxime rectifier, where  refined  cyclohexanone  oxime
product  is drawn off as bottoms.  This material can be used
directly  in   the   rearrangement   reaction   to   produce
caprolactam.

Tne overhead from the oxime rectifier is sent to a decanter,
where  reflux  water  is  drawn  off.  The separated toluene
layer is split, and part is recycled to the oxime extractor;
the remainder is sent to the process liquid extractor.

In this extractor,  the  toluene  contacts  aqueous  process
liquid  leaving  the  oximation  cascade (right hand side of
Figure 4-22).  The organic phase from the extractor is mixed
with fresh cyclohexanone and sent to the oximation reactors.
The process liquid leaving the  oximation  section  must  be
purified   thoroughly   to   protect  the  catalyst  in  the
hydroxylamine reactor.   To  achieve  this,  the  liquid  is
extracted  with toluene and subsequently stripped with steam
in  the  process  liquid  stripper.   Passage  through   the
stripping column also removes water formed during the prepa-
ration of hydroxylamine and oxime  (equations 4 and 5).

The  aqueous  process  solution  is then recirculated to the
nitrous  gas  absorber.   Hydrogen  and  nitrate  ions   are
restored  in the process liquid by production of nitric acid
(equation 3) .

Calculated process RWL's for Oxanone, Caprolactam,  and  HPO
Sections  of  the DSM plant are shown on Tables 4-1 and 4-2.
The data shown here have also been  combined  to  provide  a
total RWL for the integrated DSM caprolactam process  (bottom
of Table 4-2) .

Examination of the data indicates that the backwash from the
cation exchange resin beds in the Caprolactam Section of the
                             126

-------
DSM  process  is  a  major  waste  source not found with the
Inventa process.  The DSM route uses chemical  treatment  by
ion exchange and hydrogenation to purify the product lactam,
while  the  Inventa  process  uses  an extensive vacuum dis-
tillation train for purification.  It is  not  clear  as  to
whether  the  physical  purification  used  with the Inventa
process could be substituted for the chemical method used by
DSM.  The impurities to  be  removed  may  be  significantly
different.

The  new  HPO  process  incorporated  in the DSM scheme also
produces a significantly higher RWL than  the  hydroxylamine
section  of  the  Inventa  process.   However,  this must be
evaluated considering  the  fact  that  by-product  ammonium
sulfate formation is minimized.

The  DSM  waste  loads  shown  in Tables 4-1 and 4-2 are the
basis for BPCTCA for this process.
                                127

-------
                                   Table 4-1

                    Process Raw Waste Load Based on DSM Process
Oxanone Section
     RWL Based on Cyclohexanone
Saponified Acids & Esters

Light Ends Column Overhead
     Cyclohexanol Col. Btms.

Decant Water from Oxidation
     Reactor

Reflux Water from
     Cyclohexane Column

Hydrogen Seal Water

Flare Condensables

     Total (Based on Wastewater
              to Sewer)

Caprolactam Section
Extraction Wastewater

Backwash from Cation Exchange
     Resin Beds

Slowdown from Recycle
     Process Water
     Total  (Based on Wastewater
              to Sewer)
                                              Flow
                         COD
  (liters/kkg)         (kg/kkg)

     Sold for Product Recovery

Burned in Flare or Steam Boilers
      358


      478
  5.37


  8.35
      239                6.78

         No Data Available
     1075
 20.5
     RWL Based on Caprolactam
                                               Flow
                         COD
   (liters/kkg)

      394

    1,730
(kg/kkg)

   0.39

 37J
          No Data Ava ilable
    2,120
 37.5
                                       128

-------
                                  Table 4-2

                    Process Raw Waste Load Based on DSM Process


Hyam Phosphate Oxime (HPO) Section       RWL Based on Cyclohexanone Oxime

                                            Flow                COD
                                        (liters/kkg)          (kg/kkg)

Aqueous Reflux from                         25.5                0.011
     Cyclohexanone Oxime Rectifier

Stripper Overhead Condensate              1146                  3.43

Wastewater from Oxime Extractor            509                  1.02

Miscellaneous Run-off                      229                  1.83
     Total (Based on Waste                1910                  6.29
            Water to Sewer)
                       Average Raw Waste Load for Total Plant
                       Based on Finished Caprolactam Product
                                      Flow            BOD            COD
Plant Section                     (liters/kkg)      (kg/kkg)       (kg/kkg)
Oxanone, HPO, and Caprolactam         7057            39.1           78.1
     Process Wastewaters

Hydrogen Seal Water, Drainage         6113             3.2            6.6
     From Oxanone, HPO, and Capro.

Ground Drainage Product Loading        630             0.5            0.9

Discharge from Salt Recovery        15,268             4.3            7.4
     Section                       	          	         	
     Total (Based on Water          29,100            47.1           93.0
             to Sewer)
                                    129

-------
Product;  Formic Acid

Process:  Hydrolysis of Formaldehyde

Process RWL Subcategorv:  C

Chemical Reaction:

      2 HCONH2  +  H2SO^    + 2 H20  —* -2 HCOOH  +

                 suIfuric              formic     ammonium
      formamide     acid                 acid      sulfate

The main use for formic acid outside the United States is as
a coagulant for natural rubber  latex.   Domestically,  over
half of the total is used in place of sulfuric acid in high-
temperature  acid  textile  dyeing,  and  to  some extent in
leather tanning.

A process flow diagram for the manufacture  of  formic  acid
via hydrolysis of formaldehyde is shown in Figure 4-23.

The  feed  stock  formaldehyde,  is stoichiometrically mixed
with water and concentrated sulfuric acid  in  a  pre-mixer,
where  the  hydrolysis  reaction  occurs.   The  mixture  of
reaction products is then sent to a series of vacuum  stills
where  ammonium  sulfate  in  the  form of a solid powder is
withdrawn as the still bottoms.  The crude formic acid vapor
taken as the overhead from the still is condensed by passage
through a heat exchanger and then sent  to  a  storage  tank
before  being  discharged  into  a  purification still.  The
product formic acid is then taken as the overhead  from  the
purification  still,  while  the  residue  in  the  still is
periodically flushed.

The major water pollution  source  of  the  process  is  the
contact  water  utilized for the water eductor which is used
to pull vacuum for the distillation columns.   Although  the
residue   withdrawn   as  the  bottom  of  the  formic  acid
purification still is periodically flushed into sewer lines,
this stream can be disposed of through incineration  and  is
therefore  not  included  in the raw waste load calculation.
The following represent the median values as determined from
the sampling program:
                               130

-------
                                                     FIGURE  4-23
                                       FORMIC ACID-HYDROLYSIS  OF FORMAMIDE
U)
      H2S04,
      H20 	
    FORMAMIDE-*!
               PERIODICAL
              FLASHES
                              (NH4)2S04
                             BY-PRODUCT
                                               FORMIC
                                               ACID
                                               RECEIVER
                                                              WATER
                                                              EDUCTOR
CRUDE
FORMIC
ACID
STORAGE





PURIF.
STILL


                                                        WA!
                                                                                                   •FORMIC  ACID
                                                                                       I
                           PERIODICAL
                           FLASHES
  STEWATER
(COKTACT PROCESS WATER)

-------
PROCESS FLOW

   liter/kkg                   135,000
   gal/M Ib.                    16,000

BOD5 RWL

   mg/liter1                         7^8
   kg/kkg2                           1.05

COD RWL

   mg/literi                        33
   kg/kkg*                           4.5

TOC RWL

   mg/liter1                        10
   kg/kkg2                           1.4

iRaw waste  concentrations  are  based  on  unit  weight  of
pollutant  per  unit  volume  of process waste waters.  2Raw
waste loadings are based on unit weight of pollutant per one
thousand unit weight of product.

The high flows and low concentrations  shown  are  from  the
water  eductor used in the process.  It should be noted that
the ammonium sulfate byproduct is not considered in the  RWL
calculations.

Most  of the formic acid produced in the U.S. is obtained as
a by-product from the manufacture of acetic acid via  butane
oxidation.   Some  of  it,  however, is made by absorbing CO
either in caustic soda, followed  by  neutralization  or  in
methanol,  at  high  pressure,  followed  by  conversion  to
formaldehyde and hydrolysis.
                              132

-------
Product.:  Isopropanol

Process:  Continuous hydrolysis of propylene

Process RWL Subcategory:  C

Chemical Reactions:

CH3CH - CH2    - 75% H2S04 -» CH3CHCH3

 propylene
                           isopropyl
                           hydrogen             isopropyl
                           sulfate               alcohol
Typical Material Requirements

                        1000 kg Isopropanol
                     (87% isopropanol azeotrope)

Propylene                   820   kg
75% sulfuric acid            <1.0 kg
25% caustic                   6.5 kg
Benzene                      <1.0 kg

Isopropanol is widely used in two major  areas:    feedstocks
for the production of other organic chemicals, and solvents.
Organic chemicals which employ isopropanol as a  raw material
include  acetone,  glycerine, isopropyl acetate,  amines,  and
hydrogen peroxide.  The largest single use for   isopropanol,
which  accounts for nearly one-half the total production,  is
the manufacture of acetone by catalytic dehydrogenation.

As a solvent, isopropanol is used mainly for gums,  shellac,
and synthetic resins, competing on a price-performance  basis
with ethanol.  It is also used widely as a rubbing alcohol.

The  process  plant  visited during the sampling program  was
operated  continuously  except  for   occasional   equipment
washings.   Since  there  is contact with aqueous waters  the
process Belongs to Subcategory C.  A flow  diagram for  the
process is shown in Figure 4-24.

The  liquid  propylene  feedstock  (65 percent) combined with
recycled hydrocarbons, is absorbed in  75  percent sulfuric
acid to form a solution of diisopropyl sulfate and isopropyl
acid sulfate.  The reaction takes place at approximately  400
psig   and  60 °C.   The  sulfated  hydrocarbon   solution   is
converted to an acid solution of isopropyl  alcohol,  ether,
and  polymer  by  hydrolysis  reactions with the addition of
                               133

-------
                                               frCT
                     ISOPROPYL

                     ETHER

                     DISTILLATION
REFINED

ETHER

DISTILLATION
                                                                                      o
                                                                                      -o
                                                                                      70

                                                                                      O
                                                                                      t>


                                                                                      z

                                                                                      o
I  -n

S  o


o  S
U  m
                                                                                     O
                                                                                     •o

-------
dilution  water  in  the  hydrolyzer-stripper.    Hydrolyzed
reaction  products  are steam-stripped from the acid and the
vapors are condensed following neutralization with a caustic
solution.

Dilute acid is returned  for  reconcentration.   The  liquid
products  are  then  charged to a distillation column, where
isopropyl alcohol is separated from  isopropyl  ether.   The
ether goes overhead while remaining isopropanol is extracted
with  recycled water and returned to the crude storage tank.
The ether is then distilled and stored for subsequent  sale.
If  a dry isopropanol is required, the azeotropic mixture is
broken with benzene.

During the sampling visit, isopropanol was being produced at
the  normal  rated  capacity;  thus  the  waste  waters  are
considered  to  be  typical  of the everyday operation.  The
major sources of waste water include the  crude  isopropanol
waterwash  scrubber, the crude isopropanol caustic scrubber,
the isopropanol azeotrope distillation step, and the organic
(benzene) recovery step.  Process raw waste loads calculated
from flow measurements and the total pollutant loadings  are
indicated in the tabulation below:

               Sample Period tl  Sample Period *2

PROCESS FLOW

   liter/kkg         2,537          2,537
   gal/M Ib            304            304
BODS
   mg/literi           400            38b
   Ib/M Ib2              1.01            .979
COD
   mg/literi         1,123          1,132
   Ib/M Ibz              2.85           3.13
TOC

   mg/literi           508            530
   Ib/M Ib*              1,29           1.34

lRaw waste concentrations are based on unit weight
 of pollutant per unit volume of process
 waste waters.
2Raw waste loadings are based on unit weight of
                               135

-------
 pollutant per 1000 unit weights of product.

Waste   streams  included  in  the  above  calculations  are
continuous.  However, there are  occasional  washings  which
were  not  sampled  during  the  plant  visit.   The organic
stripper is cleaned with water once per month.  The cleaning
procedure requires approximately 100,000 gallons  of  water.
It  is  believed  that this stream should not be included in
the  RWL  calculations  since  it  can  be  disposed  of  by
incineration or combined with the process waste water stream
on  an  intermittent  basis and treated.  Although it is not
possible  to  specify  quantitative  values  for   pollution
parameters  such  as  BOD5,  COD  and  TOC  for this stream.
Therefore, the jRWL presented in the above tabulation can  be
considered   as  representative  of  the  process.   Another
discontinuous source of waste is the yearly cleaning of  the
absorption  tower  which  yields  approximately  1000 Ibs of
carbon tar for landfill disposal.

Noncontact waste water includes cooling water.  The  process
uses  approximately 100 kg of once-through cooling water per
kg of product. The treatment of  the  intake  cooling  water
consists of bar screening and chlorination.  Boiler blowdown
is  an additional noncontact flow.  The blowdown is added to
the cooling water return system.  Hot phosphate softening is
employed to treat the boiler feedwater.

The process RWL data presented was used  to  define  BPCTCA.
The wastes from this plant are neutralized and discharged to
the local municipal treatment plant.
                                 136

-------
Product:  Oxalic Acid

Process:  Nitric Acid Oxidation of Carbohydrates

Process RWL Subcategory:  C

Chemical Reaction:

       C6H12°6  *  6HN03 "*""*  3HOOCCOOtt  +  6NO   +  6H20

                 nitric                 nitric
       glucose      acid                  acid

Typical Material Requirements:

Basis:  1000 kg oxalic acid dihydrate

        Glucose (60 percent)                960 kg
        Nitric Acid  (90 percent)         2,340 kg
        Sulfuric Acid (100 percent)          52 kg

The  uses  for  oxalic  acid  center  around its calcium-ion
removal and reducing properties.  It is used  as  a  laundry
"sour",  as a bleach for removing iron stains from a variety
of materials,  and in cleaning compounds.  It also finds  use
in   automobile   radiator  cleaners,  leather  tanning  and
manufacture, chemical processing,  photography,  medicinals,
dyes, and inks.

Figure  4-25  is  a  process  flow  diagram of  oxalic acid
production  via  nitric  acid  oxidation  of  carbohydrates.
Carbohydrates   (in  the  form  of  corn  starch),  vanadium
catalyst, steam, sulfuric acid, and nitric  acid are added to
the reactor.  The reaction time is twelve hours and the  re-
actors  are sequenced so as to continuously provide products
for tne remainder of the processing equipment.  Spent nitric
acid is withdrawn  from  the  reactor  and  recovered.   The
reaction  products go to a vacuum crystallizer followed by a
wringer.  The liquid effluent from the  wringer  goes  to  a
liquid-solid  separation  step,  in  which  the  solids  are
recycled to the crystallizer while the liquid proceeds to an
evaporator.  The discharge from the evaporator  is  recycled
to  the  reactor.   The  crude oxalic acid  crystals from the
wringer are redissolved and then filtered.  The solids  from
the filter are disposed by landfill while the oxalic acid is
recrystallized   under   vacuum  conditions.   The  crystals
proceed to a second wringer and the liquid  from this wringer
undergoes a liquid-liquid separation step along with  liquid
from  the  previous  crystallization  step.   Some liquid is
recycled to the crystallizer, while  the  remaining  portion
                             137

-------
                                             FIGURE 4-25
                   OXALIC ACID-NITRIC  ACID OXIDATION OF CARBOHYDRATES
          H2S04AND  CATALYST

          CARBOHYDRATES
Ul
oo
               STRONG
               MOTHER
               LIQUOR
               TANK
             NITRIC ACID
                                          WASTEWATER
                                          (BARO.  COND. )
1

RE-DISSOLVER
                                          WASTEWATER
                                          (BARO.  COND.)
                                                                                            WASTEWATER
                                                                                            (BARO.COND.)
                   HNO
I
3
ER
»
SPRAY
TOWER
                  NITRIC ACID
                  PLANT *	
                                                                      OXALIC ACID

-------
proceeds to a second liquid-liquid  separation step.   Some of
the liquid is recycled to the reactor and the remainder goes
to  an  evaporator.   The  discharge  from the evaporator is
recycled to the liquid-liquid separator.   The  oxalic  acid
crystals from the wringer are dried and packaged for  sale.

The  waste  waters  from this process consist exclusively of
barometric condenser water.  This effluent was  sampled  and
its flow measured.  The process RWL calculated from the flow
measurements  and  the analyses of  the samples are indicated
in the tabulation below:

PROCESS FLOW

   liter/kkg                  436,000
   gal/M Ib                    52,300

BOD5 RWL

   mg/liter1                         3
   kg/kkg*                           1.31

COD RWL

   mg/liter1                        10
   kg/kkg*                           4.36

TOC RWL

   mg/literi                         3
   kg/kkg2                           1.31

*Raw waste concentrations are based on unit weight
 of pollutant per unit volume of process
 waste waters.
2Raw waste loadings are based on unit weight
 of pollutant per 1000 unit weights of product.

The high flows and  low  concentrations  seen  above  are  a
result  of  the  vacuum  system associated with the process.
These data were used to define BPCTCA.  The wastes from  the
process  are  currently  discharged to a municipal treatment
plant.

The alternate route in the manufacture of oxalic acid is via
sodium formate.  Sodium formate is  produced by the  reaction
of  solid  sodium hydroxide and carbon monoxide at 200°C and
150 psi in an autoclave.  After the reaction  is  completed,
the  pressure  is  reduced  and the temperature is raised to
400°C.  The sodium formate is converted into sodium oxalate,
which is then precipitated with calcium  hydroxide  to  form
calcium oxalate.   The calcium oxalate is then acidified with
sulfuric acid to form oxalic acid.
                                139

-------
Product;  Calcium Stearate

Process:  Neutralization of Stearic Acid

Process RWL Subcategpry;  C

Chemical Reactions:


2 C17 H35 C.OOH +  2 NaOH   +   CaCl2 —*-(C17H35COO)2 Ca + 2 NaCI  + 2 H20

                sodium      calcium
 stearic acid    hydroxide    chloride  calcium stearate
Calcium  stearate  belongs  to  a  group  of water-insoluble
metallic soaps.   Their  water  insolubility  differentiates
them  from  ordinary soap, and their solubility or solvation
in organic solvents accounts for their manifold  uses.    The
precipitation  process  is the classical method of preparing
metallic soaps, including calcium stearate.  It is now   used
primarily   in   making   high   melting-point  soaps   which
precipitate as light, fluffy powders and can be recovered by
filtration.

Raw materials for the production of calcium stearate include
stearic acid, sodium hydroxide,  and  calcium  chloride.    A
flow  diagram  of  the  process is presented in Figure  4-26.
The feedstocks are fed continuously into a reactor, where  a
two-stage  precipitation  process takes place.  In the  first
reaction, an alkali soap is formed by reacting  the  stearic
acid with caustic soda.  In the second step, the alkali soap
is  treated with a water solution of the calcium chloride to
precipitate the calcium stearate.  Sodium  chloride  remains
dissolved  in  the  mother  liquor.   The  resulting slurry,
containing  about  10  percent  of  calcium   stearate,   is
continuously   fed   to   a   filtration   step  for  solids
concentration. Vacuum filters are employed, and  the  filter
cake  is  subsequently  washed.   The partially dried filter
cax.e is then placed in  tray  dryers,  where  the  remaining
water  is  removed.   The  dried soap may then be ground and
separated to produce a powder of uniform particle size.

The major water pollution sources of the process  are   waste
water  discharged  from  the  filtration  step  and from the
"Battery-Limit"  clean-up  water.   Multiple   waste    water
samples  were  obtained during the plant visit in the survey
period.  Process RWL calculated from flow  measurements  and
                            140

-------
                                                FIGURE 4-26
                           CALCIUM STEARATE - NEUTRALIZATION OF STEARIC ACID
                                                                   TO ATMOSPHERE
                                                                    I
      WATER AND STEAM
STEARIC  ACID.

     NaOH_
    CaCI2 .
            WATER.
REACTION
  AND
PRECIPITATI
VACUUM
FILTRATION
                                                                  VACUUM
                                                                  PUMPS
MILLING
DRYING  AND
PACKAGING
                                               WASTEWATER
                                                  CALCIUM STEARATE

-------
the analyses of these streams are presented in the following
tabulation:
  PROCESS .FLOW

     liter/kkg                 54,100
     gal/M Ib                   6,460

  BOD5 RWL

     kg/kkgi                       13.8

  COD RVIL

     kg/kkg4                       32.8

  TOC £WL

     kg/kkg*                       23.1

i   Raw waste loadings are based on unit weight of pollutant
per 1,000 unit weights of product.

The high flow of the waste stream can be  explained  by  the
fact  that  a  considerable  quantity  of  water is utilized
during the filtration step to  wash  the  solid  cake.   The
analytical  results  also  indicate  high  concentrations of
calcium and chloride in the waste streams; these are  attri-
buted to excess raw material required by the reaction and to
the reaction by-product, salt.
                              142

-------
Product:  Hexamethylene Tetramine

Process;  Synthesis with Ammonia and Formaldehyde

Process RWL Subcategory:  C

Chemical Reactions:

        6HCHO     +
                               hexamethylene
      formaldehyde    ammonia       tetramlne

Two manufacturing plants were surveyed during the field data
collection  program.   Flow  diagrams designated Plant 1 and
Plant 2 are shown in Figures 4-27 and 4-28.

Both plants combine aqueous formaldehyde and  ammonia  in  a
liquid  phase  reactor  to  produce  an  aqueous solution of
hexamethylene tetramine.  The reaction shown above  produces
about  0.8  kg  of water per kg  of hexamethylene, and can be
run with either an excess of ammonia or formaldehyde in  the
reaction  mixture.   The  ammonia  is  used  preferably in a
substantially anhydrous state, in either gaseous  or  liquid
form  initially.   In  view of the high exothermic nature of
the   synthesis   reaction,   the   desired   control    and
stabilization  of  the reaction  temperature is somewhat more
readily achieved if tiie ammonia  is introduced in liquid form
so as to take advantage of the cooling  resulting  from  its
vapor i z at i on .

Reaction  temperatures  of  20°C - 75 °C constitute the range
specified for manufacture of hexamethylene  tetramine.   The
reaction  is  conducted at essentially atmospheric pressure,
although slightly superatmospheric pressures may be employed
for operating convenience.  The  production of  hexamethylene
tetramine is carried out in the  liquid phase in the presence
of  an  aqueous  solution  of  the  product  as  a rule.  No
catalyst  is  employed  in  the  reaction  of  ammonia  with
formaldehyde to give hexamethylene tetramine.

In  both  plants  the  liquid  effluent  from the reactor is
concentrated in a vacuum evaporator, where  water  from  the
reactor  and formaldehyde feedstock are drawn off.  In Plant
1, the overhead from the evaporator  is  sent  to  a  vapor-
liquid  separator  with  the  liquid  phase  recycled to the
evaporator; the water vapor from the  separator  is  passed
through  a  noncontact  surface  cooler  and  then sent to a
second vapor-liquid separator; and condensate is  drawn  off
                               143

-------
                                      FIGURE  4-27
 HEXAMETHYLENE TETRAMINE—SYNTHESIS WITH AMMONIA AND FORMALDEHYDE
                                       PLANT 1
                    STEAM
AQUEOUS
FORMALOENHYDEJ
AMMONIA
                                                     STEAM
                                                     VACUUM
                                                     JET
                              RECYCLE LIQUOR
 STEAM AND
 VAPORS
RENTED TO
 ATM.
                                                                  AIR  VENTED
                                                                            SOLID HEXA.
                                                                            PRODUCT

-------
SfrT
CD n

CD'
      HEXA
     r
PRE-
CONCENTRATOR
                                                  X
                                                  m
                                                  X


                                                  m
                                             Z
                                             >
                                         >
                                         Z
                                                  m JJ
                                                     ZK

                                                     TlO
                                                      1  «
                                                     CO
                                                     -<
                                                     Z
                                                  
                                                  CO

-------
from  this  second  separator and discharged to the sewer as
waste water.

A steam jet is used to draw vacuum on the evaporator.  Water
vapor from the second separator is drawn off into the  steam
line  as  shown  in  Figure 4-28.  The steam and water vapor
then pass through a jet and are subsequently vented  to  the
atmosphere.

The concentrated liquid effluent from the evaporator is sent
to  a  centrifuge  where solid crystals of hexamethylene are
separated.  The concentrate is recycled to the evaporator.

Hexamethylene crystals from the centrifuge are dried by  hot
air  and  pulverized  before  being  shipped  off in bags or
drums.  Air from this part of the process is  cleaned  using
dry dust collectors.

A  sampling  program  covering  several  weeks' operation at
Plant  1  was  conducted.   The  data  on  process  RWL  are
summarized below on a probability basis:

                        Process RWL Plant 1
                   Flow       EOD5     COD      TOC
               (liters/kKg) (kg/k£g)  (kg/kkg)  (kg/kkg)

10% Occurrence    3,200       4.6      18.8     4.5
50* Occurrence    3,200       9.2      29.4     9.8
90* Occurrence    3,200      13.7      40.0    15.1

It  should be noted that the RWL data presented from Plant 1
do not include the additional flows and pollutant loads from
carry-over  into  the  steam  jet   vacuum   system.    Some
appreciation  for  the  magnitude of these quantities can be
gained by examining the process used in Plant 2.

A flowsheet for this process is shown in Figure  4-28.   The
liquid   effluent  from  the  reactor  is  sent  to  a  pre-
conditioner and evaporator operating in series.   Water  jets
operating  in  a  similar  fashion to a barometric condenser
draw  vacuum  on  both  units.   Water  from  both  jets  is
collected  in  a  barometric  sump.  The warm water from the
barometric  sump  is  circulated  through  a  forced   draft
evaporative cooling tower, with the cooled water recycled to
the vacuum jets.

Sulfuric  acid is added to the water in the cooling tower to
react with the excess ammonia  present.   This  is  done  to
control  the ammonia vapors which would be stripped off with
the water  vapor  produced  by  evaporation  in  the  tower.
                             146

-------
Ammonium sulfate is produced by the reaction between ammonia
and sulfuric acid.

A  blowdown  must  be  taken  from  the  tower  because  the
evaporation loss is not  sufficient  to  balance  the  water
formed in the chemical reaction to produce hexamethylene and
the  water  present in the aqueous formaldehyde feed.  It is
also necessary to control  the  level  of  dissolved  solids
present in the circulating contact cooling water.

A  second  waste  water  stream  is  discharged  from  a wet
scrubber used with the dryer for the hexamethylene  crystal.
The  following  tabulations  summarize  the RWL contribution
from both the scrubber discharge and cooling tower blowdown.
                        Process RWL Plant 2
                   Flow       BOD5     COD    TOC
                (liter/kkg)   (kg/kkg)  (kg/kkg) (kg/kkg)

Cooling Tower
 Blowdown          5553.       71.5     116   42.7
Scrubber
 Blowdown           488.       11.7     112   28^3

  Total RWL        6041.       83.2     228   71.0

These data, from Plant 2,  are  significantly  higher,  both
witn  respect  to flow and loading, than those obtained from
Plant 1.  The  flow  and  loadings  attributed  to  the  wet
scrubber  in  Plant  2  are  not  sufficient  to explain the
difference between the two plants.  Instead, the  difference
relates  back to the fact that Plant  1 does not condense the
steam used to draw vacuum on the evaporator.  Although Plant
1  uses  a  surface  condenser  ahead  of  the  vapor-liquid
separator,   there   may   be   significant   carryover   of
contaminants to the steam jet.  These contaminants are  then
vented  to  the  atmosphere with the uncondensed steam.  The
data shown for Plant 2 also may not fully show the magnitude
of this difference in that the flow from the  cooling  tower
represents  a  blowdown  and  does  not  include evaporation
losses.

The water circulation rate between  the  cooling  tower  and
barometric  condensers  for  Plant 2 is approximately 73,900
liters/kkg of hexamethylene.

The RWL data from Plant 1  at  50%  occurrence  was   (median
value) selected as the basis for BPCTCA.  These waste waters
are  discharged  to  a municipal treatment plant,  as are the
wastes from Plant 2.
                              147

-------
Product:  Hydrazine Solutions

Process;  The Raschig Process

Process RWL Subcategory:  C

Chemical Reactions:  NaOH +  C12 —». NaOCl  + HCf

                                      sod i urn
                                   hypochlorIde

                     NaOCl +  NH3-^-NH2CI  +  NaOH

                                     chloramine

                     NH2C1 +  NH3 —^-N2H/,  + HC1

                                    hydrazfne

The principal use for hydrazine is   as  a  military  missile
fuel  in  which  anhydrous hydrazine  is required.  Hydrazine
also has a number of  nonmilitary  applications.   The  most
important  of  these  is  maleic  hydrazine,  a plant growth
regulator used  for  tobacco  suckering  and  tree  pruning.
Other  uses include wash-and-wear finishes, Pharmaceuticals,
anti-oxidants  used  in  foam,  hydrazine  monobromide,   and
soldering flux.

A  process  flow  diagram  for  the  manufacture of hydrazine
hydrate is shown in Figure 4-29.

Sodium hydroxide and chlorine are mixed in a reactor  system
to  produce  sodium  hypochlorite.    Glue  is  added  to  the
solution as an inhibitor until the mix is viscous.  A dilute
solution of ammonia  (5 to 15 percent) is added until a molar
ratio of 3 NH3 to 1 hypochlorite is  obtained.  This  mixture
forms  chloramine which, when reacted with anhydrous ammonia
in a  ratio  of  20:1  to  30:1,  produces  hydrazine.    The
reaction temperature normally reaches 130°C.

The effluent from the hydrazine reactor is fed to an ammonia
recovery  still  where   excess ammonia is taken off overhead
and recycled back to the reactors.   The tails are fed to   an
evaporator  where  concentrated  sodium chloride is removed.
The vapors from the evaporator are fractionated to yield  (as
bottoms) a commercial grade of hydrazine hydrate.

Anhydrous hydrazine may be produced  from  hydrazine  hydrate
by extractive distillation.  Hydrazine salts are produced by
neutralizing hydrazine hydrate with  the appropriate acid  and
                                148

-------
                                             FIGURE 4-29
                            HYDRAZINE HYDRATE-THE RASCHIG PROCESS
VD
         SODIUM
WATER

OUS NHq
N H _..



IDE
« ]
1






fc-
\






LU
ce
CD
3= C3
CO 1—
CD CO
>— LU
a: ce


I












LU
•C CD
ce i—
0 CO
— i «t
^E LU
co ce

i






















LU
=e
r-j
•«t
ce
C3
=




r


a
i—
CO
«r
LU
ce









t
«c
CD

^

CD
t—
— 1
1—
to
	
                                                       CC
                                                       LU
                                                       CD
                                                             EVAPORATOR
                                                      T
                                                                                 .HYDRAZINE
                                                                                  HYDRATE
                                                             WASTEWATER
                            RECYCLE WATER

-------
then  dehydrating  the resulting slurry.  The salts produced
are  hydrazine  hydrobromide,  hydrazine  hydrochloride  and
hydrazine sulfate.

The  waste  water  stream  from  this  process  is  a sodium
chloride  solution  from   the   crystallizing   evaporator.
Process  RWL  calculated  from  the  flow  measurements  and
analyses of the waste water obtained in the sampling  survey
are indicated in the following tabulation.  The extreme high
chloride  concentration  in  the  waste  water results in an
inhibitory effect on the BOD5 test  and,  consequently,  the
analytical  results show a high COD/BOD5 ratio.  The low TOC
is due to  the  lack  of  organic  carbon  involved  in  the
process.

PROCESS FLOW

   liter/kkg               30,300
   gal/M Ib.                3,630

BOD5 RWL

   mg/liter*                  300
   kg/kkg*                      9.09

COD RWL

   mg/liten                3,800
   kg/kkg*                    115

TOC JRWL

   mg/liter1
   kg/kkg*

iRaw waste concentrations are based on unit weight of
 pollutant per unit volume of process waste waters.
2Raw waste loadings are based on unit weight of pollutant
 per 1000 unit weight of product.

The process RWL shown above is the basis for BPCTCA.
                                 150

-------
Product::  Isobutylene

Process;  Extraction with Sulfuric Acid from a Mixture of Ct*
Hydroc arbon s

Process RWL Subcategory:  C

Hign-purity isobutylene is required for applications such as
the  production  of  butyl  rubber  and  the  alkylation  of
aromatics.   In  the  U.S.,  the  most  common  process  for
manufacturing pure isobutylene is extraction with 65 percent
sulfuric acid.  The feedstock is usually a mixed C4 cut from
a  refinery.  The process is continuous and is characterized
by  extensive  contact  between   water    (as   H2SCW)   and
hydrocarbons.    As   such,   it   is  assigned  to  process
Subcategory C (Aqueous Phase Reactions).  It should be noted
that  regeneration  of  the  sulfuric  acid   absorbent   is
considered as an integral part of. the process.

A flow diagram for the extraction process is shown in Figure
4-30.   The  process consists of a countercurrent extraction
system.  The effluent from the final stage  is  flashed  and
goes  to  a regenerator where heat reverses the reaction and
regenerates both acid and isobutylene.  Temperature is  kept
below the point where polymerization would become a problem.
Sulfuric  acid is removed from the bottom of the regenerator
and recycled after reconcentration.   The  regenerator  off-
gas,  containing  isobutylene and some light polymer plus t-
butyl  alcohol,   is  fractionated  to  produce  99+  percent
isobutylene,  and  the  bottoms  can be further fractionated
into t-butyl alcohol and diisobutylene.

Process RWL's for isobutylene extraction are  summarized  in
the following tabulation:

PROCESS FLOW

   liter/kkg                   20,400
   gal/M Ibs.                   2,440

BOD5 RWL

   ing/liter1                      669
   kg/kkg2                         13.6

COD RWL

   mg/liter1                    3,150
                                   64.1
                             151

-------
                                                  FIGURE  4-30
             ISOBUTYLENE—EXTRACTION FROM C4 HYDROCARBONS WITH  SULFURIC ACID
    CjCUT
                         REACTORS
   H2S04MAKEUP
K
K  ALCHOL
   STRIPPER
             T
          WASTEWATER
                                       FLASH
                                       DRUM
REGENERATOR
     JL
in
NEUTRALIZER
JL
                                                                          NaOH
             SPENT CAUSTIC
                                                    REGENERATED ACID
                          /--BUTYL ALCHOL SOLUTION
                                SPENT C4 S
                                TO NEUTRALIZATION
                            ISOBUTYLENE PRODUC1

PURIFICATION 1 	 1
1 1 i


-*

§_;
(
WATE
* 	
ALOC
                                           POLYMER
                                           GASOLINE
                                        EXTRATION
                                        TOWER

-------
TOC jRWL

   mg/liter*                      633
   jcg/kkg*                         12.9

*Raw waste concentrations are based on unit weight
 of pollutant per unit volume of process
 waste waters.
2 Raw waste loadings are based on unit weight of
 pollutant per 1,000 unit weights of product.

This  process  RWL data is the basis for BPCTCA.  The wastes
from  this  process  are  combined  with  those  from  other
processing areas and treated by the activated sludge process
before discharge.
                               153

-------
Product:  Sec-Butyl Alcohol

Process:  Sulfonation and Hydrolysis of Mixed  Butylenes

Process RWL Subcategory:  C
Chemical Reactions;

           CH3CH - CHCH3

           Butene-2


         CH3CH2CHCH3

              HSO/,
     H2SOj,

    Sulfurlc
     Acid
                      H20
         Sec-Butyl
          Sulfate
Water
                                          CH3CH2CHCH

                                           Sec-Butyl
                                            Sulfate
           CH3CH2CH(OH)CH3 +
                                   Sec-Butyl
                                    Alcohol
                         Sulfurlc
                           Acid
Secondary  butyl  alcohol  is  made   from   mixed  butylenes.
However, because  of  its  alternate  uses,   isobutylene  is
normally  extracted  from  the  C4  feedstock  prior  to the
manufacture of secondary butyl alcohol.  This is  also  done
to prevent the formation of excessive quantities of  tertiary
butyl alcohol from isobutylene.

Normal butylenes are first absorbed by concentrated  sulfuric
acid  (75  percent)  to  form  isobutyl  sulfate.    This  is
subsequently  hydrolyzed  with  water to   secondary   butyl
alcohol  and  dilute  sulfuric acid.  A  flow diagram for the
process is shown in Figure 4-31.  The extensive requirements
for contact water usage make this continuous process typical
of Subcategory F.  The reconcentration of  sulfuric acid  for
recycle  is  considered an integral part of the process.  It
should also be noted that this process for  secondary  butyl
alcohol  is  analogous  to  that  used   to produce isopropyl
alcohol from propylene.

The weak acid bottoms from the hydrolysis  are reconcentrated
by   multistage   vacuum   evaporation.     Normally,   three
evaporators   in   series   are   used   to  bring the  acid
concentration back to 75 percent strength.   However,  during
the  sampling  program,  only  two were  in service,  with the
final stage down for cleaning.  This  type   of  operation  is
possible  by  pulling  a  higher  vacuum  on  the first two
evaporators.

The overhead vapors from  the  first  evaporator  are  drawn
through   a  surface  condenser  which   utilizes  noncontact
                               154

-------
                                     FIGURE 4-31

SEC —BUTYL ALCOHOL—SULFONATION  AND  HYDROLYSIS  OF MIXED BUTYLENES
  SULFURIC ACID (85%)
                BUTYLENES
CO
o±
a
GO
                              VENT GASES
                              (RECYCLE)
                                      WATER
                            STEAM-
                                          DILUTION
                                          TANK
           ACID
           RECOVERY
                        DILUTE ACID
                                                                               SEC-BUTYL ALCOHOL
                                                               LLJ O
                                                               CC CJ
                                                               WAS'TE

-------
cooling water.  The noncondensible vapors are  entrained  in
two  barometric  condensers  operating with steam jet vacuum
pumps in series.  The second-  and  third-stage  evaporators
are also equipped with this condenser-steam jet arrangement.

Apart  from  dehydrogenation  to  butadiene, secondary butyl
alcohol production is the main end use for normal butylenes.
Secondary butyl alcohol itself is used mainly as  a  solvent
or  to  make secondary butyl acetate or methyl ethyl ketone.
It should be noted that the alcohol product is  obtained  as
an  aqueous solution in this process.  The product is really
an azeotropic binary mixture drawn as a side stream from the
crude  secondary  butyl   alcohol   scrubber-stripper.    It
contains  approximately  70  wt  percent  (36  mole percent)
alcohol and 30 wt percent  (64 mole percent)   water,  and  is
withdrawn  at a minimum boiling point of approximately 90°C.
Dehydration of the alcohol  is  accomplished  in  subsequent
processes,  and  this  waste  water  is  not included in the
wasteload computed for the alcohol process.

During  the  field  data  collection  program,  two   plants
utilizing  the  previously  described  process were sampled.
The following brief tabulation summarizes the RWL  for  each
plant:

                                     Plant 1        Plant 2

             PROCESS FLOW
                liters/kkg           64,900           626
                gal/M Ib

             BODS RWL
                mg/literi               374        22,800
                kg/kkg2                 24.3          14.2

             COD RWL
                mg/liter*             3,280        62,000
                kg/kkg«                 213            38.8

             TOC RWL
                mg/liten               665        38,300
                kg/kkg*                  43.2          23.9

*Raw  waste  concentrations  are  based  on  unit  weight of
pollutant per unit volume of process waste waters.
2Raw waste loadings are based on unit  weight  of  pollutant
per 1,000 unit weights of product.

The  RWL from Plant 2 was used to define BPCTCA.  This plant
utilizes much more internal recycle than Plant 1.
                               156

-------
Product:  Acrylonitrile

Process:  Ammonoxidation of Propylene

Process RWL Subcategory:  C

Chemical Reaction:


     2 CH2CHCH3 +  2 NH3   +   3 02  —•>•  2 CH2 CHCN   + 6 H20

     propylene     Ammonia            acrylonltrile
Acrylonitrile is used in the manufacture of acrylic  fibers,
Acrylonitrile-    Butadiene-Styrene    (ABS)   and    Stryene-
Acrylonitrile (SAN) resins, and nitrile rubber.

A typical  process  flow  diagram  for  the  manufacture  of
acrylonitrile  via  ammonoxidation  of propylene is  shown in
Figure 4-32.

Raw  materials  for  the  production  of  acrylonitrile  are
propylene,  air,  and  ammonia.   These feeds are introduced
into a fluid bed catalytic reactor operating at 5 -  30  psig
and  200°C  to 260°C.  The reactor effluent is scrubbed in a
counter-current  absorber  and  the  organic  materials  are
recovered from the absorber water by distillation.   Hydrogen
cyanide,  water, light ends, and high boiling impurities are
removed from the crude  acrylonitrile  by  fractionation  to
produce a specification acrylonitrile product.

Although  the actual ammonoxidation reaction is vapor-phase,
the process was considered within Subcategory C  because  of
the aqueous separation and purification train.

The  major  water  pollution sources of this process are the
process waste waters discharged  from  the  steam  stripping
columns  as  shown in the process flow diagram.  Process RWL
calculated from flow measurements and analyses of the  waste
streams are indicated in the following tabulation:
                               157

-------
         85T
         REACTOR
         I
       ABSORBER
 ACRYLONITRILE
 RECOVERY  COLUMN
 ACETONITRILE
 RECOVERY  COLUMN
                    T
C-O
CO
                                X* CO
                                C-3 =0
          n
          70
          -<
          O
                                               30
          IJ  W
          O  w
          Z
LIGHTS COLUMN
PRODUCTS COLUMN
                                           70
                                           O
                                           •o

-------
              	Plant_L	Plant 2  Plant 2  Plant 3
                            Sampling Periods
              #1      #2	    »3      tV       t2     	#1	
PROCESS FLOW
 liter/kkg  3,320   3,920    3,920   6,590    4,010    2,820
 gal/M Ib     471     471      471     790      480      338

BOD5 RWL
 mg/literi 18,000  18,700   19,300   3,330   13,900      	
 kg/kkg2       71.7    73.3     75.8    21.9     55.5    	

COD RWL
 mg/literi 57,400  60,300   60,700  21,100   36,200   41,100
 kg/kkg«      229     237      238     139      145      116

TOC RWL
 ing/liter* 25,600  24,000    25,100  8,700   15,300   19,100
 kg/kkg*      102      94.2      98.6   57.3     61.2     53.9


1   Raw  waste  concentrations  are  based on unit weight of
pollutant per unit volume of process waste waters.
2  Raw waste loadings are based on unit weight of  pollutant
per 1000 unit weight of product.

The  foregoing  data  indicate  that  the  RWL of Plant 1 is
higher than that of Plants 2  and  3.   This  difference  is
attributed   to   the   discharges   by  Plant  1  of  light
hydrocarbons that are  removed  as  the  overhead  from  the
acetonitrile purification column comes into the sewer lines.
The  analytical results from the sampling survey also reveal
that, in addition to the pollution parameters shown  in  the
above  tabulation,  the  concentration of parameters such as
nitrogen, sulfate, and cyanide may be at levels  potentially
hazardous to the biological pretreatment process.

An  average  of  the  RWL  data  from  Plants  2  and  3 was
considered as the basis for BPCTCA.  It should be noted that
all  of  the  plants  surveyed   currently   use   deep-well
injections  to  dispose  of  wastes  from the manufacture of
acrylonitrile.

The alternative routes for the manufacture of  acrylonitrile
include:  1)   catalytic dehydration of ethylene cyanohydrin;
2)  catalytic reaction of acetylene and hydrogen cyanide; and
3}   catalytic  reaction  of  propylene  with  nitric  oxide.
However,  present  practice  concentrates exclusively on the
ammonoxidation of propylene.
                              159

-------
Product:  Cresol (Synthetic)

Process:  Methylation of Phenol

Process RWL Subcategory;  C

Chemical Reaction;

         C6H5OH  +   CH3OH 	> CH-CgfyOH  +  H20

         phenol    methanol       cresol
Cresol (cresylic acid) is an isomeric mixture (o-,  m-,  and
p-cresol)  obtained  by  refining  the phenolic constituents
present in coal tar, refining  the  petroleum  acids  formed
during  the  thermal and catalytic cracking of petroleum, or
by  producing  cresols  synthetically.   Cresols  are   used
primarily  as  raw  materials for the production of phenolic
resins, tricresylphosphate, disinfectants, and solvents.

The facility visited during the  field  survey  produced  an
isomeric  mixture  of  cresols by the methylation of phenol.
Figure 4-33 is a process flow  diagram  of  this  production
technique.

The  first  step  in  the  process is the preparation of the
reactor feed.  Fresh and recycled methanol  and  phenol  are
mixed in a weight ratio close to 2.5:1.  The mixed stream is
then  vaporized,  and condensing Dowtherm vapors are used to
vaporize and heat  the  feed  to  300°C.   The  reaction  is
carried  out  at atmospheric pressure in a mixed-bed reactor
which contains activated  alumina  catalyst.   The  heat  of
reaction  is  removed by passing liquid Dowtherm through the
tubes imbedded in the mixed bed of the reactor.    (The  heat
of  reaction  is  approximately  20 Kcal/mole.)  Some of the
heat evolved by the reaction will be taken  up  as  sensible
heat  by  the  reactants, which are heated from 300°C to the
reaction temperature of 350°C.   The  contact  time  in  the
reactor  for  52 percent reaction completion is less than 30
seconds.  A  typical  reaction  mixture  distribution  on  a
water-free basis is given below.

                                                    Weight %

        Phenol                                         48
        o-Cresol                                       30
          m- and p-Cresol                              12
        2, 6-Xylenol                                   15
        Anisoles and Hexamethylbenzene                  5
                               160

-------
                                   T9T
      METHANOL

      DISTILLATION
      COLUMN
       COLUMN
       COLUMN
CD —

— CO
O
30
m
1
ATION

i
ATION








i
1
m s*
CO Z
°°
1-0
en
X
i —
i —






j 	


1 	


»






BENZENE
DISTILL
COLUMN

.
DISTILL
COLUMN

.
PHENOL
DISTILL
COLUMN

i
DISTILL
COLUMN


mow
i

.
UION

1
UION


1
UION

                                                                      Z

                                                                      X
                                                                      3   co
                                                                      ?   co
O
Z

O
X
m
Z
O
                                                          I

                                                         CO

-------
The  vapors  leaving the reactor are condensed and cooled to
about 25°C, and then sent to a phase separator.   The  vapor
space  is  provided  with  a  vent  in order to periodically
remove  any  noncondensables  (CO2,  CHJ4)   which  might   be
produced in the reactor.  The weight percent of water in the
liquid  phase  is  below 10 percent.Consequently, an aqueous
phase will not appear, because the water will  stay  in  the
organic  phase.   The solubility level of water in phenol is
close to 34 gms/100 gms phenol at  25°C.   The  presence  of
cresols  and  xylenol  undoubtedly  decreases the solubility
limit, but the decrease is not sufficient to form a separate
aqueous phase.

The liquid phase is sent to an extraction  column  in  which
benzene    (containing    some   methanol)    is   circulated
countercurrent to the liquid product  stream.   The  phenol,
cresols,  xylenols,  and  by-products are transferred to the
benzene phase, while the water  and  the  methanol  form  an
aqueous phase.

The  aqueous  phase  is  then  sent  to  a methanol recovery
column, in which methanol  is  removed  as  the  distillate,
while  water   (with  small  amounts  of  phenol)   remains as
bottoms.  The methanol is  recycled  to  the  reactor  feed-
preparation  section,  while  the  water is discharged.  The
organic phase, containing benzene and the reactor  products,
is  sent  to the benzene recovery column, where this solvent
is distilled overhead and recycled to the  extraction  unit.
This  column  is  operated  at atmospheric pressure, with an
overhead temperature close to 75°C.  Cooling water  is  used
in the condenser, and condensing Dowtherm vapors are used in
the reboiler.

The  bottoms  stream  leaving  the solvent recovery still is
sent to the distillation column, in which anisole and  light
by-products   are   removed  in  the  overhead.   Phenol  is
recovered in a subsequent distillation step and recycled  to
the  reactor  section.  The bottoms from the phenol recovery
column are then sent to the product  recovery  section.   In
the  first  column,  o-cresol is recovered as distillate; in
the second, m-and  p-cresol  isomeric  mixture  is  distilled
overhead.   The bottoms are sent to the 2, 6-xylenol column,
in which this co-product is distilled off, while the bottoms
containing the  heavier  by-products  (such  as  hexamethyl-
benzene) are sent to organics disposal.

The  major  water  pollution  source  is  the  water  stream
withdrawn  as  the  bottom  of  methanol  recovery   column.
Process RWL's calculated from flow measurements and analyses
                                162

-------
of  the  waste  water samples are indicated in the following
tabulation:

PROCESS FLOW

   liter/kkg                     334
   gal/M Ib.                      40

BOD5 RWL

   mg/literi                 143,000
   kg/kkg*                        47.7

COD RWL

   mg/literi                 303,000
   kg/kkg*                       101

TOC jRWL

   mg/literi                 104,000
   kg/kkg*                        34.7

*Raw waste concentrations are based on unit weight
of pollutant per unit volume of process
waste waters.
2Raw waste loadings are based on unit weight of
pollutant per 1,000 unit weights of product.

The  analytical  results  also  indicate  that  the   phenol
concentration in the waste stream is at a level which may be
hazardous  to biological treatment processes if not properly
acclimated.  The waste stream can either be pretreated  with
lime  to form calcium phenolate before being discharged into
a biological treatment processes or can be steam stripped to
reduce the phenol concentrations.

The process RWL is the basis for BPCTCA.  The waste from the
plant is currently discharged  to  the  municipal  treatment
plant.
                              163

-------
Product:  p-Aminophenol

Process:  Catalytic Reduction of Nitrobenzene

Process RWL Subcategory:  C

Chemical Reactions;
            NO,
       n'i trdbenzene
 metal
catalyst
C6Hj,(OH)NH2


p-aminophenol
                        +  HVO
Typical Material Requirements;

             Basis

          Nitrobenzene
          Sulfuric Acid
          Surfactant
          Anhydrous Ammonia
          Toluene
          Hydrogen Gas
          Nitrogen Gas

            Antioxidants

          By-Products
          Aniline
          1000 kg p-Aminophenol

                 1800 kg
                 1550 kg
                   20 kg
                  500 kg
                   80 kg
                 220 kg
p-Aminophenol is versatile in its use as a dye intermediate.
It  can be used in the preparation of disperse, nitro, acid,
mordant, direct, sulfur, and oxidation  dyes.   It  is   also
widely  used  as  a  photographic developer.  The by-product
aniline produced during the reaction also has wide  uses  in
the dye, dfug, rubber, plastics, and animal-feed industries.

Production  of  p-aminophenol is based upon the reduction of
nitrobenzene  with  hydrogen  in  the  presence  of   aqueous
sulfuric  acid  and  a metal- containing catalyst  (platinum,
palladium, or mixtures of the two), as shown in Figure 4-34.
The raw materials (nitrobenzene, deionized  water,  hydrogen
gas, sulfuric acid, surfactants, and the metal catalyst)  are
fed  into  a reactor at a temperature ranging from about 60°
to  120°C.   Prior  to  completion  of  the  reaction,    the
reduction  of  the  nitrobenzene is interrupted for catalyst
recovery  and  recycle.   During  the  reaction  a  distinct
interface  forms  between  the  reaction  products  and   the
                              164

-------
                                             FIGURE  4-34
              PARA-AMINOPHENOL-  CATALYTIC REDUCTION OF NITROBENZENE
  NITROBENZENE

WATER

SUiFURIC ACID

 H2AND  N2 GASES
 SURFACTANT
                             .SPENT  CATALYST
                             TO RECOVERY
                                               BY-PRODUCT,ANILINE

                                               .DISTILLATION
                                               BOTTOMS  TO LANDFILL
NITROBENZENE
CATALYST
RECOVERY
RECYCLE
                SOLVENT
                RECOVERY
                & RECYCLE
                     PURIF1CATI
                        AND
                     SOLATION
CATALYTIC

REACTOR
                     ANHYDROUS
                     AMMONIA
                     TOLUENE
PARA- AMINOPHENOL
                                                                         .WASTEWATER
—
CE
EC
D
«
LU




1 .
-»



LU 	
fs ^—
i— oe
OO CD
-a «t
CVI LU




1 .
                                                                                      TO LANDFILL
                     ANTIOXIDANTS

-------
catalyst-containing nitrobenzene.  To recover  the  catalyst
the nitrobenzene layer is separated and used in a subsequent
reduction step.
The   reaction   products  proceed  to  a  purification  and
isolation step.  Additional materials (anhydrous ammonia and
toluene) are added  to  facilitate  separation  of  the  by-
product aniline from product p-aminophenol.  After isolation
of  the  aniline,  solvent  is recovered and recycled to the
purification and isolation  step.   Following  purification,
the p-aminophenol is dried and packaged for sale.

The  major  pollution  sources  of the process are the waste
waters generated during the aniline recovery step and the p-
aminophenol drying step. These waste  waters  are  collected
and  passed  through  two  evaporators  connected in series.
This evaporation process separates the very concentrated am-
monium sulfate wastes for landfill disposal.  It was claimed
by the plant which was visited during  the  sampling  survey
that   the  evaporation  process  should  be  considered  as
pollution abatement facilities rather than as  part  of  the
manufacturing   process.    However,   separate  samples  of
influent to the evaporator and effluent  were  analyzed  and
the jRWL's are presented in the following tabulation.

         Influent to Evaporators     Effluent from Evaporators
               Sample        Sample                Sample
              Period t1     Period t2             Period #1
PROCESS FLOW
   Liter/kkg
   gal/M Ib

BOD5 RWL
   mg/liter1
   kg/kkg*

COD RWL
   mg/liter1
   kg/kkg*

TOC RWL
   mg/liter1
   kg/kkg2
 15,000
  1,800
 59,300
    890
115,000
  1,725
 33,600
    505
 15,000
  1,800
 59,300
    886
101,000
  1,508
 27,100
    407
4Raw  waste  concentrations  are  based  on  unit
pollutant per unit volume of process waste waters,
2Raw waste loadings are based on unit  weight  of
per 1000 unit weights of product.
12,600
 1,510
 3,300
    41.6
 5,850
    73.7
 1,730
    21.7

weight of

pollutant
                               166

-------
The  process  RWL based on the effluent from the evaporators
was considered as the basis for BPCTCA.  The  effluent  from
the  evaporators (aqueous condensate) is combined with waste
waters from other processes  and  treated  in  an  activated
sludge plant prior to discharge to surface waters.

Noncontact  waste  waters include cooling tower blowdown and
boiler condensate.    Each  of  these  wastestreams  is  bled
continuously  for  the  control  of  dissolved  solids.  The
streams are combined with the treated process  waste  waters
and eventually discharged to a receiving stream.

p-Aminophenol  can  also  be  prepared  conveniently  by the
Beehamp method of reducing p-nitrophenol in the presence  of
iron  filings in an acid medium.  Alternatively, the product
may be prepared by catalytic hydrogenation of p-nitrophenol,
by treatment of phenylhydroxylamine with an  acid  catalyst,
(such  as  sulfuric  acid),  by reduction of azoxybenzene in
acid solution,  and  by  treatment  of  p-chlorophenol  with
ammonia.
                             167

-------
 Product:   Propylene oxide

 Process:   Chlorohydrin Process

 Process RWL Subcategory;   C

 Chemical Reactions;
           HOC1
propylene hypochloric acid         propyl
                              chlorohydrin

2 HOCH2CH2CH2C1   +   Ca(OH)2  - >   2  C^CH - CH£   +  CaC12  +  2 HO

                                        ^O/

   propyl            ' ime           propylene oxide      calcium    water
chlorohydrin                                          chloride
 The  most   important  outlet  for  propylene oxide is in the
 manufacture of  propylene glycol.   It is also used during the
 production of polyethers, which are  in  turn  used  in  the
 manufacture of  urethane foams and elastomers.

 The manufacture of propylene oxide from propylene is similar
 to  that   of ethylene  oxide  by the chlorohydrin route. In
 fact, many  propylene  oxide  manufacturing  facilities  are
 converted  ethylene oxide plants which were rendered obsolete
 by  the  advent  of  direct  oxidation.   In  recent  years,
 considerable research has  been  undertaken  to  discover  a
 viable  process  for  making  propylene  oxide without using
 chlorine.  A number  of  alternatives  have  been  developed,
 including  epoxidation of propylene by means of hydroperoxide
 and direct bxidation of propylene.

 Production  of   propylene  oxide by the chlorohydrin process
 involves a reaction between  propylene  and  chlorine.   The
 process  flow   sheet  is  shown  in  Figure  4-35.   The raw
 materials  are fed into a reactor and water  is  added.   The
 reaction     products    are   primarily   chlorohydrin   and
 dichlorohydrin.  Vent gases  from  the  reactor  are  passed
 through  a  water scrubber.  A second stage caustic scrubber
 is also employed to neutralize potential acid carry-over  in
 the off-gases.

 Following   the  caustic scrubbing, the gases are passed to an
 oil  absorption   unit   where   propylene   dichloride   is
                                 168

-------
69T
                                                   -o
                                                   ye

                                                   O
                                                   O
                                                   X  -n

                                                   S  O

                                                   O  C
                                                   X  70
                                                   r-  m
                                                   O  .
                                                   *»  ^
                                                   O  w
                                                   x  o,
                                                   30

                                                   O
                                                   CO-
                                                   CA

-------
selectively   concentrated  and  recovered.   (An  activated
carison adsorption system may  be  substituted  for  the  oil
absorption  unit.)   other reactor gases, such as a propylene
and propane are often vented to a fuel gas supply.  At  some
installations, pure propane may be recovered in a dehydrator
(activated alumina).

Reaction  products,  containing  mainly propyl-chlorohydrin,
are sent to a saponificatibn. reactor.  A lime slurry is  fed
into  the  reactor  along  with live steam.  In the reactor,
propyl-chlorohydrin  is  converted   to   propylene   oxide.
Dichlorohydrin  is  also  converted to propylene dichloride,
which may be recovered as a by-product.  Following the  lime
addition,  the  products are passed through a stripper.  The
products (propylene  oxide  and  propylene  dichloride)  are
separated  from  unreacted  lime  and calcium chloride.  The
unreacted lime solution is passed through a  clarifier  from
which  the underflow, containing unreacted lime, is recycled
back  to  the  saponification  reactor;  the   overflow   is
discharged as waste water.

The  product is first passed through a recovery tower, where
propylene oxide is  separated.   The  underflow,  containing
propylene  dichloride,  is  sent  to  a steam stripper where
propylene dichloride is  separated  from  other  impurities.
The  propylene  dichloride  is  combined  with the propylene
dichloride separated from the off-gases.  Bottoms  from  the
stripper constitute a second major waste stream.

Production  facilities  for  propylene  oxide  were  visited
during the sampling period, and samples of the process waste
waters were obtained.  Process raw  waste  loads  calculated
from  flow  measurements  and analyses of these waste waters
are indicated in the tabulation below:
                   Plant 1
           Sample
           Period #1
            Sample
            Period *2
            Plant 2	
             Sample
             Period #1
         Plant 3
          Sample
          Period f1
PROCESS FLOW
 liters/kkg   60,000
 gal/M Ib.     7,150
BODS RWL
 mg/liter*
 kg/kkg*

COD RWL
 mg/liter1
 kg/kkgz
  290
 17.2
2,480
  148
             50,200
              6,020
  575
   28.9
2,740
  138
              69,300
               8,300
  480
   33.2
1,680
  116
           66,000
            7,910
  578
   38.1
2,580
  170
                              170

-------
TOC RWL
 mg/literi       310           320            365         385
 Jtg/kxg           18.6          16.0           25.3        25.4

NOTE: iRaw  concentrations  are  based  on  unit  weight  of
pollutant per unit volume of process waste waters.

2Raw  waste  loadings  are based on unit weight of pollutant
per 1000 unit weights of product.

A plant average of the values presented above  was  used  as
the  basis  for  BPCTCA.   The  waste  waters from all three
plants  are  currently  combined  with  wastes  from   other
processes  and pumped to settling basins from which they are
discharged.  The high flows may be  partially  explained  by
the  fact  that a large quantity of water is required in the
reactor and also in  the  many  scrubbers.   Furthermore,  a
large  quantity of stoichiometric water is formed during the
reaction.

It is possible that both pollutant loadings  and  flows  may
vary at other production facilities.  The pollutant loadings
may  be  greatly  increased  if  propylene dichloride is not
recovered following separation of the propylene  oxide.   At
such  an  installation,  the  flows  would probably be lower
since  the  propylene  dichloride  stripper  would  not   be
required.

An  additional  feature  of the process plant visited during
the sampling period which may differ at other  installations
relates to the recycling of unreacted lime.  A clarifier had
been  installed to remove lime and calcium chloride from the
waste water.  These materials  were  then  recycled  to  the
reactor,  thus  reducing  the  total  flow and the pollutant
loadings.  This practice  was  considered  as  part  of  the
process since required materials were recycled.
                                 171

-------
Product;  Pentaerythratol

Process:  Aldehyde Condensation

Process RWL Subcategorv;  C

Chemical Reactions;
  4HCHO     +    CH3CHO    +   NaOH    — +•    CfCt^OH)!,     + HCOONa

                              sod i urn                       sod i urn
Formaldehyde    acetaldehyde     hydroxide      pentaerythrf tol   formate
The  most  important  end  use  of  pentaerythritol is in the
manufacture  of  alkyl  resins.     Next   in  importance  are
pentaerythritol resin esters, which are  used in floor polish
and   in   flexographic   inks.     Other   applications   of
pentaerythritol esters  are  in  the manufacture  of  fire-
retardant  paints,  use  as  high   pressure  lubricants, and
production of PVC plasticizers of   low   volatility  suitable
for use in wire insulation.

A typical process flow diagram for  producing pentaerythritol
by aldehyde condensation is  shown in Figure 4-36.   The major
pollution  sources  of  the  process are  residue  from the
distillation column and mother liquors   withdrawn  from  the
purification  units.   The   condensates   from the steam jets
which are used to pull  vacuum  are recycled  back  to  the
process,  and  are not considered waste  waters.   The process
RWL calculated from the flow measurements  and  analyses  of
waste  water  samples  obtained  in the sampling period are
presented in the following tabulation;
               PROCESS FLOW

                  liters/kkg                     10,200
                  gal/M Ibs                       1,220

               BOD5 RWL

                  mg/literi                      38,100
                  kg/kkg*                           390

               COD RWL

                  mg/literi                     155,000
                  kg/kkgz                         1,580
                                172

-------
                                           FIGURE 4-36

                         PENTAERYTHRITOL —ALDEHYDE  CONDENSATION
                                              RECYCLE WATER
                                               WATER
                                               VAPOR
                                               VENT
        ACETALDEHHDE
        FORMALDEHYDE
        WATER
10
        CAUSTIC
REACTION
                                                                          1
DISTILLATION
                                 RECYCLE FORMALDEHYDE
PURIFICATION
                                                                                    PENTAERYTHRITOL
                                         WASTEWATER STREAM

-------
               TOC RWL
                  mg/literl                     81,200
                                                   830
iRaw waste  concentrations  are  based  on  unit  weight  of
pollutant per unit volume of process waste waters.
2Raw  waste  loadings  are based on unit weight of pollutant
per 1000 unit weights of product.

The above process RWL  data  were  used  as  the  basis  for
BPCTCA.   The waste water from this process is combined with
other wastes for treatment in an activated sludge plant.
                                174

-------
Product:  Saccharin

Process:  Synthesis from Phthalic Anhydride Derivatives

Process RWL Subcategory:  C

Saccharin  is  the  imide  of  the  mixed  anhydride  of  o-
carboxylbenzenesuifonic  acid.   It is a powerful sweetening
agent, having a sweetness from 550  to  750  times  stronger
than cane sugar.  Saccharin has no food value and is used as
a sugar substitute in many applications.

A  continuous  process for the manufacture of saccharin from
pnthalic anhydride derivatives is shown in Figure 4-37.

The phthalic anhydride derivatives along with water and a 50
percent sodium hydroxide  solution  enter  the  reactor.   A
metal  catalyst  is  used  during  the  reaction.  The fumes
leaving this reactor axe  scrubbed  with  water  and ,sodium
hydroxide.    The   resultant   waste   water   flows  to  a
neutralization tank, where caustic is added to raise the pH.

The  product  mixture  from  the  first  reactor   is   then
chlorinated  in  the second reactor, and the fumes from this
reaction include  chlorine,  hydrochloric  acid,  and  water
vapor.   These  fumes  are  also piped to the aforementioned
caustic scrubber.   A  portion  of  the  metal  catalyst  is
removed  from  the  second  reactor  for  regeneration.  The
catalyst is treated with sodium hydroxide and then filtered.
The filtrate goes to the neutralizer, while the catalyst  is
recycled to the first reactor.

The products from the second reactor are reacted with NH3 in
the  third reactor, while any unreacted ammonia is vented to
an absorber where the ammonia is  absorbed  with  water  and
returned  to  the third reactor.  An organic solvent is used
to extract the product saccharin from the reaction  mixture.
Tne  raffinate stream from the extraction operation is first
neutralized and then distilled to recover the solvent.   The
extracted  phase  is steam stripped to recover more solvent,
which is condensed and recycled back to the  third  reactor.
The aqueous solution leaving the stripper is precipitated by
the  addition  of  hydrochloric  acid.   The  precipitate is
further  concentrated  by  filtration,  crystallized   under
vacuum  conditions  and  then  dried  to produce the product
saccharin.   The  filtrate  is  neutralized  by  a   caustic
solution prior to its discharge to the sewer.

The  major  water  pollution  sources of the process are the
waste waters from the caustic scrubber, catalyst  filtration
                               175

-------
                                                                 FIGURE 4-37
                                  SACCHARIN- SYNTHESIS  FROM PHTHALIC ANHYDRIDE  DERIVATIVES
CHLORINE
AMMONIA
                                                                                                                          VENT
                                                                                                                          GASES
                                                                           HCL
PHTHALIC ANHYDRIDE
DERIVATIVES 	
CAUSTIC SOLUTION—
HATER-	
          CAUSTIC •
          SOLUTION
-


CK
UJ
r-j
=3
UJ
»-


1
•-» CATHYST
REGENERATION



1
t
CATALYST
FILTRATION



                                                     "EUTRALIZER
                                                                                                                                     RODUCT
                                                                                    KASTEWATER
                      »ASTE»ATER
                                                    KASTEKATER

-------
unit,  solvent  recovery still, product filtration unit, and
barometric condenser.  Process RWL's  calculated  from  flow
measurements  and  analyses  of  the waste water streams are
presented  in  the  following  tabulation.   The  analytical
results  also  indicate  that, in addition to the parameters
shown  in  the  tabulation,  pollution  parameters  such  as
nitrogen,  sulfate,  chloride,  and  metals may be at levels
which  can  be  potentially  hazardous  to  the   biological
treatment process.
              PROCESS FLOW
                  liter/kkg
                  gal/M Ib

               BOD5 RWL
                  mg/liter1
                  kg/kkg*

               COD RWL
                  mg/liter1
                  kg/kkg2

               TOC RWL
                  mg/liter1
                  kg/kkgz
269,000
 32,200
    940
    253
  3,270
    879
  1,430
    384
iRaw  waste  concentrations  are  based  on  unit  weight of
pollutant per unit volume of process waste waters.
2Raw waste loadings are based on unit  weight  of  pollutant
per 1,000 unit weights of product.
                             177

-------
Product;  o-Nitroaniline

Process:  Ammonolysis of o-Nitrochlorobenzene

Process RWL Subcategory:  D

Chemical Reaction:

                              H 0
   N00C,H, Cl  +  NH   (f>-xre>**\	?
     264      NH3  (excess)	>   N02C6VH2  +  NV

              Amm°nfa                a-NltroanMIne + ammonium
   o-nltrochlorobenzene                             chloride


Tiie  manufacture  of o-nitroaniline is similar to that of  p-
nitroaniline, which is described in  the  next  section.    A
typical process flow diagram is shown in Figure 4-38.

The   o-nitrochlorobenzene   and  ammonia  enter  the   batch
reactor, and o-nitroaniline is  formed.  The  excess  ammonia
in the reaction mixture is distilled off the absorbers,  from
which  ammonia is recycled back to the reactor.  The aqueous
stream  from  the  distillation  step  goes  to  a   washing
operation   and   proceeds   to   dehydration  and  refining
operations.  Both the dehydration and the refining  steps are
performed  under  vacuum  and   steam  jets  with  barometric
condfinsers  are  generally  used in pulling vacuum  for these
operations.  The refined o-nitroaniline may be used directly
or it may be further transformed into a flake.

The major water pollution sources of the process  are   waste
waters  withdrawn  from the scrubber in the ammonia-recovery
system, from the washing  step,  and  the  condensates  from
barometric  condensers.   Process RWL's calculated  from flow
measurements and analyses of the  waste  water  streams are
indicated  in  the  following   tabulation.   The  analytical
results also indicate that waste streams  may  contain  high
concentrations   of  nitrogen   and  chloride  which  may  be
potentially hazardous to biological treatment processes.
    PROCESS FLOW
       liter/kkg   269,000
       gal/M Ib     32,200

    BODS RWL
       mg/liter1        61
       kg/kkg*          16
                              178

-------
                                                 FIGURE 4-38
             ORTHO-NITROANILINE-AMMONOLYSIS  OF  ORTHONITROCHLOROBENZENE
                                   RECYCLED NH
VD
             AMMONIA
             0-NITRO
             CHLORUBENZENE
WASTEWATER
                                                                                    •0-NITROANILINE
                                                WASTEWATER
                                                            WASTEWATER

-------
COD RWL
   mg/literi       391
   kg/Jdcg2         105

TOG RWL
   mg/liter*       115
   kg/kJcg*          30.9

*Raw waste concentrations are based on  unit
 weight of pollutant per unit volume of
 process waste waters.
2Raw waste loadings are based on  unit weight
 of pollutant per  1000 unit weights of  products.
                            180

-------
Product:  p-Nitroaniline  (PNA)

Process:  Ammonolysis of  p-Nitrochlorobenzene

Process RWL Subcategorv:  D

Chemical Reactions:

                                H.o
   N02C6HifC1   +    NH3 (excess)	>  N02C6H4NH2   +   NH/fC1
                  Ammonia
                                                  ammonium
  p-nitroch1orobenzene               p-nitroani1ine    chloride


p-Nitroaniline is an important  intermediate   for dyes   and
pigments   and   also   for   the   preparation  of  numerous
antioxidants  and  antiozonants  of  the  N-substituted    p-
phenylenediamine type.

A  typical  process flow  diagram for  batchwise manufacturing
of p-nitroaniline is shown in Figure  4-39.

p-NitroaniJ.ine    is    manufactured    by     heating     p-
nitrochlorobenzene  with  aqueous   ammonia  at  175°C under
pressure.  A jacketed  autoclave,   provided  with efficient
stirrers,    is    used   as   the    reactor.     Molten    p-
nitrochlorobenzene is added to aqueous  ammonia (28  percent)
and  heated  gradually.   The temperature  is increased over a
period of 3 hours to 175°C at a pressure  of 530-580  psi,  and
these latter conditions   are  maintained  for   16 hours   to
complete the reaction.

Some  of  the  ammonia  gas  is then  vented to an absorption
system.  The excess ammonia in the  reaction mixture  is also
distilled  off  to absorbers, from  which  it is recycled back
to the reactor.  The  aqueous  reaction  mixture  is  passed
through  a  pressure filter and sent  to wooden crystallizing
tubs,  where  the  p-nitroaniline   separates   as  a    finely
divided,  canary  yellow  crystalline  mass.  After cooling to
30 °C, the solid product  (averaging  99  percent  purity)   is
removed  by  centrifuging.   The  centrate passes through an
elaborate  system  of  catch  boxes  to  cool   it to  room
temperature,  and  additional  product  settles out.   This is
recovered periodically by siphoning the water  from the catch
boxes.

The solid cake leaving the centrifuge is  then  passed through
drying and packaging steps.  Dust collectors   and scrubbers
                              181

-------
                                           FIGURE  4-39
      PARA-NITRO ANILINE-AMMONOLYSIS  OF  PARA -  NITROCHLOROBENZENE
00
           AMMONIA
           P-NITRO-
        CHLOROBENZENE
                                       SLUDGE  TO
                                       LANDFILL
                                                                 VENT AIR
                                                 WASTEWATER
i
                            WASTEWATER
5TALLIZATION
1
4STEWATER
L

-,
flORYING
| PACKAGI
I


FILTRATION « 	 ;
AND
NG


• WAI
^

ER
     WASTEWATER
                                                                      P-NITROANILINE

                                                 SETTLER
                                                   T
                                                WASTEWATER

-------
are  used in the drying steps to remove the dust in the vent
gases.

The major pollution sources of this process are waste waters
withdrawn  from  scrubbers,  filtration   units,   and   the
crystallization  unit.   Process  RWL's calculated from flow
measurements  and  analyses  of  the  waste  water   streams
obtained  in  the  survey  period are shown in the following
tabulation.  The analytical results also indicate  that,  in
addition   to   the  parameters  shown  in  the  tabulation,
pollution parameters such as nitrogen, chloride and  calcium
may   be  at  levels  potentially  hazardous  to  biological
treatment processes.

    PROCESS FLOW
       liter/kkg   33,100
       gal/M Ib     4,680

    BODS RWL
       mg/liter1       65
       kg/kkg*          2.55

    COD RWL
       mg/literi    2,030
       kg/kkg*         79.1

    TOC RWL
       mg/literi      570
       kg/kjcg2         22.2

    lRaw waste concentrations are based on unit
     weight of pollutant per unit volume of
     process waste waters.
    2Raw waste loading are based on unit weight of
     pollutant per 1000 unit weights of product.

These data are the basis for BPCTCA.

Continuous processes can also be employed for ammonolysis of
p-nitrochlorobenzene.  In such a process, preheated  aqueous
ammonia is forced through an inlet pipe to the bottom of the
vertical  reaction  cylinder,  then passes upward through an
annular space, and overflows through a central  outlet  pipe
leading  to  a  still,  where excess ammonia is stripped off
before the product is crystallized.   The  space  above  the
overflow  pipe provides a vapor space to absorb fluctuations
in the internal pressure.  The lower part of  the  cylinder,
where  the  major  part:  of the reaction occurs, is provided
with packing  and  is  constructed  of  stainless  steel  to
minimize  corrosion.   The  operating pressure is about 1200
psi.
                          183

-------
Product:  Pentachlorophenol

Process;  Chlorination of Phenol

Process RWL Subcategorv:  D

Chemical Reaction:
            C6H5OH + 5C12 -»  C6C15OH + 5HC1
Pentachlorophenol is widely used  as  a  wood  preservative,
especially  in such applications as residential construction
where creosote would be undesirable.  It is also used  as  a
fungicide in paint and adhesives, and in paper mills.

Although pentachlorophenol can be manufactured by continuous
processes,  it is generally produced by batch reaction as in
the facility visited during the survey period.  A simplified
process flow diagram for the production of pentachlorophenol
via the Chlorination of phenol is shown in Figure 4-40.

Phenol and  chlorine  are  fed  to  the  reactor  where  the
Chlorination reaction occurs.  The product of the first step
of   the  reaction  is  trichlorophenol,  which  is  further
chlorinated to form pentachlorophenol.

The product mixture leaving the second reactor is discharged
into a quench vessel, in which the gases are separated  from
the  molten  product  stream.   The gases proceed to the HCl
absorber and caustic scrubber, while the  liquid  stream  is
solidified in a flaker.  The solidified pentachlorophenol is
then passed into a rotary kiln for glazing.

The  major  water  pollution sources of this process are the
waste streams generated at the caustic scrubber, flaker, and
glazing  units.   Process   RWL's   calculated   from   flow
measurements  and  analyses  of  the samples obtained in the
survey period are shown in the following tabulation.

                       Sampling Period t1      Sampling Period 12

PROCESS FLOW
   iiter/kkg             2,960                     2,960
   gal/M Ib                354                       354

BODS RWL
   mg/literi               330                       306
                               184

-------
                                           FIGURE 4-40
                       PENTACHLOROPHENOL-  CHLORINATION OF PHENOL
        PHENOL
00
         CHLORINE
                       REACTOR
                                              RECYCLE CHLORINE
                                                        T
                                                     WASTEWATER

1


QUENCH
VESSEL
A



0=
LLJ
OO
oc.
cs
	 OO
C_D QD
3= «C



O=
LU
OO
OO
ce
03
CO
l+MURIATIC
ACID
AIR
t
R 	 >
FLAKER




1'^—
AIR
GLAZING
SYSTEM
                                                                                   CAUSTIC
                                                                                   SOLUTION
                                                                            WASTEWATER
                                                                                 PENTACHLOROPHENOL
 f
AIR

    WASTEWATER

-------
   kg/kkgz                   0.975                     0.906

COD itWL
   mg/literi             5,740                     6,020
   kg/kkg*                  17                        17.9

TOC RVL
   mg/liter*               768                       781
   kg/kkg*                   2.27                     2.31
     waste  concentrations  are  based  on  unit  weight  of
pollutant per unit volume of process waste waters.
2Raw  waste  loadings  are based on unit weight of pollutant
per one thousand unit weight of product.

The analytical results also indicate that parameters such as
chloride, phenol, and sulfate may be at  levels  potentially
hazardous to biological treatment processes.

The   demand   for   pentachlorophenol   in   the   U.S.  is
approximately 40  million  pounds  per  year,  of  which  15
million   pounds   are   used  in  mixtures  with  creosote.
Pentachlorophenol can also be made by caustic fusion of hex-
achlorobenzene, which is  currently  a  cheapter  route  but
gives a product contaminated with Nad.
                                  186

-------
Products;  Fatty Acids and Primary Derivatives

Process RWL Subcategory:  D

Fatty  acids  are  organic acids characterized by a straight
chain carbon structure  terminating  in  a  single  carboxyl
group.   The  carbon  structure  may  contain only saturated
carbon atoms or may contain one or more double bonds.

In general, the saturated acids having 12 to 18 carbon atoms
are of major commercial concern.  Their uses tend to reflect
their stability or lack of  easy  reactivity  at  any  point
along  the chain except at the carboxyl position.  Saturated
acids, including those saturated by hydrogenation,  comprise
about one-third of all fatty acids commercially produced.

Acids of reduced hydrogen content, having one or more double
bonds  between  carbon atoms along the chain, constitute the
other main  fatty  acid  family  of  significant  commercial
importance.   The  unsaturated acids of the ethylenic family
are made up of a number of separate series of the  following
compositions:
             CnH2n-202   (monoethenoic)
             CnH2n-402!   (diethenoic)
             CnH2n-60.2   (triethenoic)

The  chemical  reactivity  and  utility of unsaturated fatty
acids  in  various  polymeric  or  "drying"   reactions   is
determined  in  part by the number of double bonds along the
carbon chain.  These double bonds also  introduce  different
properties  arising  from the location along the chain, i.e.
conjugated  and  nonconjugated  fatty  acids.   A  different
structure  also results from a reversed positioning of those
parts of the molecule on either side  of  the  double  bond,
known as cis and trans isomerism.

To  avoid confusion of terms, it is necessary to distinguish
between fatty acids as defined by the  organic  chemist  and
fatty  acids  as  commercially  produced and sold.  The term
"stearic acid" is an example of this confusion.

Here the commercial product name has priority, going back to
the splitting of tallow for the manufacture of  hard,  high-
melting   candles,   before  individual  acids  of  definite
composition had been isolated or identified.

Historically, commercial stearic acid has been a crystalline
combination of the chemist's palmitic and stearic acids in a
                                187

-------
55 to 45fc ratio, respectively, with some small percentage of
unsaturated acids.   This  ratio  is  that  which  naturally
occurred  in  the  mixed acid derived from splitting tallow,
after most of the liquid acids were removed by the  original
pressing  method.  The liquid acids so removed were known as
oleic acid, or red oil.

Other commercial acids have been identified by origin -  for
instance,  coconut  fatty acid or cottonseed fatty acid - in
terms reflecting  the  characteristic  ratio  in  which  the
component  acids  exist when released from the glycerides of
these oils.  Fractionation to  separate  or  to  enrich  the
wanted  acids,  however,  has  made identification by origin
obsolete as a means of characterizing many of today's acids.
Blends and "cuts" are  offered  to  meet  particular  market
demands,  such  as  drying  characteristics  in paint films.
Composition expressed in terms of  component  acids  as  the
chemist  defines  them  is now finding its way more and more
into product descriptions and specifications.

TaUle 4-3 lists 15 of the most  important  commercial  fatty
acids,  along  with  their  composition in terms of specific
constituent acids.

In addition to the saturated and unsaturated acids,  primary
derivatives  based  upon  these acids modified by amination,
esterification, ozonation, and polymerization are considered
within the context of  this  study.   Also,  the  processing
associated  with the recovery and purification of by-product
glycerine is considered.  The relation between glycerine and
fatty acid production will become apparent during subsequent
discussion.  However, at this point it  is  noted  that  the
production  of  other  products  (such  as soaps) from fatty
acids  is  not  considered  within  the  context   of   this
subcategory.

Raw  materials  for  the production of fatty acids fall into
three groups:

     1.  Tall oil derived from Kraft papermaking.
     2.  Animal tallow and grease.
     3.  Vegetable oils and soap stocks.

As a raw material for fatty acid production, crude tall  oil
ranks first in volume.  Crude tall oil is a mixture of rosin
acids   and  free  fatty  acids  (in  addition  to  a  large
percentage of water and impurities) and is a  by-product  of
kraft   papermaking.    Most   of  the  crude  tall  oil  is
fractionated, and the separated rosin  acids  and  tall  oil
fatty   acids   are   sold   directly   to  consumers  after
                              188

-------
                                                     TABLE  4-3
                                                                                                        DRAFT
oo
ID
                   Some  Examples  of  Commercial  Fatty Acids  Showing Typical  Percentage  of  Constituent  Acids









Typical C-atoms
comme re i a 1 	
fatty acids Double bonds
Stearic acid (T.P. type)
Stearic acid (S.P. type)
Hi gh pa Imi t i c
Sol id fatty acid
(Hydrogenated tallow type)
Sol i d fatty acid
(Hydrogenated vegetable type)
Sol i d fatty acid
(Hydrogenated fish type)
Hi gh lauric aci d
(Di st i 1 led coconut)
Oleic acid (red oil)
(Disti 1 led)
Oleic acid
(Multiple distil led)
Animal fatty acid
(Disti 1 led)
Vegetable fatty acid
(Distilled cottonseed)
Vegetable fatty acid
(Di sti 1 led soybean
Vegetable fatty acid
(Fractionated soybean)
Ta 1 1 oil fatty ac id
Distilled linseed fatty acid
u

o o u o <->
.— — — .— t/i
0 — l- 1-
!_ >. Q_ D !_
O. Q_ 03 fD >-
ro ra o — i z
o o
68 10 12 lit
00 000

1

2

1

10

1 7 L>9 17

2

3

it

1







u

4-1
._
E

TO
Q-

16
0
50
51
75
35

29

35

9

7

5

25

2k

11



2
6
0
O -D O

~ !n 'c
ro u 
-------
purification.  The fatty acids derived  directly  from  tall
oil  can  be  used in the manufacture of primary derivatives
such as dimers, polyamides, nitriles,  primary  amines,  di-
fatty   tertiary   amines,   and  fatty  quatenary  ammonium
chloride.  The major constituents of tall oil fatty acid are
oleic acid and linolenic acid which contain  two  and  three
double  bonds  respectively  (see  Table 4-3).  It should be
noted that the production of tall oil  fatty  acid  involves
only  distillation  of  free  acids  and is simpler than the
processes used to manufacture fatty acids  from  animal  and
vegetable sources.

There  are  four  main types of animal fats:  edible tallow,
inedible tallow, lard and inedible grease.  Inedible  tallow
and  grease  are important raw materials as a primary source
of stearic and oleic acids.  These materials are supplied to
fatty acid manufacturers from  meat  packing  an4  rendering
plants.   It should be noted that fatty acid production is a
relatively small part of the tallow market, with i the  major
end use of tallow being in the production of soap.

Coconut  oil (obtained by crushing coconuts) is an important
vegetable raw  material  for  fatty  acid  and  fatty  ester
production,  because  of  its  high C8, C10, and C12content.
Although soybean and cottonseed oil are  produced  in  large
quantities,   they   are  not  often  used  for  fatty  acid
manufacture because  of  their  high  costs.   However,  by-
products  from the refining of these oils for other end uses
are used in the  manufacture  of  fatty  acids.   These  by-
products  are  called  "soap  stocks" or "foots" and vary in
composition, depending on the refining process by which they
are produced.

It should be noted that fatty acids are  present  in  animal
and vegetable sources as glycerides.  Tall oil, which is not
a  glyceride,  is  the only raw material which contains high
concentrations  of  free  fatty  acids.   The  three-pronged
glycerol  linkage,  typical  of all fats, must be severed in
the production of all fatty acids derived  from  animal  and
vegetable  sources.  The chemical reaction for this cleavage
involves the following hydrolysis:
             0
             II
            R-C-O-CH,
                 CH
      0
      II
    R,-C-0-

      0
      II
   R2-C-0-CH2

Fat (triglyceride)
                                CH9-OH
                                i ^
                                CH -- OH
                                CH2--OH
                              Glyceri ne
                                     R—COOH
4-  R^COOH

    R -COOH
    Fatty acids
                             190

-------
The products of the reaction are crude glycerine  and  fatty
acids.

Depending  upon  the nature of the feedstock and the desired
end-product  fatty  acids,  different  combinations  of  the
following  processing  steps  may  be  found in a fatty acid
plant:

    1.  Pretreatment for Purification of Feedstock
    2.  Saponification/Acidulation of Feed or Products
    3.  Hydrogenation of Feed or Product Acids
    4.  Hydrolysis of Feed (Fat Splitting)
    5.  Distillation of Product Acids
    6.  Distillation for Glycerine Recovery
    7.  Separation of Saturated and Unsaturated Acids

The following paragraphs  briefly  describe  each  of  these
processing   steps.   A  generalized  process  flow  diagram
showing their interrelation is presented in Figure 4-41.

    Pretreatment

Many  of  the  impurities  present  in  the  feedstock  will
decompose,  volatilize, or contaminate the product acids and
must  be  removed.   Water-soluble  salts  will  deposit  on
heating  surfaces.   Mineral acid will attack the fatty acid
upon heating and  attack  the  equipment  as  well.   Water-
washing  and drying of feedstock containing these impurities
are essential.

Feedstock containing gums, proteinaceous material,  calcium,
and  iron soaps should also be acid-washed.  Acid-washing is
generai-Ly performed in lead- or monel-lined tanks.  A common
method is to treat a charge of melted fat at about 60°C with
2 to 4% sulfuric acid in a fairly concentrated (30  to  50%)
solution, with good agitation for about 1 hr.  The charge is
then  heated  to  90°C with open steam.  After settling, the
acid water is drawn off, and the charge is washed with water
to remove the mineral acid.  Acid-washing breaks up  calcium
and  iron  soaps  that  act  as catalysts forming ketones or
remain as soap in  still  bottoms.   Sulfuric  acid  removes
proteins and other organic impurities.

Acid-washing also removes impurities that hinder hydrolysis.
Bleaching  with acid clays is effective in removing oxidized
acids  and   impurities   that   hinder   splitting   and/or
hydrogenation.

    Saponification/Acidulation
                            191

-------
                                             FIGURE  4-41

                     GENERALIZED PROCESS FLOW DIAGRAM  ILLUSTRATING THE

                   MANUFACTURE OF FATTY ACIDS FROM GLYCERIDE FEEDSTOCKS
B
to
   GLYCERIDE
   FEEDSTOCK
                SIGNIFICATION
ACIDULATION
                                    HYDROGENATION
                   HYDROLYSIS
                                                                                      PRODUCT
                                                                                      ACIDS
DISTILLATION
OF ACIDS
(SATURATED
PRODUCT
ACID
                                                                                          UNSATURATED
                                                                                          PRODUCT
                                                                                          ACID
                                                                    DISTILLATION
                                                                    OF GLYCERINE
                                              •GLYCERINE
                                               PRODUCT

-------
In  special  cases  where  feedstock is the by-product "soap
stock" or  "foots"  produced  in  the  caustic  refining  of
vegetable  oils,  the saponification of the feed followed by
acidulation is a convenient  means  of  manufacturing  fatty
acids.   It has an advantage in the handling of raw refinery
foots  because  very  little  additional  caustic  soda   is
required  to  complete  the saponification prior to the acid
treatment.  Completely  saponified  foots  upon  acidulation
yield  raw material satisfactory for distillation.  Although
more expensive than the other methods using water, it  gives
practically  100X  conversion  and  avoids  the  use of high
temperatures.  The splitting of fatty acids from  waxes  and
sperm   oil   is  done  by  complete  saponification,  using
anhydrous alkali, followed by steam distillation  to  remove
the high molecular weight alcohols.  Subsequent splitting of
the soap is performed with sulfuric acid.

    Hydroqenation

Hydrogenation is the process of adding hydrogen to materials
that  are  deficient  in  hydrogen,  e.g.  oleic acid, which
requires one molecule of hydrogen to form the C18  saturated
acid.   Either  the  glyceride  or  the  fatty  acid  can be
hydrogenated.  The process is essentially the same, with the
exception that the acid must be processed  in  a  corrosion-
resistant apparatus, usually stainless steel.

Refined  oils,  fats and fatty acids that have been properly
distilled are hydrogenated with little  difficulty.   Impure
materials  or  mixtures of fatty acids and neutral oil, such
as acidulated foots, are hydrogenated only after  they  have
been specially treated, and then usually with difficulty.

Hydrogen  addition  to the unsaturated groups occurs only by
means  of   a   catalyst.    Reduced   nickel,   the   usual
hydrogenation  catalyst,  is  made by reducing nickel salts,
i.e., formate, carbonate, or the aluminum nickel alloy.

Hydrogenation  is  done  in  both   batch   and   continuous
processes.   The  batch  process,  which is older and not as
generally used today, uses a vessel that is equipped with  a
top-entering  agitator and a system for heating and cooling.
It is built to operate at pressures of from 25  to  250  psi
(in  some  instances  up to 500 psi and higher).  The nickel
catalyst is added to the pre-dried charge in amounts varying
from about 0.05 to 0.5S4.  The vessel is purged several times
with hydrogen and then brought up  to  reaction  temperature
with   steam.    Once   reaction   starts,  however,  it  is
exothermic, and cooling is required to  prevent  overheating
of   the   catalyst  and  stock.   The  exothermic  heat  is
                                193

-------
significant with the absorption of  1  Ib-mole  of  hydrogen
releasing about 40,000 Btu, and requires substantial cooling
surface  as  well as good agitation.  Good agitation is also
required to keep replenishing  the  reaction  with  hydrogen
gas.   Eeactors in use today vary in size from those holding
a few pounds to large ones holding 50,000 Ibs.

Continuous methods for the hydrogenation of all  classes  of
chemicals have been developed in recent years, especially in
connection  with petrochemicals and for petroleum processing
in general.  The fat and fatty  acid  industries  have  been
much  slower  in  developing  and  using continuous methods,
owing perhaps to the wide variety of products produced,  the
relatively  smaller  volumes, and the need for modifying the
product by partial and selective hydrogen addition.

    Hydrolysis

Hydrolysis or splitting is the process of reacting  the  fat
with  water  to  form glycerine and fatty acid.  A series of
three hydrolysis steps is required to obtain free  acid  and
free  glycerine.   It  is  believed  that  the reactions are
homogeneous taking place mainly in the  fat  phase,  as  the
solubility of water in fat is greater than the solubility of
fat in water.

It  is  necessary  only  to mix fat with water to cause some
hydrolysis, but the reaction is very  slow.   However,  when
sulfuric  acid  is  added  to  fat,  the sulfonated products
formed  increase  the  solubility  of  water  in  fat,   and
hydrolysis  takes  place  at  a  faster rate.  Solubility is
further increased by the use of an alkaline catalyst,  i.e.,
zinc oxide, magnesium hydroxide, or calcium oxide.

A  major  development  in  hydrolysis techniques was made by
Twitchell, who developed the sulfonic acid catalyst  bearing
his  name.   Since  the solubility of water in fat increases
very rapidly at high temperature, high-pressure  autoclaves,
both of the batch and continuous type, have been developed.

Commercial   fat   splitting   is  carried  out  by  several
processes, each of which has advantages  and  disadvantages.
The selection depends upon the type of raw material, size of
the  operation,  and  the  number  of different kinds of raw
materials handled.

    A.  Twitchell Process

    The Twitchell process, developed in 1890, is still  used
    to  some extent in the United States.  It is carried out
                            194

-------
in a lead- or monel-lined tank at atmospheric  pressure.
The  charge  consists  of  fat  mixed with about 50 wt.X
water, 1% sulfonic  acid  catalyst,  and  0.5JI  sulfuric
acid.  The mixture is then boiled with open steam for 16
to  24  hrs,  allowed  to settle, and the sweet water is
drawn off and replaced with fresh water.  The boiling is
continued until a split of about 95%  is  reached.   The
overall split depends upon the glycerol concentration of
the sweet water.

By countercurrent use of water, it is possible to obtain
high  splits  and  high  concentrations  of sweet water,
usually 10 to 15X.   The  advantages  of  the  Twitchell
operation  are  its  relatively simple equipment and the
use of low temperatures.  Low-temperature  operation  is
highly   desirable   for   splitting  stocks  containing
multiple unsaturation.  Disadvantages are the length  of
time  required, high steam consumption, and poisoning of
the catalyst, which necessitate the pretreatment of most
stocks, especially the lower grade variety.

B.  Batch Autoclave

Batch autoclaving  is * a  very  old  method,  which,  as
originally developed, used a closed cylindrical pressure
vessel  with  agitation provided by open-steam injection
to a continuous vent.  Typical  temperatures  are  about
185°C,  equal  to  about  150  psi.  About 2% lime, zinc
oxide, and so forth are used.  The amount  of  water  is
about  50  wt.% of the fat.  The degree of split reaches
an equilibrium at about 90*.  To obtain a higher  split,
the glycerine water must be replaced with fresh water.

This  catalytic  autoclave  process  is suitable for all
types of fats and has the advantage over  the  Twitchell
process  of a shorter reaction period and the production
of lighter colored fatty acid because of the absence  of
air.   A  more recent development in autoclave splitting
is the use of higher temperatures and  higher  pressures
requiring  no catalyst.  This process is usually carried
out using mechanical  agitation,  with  the  temperature
held  at  about  238°C  under  a  pressure  of  450 psi.
Splitting is rapid, and there is no catalyst to  remove.
Its  disadvantage  is  the effect of high temperature on
stocks having a high degree of unsaturation.

C.  Continuous Countercurrent Splitting

Over the past 30 years, several companies have  designed
and  built  successful continuous hydrolyzers which have
                          195

-------
    replaced the older methods.   Fat enters near the base of
    the hydrolyzer and passes upward through the column  and
    exits through a pipe near the top.   Steam from the high-
    pressure  steam  boiler,   at 750 psi,  is injected at two
    locations, the top addition  into  a  water-distributing
    tray  and the lower addition through a sparger pipe near
    the fat-water interface.

    The fat rises slowly through the column in a  continuous
    phase  while  the water drips through it, constantly re-
    placing the glycerine-laden water that is in solution in
    the fat.  At the bottom  of  the  tower,  the  glycerine
    water collects and is removed continuously to maintain a
    constant interface level near the base of the tower.

    The  fatty  acid  leaves  the top of the tower through a
    pressure control valve set to maintain  about  720  psi,
    sufficiently  high  to  prevent vaporization of water at
    the required operating temperature, usually about 250 to
    260°C.

    The fat must be under pressure for about 2 hrs to  reach
    a  split  of  56 to 99%.   The reaction time required may
    vary, depending upon the type of  fat  and  quantity  of
    water  used.  It is usual practice to remove sweet water
    with a concentration between 12 to 20% glycerine.

    Continuous splitting has the advantage of yielding  high
    splits  and  more  concentrated glycerine solutions than
    any other process.  It has a  high  capacity  and  short
    reaction  time.   It  requires  less  room, less process
    inventory, and less labor.  It does,  however,  restrict
    flexibility  in changing stocks.  The high temperatures,
    as mentioned above, have the advantage  of  speeding  up
    tne   hydrolysis   reaction;  however,  it  has  a  real
    disadvantage when handling highly unsaturated fat,  such
    as fish oil, because these oils tend to polymerize.

    Recovery and Purification of Glycerine

The  dilute   (10-20 wt.X) glycerine solution ("sweet water")
may  be  concentrated  by  taking  water  overhead   in   an
evaporator or distillation column.  In most operations, non-
contact  steam  is  used  to  drive  off  the  water  to  an
approximate 8OX  glycerine  concentration.   The  noncontact
steam  may  be condensed and used in the hydrolysis reactor.
The separated water vapor and some  glycerine  are  normally
condensed   in   a   barometric  condenser  and  discharged.
Additional treatment steps  for  purification  of  glycerine
                            196

-------
water  may  include  filtration, ion exchange, and activated
carbon adsorption.

    Distillation

Distillation as a means of purifying fatty acids has been in
use for the better part of a century.  It is  an  economical
and  successful method of producing high-purity fatty acids.
It is beset with many problems because fatty acids have high
boiling  points  and  decompose  when   held   at   elevated
temperatures.   The  early  distillers  soon discovered that
processing temperatures must be held at about 250°C  maximum
to limit decomposition.  At higher temperatures, fatty acids
first  lose  water,  forming  anhydrides,  and  later, under
continued heating, break down into ketones and hydrocarbons.
Unsaturated fatty acids polymerize, forming dimers, trimers,
and so forth.

The early stills were operated at atmospheric  pressure  and
large quantities of injected steam were used to maintain the
temperature at 250°C.  As better equipment became available,
the  stills were operated at lower and lower pressures until
today most fatty acid stills operate at pressures of between
5 and 50 mm Hg abs.  At  low  pressures,  fatty  acids  will
distill  without injected steam, but it is usually desirable
to use some injected steam because even a small amount  will
aid  in preventing the formation of anhydrides.  When stills
are operated at pressures lower than the vapor  pressure  of
the  available  cooling  water, it is necessary to provide a
steam compressor in addition to the ordinary  air  pumps  to
maintain desired operating pressures.

Fatty  acid stills now in general use may be classified into
three general types:   1)  those  for  semicontinuous  batch
operation;  2) those for continuous simple distillation; and
3) those for continuous fractional distillation.  If only  a
decolorizing   step  is  necessary   (one  that  removes  the
unhydrolyzed oil, polymers, and high-boiling color  bodies),
a simple distillation will produce satisfactory results.  If
considerable    amounts   of   color   bodies   (low-boiling
unsaponifiable  matter  and  compounds  that   cause   color
reversion)   are   present,   some   means  of  fractionally
concentrating these  "low  boilers",  either  by  fractional
distillation  or  fractional  condensation, is required.  If
the  component  acids  must  be  separated,   an   efficient
fractionating still is necessary.
                            197

-------
    Separation Processes

Separation  of tallow fatty acids into solid (saturated) and
liquid  (unsaturated)  components cannot  be  accomplished  by
the fractionation methods previously described because major
components  have  the same chain length and an insignificant
difference  in  molecular  weight.   Two  major   separation
processes  have  achieved  commercial  significance  in  the
separation of solid saturated acids from liquid  unsaturated
acids,  namely,  the panning and pressing method and solvent
crystallization.

Tne panning and pressing process at one time accounted for a
major portion of the total production of stearic  and  oleic
acids.   The  idea of pressing liquid fatty acids from solid
fatty acids probably occurred from observing the  production
of  lard  oil.   In fact, equipment used for the pressing of
grease  to  yield  lard  oil  was  initially  used  for  the
separation  of  fatty  acids.   This  method is used for the
separation of  animal  fatty  acids  to  produce  commercial
stearic  and  oleic acids.  Simply, this method involves the
crystallization of solid  or  saturated  fatty  acids  in  a
solvent of liquid or unsaturated fatty acids.  Consequently,
the  solid (saturated)  fatty acids must exhibit a reasonably
good crystal formation so  that  the  liquid  acids  may  be
easily and efficiently expressed.

In  the  production  of commercial stearic acid, the optimum
crystal structure is attained when the  saturated  acids  of
the  fatty  acid  mixture have a composition of 55% palmitic
acid and 45% stearic acid.  Limited variation in this  ratio
may  be  tolerated  in actual practice, but the variation in
normal  animal  fats  is  sufficient  so  that  blending  is
necessary  to  secure a proper crystalline structure.  Fatty
acid mixtures of a noncrystalline structure may be partially
separated by the pressing method.

In the panning and  pressing  operation,  properly  prepared
melted  fatty  acids  are cascaded into rectangular aluminum
trays, which are stacked in  racks  in  cold-storage  rooms.
Cooling  takes  place very slowly to assure the formation of
large and  well-defined  crystals.   Cooling  by  mechanical
refrigeration to a final temperature of 180°C is attained in
a  cold-storage  room  in  about 6 to 8 hrs.  The solidified
cakes of fatty acids are removed from the trays, wrapped  in
burlap  or  cotton cloths, and stacked in vertical hydraulic
presses.  Metal sheet separators are  placed  between  every
two  layers  of  wrapped  cakes  to  serve as stabilizers to
conduct the expressed oleic acid to a trough at the edge  of
the  press.  Pressure is very slowly applied to the stack of
                            198

-------
cakes  until  a  maximum  of  approximately  3,000  psi   is
attained.   The  expressed oleic acid amounts to about 50 to
6034  of  the  original  fatty  acids.   Depending  upon  the
temperature  of the cakes of fatty acid during pressing, the
titer of the oleic acid will range from 6 to 10°C.

The pressed cake, now referred to as "cold pressed cake", is
melted, again cascaded into racks of aluminum  trays  in  an
open room, and allowed to solidify at room temperature.  The
solidified  cake  is  placed  in  hair  mat slings suspended
between steam-heated hollow metal plates in a horizontal ram
press.  Application of pressure and heat removes most of the
oleic acid along with a small portion of  the  solid  acids,
resulting  in  a  mixture of fatty acids known as "hot press
oil".  The pressed cake from this "hot  pressing  operation"
is  called "double-pressed" stearic acid.  It contains about
5 to 834 oleic acid and has a titer of  approximately  54  to
55°C.   In  much  the  same  manner "triple-pressed" acid is
produced with the additional production of  hot  press  oil.
Triple-pressed stearic acid contains from 1 to 3% oleic acid
and  has a titer of approximately 55 to 56°C.  The hot press
oil has a composition of  saturated  and  unsaturated  acids
similar  to  the  feedstock  and is therefore mixed with the
incoming fatty acid feed.  As a result,  about  40X  of  the
fatty acids in this process is being recycled.

The  panning and pressing method is gradually being replaced
by  the  newer  solvent  methods,  as   has   countercurrent
extraction by immiscible solvents.

Solvent   processes  utilizing  a  liquid-liquid  extraction
method have been proposed, but the solubility of mixed fatty
acids in solvents  results  in  an  inefficient  separation.
This has limited the commercial use of these methods.

Separation  methods  involving  the  crystallization of one-
componer^t fatty acids from a solvent solution of  a  mixture
of  fatty  acids eliminate, to a large extent, the effect of
mutual solubility.  Solvent crystallization methods  may  be
applied  to  the  separation  of  most  fatty acid mixtures,
provided the component acids can be selectively removed in a
solid state, from a solvent solution of the mixture.

Of  the  many  solvent  crystallization  separation  methods
proposed,  the  Emersol  Process  is most commonly employed.
This process  involves  the  controlled  crystallization  of
fatty  acids from a polar solvent to achieve a separation of
solid fatty acids from liquid fatty  acids.    Separation  of
saturated   acids   or   of   triglycerides   may   also  be
accomplished.   One  of  the  best  illustrations   of   the
                            199

-------
application  of  this process is in the separation of animal
fatty acids to yield commercial stearic acid and oleic acid.

Animal fatty acids are dissolved in 90% methanol to yield  a
25 to 30% concentration.  The methanol solution of the fatty
acids  is pumped continuously to a multitubular crystallizer
fitted with agitator scraper  blades  and  cooled  to  about
-15°C.   Cooling 4-s accomplished by circulating refrigerated
methanol through the  jackets  of  the  crystallizer  tubes.
During  chilling  the solid fatty acids crystallize from the
solvent solution to form a slurry that is fed  to  a  rotary
vacuum  filter.   The solid acids filter to form a cake that
is continuously washed with  fresh  90%  methanol  and  then
discharged from the filter.  This filter cake containing ap-
proximately  40  to  6058  methanol is melted and pumped to a
solvent recovery still in which the solvent is removed  from
the fatty acids and returned to the system.  The solid acids
are  discharged  from  the  still  ready  for  finishing and
packaging operations into commercial stearic acid.

The filtrate containing the liquid acids is passed through a
heat exchanger to a solvent recovery still.  The  discharged
liquid  acids  from  the  still  are ready for finishing and
packaging into commercial oleic acid.   Reported  capacities
of  the  Emersol  units range from 2000 to 5000 Ibs of fatty
acids per hour.   At  present,  there  are  seven  units  in
operation  in the United States, Great Britain, Holland, and
Australia.

Certain  other  separation   methods,   although   not   yet
commercial,   have  interesting  possibilities.   A  solvent
crystallization process for separating  tallow  fatty  acids
using  hexane as a solvent has been employed.  Much has been
published on the separation of fatty acid mixtures by use of
urea or thiourea complexes.  Urea  or  thiourea  adducts  or
complexes  of fatty acids have varying degrees of stability,
depending on the carbon chain length  and  configuration  of
the  molecule.   This  difference in adduct stability is the
basis for obtaining a separation of the fatty acids.

    Recovery of Fatty Acids from Tall Oil

When nonglyceride feedstocks such as tall oil  are  used,  a
different  process  from  that  shown in Figure 4-41 must be
used.

In the production of tall  oil  fatty  acids  and  rosin  by
fractional  distillation, crude tall oil is passed through a
vaporizer into a fractionating  column  where  the  volatile
rosin  and fatty acids are separated from higher-boiling and
                            200

-------
nonvolatile impurities, which are drawn off as  pitch.   The
vapor  enters the fractionation column and is separated into
three fractions:  1) rosin that is taken off at  the  bottom
of the column, 2) a fatty acid containing from 1 to 5% rosin
near  the  top  of  the  column,  and  3)  a  heads fraction
overhead, containing a high percentage of low-boiling  fatty
acids  (mainly palmitic), unsaponifiables, and color bodies.
The fatty acid fraction is then passed into a  third  column
where  it is further stripped of rosin, unsaponifiables, and
color and odor bodies  to  yield  a  product  with  a  rosin
content of 0.3 to 2.031 and unsaponifiables content of 0.3 to
1.5*.  The fraction containing 25 to 35X rosin, taken off at
the  bottom  of  this  column,  is  either  sold  as such or
refractionated.  By taking fatty acids  off  at  the  second
column  or  at various points on the third column, the rosin
content of the fatty acids can be varied.

The fractionation of tall oil presents a number of problems.
Both rhe fatty acids and the rosin have low vapor  pressures
and  are  subject  to decomposition on heating.  Either very
high vacuum or vacuum with the addition of superheated steam
is needed to keep the  temperature  low  enough  to  prevent
damage  to  the  products.   Overheating  must  be prevented
during vaporization by  creating  high  flow  velocities  in
heaters   and  vaporizers,  and  entrainment  must  also  be
prevented.   The  equipment  is,   therefore,   specifically
designed  for  the  purpose.  Various types of fractionating
trays, grid trays, sieve trays,  and  bubble-cap  trays  are
used;  all of them have certain advantages and disadvantages
and unless they are carefully chosen and  designed  for  the
purpose, will fail to produce the desired results.

Different   operating   schemes  are  used  by  the  various
producers, employing single and multiple  tower  system.   A
two-tower   system   can   produce   excellent   results  by
refractionating the fatty acids.  This raises the  operating
cost but the investment cost for the plant is lower.

For  the  purposes  of  this study, the previously described
unit operations and chemical conversions are defined  to  be
the  basic  steps  necessary  to produce fatty acids.  Field
sampling was used to establish raw waste  loads  for  plants
encompassing  these  steps.   Because  of the batch or semi-
continuous nature of the operations, it was not possible  to
break  out  the  total  RWL  according  to  individual  step
sources.  Rather,  combined  waste  streams  from  the  acid
production  areas  were sampled in most cases.  A total of 6
plants were  sampled.   Table  4-4  indicates  the  specific
operations  relating  to  acid  and  derivatives production.
Table 4-5 summarizes the RWL data related to acid production
                              201

-------
                                                               TABLE 4-4

       CHEMICAL CONVERSIONS AND UNIT OPERATIONS CONTRIBUTING TO PROCESS  RAW WASTE  LOADS  FOR THE  MANUFACTURE  OF  FATTY ACIDS AND

                                                 PRIMARY DERIVATIVES (BASED ON PLANTS  SURVEYED)

Plant 1
Acid Production
1 .

2.

3.

4.

5.

>
)
1 .

2.

3.
'

Acid Washing

High Pressure
Fat Spl i tting
Glycerine Recovery
and Purification
Solvent Separation
of Fatty Acids
Hydrogenat ion of
Fatty Acids
Derivatives

Dimerizat ion £•.
Trimerizat ion
Ozonat i on

Esterif ication
Amrn i na t i o n


Plant 2
Acid Production
1 . Pretreat. by Fi It.
and Acid Wash
2. Hydrogenat ion
of Tal low
3. Hydrolysis by
Twi tchel I Proc.
k. Glycerine Recovery

5. Distil lation of
Fatty Acids
6. Separation of
Acids by Pressing







Plant 3
Acid Production
1 .

2.

3.

k.

5.
6.

(b)




1.
2.
Saponi f ication

Acidulation

Hydrogenat ion

Fat Spl itting

Glycerine
Recovery (b)
Disti 1 lation

Wastewater from
Glycerine Re-
covery Sampled
Separately.
Derivatives
Esterif ication (c)
Ammi nation (c)
Plant k
Acid Production
1 . Pretreat. by Fi It.

2. Hydrogenat ion

3. Fat Splitting

4. Glycerine
Recovery
5. Distillation
Derivatives

1 . Esteri f ication



Plant 5 (d)
Acid Production
1 .

2.

3.

4.


1 .

2.
(d)

Hydrogenat ion

Fat Splitting

Glyceri de
Recovery
Distil lat ion

Deri vat i ves
Esteri f ication

Ammi nation
Production Units
for Acids &
Plant 6 (e)
Acid Production
1. Distillation from
Tall Oi 1

Derivatives
1 . Dimerizat ion &
Trimerizat ion
2. Ammi nation

(e) Only production units
for derivatives
were sampled.




Derivatives could






not be sampled
separate! y.





Wastewater included with
 acid product.
(c)   Esters & Ammi ne
      Sampled Separately

-------
for 5 plants, and presents an arithmetic average  for  these
operations.   It  is  noted  that  the RWL data presented in
Table  4-5  are  based  on  samples  taken   after   gravity
separation  of  fatty  acids  from  the  waste water.  It is
common practice to recycle the skimmed material back to  the
acid pretreatment section of the plant for recovery.

Table  4-6  summarizes  the  raw waste loads calculated from
production of primary derivatives.  The data shown relate to
groups  of  processes  in  operation  during  the   sampling
program.    Primary   derivative  products  include  esters,
amines, nitriles, dimers and trimers, polyamides, and  fatty
quaternary  ammonium  chloride.   An  average  RWL value for
these processing operations is provided in Table 4-6.

The average values shown in Tables 4-5 and 4-6 are the basis
for BPCTCA,
                              203

-------
                             TABLE 4-5
          PROCESS RWL ASSOCIATED WITH MANUFACTURE OF FATTY ACIDS
          (ALL RWL BASED ON SAMPLES TAKEN AFTER GRAVITY SKIMMING
          FREE FATTY ACIDS FROM WASTEWATER)
                         Flow         BOD        COD        TOG
                      (lit./kkg)   (kg/kkg)    (kg/kkg)    (kg/kkg)

Plant 1 (1 day)       10,300 (a)     12.7        44.3       4.89
        (1 day)       10,300 (a)     18.5        52.5      10.3
Plant 2 (1 day)       63,900         12.8        23.6       4.41
Plant 3 (1 day)        3,700 (b)     11.7        37.3      10.6
        (1 day)       45,500 (c)     14.6        41.6      14.3
Plant 4 (1 day)       65,900          5.8        21.5       1.2
Plant 5 (1 day)       12,100 (d)     15.6        42.4      13.6
        (1 day)       12,100 (d)     37.5        53.2      18.9
Average               28,000         16.1        39.6        9.8
(a)  RWL includes wastewater from dimerization
(b)  RWL does not include wastewater from glycerine recovery
(c)  RWL based only on glycerine recovery (i.e., based  on  glycerine)
(d)  RWL includes small contribution from derivatives
                                   204

-------
                            TABLE  4-6
     PROCESS RWL ASSOCIATED WITH MANUFACTURE OF PRIMARY DERIVATIVES
     FROM FATTY ACIDS (NOTE RWL BASED ON SAMPLES TAKEN AFTER GRAVITY
     SKIMMING FREE OIL INDICATED BY ASTERISK)
Plant 1* (1 day)

         (1 day)

Plant 3
    Esters (1 day)

    Amines (1 day)

Plant 4* (1 day)

Plant 6* (1 day)
                        Flow           BOD         COD          TOC
                    (lit./kkg)       (kg/kkg)    (kg/kkg)    kg/kkg)
Average                6,400           18.0        27.9         8.47
  (Exclude Plant 3)
4,590
4,590
127.0001
18.8002
8,920
5,700
16.5
17.0
26,500
495
28.6
9.82
32.6
41.3
54,700
1,070
14.7
23.0
9.75
14.7
13,600
245
5.7
3.73
 Sample taken prior to methanol recovery
2
 Sample from blowdown on recirculating system
                                 205

-------
Product;  Jonone and Methylionone

Process;  Condensation and Cyclization of Citral

Process RWL Subcategory:  D

Chemical Reactions;

         Citral + Acetone	NaOH >  pseudo-lonone

         pseudo-lonone  H2S04   >e<- lonone + (3-lonone
lonones and methylionones are used in perfumery and flavors;
the beta ionone isomer is an intermediate in the manufacture
of vitamin A.
                              /

The production of ionones  and  methylionones  involves  two
steps.    First,   the  pseudo-ionone  is  prepared  by  the
condensation of citral obtained from  lemongrass  oil.   The
condensation  reaction  uses  either acetone or methyl ethyl
ketone  to  produce  pseudo-ionone  or  pseudo-methylionone.
Then   these   pseudo-ionones  are  cyclized  with  an  acid
catalyst.  Commercial ionones are generally mixtures of  the
alpha and beta isomer, with one form predominating, although
separations are sometimes made through bisulfite compounds.

A    typical    process    flow    diagram   for   producing
ionone/methylionone  is  shown  in  Figure  4-42.    Citral,
acetone/methyl  ethyl  ketone, sodium hydroxide, and organic
solvent are put into the first batch reactor.   The  solvent
from  tnis reaction step is recycled, and the product vapors
are condensed and stored in a receiver.  The  crude  product
from  the receiver is then distilled to remove the heavy-end
residues  and  washed  with  caustic  solution   to   obtain
pseudo-ionone (or pseudo-methylionone).

These  materials  are  fed  into  the  second reactor, where
cyclization is accomplished via  a  carbonium  ion  reaction
with  H3P04,  H2SO4;,  or  BF3  as  catalyst.   The  reaction
products proceed through a series of  washing  tanks,  where
the products are quenched with sulfuric acid and then washed
by water, caustic solution,, and acid solution.

After  the  washing steps, the product mixture is discharged
into a series of distillation  columns,  where  the  organic
solvent  and  heavy  end residue are recovered and withdrawn
from the main product stream.  The product vapor leaving the
                              206

-------
LQZ









STIL






J

rn
CD


CD -
•z «

m c
rn
—i









L






^"
f

«"



13
!O
3
•o
H













C
C
a
c
n
a
&
n
=i

J





















o
3
3
n
=
o
r|
3



















•••••





















i


















CD
CD m
TO
-. 1 .

CO — 1 ^
— * m co
=03* CD
* m
ac
rri
CO 1

rn
as rn

m c=


3» CO %
CO C= *•
— r— co
cs -n —i
cz m
=o *^—
CO -H
m
m * 1
CO CO
«"* m m
* — i —i
i" m CD
to =0 33

£ r^r-
m sc co »•
-H 3C
s *—


RECOVERY
ST LL
J I
-z.
j m

—I i m
I | !H
co i— H
^ m ^^
CD 3C 1"
EH o
m CD ^
rn x_J
J •* z

m i
O

o ""
3m O
z c
^. m
- * z! ^
ss i Ok
*-~!5 Z K>

Z
o

2 1 -
c= rn few I
^ — t m ^.
— co" a -H
CD —
i O
^ <^B
CD
_» *• ^s1
CD -o -n
CO

1 1 ?
_ 3D C/J -<

-------
last distillation column is condensed and sent to a  liquid-
liquid separator for removal of water.

Trie  major water pollution sources of this process are waste
waters from the various  washing  steps  arid  from  periodic
reactor  washings.  During the sampling visit, pseudo-ionone
was being produced; hence the waste water  samples  obtained
at the facility reflect ionone production RWL.  However, the
RWL  of methyl-ionone is believed to be of the same order of
magnitude as that of ionone.  Process RWL's calculated  from
flow  measurements  and  the  analyses  of  the  waste water
streams are indicated in the following tabulation:

         PROCESS FLOW

            liter /Jckg   9,370
            gal/M Ib    1,120

         BODS RWL

            mg/literi        2,600
                                24
         COD RWL
            mg/liter1       10,000
            kg/kkg2             98
         TOC RWL
            mg/liter *        3,600
                                34
         »Raw waste concentrations are based on unit weight of
          pollutant per unit volume of process waste
          waters.

         2Raw waste loadings are based on unit weight of pol-
          lutant per 1,000 unit weights of product.

The analytical results also indicate that,  in  addition  to
the parameters shown in the tabulation, pollution parameters
such  as  pH,  sulfate,  oil,  and chloride may be at levels
potentially hazardous to biological treatment processes.

These data, shown above, were used to determine BPCTCA.  The
wastes  from  this  plant  are  discharged  to  a  municipal
treatment plant.
                                  208

-------
Product;  Methyl Salicylate

Process:  Esterification of  Salicylic Acid with Methanol

Process RWL Subcategory:   D

Chemical Reactions:

Methyl  salicylate, the methyl  ester of  salicylic acid, also
known as  "oil  of  wintergreen"   is  used  as  a  flavoring
compound  in mouthwash and certain food  products.  A diagram
of process is shown in Figure 4-43.
            COOH   +  CH3OH       _*       Cg

   salicylic acid methanol                 methyl salicylate
Raw waste loads for the  production of methyl salicylate  are
indicated in the following  tabulation:

         PROCESS FLOW

            liter/kkg    1,735

         BODS RWL

            kg/kkg       22.0

         COD RWL

            kg/kkg       93.9

         TOG RWL

            Jcg/kkg       37.9
                                209

-------
                          FIGURE  4-43
METHYL SALICYLATE	ESTERIFICATION OF SALICYLIC ACID
     SALICYLIC ACID
     METHANON
ESTERFICATION
  SYSTEM
                                                 METHYL
                                                 SALICYLATE
                           210

-------
Products:  Miscellaneous Batch Chemicals
           Intermediates
           Dyes
           Rubber Chemicals
Process:  Numerous Batch Processes  (Batch Chemicals Complex)

Process RWL Subcategory:  D

The  RWL  data  presented  and  discussed  in  the following
paragraphs were obtained by sampling the total effluent from
a large chemical plant.  This plant  manufactures  thousands
of   chemicals   within  the  five  general  classifications
indicated above.  In this case, it was impossible to  sample
each of the process operations on an individual basis.

Daily  24-hour composite samples were taken over a period of
9 days, followed by three 5-day composite samples  over  the
next   15  days.   The measured flows and concentrations were
put on a production basis by means of  a  weekly  production
activity  report supplied by the manufacturer.  The RWL data
obtained in this manner are summarized in Table 4-7.

The RWL data shown in Table  4-7  represent  the  total  raw
waste  from the plant.  Examination of the data based on the
nine  consecutive  24-hour   composite   samples   indicates
significant variation.  For example, the calculated mean for
BOD  is  20.4  kg/kkg of product with high and low values of
27.4 and 11.9 during the nine-day period.

It is significant to note that  the  three  5-day  composite
samples  show  approximately  the same range of variability.
The calculated average BOD raw  waste  load  for  the  three
periods is 24.1 kg/kkg, with high and low values of 35.8 and
14.1  respectively.   BPCTCA  raw  waste loads for the batch
chemicals  complex  was  based  upon  the  5  day  composite
samples.

This type of variation may be caused principally by the fact
that  in  this  type  of  chemical  plant it is difficult to
relate production data to the exact  sampling  periods,  and
consequently,  calculated  ratios will always have this type
of error present.

Production at a batch chemical complex involves the  startup
and  shutdown  of  thousands  of  discrete  batch processing
operations  on  a  day-today  basis.   Although  the   plant
maintains  a  materials  inventory,  this is usually updated
only on a monthly  basis.   In  this  particular  case,  the
manufacturers expended considerable effort to provide weekly
production   figures  based  on  changes  in  the  materials
inventory.
                            211

-------
                         Table 4-7

            RWL Data for Batch Chemical  Complex
Sample Period              Flow         BOD        COD       TOC
                           L/kkg     (kg/kkg)    (kg/kkg)    (kg/kkg)

2k hr. composite
 n        n
Average

5-day composite
 n        M
 M        n
Average
65,300
74,800
90,100
89,300
71,300
113,000
68,800
70,400
78,700
80,100
70,600
65,500
100,000
78,700
19.6
16.5
27.0
27.4
23.8
27.4
11.9
13.0
16.9
2CK4"
22.4
14.1
35.8
24.1
63.5
68.4
90.1
96.4
83.9
99.4
55,3
60.4
77.0
77.2
80.9
76.6
144.
100.5
17.0
19.5
23.4
29.9
22.1
29.2
M. 9
23.9
23.6
22.9
27.1
27.1
40.1
3K4
                               212

-------
Products:  Citronellol and Geraniol

Process:  Distillation of Citronella Oil

Process RWL Subcategory:  D

Chemical Structure;


             (CH3)2  C  = CH-(CH2)2-CH-CH2CH2OH


            citronellol

                >2~C =  CH(CH2)2-C  = CHCH,OH
                                     I   *
                                     CH
            Geraniol

Citronellol and Geraniol are used as odorants in  perfumery.
Natural   geraniol   is  produced  by  the  distillation   of
citronella   oil.    Citronellol   is   made   by     limited
hydrogenation  of  geraniol.   Figure 4-44  is a process flow
diagram of geraniol and Citronellol production.   Citronella
oil,  the  raw  material,  is  vacuum  distilled to  separate
Citronellol.   The  remaining  citronella   oil   components
undergo  a  three-stage potassium hydroxide washing  prior  to
vacuum steam distillation followed by  vacuum  distillation.
In  this  step,  geraniol and Citronellol are recovered; the
geraniol fraction  is washed with a caustic  solution  and then
water.   The  geraniol  terpene  fraction   then   undergoes
boration and washing prior to being rerun through the vacuum
distillation step.

As  shown  in  Figure  4-44, the major wastestreams  from the
process are vacuum jet  condensates  and  waste  water  from
product washes.  The following tabulation summarizes the RWL
calculated for the process:

               Flow
               liters/kkg          10,000
               gal/1000 Ib          1,199

               BODS
               mg/1                 5,810
               kg/kkg               58.1

               COD
               mg/1                11,100
                              213

-------
  DISTILLATION

  COLUMN
       O ^
     * m z MM

     ipr
   DISTILLATION

   COLUMN
r
   DISTILLATION

   COLUMN
  •HI
  •I — 1  C3 CT3
  :\^  m —
        =o 	
        sr
        r=i
FU"
m 	1
                o
                —«
                70

                O
                z
                z
                o


                O
                m
                71
                > -n

                ? 5
                   o

                   5
                   o
                   z
                   o
                   ^

                   D
                   O
                   z

-------
               kg/kkg                 111

               TOC
               mg/1                 3,770
               kg/kkg               37.7

The foregoing values used to define BPCTCA.
                                215

-------
Product;  Plasticizers

Process:  Condensation of Phthalic Anhydride

Process RWL Subcategory:  D

Plasticizers   are  organic  chemicals  that  are  added  to
synthetic resins to improve workability during  fabrication,
to  modify  the  natural  properties of these resins, and to
develop new improved properties not present in the  original
resins.   This  type  of chemical is manufactured by liquid-
phase batch reactions.

A generalized process flow diagram is shown in Figure  U-45,
while tne overall chemical reaction is given below:
                       2ROH
     phthalic anhydride     alcohol            phthalate
Feed  materials,  an alcohol and an anhydride, along with an
acid catalyst, are fed into a reactor.   The  esterification
is  carried  out  at  a  pressure  of  about  10 psig and at
temperatures ranging from 35 - 180°C, for six to  20  hours,
depending  on the feed and the desired product.  The reactor
effluent is either sent directly to a wash  tank  or  passed
through  a  filter  press  to  remove  solids,  depending on
whether activated charcoal or  a  catalyst  neutralizer  has
been added to the reactor.

Caustic  soda   (or  soda  ash)  is  used in the wash tank to
remove unreacted acid and anhydride.  Waste water  from  the
washing  is  sent to a series of settling tanks before being
discharged to the sewer.  Oil removed in the settling  tanks
is recycled back to the reactor.

The  plasticizer  stream  from  the  wash  tank  flows  to a
stripper, where any remaining alcohol is taken overhead  and
recycled  to  the  batch  reactor.  The main stream from the
stripper is further polished by an activated  carbon  filter
to obtain 99.5* percent purity plasticizer.
RWL  data obtained from a plant survey are summarized in the
following tabulation.  Since the plant surveyed is  designed
                            216

-------
                                              FIGURE  4-45

                      PLASTICIZERS—CONDENSATION OF  PHTHALIC ANHYDRIDE
                    RECYCLE ALCOHOL
       ALCOHOL
     ANHYDRIDE
N)
                      I
                                   WASTEWATER
FILTER
            I
NEUTRAL-
IZATION
ACTIVATED
CARBON
                                                               SETTLING
                                                               TANK
                                                                              -*WASTEWATER
PRODUCT

-------
strictly  for  manufacturing  of  one  plasticizer   (diethyl
phtiialate) , it requires less frequent reactor clean-up.

               PROCESS FLOW

                     liter/kkg           653
                     gal/M Ibs            78.3

               BODS RWL
                     rag/liter*        82,600
                     kg/kkg2              53.9

               COD   RWL
                     mg/literi       127,000
                     kg/kkg2              82.6

               TOG   RWL
                     mg/literi        51,200
                     kg/kkgz              33.4

               iRaw waste concentration are based on unit
                weight of pollutant per unit volume of
                process waste waters.
               2Raw waste loadings are based on unit weight
                of pollutant per 1000 unit weights of product.

These data were used as the basis for BPCTCA.
                             218

-------
Product:  Dyes and Dye Intermediates

Process:  Batch Chemical Reactions

Process RWL Subcategory:  D

Dyes may be defined as intensely colored  substances  which,
when  applied to a substrate, impart color to this substrate
by a process  which,  at  least  temporarily,  destroys  any
crystal  structure  of the colored substances.  The dyes are
retained in  the  substrate  by  adsorption,  solution,  and
mechanical  retention,  or  by  ionic  or  covalent chemical
bonds.  Pigments, on the other hand, are usually applied  in
vehicles  (although  the  substrates themselves may serve as
vehicles,  e.g.,  in  the  mass  coloration   of   polymeric
materials),  and  retain,  to  some degree, their crystal or
particulate structure.

The color of a dye is due to electronic transitions  between
molecular orbitals of the molecule, the probability of these
transitions  determining  the  intensity  of the color.  The
energy differences between the  orbitals  determine  whether
the  "color"  falls  in  the  visible  range of the electro-
magnetic spectrum and, if it does, the precise shade or hue.
Only   organic   molecules   of   considerable   complexity,
containing   extensive   conjugated  systems  and  polar  or
semipolar substituents, are useful as dyes.

Much of the complexity of present-day dye technology  arises
from  the  great  diversity of materials to be dyed, such as
foods, drugs, cosmetics, waxes, greases, solvents, plastics,
rubber,  photographic  film,  leather,  fur,   paper,   and,
primarily, textiles.  In the textile field, the introduction
of  synthetic  fibers,  such  as  cellulose  acetate, nylon,
polyester,    acrylics,    cellulose     triacetate,     and
polypropylene,  as  well  as the more stringent fastness re-
quirements  and  the  continuous-dyeing   techniques,   have
presented  the  dye manufacturer and user with new problems.
Tnese problems cannot be separated from  one  another.   For
example,  the  new  polyester fibers are sometimes dyed by a
continuous heat-treatment process requiring new dyes with  a
new  fastness  property,  sublimation fastness and a special
physical form.   Dispersed  dyes,  for  instance,  are  more
hydropnobic   than   those  used  previously  for  cellulose
acetate.  They must  also  be  nonvolatile  (i.e.  must  not
sublime  off  the  fiber during the heat treatment)  and must
have a physical form, either powder or  paste,  which  gives
rapid and stable dispersions in the dye bath.
                               219

-------
Dye  intermediates  are  derived  from  a  wide  variety  of
aromatic organic compounds, such  as  benzene,  naphthalene,
anthracene/     higher     polycyclic    derivatives,    and
heterocyclics.  The United States  Tariff  commission  lists
some 230 compounds under the heading "cyclic intermediates",
of  which  more than 210 are used in the dye industry.  Many
of the  large-volume  intermediates  have  a  principal  use
outside  the dye industry.  For example, about 60 percent of
the aniline produced is used in  the  rubber  industry,  and
practically   the   entire  phenol  and  phthalic  anhydride
production   is   consumed   by   the   plastics   industry.
Originally,  however,  all  three  of  these  materials were
exclusively dye intermediates.

The dyes themselves are usually much more  complicated  than
the  intermediates  from  which they are derived.  Some dyes
are mixtures, while  others   (such  as  aniline  and  sulfur
colors) are still unknown structures.  Therefore, systematic
chemical names are rarely used.  Almost all dyes also have a
multiplicity  of  trade  names  in  addition to their common
names.  Despite the diversity  of  trade  names,  a  certain
amount  of  rationality  can be found in these names.  Thus,
most may be considered to be divided into three parts, as in
the example of Cibacete/Brilliant Blue/BG.  The  first  part
usually  gives  the  particular dyeing class, and, from this
trade name, we learn that the dye is a disperse dye intended
for application on acetate.   Cibanone  would  be  the  same
manufacture's  designation  for  a vat dye of high fastness.
The second part of the name is obviously the color, and  the
third part (BG in this case) refers to the shade.  Often the
letters  subdivide  the  numerous  reds, oranges, blues, and
greens into bluish (B), greenish  (G), yellowish   (Y)   (or  G
for the German "gelb"), and reddish  (R) shades.  A number in
front of these letters indicates their depth, as in the name
"Crystal  Violet  6B".  Other letters show other properties.
Thus, K stands for cold dyeing (the German  "kalt"),  L  for
lightfastness, M for new, CF for copper free  (as in the case
of  goods to be vulcanized), A for acetate left unstained, W
for washfastness, and S for sublimation fastness.   Strength
and  physical  form are designated at times by such terms as
Cone,  (concentrated),  Dbl.  Pst.   (double-strength  paste),
Pdr.  (powder) , etc.

Dyes  have  been  classified  by  a wide variety of schemes.
Classes based on usage and application  are  useful  to  the
dyer  and  also  to the dye manufacturer who must supply the
demands.   However, this type of classification  results  in
groups  containing a great diversity of chemical structures.
Table 4-8 is  arranged according to  a  usage  classification
and  indicates  briefly  the  major  substrates,  method  of
                              220

-------
                                                                               Table  4-8
 Azoi c dyes and com-
 ponents (1ngrai n)
 Di sparse
• Mordant
                                  Major jubstrate^
                                2
                           Wool,   silk, nylon,  and
                           polyacryIi c
Cotton  '  (also silk, wool, and
fur) and blacks on acetate and
polyester
                           Cotton  '  leather, paper, wool,
                           silk, polyacrylics, and other
                           synthet ics
                           Cotton,  '  paper, and nylon
                           CelIulose acetate, tr iacetate ,
                           nyIon, polyacry1ic, and poly-
                           ester
Cotton,  '  wool, silk, and
nylon
     2
Wool,  silk, ny Ion, and
anod i zed a 1 urn i num
                                          Usage  Classification  of  Dyes

                                        Method ol App 1 i cat i on

                                    Applied  usually  from neutral
                                    to aci d  dyebaths
Fiber impregnated with
coupling component and
treated with solution of
stablIized diazonium salt

Dyed on tannin mordanted cotton,
directly on other materials
Applied from neutral  or
slightly alkaline baths
contai ni ng add!tiona 1
electrolyte

F i na aqueous di spers ions often
applied by high  temperature
"pressure" or  lower temperature
"carrier" dyeings.  On cloth
padded dye may be baked on or
"thermof ixed"

Fixation on the  fiber  under
alkaline conditions

Applied in conjunction with
chelatlng salts  of Al, Cr,
and Fe
                                        Major Chemical  Types

                                    Azo , i ncluding premeta11i zed
                                    dyes, anthraquinone,  triphenyl-
                                    methane, azine, xanthene,  nitro,
                                    and nitroso

                                    Azo
                                                                        Tr iaryImethane,  azo,  azi ne,
                                                                        xanthene,  th i azi ne,  poly-
                                                                        methi ne,  oxazi ne,  and
                                                                        acr i d i ne

                                                                        Disazo, trisazo,  and  polyazo as
                                                                        well  as a small  number of
                                                                        phthalocyanine,  stiIbene,
                                                                        oxazi ne,  and thi azole

                                                                        S imple azo, anthraqu i none,
                                                                        and ni troarylami ne
                                    Azo , anthraqu i none ,  phthalo-
                                    cyan i ne , and sti Ibene

                                    Anthrqu i none , azo , oxazine ,
                                    tri pheny Imethane , ni troso ,
                                    and xanthene
                                                                                   Remarks

                                                                        The very important premetal1ized
                                                                        dyes are members of this class
                                                                                                                                       "Cat i on ic Dyes"
                                                                                                                                       Second most important class of dyes
                                                                        New fast-growing field of dyes im-
                                                                        portant for synthet ic f i bers
                                                                                                                                       New class first introduced in 1956;
                                                                                                                                       bonds chemically to the fiber
 Sol vent
                           Organic solvents; examples
                           are i nks, gasoli ne, 1axquers,
                           wood sta i n, cosmet ics, plastics,
                           and wax

                           Cotton
                                    Dissolution in the appro-
                                    priate solvent or med i urn
                                                               Dissolved in water (with
                                                               the addition of sodium
                                                               sulfide for the insoluble
                                                               types); exhausted with
                                                               Glauber's salts
                                    Azo, tri pheny Imethane ,
                                    anthraqu i nones , and copper
                                    phthalocyanine derivatives
                                                                                                   Sulfur dyes
                                                               By vatting (dye solubtlized
                                                               by reduction with sodium
                                                               hydrosulfite), exhaustion on
                                                               the f i ber and reoxi dat ion
                                                                        Anthraqui none , polycyc 1 ic
                                                                        qu inones, and i ndi go
 Opt ical Br ighteners
All F i bers ,  soaps, deter-
gents , oils, paints, and
plastics
From aqueous solution or di s-
persion or by incorporation in
the mass
                                    StiIbene, dibenzothio-
                                    phenes, azoles, coumar i n,
                                    and pyrazi ne
 ~For Food, Drug, and Cosmet ic dyes see Colors for foods, drugs, and cosmet ics.
 -Indicates major use*
 ^Includes all other cellulosic  fibers and  viscose.
  See Brighteners, optical.

-------
application, and representative chemical  types.    A  second
type  of classification based on chemical structure has also
been used in the industry.  Table 4-9 is arranged  according
to  chemical  classification, giving typical examples of the
characteristic structural units and  the  application  dying
classes  which fall in each chemical group.  Tables 4-10 and
4-11 show U.S. production and sales of  dyes  by  usage  and
chemical classification.

The  primary  source  of  organic  raw materials for the dye
industry has traditionally been products recovered from  the
fractional distillation of coal tar.  Hence, the name "coal-
tar  dyes"  is  frequently used in place of the more correct
"synthetic  dyes".   Coal  tar  is  a  by-product   of   the
gasification  (or carbonization)  of coal, the primary purpose
of which is the production of coke for steel manufacture and
the  gas  for industrial and domestic heating.  The coal tar
is refined by distillation.  From over  300  products  which
have  been isolated and characterized the most important for
the dye industry are benzene, toluene, xylene,  naphthalene,
anthracene,   acenaphthene,   pyrene,  pyridine,   carbazole,
phenol,  and  cresols.   The  petroleum  industry   is   now
supplying  an  increasing  proportion  of  the  primary  raw
materials,  notably  benzene,  toluene,  xylene,   and   more
recently, naphthalene.

In  addition to the organic materials above, a great variety
of inorganic chemicals are used in the dye industry.   These
include sulfuric acid and oleum for sulfonation,  nitric acid
for   nitration,  chlorine  and  bromine  for  halogenation,
caustic soda potash for fusion and neutralization and sodium
nitrate for diazotization,  as  well  as  hydrochloric  acid
sodium  carbonate,  sodium  sulfate,  sodium sulfite, sodium
sulfide, aluminum  chloride,  sodium  dichromate,  manganese
dioxide, iron powder, and many others.

The  great number of intermediates used to manufacture dyes,
and  the  comparatively  small   tonnages   involved,   make
manufacture    by    continuous    processes   uneconomical.
Anthraquinone, produced from  anthracene  by  catalytic  air
oxidation,  is one of. the very few intermediates used solely
by the dye industry that is made by  a  continuous  process.
Other  large-volume  intermediates   (e.g., aniline, phthalic
anhydride, and phenol) are also manufactured  by  continuous
process but, as mentioned previously, the bulk of production
is used in other industries.

The   batch   processes  for  the  production  of  dyes  and
intermediates are carried out in reaction kettles made  from
cast  iron,  stainless  steel,  or  steel,  often lined with
                              222

-------
                                          Table 4-9

                              Chemical Classification or Dyes
       Class
N itroso

Nitro
Azo
   monoazo
   di sazo
   trisazo
   polyzao
Azoic
StiIbene
D i phenyI methane
   (ketone  imi ne)

Tr i ary tmethane
Xanthene

Acrid!ne
 ji noli ne
Methine and
   Polymeth ine

Thi azole
 Indamine and
   i ndophenol

Az ine
Su1 fur
Aminoketone and
   hydroxyketone

Anthraqu inone
Indigo id


Phthalocyani ne




Oxidation bases
   Dyeing Classes

Ac id, disperse, mordant

Ac id, disperse, mordant

Acid, d i rect, mordant,
d i sperse, bas i c , react i ve
                            Azoic
                            Di rect, react ive
Basic, acid, mordant


Bas ic ac id , mordant

Basic (suIfur)
                            Ac id , bas ic, di rect,
                            di sperse
                            D i rect, basic, reactive
                            (sulfur)
                            Ac id, bas i c, oxi dat i on
                            (sulfur)
                            Bas i c, mordant d i rect
                            (sulfur)

                            Basic, mordant vat
                            (sulfur)

                            Sulfur, vat
                            Aci d ,  mordant, vat,
                            di spersed, bas ic,
                            di rect, reactive

                            Vat, acid
Aci d, direct,  azoic ,  vat,
sulfur, basic  reactive
                            Incompletely characterized
                            oxidation products from
                            ami nes ,  d i ami nes,  and
                            ami nophenols
                                                              Dyed as a metal chelate
A large and varied class
produced almost without
exception by the coupling
of a diazotized aromatic
amine to a phenol, amine,
pyrazolone, or other cou-
pling component

Insoluble dye formed di-
rectly on fiber from sol-
uble components by di-
azotization and coupling

Class also includes mix-
tures of indeterminate
constitution made for
example by condensation
of nitro stiIbene compounds
and aromatic amines
Brilliantly colored dyes of
only moderate  1 ightfastness

Pure, bri ght hues

Basic dyes used chiefly on
leather; also  for ant i -
septIcs

Used for cotton, paper, and
more recently  in disperse
dye i ng

Important i n photography
                                   Intermediates for photo-
                                  graphic and sulfur dyes

                                  The first comrnerci ally im-
                                  portant synthetic dye;
                                  Perkin's Mauve belongs
                                  to thi s class
Obtained by heating a vari-
ety of organic compounds
with sulfur or polysulfides
to give disulfide or sulf-
oxide bridges

The natural dye logwood is
included in this class

Condensed polycyclic quin-
onoid dyes of great im-
portance

Derivatives of indigo and
th i oi nd i go

Only blue or green dyes and
pigments  (of high light-
fastness) are found in this
cl ass
                                  Ani 1 ine Black
                                  of this class
                                                                             s a member
                                          223

-------
                          Table  4-10

                     U.  S. Production of Dyes
                 by  Classes  of Application,  1965
                                                        Sales


Class of Application
Total
Acid
Azoic dyes and components:
Azoic compositions
Azoic diazo components, bases
(fast color bases)
Azoic diazo components, salts
(fast color salts)
Azoic coupling components
(naphthol AS and derivatives)
Basic
Di rect
Disperse
Fiber-reactive
Fluorescent brightening agents
Food, drug, and cosmetic colors
Mordant
Solvent
Sulfur
Vat
All Other

Production
in 1,000 Ibs.
207.193
20,395

2,100

1,558

2,835

3,172
10,573
36,080
15,514
1,586
19,420
2,923
4,745
9,837
18,648
57,511
296

0_uantity
in 1 ,000 Ibs.
189,965
18,666

2,043

1,310

2,646

2,429
9,553
33,663
13,522
1,558
18,284
2,736
4,246
8,930
17,471
52,439
469

Value
in $l,000's
292,284
39,025

3,968

2,057

2,683

4,669
23,907
50,970
32,878
6,744
34,516
10,238
5,706
15,351
9,960
48,728
884
Unit
Value
$/lb.
1.54
2.09

1.94

1.57

1.01

1.92
2.50
1.51
2.43
4.33
1.89
3.74
1.34
1.72
0.57
0.93
1.88
Source:    Synthetic  Organic  Chemicals,  U.  S. Tariff Commission

                              224

-------
                              Table 4-11

                  U. S. Production and Sales of Dyes
                    by Chemical Classification 1964
                                                    Sales
                       Production       Quantity         Value
Chemical Class        jn 1,000 Ibs.   in 1,000 Ibs.    in $1,OOP's

Total                    184,387         178,273        264,023     1.48
  Anthraquinone           4l,661          40,675         66,889     1.64
  Azo, total              57,897          57,367         96,579     1.68
  Azojc                    8,787           7,399         12,l4g     1.64
  Cyanine                    373             362          1,113     3.07
  Indigoid                 5,729           6,144          3,302     0.54
  Ketone Imine               731             782          1,614     2.06
  Methine                  1,074             974          3,367     3.46
  Nitro                      720             679          1,258     1.85
  Oxazine                    172             144            601     4.17
  Phthalocyanine           1,987           1,868          4,800     2.57
  Quinoline                  637             519          1,658     3.19
  Stilbene                18,488          17,640         29,166     1.65
  Sulfur                  17,776          17,268          9,798     0.57
  Thiazole                   462             480          1,043     2.17
  Triarylmethane           5,607           5,312         12,682     2.39
  Xanthene                 1,312             737          3,473     4.71
All Other                 20,974          19,923         14,531     0.73
         Source:  Synthetic Organic Chemicals, U. S. Tariff Commission
                  in 1965 total dye production increased 12.5% to
                  207 million Ib.
                                  225

-------
rubber, glass  (enamel), brick,carbon  blocks,  or  stainless
steel.   These  kettles  have capacities ranging from 500 to
10,000 gallons and are equipped with  mechanical  agitators,
thermometers, condensers, etc., depending upon the nature of
the  operation.   Products are transferred from one piece of
equipment to another by gravity flow, pumping, or by blowing
with air or inert  gas.   Plate  and  frame  filter-presses,
boxes,  and centrifuges are used for the separation of solid
products from liquids.  Where  possible,  the  intermediates
are   used   for   the   subsequent   manufacture  of  other
intermediates or  dyes  without  drying.   Where  drying  is
required,  air  or  vacuum  ovens  (in  which the product is
spread  on  trays)  and  rotary  dryers  are   used.    Less
frequently  used are drum dryers (flakers)  and spray dryers,
although the latter are becoming increasingly important.

Most of the material handling is  manual,  and  labor  costs
represent  a  significant  part  of  the  final  dye  price.
Automatic  process   control,   based   on   feedback   from
temperature,  redox potential, and pH measurement is finding
increasing use in the industry.

The actual manufacture of intermediates and dyes proceeds by
a series of chemical reaction steps.   The  major  steps  and
associated  chemical reactions typical of each are listed as
follows:

    Step 1 -  Addition of Functional Groups to JRaw Materials

         The attachment of one or more  chemical  groups  to
         the  aromatic  hydrocarbon  raw  material.  Typical
         reactions    include    sulfonation,     nitration,
         halogenation,   and   oxidation.    Normally,   the
         starting raw material  (such  as  benzene,  toluene
         anthracene,  etc.)   is  reacted  in the presence of
         aqueous sulfuric or nitric acid.

    Step 2 -  Replacement of Functional Groups on
              Intermediates Produced in Step 1

         The replacement of the functional groups introduced
         in Step 1 by  other  groups  of  higher  reactivity
         which  cannot be introduced directly.  The starting
         materials for this step  may  be  the  intermediate
         produced  in Step 1 or intermediates purchased from
         another manufacturer.  Typical  reactions  include:
         caustic  fusion,  to  replace a sulfonic acid group
         with a hydroxyl group; replacement  of  a  sulfonic
         acid  group  by  an  amino  group  by reaction with
                                226

-------
         ammonia;  and  replacement  of  halogen  atoms   by
         hydroxyl or amino groups.

    Step 3 -  further Modification of Functional Groups
              On Intermediates from Step 2

         This step  involves  the  further  modification  or
         development  of  functional  groups  on  the inter-
         mediates produced in Step 2  (or  purchased  inter-
         mediates) .   There can be few generalizations about
         these reactions, as each particular case depends on
         the specified end product  required.   Examples  of
         these  reactions  include  alkylation of functional
         groups by reactions of  the  intermediate  with  an
         alcohol,  acylation  with organic acid chlorides or
         anhydrides, and other rearrangements.

    Step 4 -  Combination of Two or More Intermediates to
              Form a Dye

         In this step, two or more  intermediates  are  com-
         bined  to  form a product having a skeletal, if not
         complete, dye structure.  Typical reactions include
         diazotization and coupling,  condensation  and  di-
         merization.   It should be noted that many of these
         products may themselves also  be  intermediates  in
         the synthesis of dyes of greater complexity.

When  defining the production of dyes and intermediates at a
specific  plant,   it   must   be   understood   that   some
manufacturers  purchase  the  intermediates  associated with
Steps 1, 2, and 3, so that Step 4 may be the  only  chemical
reaction  processing done at the plant.   Other manufacturers
carry out Steps 1, 2, 3, and 4 in the  synthesis  of  a  dye
product.   Although the final quantities of dye product sold
at each plant might  be  the  same,  the  actual  production
activity   (as measured by intermediates production)  would be
drastically different.

It should also  be  noted  that  production  schedules  vary
drastically in dye plants.

Both   the   types  and  specific  quantities  of  dyes  and
intermediates which are manufactured change  on  a  week-to-
week basis.

Because  of  the  nature of the batch operations, it was not
possible to isolate dye products according  to  chemical  or
usage classification for the development of production-based
raw  waste load data.  Instead, the entire plant was sampled
                               227

-------
for periods up to one month.  Waste water flows and analyses
were developed on a 24-hour composite basis.  Production for
the corresponding period was defined to include all dyes and
intermediates which were separated within the  establishment
during  the  sampling  period.   A  commodity was considered
separated when it was isolated  from  the  reaction  mixture
and/or when it was weighed, analyzed, or otherwise measured.

It  should  be noted that in some cases, it was not possible
to differentiate between production as 100  percent   active
ingredients  and  as  standardized material.  The difference
between these two relates to quantity of inert diluent which
is added to some dyes prior to shipment to  the  user.   The
raw   waste  load  data  presented  subsequently  are  based
primarily  on   standardized   material.    The   ratio   of
standardized  material to 100 percent active ingredients can
be as high as 10 to 1.  This means that  if  the  raw  waste
loads were based on 100 percent active ingredients, the data
reported  should  be increased by a factor of ten  (depending
on the specific plant.)

The following tabulation summarizes the raw waste load  data
obtained  from six plants sampled during both phases of this
study.

               Process RWL for Dyes and Intermediates

  Plant               Flow          BODS     _COD      TOC
                   (lit./kxg)    (kg/kkg)    (kg/kkg)   (kg/kkg)

1.(10X occurrence)                  5           50       40
   (50* occurrence)   795,000       79        1,850      790
   (90* occurrence)                156        3,700    1,580

2. (10% occurrence)                 17          104       25.0
   (50% occurrence)   205,060       62          212       57.0
   (90* occurrence)                106          318       89.5

3.(10X occurrence)                278        1,060      350
   (50* occurrence) 1.840,000      602        1,595      502
   (90* occurrence)                930        2,155      656

4.(sampled 3 days)    32,800       -           195      205
                      32,800        1.18        19.5      5.24
                      32,800       -           189       49.2


           Process RWL for Dyes and Intermediates
                         (continued)
                              228

-------
(lit./kkg)
114,000
114,000
175.000
(kg/kkg)
220
126
59
(kg/kkg) (kg/kkg)
1,075 450
652 269
175 60
     Plant        	Flow	BQDfL	COD	TQC_


5. (sampled 2 days)


6. (sampled 1 day)

Mean based on 50%
Plants 1, 2, 3      395,000         248        1,219    449

Only Plants 1, 2, and 3 were used to compute  the  mean  RWL
shown,  as they were sampled for  1  month (30 days.)   In such
case, the 50Dt occurrence value was used.
                               229

-------
Product:  Toner and Lake Pigments

Process RWL Subcategory;  D

Pigments are various organic and inorganic  water  insoluble
substances.   They are used in surface coatings, and also in
the ink,  plastic,  rubber,  ceramic,  paper,  and  linoleum
industries  to impart color.  A large number of pigments are
produced because different  products  require  a  particular
choice  of  material  to  give  maximum  coverage,  economy,
opacity, color, durability, and desired reflectance.

Organic pigments may be subclassified into toners and lakes.
Toners are insoluble organic dyes that may be used  directly
as  pigments because of their durability and coloring power.
Toners are used in paints, printing  inks,  and  wallpapers,
and especially for the pigment printing method for textiles,
which  employs  pigments  of metal phthalocyanines and other
types.  Lakes  result  from  the  precipitation  of  organic
colors,  usually  of synthetic origin, with salts of Ca, Ba,
Cr,  Al,  or  phosphomolybdic  acid.    The   dye   molecule
frequently  contains  -OH or -SO3H groups.  Such lakes, when
ground in oil or other media, form the pigments of  many  of
our  paints  and  inks.   Some  basic  dyes are used for the
tinting   of   paper   in   a   water-dispersed   form    or
phosphomolybdic   (or  tungstic)   acid lakes.  Wallpapers are
frequently colored with lakes from basic dyes  containing  a
sulfonic  acid  group.   The  use  of pigments in the "dope"
before spinning rayon,  acetate,  and  synthetic  fibers  is
growing   rapidly  and  is  producing  excellent  colors  of
outstanding all-around fastness.

One facility visited during the field survey produced toners
for the pigment printing of  textiles.   Figure  4-46  is  a
process  flow  diagram  for the manufacture of this product.
Hydrochloric acid, sodium  nitrite,  water,  an  amine,  and
sulfamic  acid  are put into the first reactor.  The coupler
is  prepared  in  the  second  reactor.   This  entails  the
addition  of  a coupling agent,  sodium hydroxide, water, and
steam.   The  reaction  products  from  both  reactors  then
proceed  to  a  third  reactor,  where they are combined with
acetic acid, sodium acetate, and water.  The  pigment  which
forms  in  this  reactor  is  filtered.   The solid phase is
recovered as the pigment dye, while  the  mother  liquor  is
presently discharged into the sewer.

Samples were obtained on two successive days to characterize
the  wastewater  from this process.  The samples for the two
days indicate that the characteristics of  the  waste  water
are  quite variable, attributable mainly to the batch nature
                             230

-------
                                                FIGURE  4-46
                             PIGMENT DIAZOTIZATION  AND COUPLING
to
OJ
I-1
AMINE
HYDROCHLORIC ACID
SODIUM NITRITE
WATER  	
             SULFAMIC ACID
  REACTOR
          COUPLER
          SODIUM HYDROXIDE
          WATER  	
          STEAM
REACTOR
ACETIC ACID
SODIUM ACETATE
WATER
1
                                                        REACTOR
                                                                   PIGMENT
                                                       WASTEWATER

-------
of the operation.  The second plant produced lakes  for  use
in paints.

The  following  tabulation  of  process RWL, calculated from
flow measurements  and  the  analyses  of  the  waste  water
stream, includes data obtained for both plants.

                 Plant 1 (Toners)       Plant 2  (Lakes)
    PROCESS FLOW
       liter/kkg
       gal/M Ib

    BOD5RWL
       mg/literi
       kg/kkg*

    COD RWL
       mg/liter»
       kg/kkg2

    TOC RWL
       mg/literi
       kg/kkg*

    1Raw waste concentrations are based on unit weight of
     pollutant per unit volume of process waste waters.
    2Raw waste loadings are based on unit weight of pollutant
     per 1,000 unit weight of product.

The average RWL from Plant 1 was considered as BPCTCA for toners
while the RWL from Plant 2 was considered as BPCTCA for lakes.
1st Day
313,000
37,500
3,000
940
11,300
3,520
750
235
313,000
37,500
640
200
1,000
315
570
178
2nd Day
1,000,000
1,470
4,930
819
                              232

-------
Product:  Citric Acid

Process:  Fermentation of Molasses

Process RWL Subcategory:  D

Reactions:
            V.2'6  +  V    -*  W7  *  C°2  +  V
                                                uater
Typical Material Requirements

                    1000 kg citric acid

Molasses                  2500 kg
Nutrients                 10 to 15 kg
Sulfuric Acid  (95%)       1100 kg
Lime                      700 kg

Citric  acid  is  one  of the widely employed organic acids.
Its major use is as an acidulant  in  carbonated  beverages,
jams,  jellies, and other foodstuffs.  Another important use
of citric acid is in  the  medicinal  field,  including  the
manufacture of citrates and effervescent salts.  There are a
few industrial uses, including citric acid as a sequestering
agent,   and  acetyl  tributyl  citrate  as  a  vinyl  resin
plasticizer.

Except for small amounts produced from citric fruit  wastes,
citric acid is manufactured by aerobic fermentation of crude
sugar  or  molasses.   The  fermentation  changes  sugar,  a
straight-chain compound, into a branched chain.

Production of citric acid  may  proceed  by  either  of  two
methods:   fermentation  in shallow pans, or fermentation in
aerated tanks.  Both processes may be used simultaneously as
shown in Figure 4-47.  In the tray process, a sugar solution
is placed in the trays, and air is circulated for  9  to  12
days  over  hundreds  of  shallow, pure-aluminum trays.  The
trays  are  placed  in  a  closed  cabinet   provided   with
facilities  for  sterilization, ventilation, and temperature
                            233

-------
                                                          FIGURE  4-47
                                     CITRIC ACID-OXAUC ACID-FERMENTATION OF MOLASSES
MOLASSES —fci
WATER — *

DEEP TANK
FERMENTATION
1
WASTEWATER (
FIL
ACI
"
T
!"-t
ROTARY

i
•YCELIUM
3 LANDFILL


                                                     CaSO,
                                                                              LIME-
MOLASSES
   HATER
N;
OJ
             »ASTE»ATER(2)
              WATER
TROMMEL
SCREEN


)



t



PERCOLATION
TANK

l i


_fe
r

TROMMEL
SCREEN

"

CALCIUM
OXALATE
PRECIPITATION





^


-h


BELT
FILTER




CALCIUM
CITRATE
PRECIPITATION
FILTRATION




CALCICUM
CITRATE
DECOMPOSITION
FILTRATION
WASTEWATER (3) SLUDGE




CRYSTALLIZER
fr OXALIC ACID

                                         MYCELIUM
                                         TO  LANDFILL
                                                               SLUDGE
                                                                             WASTEHATER (4)
                                                                             (BAROMETRIC CONDENSER)
                                                                       WASTEWATER
                                                                     (BAROMETRIC
                                                                       CONDENSER)
                                                                                                            SLUDGE
                                      FINISHED
                                      CRYSTALLIZER
WASTEWATERl 5)
(BAROMETRI C  CONDENSER)

  ^ ClTRIC ACID
                              SOLIDS TO LANDFILL

-------
control.  After fermentation, the mycelium  from  the  yeast
used  is  removed  from the broth by screens or filters, and
the spent mycelium is washed and disposed.   Mycelium  wash-
water containing citric acid is combined with acid separated
in the filtration step.  The citric acid then passes through
an  oxalic  acid  recovery stage.   (Oxalic acid is available
for recovery only from the tray process.)  The  addition  of
calcium  sulfate precipitates calcium oxalate.   Addition of
sulfuric acid recrystallizes the calcium  sulfate,  and  the
solids  are  removed  by filtration.  Hydrous oxalic acid is
then crystallized under a  vacuum  pulled  by  a  barometric
condenser.

After removal of the oxalic acid, the broth is combined with
the  liquor produced in the deep tanks.  The essential steps
of the deep tank process are similar to  the  tray  process,
but a different type of mycelium culture is grown and oxalic
acid  is  not generated as a by-product.  Molasses and water
are first introduced into the deep fermentation tanks.   Air
is introduced to maintain aerobic conditions and to keep the
tank  contents  well  mixed.   The  fermentation  process is
complete after approximately 4 to 9 days at 30 to 32°C.  The
tanks are then emptied and  partially  filled  with  boiling
water  to sterilize them prior to the next batch.  The crude
liquor is filtered to remove the mycelium, and the broth  is
combined with the broth produced in the tray processes.

Citric  acid  is  recovered  from the broth by precipitation
with calcium hydroxide.  The solution is then passed through
a series of filters for removal of the crystallized  calcium
citrate.   Both  filtrate  and  washwater  used  during  the
filtration process are discharged  as  waste.   The  calcium
citrate  is  then  chemically  reacted with sulfuric acid to
form calcium sulfate and citric acid.  The  calcium  sulfate
is removed by filtration to purify the citric acid.  Some of
the filter cake is recycled to the oxalic acid precipitation
process,  while  the  remainder is wasted.  The crude citric
acid is then concentrated from 30 to 60 percent in a double-
effect evaporator equipped with a  two-stage  steam  jet  to
pull   the   vacuum.   Barometric  condensers  are  employed
following the steam jets.  Since the citric  acid  does  not
vaporize, the only loss in the evaporator is by entrainment.
Thus,  entrainment  separators  are  used  prior to the con-
densers .

The crude product crystals are redissolved in  water  during
the finishing step.  Treatment processes, including granular
activated  carbon, are employed to remove trace heavy metals
and color.  The white liquid is then crystallized (utilizing
a barometric condenser), dried, and packaged for sale.
                              235

-------
To determine the raw waste  load,  samples  of  the  various
wastestreams  were  obtained.   These  wastestreams included
tray and deep tank washwaters,  filtrate  from  the  calcium
citrate  filtration  step,  and barometric waste waters from
the purification steps.  A waste  water  stream  (barometric
condenser  waste  water)   resulting from the purification of
oxalic acid was  included  in  the  raw  waste  load;  thus,
production  is expressed as the combined total of oxalic and
citric acids in their anhydrous forms.   Process  raw  waste
loads  calculated from flow measurements and the analyses of
these streams are indicated in the following tabulation:

                  Oxalic plus Citric Acids (Anhydrous form)

Process Flow
     liter/Jdcg                    477,000
     gal/M Ib                      57,200

BODS RWL
     mg/liter1                        690
     kg/kkg*                          328
COD RWL
    mg/liter*                       1,380
    kg/kkg*                           657

TOG .RWL
    mg/literi                         507
    kg/kkg2                           242

tjRaw waste  concentrations  are  based  on  unit  weight  of
pollutant  per  unit  volume  of process waste waters.  2Raw
waste loadings are based on unit  weight  of  pollutant  per
1000 unit weights of product.

The  foregoing  data  was used as the basis for BPCTCA.  The
wastes from this plant are currently discharged  to  surface
water without treatment.

The  analytical  results  also indicate that, in addition to
the parameters shown in the tabulation, pollution parameters
such as sulfate, nitrogen, chloride, calcium, magnesium, and
zinc may be at levels potentially  hazardous  to  biological
treatment  processes.   Proper  pretreatment  to  reduce the
aforementioned  parameters  may  be  necessary  before   the
                             236

-------
wastestreams can be discharged into any biological treatment
unit.

Noncontact  waste  waters  include  cooling  water and steam
condensate.  The total cooling water usage is  approximately
107,000  gallons  per 1000 Ibs of product.  A large quantity
of the cooling water  is  employed  in  tube-and-shell  heat
exchangers.   The  total steam usage (live plus reboiler) is
estimated to be 15,500 Ibs per 1000 Ibs of product.
                               237

-------
Product:  Naphthenic Acid

Process;  Extraction and  Acidification  of  Caustic  Sludge
from Petroleum Refinery

Process RW.L Subcateqory;  D

Chemical  Structure;   Naphthenic acids are cyclo-paraffinic
organic acids and usually are mono-carboxylic

The term "naphthenic acid" is  applied  to  the  mixture  of
carboxylic   acids   obtained  from  the  alkali  washes  of
petroleum fractions.  They are complex  mixtures  of  normal
and   branched   aliphatic   acids,   alkyl   derivates   of
cyclopentane-   and   cyclohexane-carboxylic   acids,    and
cyclopentyl  and  cyclohexyl  derivates  of aliphatic acids.
Naphthenic acids are used chiefly in the  form  of  metallic
salts  which  are  soluble  in  oils  and  organic solvents.
Copper naphthenate is an excellent fungicide  for  wood  and
canvas  treating.  The lead, manganese, zinc, and iron salts
are used as dryers  (oxidation  catalysts)  for  paints  and
varnishes.

The naphthenic acids are present in caustic sludge primarily
as  sodium  naphthenates.   Figure  4-48  is  a process flow
diagram of naphthenic acid recovery.   The  caustic  sludge,
which  has been used to scrub the light distillate crude oil
fractions,  is  treated  with  water  and  an  alcohol  soap
solvent.   The  resulting oil and soap phases are separated;
the oil phase is stripped with the oil going to fuel and the
solvent recovered overhead.  The soap phase is treated  with
an  oil solvent, and another oil phase/soap phase separation
takes place.  The oil  phase  is  recycled  to  the  caustic
sludge,  while  the soap phase is treated with an acid.  The
naphthenic acids are then separated from the solvent.

The solvent proceeds to a stripper where it is recovered  as
the  overhead and sent to solvent storage.  The bottoms from
this column are quenched with water and  discharged  to  the
sewer.   The  extracted  naphthenic  acids go to a stripper,
where solvent is taken overhead and sent  to  storage.   The
bottoms from the stripper are vacuum distilled.  The bottoms
from the vacuum still are sent to fuel, while the naphthenic
acids are recovered.

Process  RWL  calculated  from  flow  measurements  and  the
analyses  of  waste  water  streams  are  indicated  in  the
following    tabulation.     In    addition,   the   sulfate
concentrations in the waste water are extremely high may  be
potentially hazardous to biological treatment processes.
                              238

-------
                                                      FIGURE 4-48
                                   NAPHTHENtC ACID - EXTRACTION AND ACIDIFICATION
                                      OF CAUSTIC  SLUGE  FROM PETROLEUM REFINERY
K)
l J
'.a
 WATER

CAUSTIC
SLUDGE '

SOAP
SOLVENT
           J
OIL & AQUEOUS
PHASES
SEPARATOR
    OIL SOLVENT
        ACID
                                                                      SOLVENT TO  STORAGE
                                                                                                             STEAM
                                             OIL TO FUEL
                                      OIL & AQUEOUS
                                      PHASES
                                      SEPARATOR
                                        T
                                                                                                     STEAM JET
                                                                                                       AND
                                                                                                     BAROMETRIC
                                                                                                     CONDENSER
                                                                                                            L
                                                                                                               WASTEWATER
                                                                                                     NAPHTHENIC ACID
                                                                                                     TO FUEL
                                                                                         QUENCH  WATER
                                                                          WASTEWATER  (2)

-------
    PROCESS FLOW
       liter/kxg   39,800
       gal/M Ib     4,760

    BOD5 RWL
       mg/literi    3,550
       kg/kkg*        141

    COD RWL
       ing/liter*    7,500
       kg/kkg*        298

    TOC RWL
       mg/literi    2,630
       kg/kkg*        104

    *Raw waste concentrations are based on unit
     weight of pollutant per unit volume of
     process waste waters.
    £Raw waste loadings are based on unit weight
     of pollutant per 1,000 unit weights of product.

These data presented above were the basis for BPCTCA.

The  process  plant visited during the field data collection
program  used   direct-contact   cooling   to   reduce   the
temperature  of  the  bottoms stream from the soap stripper.
The substitution of  noncontact  cooling  would  reduce  the
water requirements for this process by approximately 75 per-
cent.   However,  the raw wasteload would not be appreciably
affected.
                               240

-------
Product;  Monosodium Glutamate (MSG)

Process:  Batch  Fermentation of Beet Sugar Molasses

Process RWL Subcategory;   D

Chemical Reaction:

Fermentation  (Glutamic Acid Production)

      Fermentation (Glutamic Acid Production)

          Beet Sugar  + Bacteria Culture  + 02  + NH3      >
          (sucrose)

          NH -CH-COOH + H20  + C02   +  Bacteria Mass

              CH2-CH2-COOH

          gltitanic acid
          MSG Conversion and Neutralization

          NH -CH-COOH  + NaOH 	>  NH2-CH-COOH       +  H20
            2 1                       ]
              CH2-CH2-COOH              CH2-CH2-COONa
                                  mono sodium glutamate

Typical Raw Materials

    Beet Sugar Molasses,  Ammonia  (NH3),  Bacteria   Culture,
    Nutrient   Salts,  Compressed  Air,  Diatomaceous  Earth,
    Filter Aid,  Hydrochloric Acid   (HCl),  Sodium   Hydroxide
     (NaOH),   Steam  Cooling  Water  and Bleaching  Activated
    Carbon

Monosodium Glutamate (MSG)  is an amino  acid   salt   which  is
used   as  a   flavor  enhancer.   MSG   is  produced  by  the
conversion of Glutamic Acid (GA)  with   caustic.   There  are
several  routes  to obtaining the GA, including hydrolysis of
Steffen's Waste  Liquor with caustic or  acid,  acid hydrolysis
of  wheat  and   corn   gluten,   and    fermentation   of   a
carbohydrate.

The process visited during the field data collection program
was  the  fermentation of beet molasses (sucrose) to produce
glutamic  acid.    This  fermentation  reaction   is   a  batch
reaction; subsequent separation processes and the conversion
of  the  glutamic  acid to monosodium glutamate are  done on a
semi-continuous  basis (refer to Figure  4-49).
                              241

-------
                      FIGURE 4-49
SODIUM GLUTAMATE— FERMENTATION OF BEET SUGAR MOLASSES
WH-
u
11 R

CULTURE 1
BEET SUGAR
MOLASSES ' FERMENTATION
VESSELS
T

1
FILTER
AID
CENTRIFUG-

CONDENSATE RECYCl
WASTEWATER
2ND. CROP
CRYSTALLIZATION
-

	
FILTER / \
_,__,AIQ .^.^ / RFCYCIF V— 1
' RECOVERY 1 1 COOLING j I
WASTEWATER \^^_^^ *
1 f COOLING TOWER
Jk I Bl OWDOWN
HEAT-VCOAGULATION
AND FILTRATION — , EVAPORATION 	 ^

r 1 '
E HIM.
CRUDE
GLUTAMIC
RECYCLE WATER ACID
CRYSTALL-
CRYSTALLIZATION IZATION
AND SEPARATION
—^——— —— — u t nu
I .

MSG
CRYSTALLIZATION
AND
SEPARATION
4—
PH ADJUSTMENT
AND FILTRATION *-
I
MSG DRYING, SCREENING,
PACKAGING AND
SHIPP NG
L.
MSG CONVERSION GA CRYSTALS 4—
FILTRATION AND V FILTRARION AND
DECOLORIZING WASHING ^.BY-PRODUCT
SALES
i i
i i
SPENT CARBON
RECOVERY 	
I WASTEWATER
       SALES

-------
Tiie aerobic fermentation of the sugar beet  molasses  occurs
in a jacketed vessel, which is either steam-heated or water-
cooled  to  maintain  temperature.  The cooling water may be
recirculated  without  organic  pickup.   The  pH   of   the
fermenting liquor is monitored and controlled by ammonia ad-
dition.   The added ammonia also supplies the amino group in
the product formulation and supplements the nitrogen content
of the  raw  molasses  for  bacteria  culture  growth.   The
surplus  air  from  the fermentation vessels contain odorous
compounds; therefore, these gases are sent  to  the  boilers
for  air  makeup,  and  the  odorous materials are thermally
destroyed.

At the completion of. the fermentation reaction, the bacteria
cell mass (cell cream)  is  separated  via  centrifuges  and
discarded (point No. 2).  This cell mass represents the most
significant  part of the raw waste load.  The high pollutant
loading and commensurate  high  substrate  content  of  this
waste  stream  make  it  a  prime  candidate  for by-product
recovery and sale.

The  clarified  centrate  is  heat  treated  to  precipitate
miscellaneous   proteinaceous  material.   The  precipitated
material and any fugitive cell mass  are  then  removed  via
vacuum   filtration.    The   resulting  sludge  is  cyclone
classified to recover most of the filter aid material.   The
waste   stream    (point   B,  appcor  cyclone  overflow)  is
characterized as heavily contaminated with inert and organic
suspended solids.  Intermittent discharge of filter  precoat
material  impacts considerably on the RWL for all parameters
measured  (point No. 3).

The  clarified  filtrate    (glutamic   acid   solution)    is
concentrated  via  a  two-stage  evaporation  process.   The
condensate of the first effect is recycled as water  make-up
to  the  fermentation  process.  The second-stage vapors are
condensed in barometric contact condensers.  The  barometric
condenser system is serviced with recirculated cooling-tower
water.   The  blowdown (point No. 7)  from this cooling-tower
system was found to be highly  contaminated  with  materials
exerting a significant biochemical oxygen demand.

The concentrated glutamic acid (GA)  solution is treated with
concentrated   hydrochloric   acid  to  a  pH  of  3.2,   the
isoelectric point of GA.  The  GA  is  crystallized  out  of
solution,  filtered,  and  washed.   The  wash  water, which
represents the major blowdown of impurities from the system,
is  recovered  and  sold  as  an  animal  feed   supplement,
"Dynaferm".    The primary constituent of Dynaferm is GA, but
it  also  contains  many  other  salts   and   proteinaceous
                               243

-------
impurities  which  escape  the  heat coagulation/ filtration
treatment.  This stream was not  sampled  during  the  data-
gatnering  survey, but its recovery and sale probably impact
very favorably in reducing the RWL.

The GA crystals are then solubilized and partially converted
to MSG with caustic.  The  GA/MSG  solution  is  decolorized
with  activated  carbon.   The spent carbon is recovered and
thermally regenerated; this  represents  a  significant  in-
process  pollution  control measure because the color bodies
and  other  adsorbed  impurities   are   oxidized   in   the
regeneration   furnace.    There   are   three  small  water
discharges  (points  No.  4,  5  and   6)    which   do   not
significantly impact on the RWL.

Potential  odors  in  the  exhaust  gases  from  the  carbon
regeneration  facilities  are   oxidized   via   a   thermal
afterburner.  The three discharges (point D) from the carbon
regeneration are significant in volume but contribute little
of any of the pollutants monitored during the survey.

Further  downstream  processing  includes:   pH  adjustment,
filtration, MSG crystallization, and separation of water and
GA.  These streams are recycled in order to retain  valuable
product and by-product materials.

The  results  of  combining  the  two grab composites of all
major contributing sources to waste water discharges yielded
values which compare to  62  percent  and   11  percent  BOD5
occurrence   probability   of   the  historical  data;  this
indicates that the samples are  representative  of  the  MSG
production facility surveyed.

The  RWL  can  be reduced significantly from those levels of
pollutants measured during the data gathering  survey.   The
approach with the greatest potential for reducing the RWL is
the recovery and sale of cell cream (point No. 2) for animal
feed.   It  is not possible to mark the impact of cell cream
recovery precisely, but it is estimated  that  approximately
20  to  50  percent  of  the  suspended  solids RWL could be
removed.  A somewhat  similar  impact  on  the  organic  and
oxygen-demanding  parameters would also be experienced.  The
prospects for  recovery  of  this  material  depend  on  the
development of nearby markets and favorable economics.

The  recovery  of  the  precoat waste water (point No. 3) is
also an attractive alternative to discharge.  This material,
soluble and suspended,  could  be  recirculated  to  achieve
almost total recovery.
                               244

-------
The  RWL  for  MSG  production  during  the  survey  and the
estimated impact on RWL in regard to recovery of cell  cream
and precoat wastes are shown in the following tabulation:


                     Sample            Sample       RWL after
                   Period fl         Period 12      Reduction

PROCESS FLOW
   liter/kkg       67,000           67,000          62,200
   gal/m Ib         8,030            8,020           7,460

BOD5 RWL
   mg/literi        1,510            1,020             980
   jcg/kkg*            101               68.4            61

COD .RWL
   mg/literi        4,060            4,410           3,600
   kg/kkg*            272              296             224

TOC RWL
   mg/literi        1,360            1,350           1,090
   kg/kkg«             91.4             90.5            67

1   Raw waste concentrations are based on unit weight of
pollutant per volume of process waste waters.
2   Raw waste loading are based on unit weight of pollutant
per 1,000 units of products.
                                 245

-------
Product:  Tannic Acid

Process:  Extraction of Natural Vegetable Matter

Process RWL Subcategory;  D

Tannic  Acid, a glucoside of gallic acid, can be obtained by
extraction of natural  vegetable  matter  with  water.   The
water  extract  is  then concentrated and upon drying yields
technical tannin, which is used as a mordant in  dyeing  and
as  a  source  of  gallic acid.  Extraction of nutgalls with
alcohol  or  other  blcachings,  or  extraction  with   mild
reducing  agents  (such as sodium bisulfite) and evaporation
of the extract yield medicinal grade tannin.  Tannic acid is
commonly used for burns, as an astringent, in  gargles,  and
to precipitate proteins in wineries and breweries.

Figure  4-50  shows  a  typical flow diagram for tannic acid
manufacture.  The raw materials (natural nutgalls)  are  fed
into  the  preparation section and ground into small pieces.
The ground material is  then  batchwise  extracted  with  an
organic solvent.  The slurry raffinate phase is diluted with
water,  put  through  a steam stripper for solvent recovery,
and discharged into the sewer.  The extract phase, a mixture
of organic solvent, extracted material, and a  small  amount
of water, is steam stripped for removal of the solvent.  The
solvent  is  then  condensed  and recycled to the extraction
step.

The steam-stripped aqueous solution containing  tannic  acid
is  cooled  and passed through a filter press for removal of
suspended solids.  The filtrate (containing tannic acid)  is
concentrated  in  an  evaporator  before  final  drying  and
packaging.  The evaporation step employs steam jets to  pull
a  vacuum,  and  the  gases  are  subsequently  condensed in
barometric condensers.  Waters from the barometric  leg  are
recycled to the cooling towers for reuse.

The  major  pollution  source from the process is the slurry
waste stream  withdrawn  as  the  bottom  of  the  raffinate
stripper.   The  intermittent  reactor  washings, as well as
"battery limits" clean-up, also contribute to the RWL of the
process.  The amounts of contaminants were estimated to be 5
percent of that of the major waste stream.  The  results  of
the   sampling   survey  are  summarized  in  the  following
tabulation.
                              246

-------
                  FIGURE 4-50
TANNIC ACID- EXTRACTION OF NATURAL VEGETABLE MATTER
1 	 NON-CONTACT
1 COOLING WATER
MAKE-UP 	 »
SOLVENT
-j
wiiTFn nun TT F ii u

FEED ^
RAW MATERIAL PREPARATION fc

SOLVENT
RECOVERY

i i
NON-C
COOL
EXTRACTION
AND
STEAM
STRIPPING
1 1
SOLIDS, TRASH WASTEHATER
TO LANDFILL
i



ONTACT
NG WATER . 	
r

FILTRATION
FILTER CAKE
TO LANDFILL


• WATER


£ WATER
STEAM JET
fc AUn
BAROMETR C
CONDENSER


EVAPORATION . UH!"18 TANNIC^ACID

PACKAGING


-------
                              Tannic Acid
                    Sample    Sample    Sample
                   Period »1 Period *2 Period »3

    .PROCESS FLOW
       liter/kkg    10,000    10,000    10,000
       gal/M Ib      1,200     1,200     1,200

    BODS JRWL
       mg/literi    16,100    14,700    15,100
       kg/kkg2         161       147       151

    COD RWL
       mg/literi   109,000    99,400   112,000
       kg/kkg2       1,093       995     1,120

    TOC RWL
       mg/literi    14,000    16,800    21,000
       kg/kkg2         140       168       210

    *Raw waste concentrations are based on  unit  weight  of
    pollutant per unit volume of process waste water.
    2Raw   waste  loadings  are  based  on  unit  weight  of
    pollutant per 1,000 unit weight of product.

The water from the barometric condensers in the  evaporation
step  was  not  included  in the foregoing RWL calculations.
Since the organics in the evaporation step are not volatile,
the pollutant  loading  in  the  barometric  water  is  low.
Furthermore,  this water has been totally recycled for reuse
in tne process.

The analytical results indicate that the high  RWL  of  this
process  is  attributable  to  the high amounts of suspended
organic vegetable matter present in the slurry stream.   The
removal   of   suspended   solids   from   this  stream  can
substantially  reduce  the  RWL  of  the  process.   As  was
indicated  during  the  sampling survey, the following three
possible methods for removal/disposal  of  suspended  solids
are being investigated.

1.   Filtration  and  landfill  disposal of Suspended Solids
(SS).

2.  Filtration and incineration of SS.

3.  Filtration and  recycle  of  SS  into  other  industrial
and/or agricultural uses.
                              248

-------
The  RWL  of  the  process should be based on the amounts of
contaminants in the filtrate,  and  is  subject  to  further
investigation.   Noncontact cooling water is employed in the
solvent recovery area and prior to  filtration.   The  total
quantity  of  noncontact  cooling  water  is estimated to be
approximately 6tH Ibs per Ib of product.
                               249

-------
Product:  Vanillin

Process;  Alkaline oxidation of spent sulfite liquor

Process RWL Subcategorv:  D

Chemical Reactions:


      Spent  sulfite liquor + 02 + NaOH—> C£Ho (OCH )   (CHO) OH

      (1ignosulfonic acid)                     vanillin
Vanillin is one of the most widely used food flavors.  Jt is
also  used  in  perfumery  and   in   the   deodorizing   of
manufactured   goods.    During  the  plant  visit,  company
representatives indicated that approximatley one-  third  of
the vanillin produced at this plant is used for flavor manu-
facture, with the remaining two-thirds used for perfumes and
other miscellaneous items.

A  typical  process  flow  diagram  for  the  manufacture of
vanillin is shown in Figure 4-51.

Waste sulfite liquor containing  about  15  percent  sulfite
solids  (mainly lignosulfonic acid), supplied by paper mills,
is  treated  with  lime  in a series of three tanks.  In the
first  stage  (pH  =  10.5)  calcium  sulfate   (principally)
precipitates.  In the second, the pH is increased to 12.0 to
precipitate  calcium lignosulfonate.  In the third a further
excess of lime is added.  Thickened liquors from  the  third
stage  are then reused as a supplementary lime source in the
first tank.  The precipitated  calcium  lignosulfonate  from
the second tank is filtered under vacuum, and redissolved in
a  caustic  soda solution to yield a solution containing 3.5
percent lignin solids and 10 percent caustic soda.

The alkaline solution  is  then  pumped  to  a  falling-film
contactor  countercurrent  to a carefully controlled flow of
air, which oxidizes the sulfonate to sodium  vanillate.   In
one  application  of  the process, the oxidation reaction is
carried out at 1,500 psi and 225°C.  Residence time  of  the
liquid  in  the contactor is on the order of 4 minutes.  The
overall liquor-oxygen ratio equals 0.02  volumes  of  liquor
per  volume  of air  (STP).  At these conditions, an  18 to 20
percent conversion of lignin to vanillin  is  effected,  and
minimum overoxidation is minimized.  Because the reaction is
exothermic,  the temperature of the effluent liquor rises to
about 250°C.   The  vanillate  from  the  oxidizer  is  then
                              250

-------
TSZ
                                      <
                                      >
                                      Z
                                      z

                                      I
                                      >
                                      p-

                                      >
                                      r^
                                      Z
                                      m

                                      O
                                      x
                                      o
                                      O   =
                                      Z   O

                                      O   *>
                                      m   Oi
                                      Z
                                      c
                                      r-

                                      C

                                      O

                                      r;

                                      O
                                      c
                                      O

-------
extracted   with   organic   solvents,  such  as  butane  or
isopropanol,   in   a   conventional   one-   or   two-stage
countercurrent  process.   Both  the extracted and raffinate
phases are steam stripped to recover, respectively,  organic
solvents  and vanillate, which are then recycled back to the
process line.  The  vanillate  separated  from  the  organic
solution   is   further   purified   by   vacuum  extractive
distillation followed by acidification.   Vanillin  is  then
recovered   by  vacuum  crystallization,  centrifuging,  and
vacuum tray-drying.

The air oxidation process described has  replaced  a  former
process  in  which  nitrobenzene  was  used as the oxidizing
agent.   Also,  a  Canadian  plant  has  installed  an   air
oxidation  process  similar to that described, but with lime
replacing caustic as the alkaline agent.  Other  differences
are  the use of carboyhydrate-free waste sulfite liquor from
an alcohol plant, the  use  of  toluene  as  the  extracting
agent,  and  vacuum  distillation  to separate vanillin from
contaminating by-products.

The major  pollution  sources  of  the  process  are  waters
discharged  from  the  pretreatment of sulfite solution, the
raffinate stripper, the centrifuge filtration, and the steam
jets connected  with  the  barometric  condensers.   Process
RWL's  calculated from the flow measurements and analyses of
the  aforementioned  waste  streams  are  presented  in  the
following tabulation.

                   Sample Period t1    Sample Period #2

    PROCESS FLOW
       liter/kkg        133,000        133,000
       gal/M Ib          15,900         15,900

    BODS RWL
       mg/literi         17,900         17,500
       kg/kkg2            2,380          2,320

    COD RWL
       mg/literi        118,000        116,000
       kg/kkg2           15,600         15,400

    TOC RWL
       mg/literi         30,400         29,900
       kg/kkg2            4,030          3,960

    1Raw  waste  concentrations  are based on unit weight of
    pollutant per unit volume of process waste waters.
                              252

-------
    2Raw  waste  loadings  are  based  on  unit  weight   of
    pollutant per 1,000 unit weights of product.

The  high  raw  waste  loads  shown in the tabulation may be
explained by the fact that spent sulfite liquor is  a  waste
product  from  paper mill operations producing only 15 to 20
percent yield to vanillin.   The  remaining  unusable  spent
sulfite   liquor   must  be  discharged  as  a  waste.   The
analytical results also indicate that, in  addition  to  the
parameters  shown  in  the  tabulation, pollution parameters
such as dissolved solids, sulfate, and phenol concentrations
may  be  at  levels  potentially  hazardous  to   biological
treatment processes.

An  average  for  the  two sampling periods was used was the
basis for BPCTCA.

The primary noncontact waste water flows are  cooling  tower
and  boiler  blowdown.   Samples of the boiler blowdown have
been taken, and the flow has been estimated.  Samples of the
cooling tower  blowdown  were  not  taken,  because  typical
analyses  were  not  available  and  the  flows  are  highly
variable.  The cooling tower make-up averages  approximately
120  gpm and the cooling water makes approximately 3 cycles.
A phosphate corrosion inhabitor and a biocide are  added  to
the make-up.
                              253

-------

-------
                         SECTION V

                   WASTE CHARACTERIZATION
The  process  RWL data obtained for each of the 55 Secondary
Organic Products were discussed previously in Section  IV  -
Industry categorization.  These descriptions related the raw
waste  flows  and  loadings  to  specific  sources  such  as
chemical  conversions  and  unit  operations   within   each
product-product  grouping.   The discussions in this section
relate to the RWL values assigned to  each  product/process,
and   compare  waste  loadings  and  concentrations  between
product/processes.

The RWL data for each product/process shown in  Tables  5-1,
2,  3,  and  4  have  been  inserted  in  the  major process
Subcategories  A,   B,   C,   and   D.    For   orientation,
concentrations  have  been  calculated for each parameter by
dividing the raw waste loading by the corresponding  contact
process   waste  water  flow.   Examination  of  these  data
indicates quite a  large  spread  in  flows,  loadings,  and
resulting   concentrations.    These   values   include  the
following parameters:

     Process Waste Water Flow (liters/kkg of product)
     BOD Raw Waste Load (kg BOD/kkg of product)
     COD Raw Waste Load (kg COD/kkg of product)
     TOG Raw Waste Load (kg TOC/kkg of product)

Although the sampling data indicate that in some cases there
is considerable  variation  between  two  manufacturers  who
nominally  operate  the  same process, and between different
time sampling periods for the  same  manufacturers,  it  was
necessary  to  specify  one  set of values for each product-
process grouping.  This  was  done  in  the  most  equitable
manner  possible  from  the  data  available.   Rather  than
arbitrarily choosing the  lowest  observed  value  for  each
product-product  grouping,  an  effort  was  made  to choose
values which represent the most complete and  reliable  data
base.   Other  factors  such  as  the  application  of  good
housekeeping and in-process controls were also considered in
selecting   the   raw   waste   loads   values   for    each
product/process.  In cases where alternate means of disposal
are  used,  such  as in the use of deep wells, the total raw
wastes were accounted for  as  input  to  the  model  BPCTCA
biological   treatment   system.    Thus,   limitations  for
processes where  deep  wells  or  other  alternate  disposal
                                255

-------
methods  are  used  would apply in the situation where these
alternate disposal methods were no longer feasible.


The BOD concentrations  shown  are  based  on  waste  waters
coining  directly  from  the  process  and do not necessarily
represent the waste concentrations which  a  typical  single
stage biological waste treatment plant would accept.  If the
plant   manufactured   a   single  product  which  generated
concentrated  wastes,  these  may  be  diluted  with   steam
condensate  or  other  noncontact waters prior to biological
treatment depending upon the design and  management  of  the
plant   in   question.    In   a  multi-product  plant,  the
concentrated  waste  water  could  be  diluted   with   less
concentrated  wastes  from  other  processes.  In almost all
instances, the actual  treatment  plant  which  accomplishes
waste  reduction  will be accepting the combined wastes from
multiple processes, whose overall concentrations are  lower,
because    of    the   addition   of   waste   waters   from
product/processes of smaller loads and slightly contaminated
waste waters such as steam condensate, pump seals, etc.

Those 27 product/processes which were selected for  effluent
limitations  guidelines are included  in Table 5-1 thru 5-4.
As indicated in an earlier section of this report, the Phase
II  effluent  limitations  for  organic  chemicals   involve
process-by-process  determinations.   This  approach differs
from that taken in Phase I where  process  raw  waste  loads
from  processes  with  similar raw waste loads were combined
and averaged.  Effluent limitations  were  then  derived  by
application  of  a  reduction factor or concentration to the
average or mean raw waste load for the group of processes.
                                256

-------
                                                                     TABLE 5-1

                                                    Major Subcategory A Process  Raw Waste Loads
                                                                                                          Process  Raw Waste  Loads
     Product
     BTX Aromatics
     Cumene
     p-Xylene
                                               Process  Description
Fractional Distillation
Alkylation of Benzene with Propylene
Isomerization, Crystallization,  and Filtration
of mixed Xylene
 Flow
1/kkg

46.7

44.3
                                                                      BODS
kg/kkg (mg/1)

0.015 (322)

0.01(238)
                                                                                        COD
                                      TOC
kg/kkg (mg/1)   kg/kkg (mg/1)

0.053 (1137)    0.015 (328)

0,025(580)      0.007(159)
to
on
     Product
     Adiponitrile
     Benzole Acid and
       Benzaldehyde
     Chlorinated Methanes
     Chlorobenzene
     Chlorotoluene
     Diphenylamine
     Hexamethylene Diamine
     Hexamethylene Diamine
     Maleic Anhydride
     Methyl Chloride
     Methyl Ethyl Ketone
     Perchloroethylene
     Phthalic Anhydride
     Phthalic Anhydride
     Tricresyl Phosphate
                                   TABLE 5-2

                  Major Subcategory B  Process Raw Waste Loads


             Process Description
Chlorination of Butadiene
Catalytic Oxidation of Toluene with Air

Chlorination of Methyl Chloride & Methane Mixture
Chlorination of Benzene
Chlorination of Toluene
Deamination of Aniline
Hydrogenation of Adiponitrile
Ammonolysis of 1,6 - Hexanediol
Oxidation of Benzene
Esterification of Methanol with Hydrochloric Acid
Dehydrogenation of Sec. - Butyl Alcohol
Chlorination of Chlorinated Hydrocarbons
Oxidation of Naphthalene
Oxidation of o-Xylene
Condensation of Cresol and Phosphorus Oxychloride
                                                                                                         Process Raw waste Loads
Flow
1/kkg
9770
2840
2800
50
121,000
526
1,010
1,100
2,300
583
1,310
5,400

593
28,000
BODS
kg/kkg (mg/1)
19.2 (1970)
25.6 (9010)
0.22(77)
0.015 (300)
0.24 ( 2 )
0.087(164)
3.97 (3930)
4 (3640)
108 (47,000)
0.92(1569)
3.92 (3000)
0.44 ( 80 )
Incinerated
0.13 (215)
1.12 ( 40 )
COD
kg/kkg (mg/1)
135 (13,800)
50.8 (17,900)
0.94(335)
0.38 (7700)
1.82 ( 15 )
0.31 (600)
21.1 (20,900)
11.7 (10,600)
287(126,000)
67.8(116,300)
2.1 (1630)
2.83 (525)

0.64 (1080)
11.4 (410)
TOC
kg/kkg (mg/1)
44 (4500)
19.6 (6900)
0.37(132)
0.24 (4780)
0.24 ( 2 )
0.23 (430)
5.15 (5100)
2.5 (2260)
120 (52,500)
17.6 (30,270)
0.68 (520)
0.17 ( 30 )

0.02 ( 34 )
1.96 (70)

-------
                                                              TABLE 5-3

                                                Major Subcategory C Process Raw Waste Loads
                                                                                                       Process Raw Waste Loads
Product
Acetic Esters
   Ethyl Acetate
   Propyl Acetate
Acrylonitrile
p-Aminophenol
Calcium Stearate
Caprolactam
Cyclohexanone Oxime
Cresol, Synthetic
Formic Acid
Hexamethylene letramine
Hydrazine Solutions
Isobutylene
Isopropanol
Oxalic Acid
Pentaerythritol
Propylene Glycol
Propylene Oxide
Saccharin
Sec. Butyl Alcohol
                                          Process Description
Esterification of Ethyl Alcohol with Acetic Acid
Esterification of Propyl Alcohol with Acetic Acid
Ammoxidation of Propylene
Catalytic Reduction of Nitrobenzene
Neutralization of Stearic Acid
DSM Caprolactam Process
Hydroxylamine Process
Methylation of Phenol
Hydrolysis of Formamide
Synthesis with Ammonia
The Raschig Process and Formaldehyde
Extraction from a Mixture of C4 Hydrocarbons
Hydrolysis of Propylene
Nitric Acid Oxidation of Carbohydrates
Aldehyde Condensation
Hydrolysis of Propylene Oxide
Chlorohydrin Process
Synthesis from Phthalic Anhydride Derivatives
Sulfonation and Hydrolysis of Mixed Butylenes
Flow
1/kkg
1,299
1,190
4,470
12,600
54,100
29,100
1910
334
135,000
3,200
30,300
20,400
2,540
436,000
10,200
5,500
63,500
269,000
626
BODS
kg/kkg (mg/1)
0.049 (38)
0.008 (7)
38.7(8620)
41.6 (3300)
13.8 (255)
47.1 ( 1620)
—
47.7 (143,000)
1.05(7.8)
9.2(2875)
9.09 (300)
13.6 (670)
0.99 (393)
1.31 (3)
390 (38,100)
0.016 (3)
31.5 (495)
253 (940)
14.2 (22,800)
COD
kg/kkg (mg/1)
0.102 (79)
0.012 (10)
133(32,800)
73.7 (5850)
32.8 (605)
93 (3200)
6.29 (3300)
101 (303,000)
4.5 (33)
29.4 (9200)
115 (3800)
64.1 (3150)
2.99 (1130)
4.36 (10)
1580 (155,000)
0.055 (10)
143 (2250)
879 (3270)
38.8 (62,000)
TOC
kg/kkg (mg/1)
0.034 (26)
0.005 (4)
57.5(14,400)
21.7 (1730)
23.1 (430)
—
—
34.7 (104,000)
1.4 (10)
9.8 (3060)
0.18 (6)
12.9 (630)
1.32(520)
1.31 (3)
830 (81,200)
0.006 (1)
22.7(355)
384 (1430)
23.9 (38,300)

-------
                                                                    TABLE  5-4

                                                     Major  SubcategoryD Process Raw Waste Loads
                                                                                                          Process  Raw Waste  Loads
KJ
Ul
VD
     Product
Citric Acid
Citronellol and Geraniol
Dyes and Dye Intermediate
Fatty Acids
Fatty Acid Derivatives
lonone and Methylionone
Methyl Salicylate
Miscellaneous Batch
  Chemicals
Monosodium Glutamate
Naphthenic Acid

o-Nitroaniline
p-Nitroaniline
Pentachlorophenol
Pigments
  Toners
  Lakes
Plasticizers
Tannic Acid
Vanillin
                                          Process Description
                                  Fermentation of Molasses
                                  Citronella Oil Distillation
                                  Batch Manufacture
                                  Hydrolysis of Natural Fats

                                  Condensation and Cyclization of  Citral
                                  Esterification of  Salicylic  Acid with Methanol
Fermentation of Beet Sugar Molasses
Extraction and Acidification of Caustic Sludge
  from Petroleum Refinery
Ammonolysis of o-Nitrochlorobenzene
Ammonolysis of p-Nitrochlorobenzene
Chlorination of Phenol
Diazotization and coupling of amine,  sulfuric, etc
                                  Condensation of Phthalic Anhydride
                                  Extraction of Natural Vegetable Matter
                                  Alkaline Oxylation of Spent  Sulfite Liquor
Flow
1/kkg
477,000
10,000
947,000
28,000
6,400
9,370
1,735
78,700
62,200
39,800
269,000
39,100
2,960
313,000
1,000,000
650
10,000
133,000
BODS
kg/kkg (mg/1)
328 (690)
58.1(5810)
248 (260)
16.1 (575)
18 (2810)
24 (2600)
22 (12,680)
24.1 (306)
61 (980)
141 (3550)
16 (61)
2.55 (65)
0.94 (318)
570 (1820)
1470 (1470)
54 (82,600)
153 (15,300)
2350 (17,700)
COD
kg/kkg (mg/1)
657 (1380)
111 (11,000)
1219 (1290)
39.6 (1410)
27.9 (4360)
98 (10,000)
93.9 (54,100)
101 (1280)
224 (3600)
298 (7500)
105 (390)
79.1 (2030)
17.5(5880)
1920 (6100)
4930 (4930)
82.6 (127,000)
1070 (107,000)
15,500(117,000)
TOC
kg/kkg (mg/1)
242 (507)
37.7(3770)
450 (475)
9.8 (350)
8.47(1320)
34 (3600)
37.9 (21,800)
31.4 (400)
67 (1090)
104 (2630)
30.9 (105)
22.2 (570)
2.29 (775)
207 (660)
820 (820)
33.4 (51,400)
173 (17,300)
4000 (30,200)

-------

-------
                         SECTION VI

             SELECTION OF POLLUTANT PARAMETERS
Twenty-eight, parameters were examined during the field  data
collection program.  These parameters are listed in Table 6-
1,  and all field sampling data are summarized in Supplement
B.   Based  on  the  degree  of  impact   on   the   overall
environment,  the pollutants which are applicable to control
and treatment were then determined.

The rationale and justification for the major pollutants are
discussed.  This  discussion  will  provide  the  basis  for
selection  of  parameters  upon  which  the  actual effluent
limitations were postulated and prepared.  These  pollutants
parameters  for  which  no effluent limits were established,
but which may be of concern  to  water  quality  in  certain
locations, are also discussed.

Pollutants observed from the field data that were present in
sufficient  concentrations  so  as  to  interfere  with,  be
incompatible with,  or  pass  inadequately  treated  through
publicly-owned works are discussed in Section XII.

      RATIONALE FOR SELECTION OF IDENTIFIED PARAMETERS

           5-Day Biochemical Oxygen Demand (BOD5_)

This  parameter  is  an  important  measure  of  the  oxygen
consumed by microorganisms in the aerobic  decomposition  of
the  wastes at 20°C over a five-day period.  More simply, it
is an  indirect  measure  of % the  biodegradability  of  the
organic pollutants in the waste.  BOD5_ can be related to the
depletion  of  oxygen  in  the  receiving  stream  or to the
requirements of the waste treatment.  Low BOD5. values in the
raw waste  are  frequently  the  result  of  the  dilutional
effects  of  non  process  waters or less contaminated waste
streams.  High values are due to a combination  of  factors,
such  as  undiluted condenser waters, frequent spills, and a
relatively large amount of drainage of high strength liquids
from the raw material.

Biochemical oxygen demand (BOD) is a measure of  the  oxygen
consuming  capabilities of organic matter.  The BOD does not
in itself cause direct harm to a water system, but  it  does
exert an indirect effect by depressing the oxygen content of
the  water.  Sewage and other organic effluents during their
processes of decomposition exert a BOD,  which  can  have  a
catastrophic effect on the ecosystem by depleting the oxygen
                              261

-------
                            Table 6-1
              List of Pollutants and Indicators of Pollution
                Examined for the Organic Chemicals Industry
Chemical Oxygen Demand
Biochemical Oxygen Demand
Total Organic Carbon
Total Suspended Solids
Oil (Freon extractables)
Ammonia Nitrogen
Total Kjeldahl Nitrogen
Phenol
Cyanide - Distillation
Color
Sulfate
pH
Acidity
Alkalinity
Chlorine, residual
Total Dissolved Solids
Chlorides
Hardness - Total
Total Phosphorus
Calcium
Magnesium
Zinc
Copper
Iron
Chromium - Total
Cadmium
Col bait
Lead
Nickel
Vanadium
                               262

-------
supply.   Conditions are reached frequently where all of the
oxygen is used and the continuing decay process  causes  the
production of noxious gases such as hydrogen sulfide.  Water
with  a  high  BOD  indicates  the  presence  of decomposing
organic matter  and  possible  high  bacterial  counts  that
degrade its quality and potential uses.

If  the  BOD5  of the final effluent of an organic chemicals
plant discharged into a receiving body is too high, it  will
reduce  the dissolved oxygen level in that stream to below a
level that will sustain most fish life; i.e., below about  4
mg/1.   Many states currently restrict the BOD5 of effluents
to below 20 mg/1 if the stream is small in  comparison  with
the  flow  of the effluent.  A limitation of 200 to 300 mg/1
of BOD5 is often applied for discharge to a municipal sewer,
and surcharge rates often apply if the  BOD5  is  above  the
designated limit.

If  a  high  BOD  is  present,  the  quality of the water is
usually visually degraded by  the  presence  of  decomposing
materials   and   algae   blooms   which   result  from  the
decomposition and oxidation of the organic matter.

A 20-day biochemical oxygen demand (BOD20J , sometimes called
"ultimate" BOD is usually a better measure of the waste load
than BOD5,  However, the test for BOD20 requires 20 days  to
run, and is an impractical measure for most purposes.

Dissolved  oxygen   (DO)  is a water quality constituent that,
in appropriate concentrations, is essential not only to keep
organisms living but also to sustain  species  reproduction,
vigor,   and  the  development  of  populations.   Organisms
undergo stress at reduced DO concentrations that  make  them
less  competitive  and  able to sustain their species within
the  aquatic   environment.    For   example,   reduced   DO
concentrations  have  been  shown  to  interfere  with  fish
population through delayed hatching of  eggs,  reduced  size
and  vigor  of  embryos, production of deformities in young,
interference with  food  digestion,  acceleration  of  blood
clotting,  decreased tolerance to certain toxicants, reduced
food  efficiency  and  growth  rate,   and  reduced   maximum
sustained  swimming speed.  Fish food organisms are likewise
affected adversely in conditions with suppressed DO.   Since
all  aerobic  aquatic  organisms  need  a  certain amount of
oxygen, the consequences of total lack of  dissolved  oxygen
due to a high BOD can kill inhabitants of the affected area.

The  accepted  method  for  BOD analyses is described in the
Standard Methods for the  Examination  of  Water  and  Waste
Waters  published by the American Public Health Association.
                             263

-------
The BOD test is a biochemical test for which  microorganisms
are  used  to  oxidize the organic matter in the wastewater.
Standard Methods notes that for certain  industrial  wastes,
more meaningful results may sometimes be realized by the use
of specialized seed material containing organisms adapted to
the  use  of  the  organic  compounds  present.   The use of
acclimated seed does not always result  in  more  meaningful
results  or  higher  numerical  values.  Data using specific
organic chemicals indicated that the use of acclimated  seed
can  result  in lower BOD values than were obtained by using
non-acclimated seed.

The BOD analyses obtained as part of the sampling  conducted
during  this  study  were  run  using reasonable and prudent
steps to evaluate and overcome any potential problems due to
acclimation of seed.  The technique that was  used  in  this
study  was  compared with that used by the laboratory of one
of the large organic chemical  industries.   The  comparison
was good.

BOD5  is  included  in  the recommended effluent limitations
because its discharge to a stream is harmful to aquatic life
since it  depletes  the  oxygen  supply.   It  is  also  the
parameter  most  widely used by the industry to characterize
its  untreated  and  treated  wastes  and  is  an  important
parameter  in  the  design  of  biological  waste  treatment
systems.

                Chemical Oxygen Demand  (COD)

COD is another measure of oxygen demand.   It  measures  the
oxygen  required  to  oxidize  organic  (and some inorganic)
pollutants under  a  carefully  controlled  direct  chemical
oxidation  by  a  dichromate  sulfuric  acid  reagent  using
specific catalysts.

COD is a much more rapid measure of oxygen demand than BOD5,
and is potentially very useful.  However, it does  not  have
the  same  significance,  and  at the present time cannot be
substituted for BOD5, because COD:BOD5 ratios vary with  the
types  of  wastes.   The  COD  measures more than only those
materials that will readily  biodegrade  in  a  stream  and,
hence, deplete the stream's dissolved oxygen supply.

A   major  disadvantage  is  that  the  COD  test  does  not
differentiate  between  biodegradable  and  nonbiodegradable
organic  material.   In  addition, the presence of inorganic
reducing  chemcials  (sulfides,  etc.)  and  chlorides   may
interfere with the COD test.
                               264

-------
Standard  Methods,  the  principal  reference for analytical
work in this field, cautions  that  aromatic  compounds  and
straight-chain  alphatic  compounds,  both  prevalent in the
organic chemicals  industry,  are  not  completely  oxidized
during  tne  COD  test.   The  addition of silver sulfate, a
catalyst,  aids  in  the  oxidation  of  the  straight-chain
alcohols   and   acids   but   does   not   affect  aromatic
hydrocarbons.  The exact extent of  this  partial  oxidation
has not been documented in the literature.

COD  provides  a  rapid determination of the waste strength.
Its measurement will indicate a serious plant  or  treatment
malfunction  long before the BODjj can be run.  A given plant
or waste treatment system usually has  a  relatively  narrow
range  of  COD:BOD5 ratios, if the waste characteristics are
fairly constant, so experience permits a judgment to be made
concerning plant operation from COD values.

The organic chemicals industry does produce chemicals  which
may  be in the effluent from a secondary treatment plant and
which can be a source of chemicals in the  environment  that
can  be  hazardous  to  humans,  animals,  and aquatic life.
These chemicals can be effectively reduced by  incorporating
the COD limit in the industry effluent limitation.

The   COD   test  measures  the  presence  of  both  rapidly
biodegradable  and   less   biodegradable   oxygen-demanding
matter.   For  a  specific waste, the difference between the
measured BOD and COD value is an index of the oxygen  demand
of   organic   matter  which  is  resistant  to  short  term
biodegradation.  While the laboratory conditions employed in
the COD test will not be found  in  a  receiving  stream,  a
portion  of  the  oxygen  demand measured by the COD will be
exerted in the receiving stream.  It is  the  latter  oxygen
demand  that  is  of  concern  in  water  pollution  control
activities and which  requires  control,  especially  in  an
industry where many residues may not degrade rapidly.

The  COD  test  is  a  reasonable  index for the presence of
organic chemicals in a waste or effluent,  is  a  reasonable
estimate  of  the  ultimate oxygen demand of the wastes from
this industry, and can be a measure of  hazardous  materials
in the environment.

Effluent limitations guidelines were established for the COD
pollutant  parameter  for BATEA.  Its use for BPCTCA and New
Sources is not precluded if a suitable correlation with BODS
is established.

                 Total Organic Carbon (TOC)
                            265

-------
TOC is a measure of the amount  of  carbon  in  the  organic
material   in  a  waste  water  sample.   The  TOC  analyzer
thermally oxidizes a small volume of sample at  150°C.   The
carbon  dioxide from the combustion chamber is condensed and
sent to an infrared analyzer, where the  carbon  dioxide  is
monitored.   This  carbon  dioxide  value corresponds to the
total inorganic value.  Another portion of the  same  sample
is  thermally  oxidized  at  950°C,  which  converts all the
carbonaceous  material  to  carbon   dioxide;   this   value
corresponds to the total carbon value.   TOC is determined by
subtracting  the  inorganic  carbon  from  the  total carbon
value.  Only organic matter capable  of  being  incorporated
into  the small sample volume (approximately 40 millimeters)
can be measured.  Primarily soluble  and  colloidal  organic
material can be measured by this analysis.

The  TOC  value  is  affected  by  any  one  or  more of the
following:

    1.   The water vapor may be only partially condensed and
         may appear  in  the  infrared  adsorption  band  of
         carbon   dioxide  and  can  therefore  inflate  the
         reported value.

    2.   The sample volume involved in the TOC  analyzer  is
         so small (approximately 40 microliters)  that it can
         easily become contaminated, with dust, for example.

    3.   Industrial  wastes  from  the   organic   chemicals
         industry  with low vaporization points may vaporize
         before 150°C and therefore be reported as inorganic
         carbon.

Effluent  limitations  were  not  established  for  the  TOC
parameter,  although  its use is not precluded if a suitable
correlation with BOD5 or COD is established.   It  has  only
been  in recent years that TOC has been used as a measure of
waste water quality.

                Total Suspended Solids (TSS)

This parameter measures the suspended material that  can  be
removed  from  the  waste  waters  by laboratory filtration.
Suspended solids are a visual and easily determined  measure
of  pollution  and  also  a measure of the material that may
settle in tranquil or slow-moving streams.  A high level  of
suspended  solids is an indication of high BOD£.   Generally,
suspended solids range from one-third  to  three-fourths  of
the BOD_5 values in the raw waste.  Suspended solids are also
                               266

-------
a  measure  of  the  effectiveness of solids removal systems
such as clarifiers and fine screens.

Suspended solids frequently  become  a  limiting  factor  in
waste  treatment  when  the BOD5 is less than about 20 mg/1.
In fact, in highly treated waste, suspended  solids  usually
have  a higher value than the BOD5, and in this case, it may
be easier to lower the BODJ5 even further, perhaps to 5 to 10
mg/1, by filtering  out  the  suspended  solids.   Suspended
solids  in the treated waste waters generally correlate well
with BOD5, COD, and total volatile solids.

Suspended solids also  may  inhibit  light  penetration  and
thereby   reduce   the   primary   productivity   of   algae
(photosynthesis).  Because of the  strong  impact  suspended
solids  can  have on receiving waters, suspended solids were
included in the effluent  limitations  recommended  in  this
report.

Suspended   solids   include   both  organic  and  inorganic
materials.  The inorganic components include sand, silt, and
clay.  The  organic  fraction  includes  such  materials  as
grease,   oil,   and   various   organic   matter  from  the
manufacturing process.  These solids may settle out  rapidly
and  bottom deposits are often a mixture of both organic and
inorganic  solids.   They  adversely  affect  fisheries   by
covering  the bottom of the stream or lake with a blanket of
material that destroys the fisia-food  bottom  fauna  or  the
spawning   ground  of  fish.   Deposits  containing  organic
materials may deplete bottom  oxygen  supplies  and  produce
hydrogen sulfide, methane, and other undesirable gases.

In  raw  water  sources for domestic use, state and regional
agencies generally specify that suspended solids in  streams
shall  not  be  present  in  sufficient  concentration to be
objectionable  ox  to  interfere   with   normal   treatment
processes.   Suspended  solids  in  water may interfere with
many industrial processes, and cause foaming in boilers,  or
encrustations  on  equipment exposed to water, especially as
the temperature rises.  Suspended solids are undesirable  in
water  for  textile  industries,  paper and pulp, beverages,
dairy  products,  laundries,  dyeing,  photography,  cooling
systems,  and  power plants.  Suspended particles also serve
as a transport mechanism for pesticides and other substances
which are readily sorbed into or onto clay particles.

Solids may be suspended in water for a time, and then settle
to the bed of the stream or lake.  These  settleable  solids
discharged   with   man's   wastes   may  be  inert,  slowly
biodegradable materials, or rapidly decomposable substances.
                              267

-------
While in suspension, they  increase  the  turbidity  of  the
water,    reduce    light   penetration   and   impair   the
photosynthetic activity of aquatic plants.

Solids in suspension are  aesthetically  displeasing.   When
they  settle  to  form sludge deposits in the stream or lake
bed, they are often damaging to the life in water, and  they
retain  the  capacity to displease the senses.  Solids, when
transformed to sludge deposits, may do a variety of damaging
things, including blanketing the  stream  or  lake  bed  and
thereby  destroying  the  living  spaces  for  those benthic
organisms that would otherwise occupy the habitat.  When  of
an  organic  and therefore decomposable nature, solids use a
portion or all of the  dissolved  oxygen  available  in  the
area.   Turbidity  is  principally  a  measure  of the light
absorbing properties of suspended solids.  It is  frequently
used  as a substitute method of quickly estimating the total
suspended solids when the concentration is relatively low.

TSS RWL  values  for  the  Phase  2  products  surveyed  are
presented  in  Tables  6-2 through 6-5.  TSS raw waste loads
are generally not a significant factor in this industry.
Much of the TSS eventually discharged to surface waters  are
biological  solids  which  have been produced in the end-of-
pipe biological  treatment  facilities  many  of  which  are
removed before effluent discharge.  The effluent limitations
are  partially  based on a concentration value which will be
attainable with adequate solids handling  facilities.   This
subject is discussed in detail in Section VIJ.

                Total Volatile Solids  (TVS)

The  total volatile solids measurement is a rough measure of
the amount of organic matter in the waste water.   Actually,
it  is  the amount of combustible material in both the total
dissolved solids and total suspended solids.  Total volatile
solids in  the  raw  and  treated  waste  waters  from  this
industry  generally  correlate  fairly well with SS, grease,
and COD.  Because of these correlations  and  because  total
volatile solids is a relatively easy parameter to determine,
it  could  be  used as a rapid method to determine a serious
plant or treatment system malfunction.  Volatile  solids  in
receiving waters are food for microorganisms.

Effluent  limitations  for  total  volatile  solids were not
established because TVS will be limited  by  limitations  on
other  pollutant  parameters  such  as  BOD5_  and  suspended
solids.

                            Oil
                             268

-------
       Table 6-2
Miscellaneous RWL for Subcategory A
Flow, gal/1 ,000 Ibs
Phenol
mg/1
kg/kkg
NH -N
•Wl
kg/kkg
TKN
mg/1
kg/kkg
CN
mg/1
kg/kkg
Sulfate
mg/1
kg/kkg
Oil
mg/1
kg/kkg
T-P
mg/1
kg/kkg
Zn
mg/1
kg/kkg
Cu
mg/1
kg/kkg
Fe
mg/1
kg/kkg
Cr-Total
mg/1
kg/kkg
Cd
mg/1
kg/kkg
TSS
mg/1
kg/kkg
IDS
mg/1
kg/kkg
cr
mg/l
kg/kkg
Phase
p-Xylene
5.25
.16
.00001
1.0
.00005
3.12
.00013

2.6
.00011
7^6
.0327
it. 76
.00021
.287
.00001
.44
.00002
2.30
.00010
2.50
.00011
< .05
0
17.3
.00076
162
.0711
32
.0014
I I Data
Cumene
.04
14.6
Negl igible
3.4
Negligible
8.2
Negl igible
.02
Negligible
12.3
Negl igible
21
Negligible
.005
Negl igible
.13
Neg 1 i g i b 1 e
.05
Negligible
109
.00003
.01
Negl igible
.01
Negligible
100
.00003
138
.00004
37
.00001
Supplementary Phase 1 RWL Data
BTX
87.5
.155
.00009
1.27
.0010
4.05
.0028

140
.0872
251
.709
.45
.00035
1 .49
.00095
< .08
< .00006
1.45
.00090
5.16
.00315
< .05
< .00005
44.5
.0270
2,045
.343
168
.103
BTX
52.3
1.98
.00087
18.0
.00785
49.3
.0215

5,860
2.56
26
.011
1.112
. 00049
.116
. 00005
.09
.00004
13.8
.006
.171
. 00008
.127
.00006
331
.1445
47,600
20.8
3,280
1.43
BTX
5.56
.2
.00001
142.7
.00662
322.4
.0154
.818
. 00004
1,400
.0649
9
.0004
.033
.00000
.343
.00002
.05
.00000
1.57
.00007
.01
.00000
.01
.00000
9
.0004
21
.00097
36
.00169
Ethyl Benzene
55.5
1.94
. 00069
13.2
. 00546
18.2
.00772

23.9
.0160
55
.0318
.079
. 00004
2.46
.00087
.18
.00006
2.55
. 00096
1.26
.00089
.052
.00003
61.5
.0254
20,300
6.68
4,410
1.48
Ethyl Benzene
39.7
1.03
.000335
11.8
.00387
105.5
.0355

12.8
.00578
9
.00298
.0178
.00006
30.5
.0102
21.5
.00721
7.9
.00149
.807
.00027
.051
.00002
5
.00172
13,200
4.44
50,800
16.9
            269

-------
       Table  6-3
Miscellaneous 1?WL for Subcategory  B

Product
Benzole Acid via Benzene
Maleic Anhydride via Benzene
Maleic Anhydride via Benzene
Adiponi t ri le
Chloromethanes
Chloromethanes
Chlorotolulene
Methyl Ethyl Ketone
Methyl Ethyl Ketone
Di pheny 1 ami ne
HMDA (Adiponitrile)
HMDA (Adiponitrile)
Hexamethylene Diamene (Hexanediol)
Methyl Chloride
Methyl Chloride
Methyl Chloride
Perch loroethylene
Phthalic Anhydride (o-xylene)
Tricresyl Phosphate
Flow
qal/1000 Ib
340
788
274
1170
V3C.
33o
71.6
14, 500
156

63
203
121
132
1,430
101
69.9
642
71.2
3,350

mq/1
.16
2.10
1.47
.103
.03
.035
nit
. UH
.01

.638
.073
.01
.01
.07
.05
.09
.21
10.8
Phenol
kq/kkq
. 00044
.014
.0034
.00102
nnnm
. UUUU/
.00002
nnli.3 (\
, UUH-jD
.00001

.00108
.00073
.00001
.00011
.00006
.00003
.00048
.00013
.304
NH--
mq/l J
<15.3
16.6

1,940
-i
1.95
< 1.4
2.1
15,500
4,540
3,080
7,630
.1
1.9
.55
.2
10.4
3.65
N
kq/kkq
0.043
.109

18.9
nm Q 1
. uu I y r
.00116
< .0018
.00167
8.15
7.69
3.1
8.40
.0012
.0016
.000325
.00107
.00618
.102

mg/1
33.5
16.6

3,730
21
. I
6.05
5.2
4.5
16,700
4,000
4,400
9,170
1.9
69.3
1.9
4.6
18.8
11.8
TKN
kq/kkq
.095
.109

36.4
nncQ i
. UU5j I
.0036
.0068
.00355
8.78
6.78
4.44
10.10
.0230
.0585
.00110
.0247
.0112
.344
CN
mq/1 kq/kkq
0 0



187 1.83





.638 .00108
16.7 .0202







Supplementary Phase 1 RWL Data
Acetone
Ethylene Dichloride
Vinyl Chloride
Vinyl Chloride
Styrene
Styrene
276
28.2
17.0
135
733
250

.27
<.01
.36
1.83
1.13

.00006
0
. 00040
.0112
.00252
0
10.4

.7
23.5
5.15
0
.0024

.00079
.143
. 00763
1.8
17.9
4.6
2.85
29.8
12.3
.0041
.0042
. 00066
.00379
.182
.0364







-------
Table 6-3
(continued)
Miscellaneous RWL for Subcategory B

Product
Benzole Acid via Benzene
Maleic Anhydride via Benzene
Maleic Anhydride via Benzene
Ad i pon i t ri 1 e
Chloromethanes
Chloromethanes
Chlorotolulene
Methyl Ethyl Ketone
Methyl Ethyl Ketone
Diphenylamine
HMDA (Adiponitrile)
HMDA (Adiponitrile)
Hexamethylene Diamene (Hexanediol)
Methyl Chloride
Methyl Chloride
Methyl Chloride
Perch 1 o roethy 1 ene
Phthalic Anhydride (o-xylene)
Tricresyl Phosphate

mg/1
.78
101
30
1.58
14.3



.68
.29
.30
1.11
.25
5.81
18.8
4.12
5.98
.5
1.31
Fe
kg/kkg
.00222
.665
.069
.0154
.0403



.00054
.000155
.00219
.000113
.00028
.0695
.0159
.0024
.0321
.0003
.0366
Cr-Total
mg/1
.076

1.74
.0973
7.7



.05
.05
.141
.053
.02?
.050
.644
.088
9.45
4.01
.041
kq/kkq
.00022

.0040
.000953
.0217



.00004
.00003
.00024
.000053
.00003
.00060
.00054
.00005
.0507
.00238
.00115
Ca
mg/1
.10
.42
< .05
.161
.050



.05
.05
.05
.05
.027
.052
.050
.215
.05
.01
.041
Supplementary Phase 1
Acetone
Ethylene Dichloride
Vinyl Chloride
Vinyl Chloride
Styrene
Styrene
37.7

2.06
13.6
.33
7.9
.0089

.00029
.0153
.00199
.00149
.05

.06
2.55
.056
.015
.00001

.00001
.00287
.00034
.00002
.10

<.05
.05
< -05
.055
kq/kkq
.00029
.0028
<. 00011
.00156
.00014



.00004
.00003
.000085
.00005
.00003
.00062
. 00004
.000125
.00027
.00001
.00115
RWL Data
.00002

.00001
.00006
.00031
.000025
TSS
mg/1
118
17
2,380
56.3
89
1,170



8.5
53.5
4

28
7,100
1,380
25.5
29
4

14.5

26
68
8.5
1,230
kg/kkg
.334
.109
5.44
.55
.251
.702



. 00447
.0905
.00404

.333
6.001
.802
.136
.0172
.110

.00341

.00369
.0766
.0504
.118
TDS Cl"
mg/1
34,900
56,000
53,700
124,000
28,300
4,100
467


16
3,600
535
29
336
23,500
117,000
1,700
541
615

46,000

85,200
13,300
69.8
42.5
kq/kkq mg/1
98.9 290
371
122 18
1,210 83,400
79.3
2.45 3,570
56.5 325

56
.00842 6,300
6.10 26
. 541 489
.0316 5,190
4.01 11,500
19.8 2,760
Aft 1

9.20 33,600
.321 92
17.2 2,560

10.8 18,900

12.1 18,900
15.0 11,300
.263 7.7
.114 3.5
kq/kkg
.823

.0421
814

2.12
39.3

.0446
17.6
.0437
.492
5.71
137
2.330


180
.0547
71.5

4.45

4.45
12.7
.0472
.0072

-------
Table 6-3
(continued)
Miscellaneous RWL for SubcategOry B
Sulfate
Product
Benzole Acid via Benzene
Maleic Anhydride via Benzene
Maleic Anhydride via Benzene
Ad i pon i t ri 1 e
Chloromethanes
Chloromethanes
Chlorotolulene
Methyl Ethyl Ketone
Methyl Ethyl Ketone
D i pheny lami ne
HMDA (Adiponitrile)
HMDA (Adiponitrile)
Hexamethy 1 ene Diamene (Hexanediol)
Methyl Chloride
Methyl Chloride
Methyl Chloride
Pe rch 1 o roet hy 1 ene
Phthalic Anhydride (o-xylene)
Tricresyl Phosphate

Acetone
Ethylene Dichloride
Vinyl Chloride
Vinyl Chloride
Styrene
Styrene
mg/1
36.3


156
349
2,590
28.0
1.20
1.0
1.0
5.12
15.7
.538
3,020
482
5,800
6,840
106
54

3.60
21.0
4.0
145
< 4.29
1.0
kq/kkq
.103


1.53
.98
10.5
3.39
.0016
. 00079
.00053
.00869
.0158
.00059
36
8.85
446
36.6
.0630
1.513

.0083
.0049
.00057
.163
.0265
.00208
Oil
mq/1 kg
43
482 3.
2,020 4.
1,270 12.
12
0


441
280
18
1,380 2.
1,270 12.
36
460 5.
33
121
0
6
10.5
Supplementary Pha
2,370 5.
13
19
7
<29
18

|/kkq
121
17
62
400
0335
00017


576
222
0096
33
3
0398
500
0278
0707
000445
00351
297
wl RWL
47
0029
00264
00744
181
0013
T -
mq/1
.27
137

12.3
.678
.12


.005
.02
1.057
.375
2.03
.212
.057
.172
.039
.0535
1.24
1.19
Data
.388
.048
1.36
.059
.027
.015
P
kq/kkq
.00078
.902

.12
.00190
.000075


.00001
.00002
. 00056
.000635
.00205
. 00023
.00068
.00015
.00002
.000285
.00074
.0335

.00090
.00001
.00019
.00055
.00016
.00001
Zn
mq/1
4.19
5.42
.26
.328
5.16
8.06



.49
.085
74.5
.28
.022
14
23.6
33.8
4.05
.72
.327


.11
.33
2.0
.053
.135
kq/kkq
.012
.036
.00059
.0032
.0145
. 00482



.00039
. 000045
.000125
.000283
.00002
.168
.200
.0198
.022
. 00043
.0914


.00002
.00005
.00226
.00032
.00019
Cu
mq/1
.06
2.20
.17
48
.19

.15

.08
.05
.185
.05
.08
.07
26.3
.125
.06
.07
.07


.85
.70
.205
<.05
.115
kg/kkq
.00017
.014
.00039
.479
.00054

.0182

.00006
.00003
.00032
.00005
. 00003
. 00084
.0223
.000075
.00032
.00004
.00197


.00020
.00010
. 00023
.00031
.00011

-------
          Table   6-4




Miscellaneous RWL for* Subcategory c
Product
Hexamethy 1 ene Tetramine
Hexamethy 1 ene Tetramine
Synthetic Cresols
Sec. Butyl Alcohol
1 sobuty 1 ene
Pentaerythritol
Ethyl Acetate
Propyl Acetate
Calci um Stearate
Hydrazi ne
N) . ,
~J Isopropanol
Acryloni tri le
Acryloni tri le
Propylene Glycol
Propyl ene Oxide
Saccharin
Formic Acid
Oxal ic Acid
Flow
ga 1/1 000 Ib
557
384
250
7,780
2,440
1 ,230
155
142
6,460
3,630
304
338
570

6,580
32,200
16,000
52,300
Phenol
mg/1
.16
< .01
6,500
• 38
.01
.17
0
0
.014

.01
2.28
.165

1.15
.01
.0056
—
kg/kkg
.00072
< .00002
13.6
.025
.00012
.00178
0
0
.00067

.00003
.0064
.000705

.0381
.0032
.00087
—
NH^-N
mg/1
395
7,040
2.7
0
9.4
< 1.1
.8
.7
.8
1.0
1.1
13,600
2,600

1.5
130.3
1.43
3.2
kg/kkg
2.39
22.5
.0057
0
.190
< .012
.00104
.00083
.0568
.0297
.00281
38.3
10.26

.0875
35.0
.193
1.41
TKN
CN
mg/1 kg/kkg mg/1 kg/kkg
6,650 32.90
8,260 26.50
4.9
3.1
12.6
2.3
<2.0 < .
1.8
6.0
11.3
1.95 .
22,000 62.
4,040 16.

3.8
5,980 604
5.07 .
5.9 2.
0102 < .02 < .00004
200
256
023
00259
00213
322 .0202 .00110
342
00501
1 270 .755
9 197 .970

209

686 .02 .00267
56 .02 .00873
Sulfate
mg/1
367
<9.3
<6.5
1 ,280
1 ,210
2,570
1 .0
1.4
112
—
366
2,700
5,300

—
2,060
4.67
5.6
kg/kkg
2.22
•C.0050
< .0136
83.2
24.50
26.20
.00129
.00166
6.06
—
.931
64.10
74.3

—
553
.623
2.44
Oil
mg/1
50
131
5,600
408
1 ,030
369
203
265
169.2
19
15
168
135

98.5

43.4

kg/kkg
.19
.419
11.6
26.4
20.9
3.77
.263
.314
9.10
.569
.0380
.475
.657

5.45

5.77

T-P
mg/1
1.07
.177
.169
.079
1.07
.081
0
.05
.0134
.176
.153
.152
6.15

1.04
.07
.042
.02
kg/kkg
.0044
.00057
.00035
.0051
.0217
.00082
0
.00006
.00072
.00533
.00039
.00043
.0298

.061
.0189
.00561
.00873

-------
Table 6-^
(cont i nued)
Miscellaneous RWL for Subcategory C
Product

Hexamethy lene Tetramine
Hexamethy 1 ene Tetramine
Synthetic Cresols
Sec. Butyl Alcohol
1 sobuty lene
Pentaerythri tol
Ethyl Acetate
Propyl Acetate
Calcium Stearate
ij Hydra zine
1 sopropanol
Aery loni t r i le
Acrylonitri le
Propylene Glycol
Propylene Oxide
Sacchari n
Formic Acid
Oxalic Acid
In
mg/1
I.It
.19


.543
.43
.07
.049
.13
2.84
.052
2.10

26.6
.071
.107
.01
kq/kkg
.0085
.0004


.0055
.00056
.00008
.00262
.00394
.00722
.00002
.00922

1.56
.0190
.0142
.00436
Cu
mg/1
.07
<.05


.20
.77
3.49
.04
.14
.17
<.05
.05

.25
27.6
.08
.05
kq/kkq
.00032
<.0001


.0020
.001
.00414
.00221
.00424
.000435
< .00014
.000235

.0138
7.43
.0107
.0218
Fe
mg/l
1.61
6.07


8.65
.55
1.15
.108
4.30
2.88
3.13
4.24

23.9
.25
.05
.01
kg/kkg
.0097
.013


.088
.00071
.00136
.00590
.130
.00731
.0088
.0182

1.39
.0665
.0104
.00436
Cr-Total
mq/1
2.02
<.05


1.44
<.05
<.05
.041
.15
.051
<.05
.01

.334
.051
.089
.1
kg/kkq
.012
< .0001


.0148
< .00007
<. 00006
.00221
.00454
.00013
<. 00014
.00005

.0191
.0138
.0119
.0436
mg/1
<.05
<-05


.093
<.05
< .05
.041
.23
.051
<.05
.052

.111
.062
.05
.05
Cd
kg/kkg
<. 00023
< .0001


.00095
<. 00007
<. 00006
.00221
.00697
.00013
<. 00014
.00024

.00614
.0166
.00668
.0218

mq/1
27
6
9


129
1
10
26,
1,180
4.
630
184

4,520
33
6.
10
TSS
kq/kkg
.106
.0192
.0188


1.31
.00129
.0119
.7 1.43
35.8
,5 .0121
1.78
.915

263
8.83
,8 .902
4.36
TDS
mq/1
2,320
971
33.5


289,000
66
85
6,020
118,000
2,550
57,200
36,500

44 , 700
14,500
40.9
36
kq/kk
10
3



2,960


324
3,590
6
161
181

2,460
3,900
5
15
Cl
g_ mq/1
.1 40.5
.11 234
.0699 1.5


868
.085 7
.101 3
3,870
98,700
.46 214
858
125

24,800
5,050
.45 6
.7 6
-
kq/kkg
.149
.75
.0034


8.86
.00917
.00335
208
991
.542
2.42
.616

351
356
.792
2.58

-------
            Table 6-5
Miscellaneous RWL for Subcategory D
Product
Fatty Acids
Fatty Acids
Fatty Acids S- Derivat.
Fatty Acids S- Derivat.
Fatty Acids
Pentachloro Phenol
Esters from Fatty Acids
Methyl Esters
Fatty Acid Derivatives
Fatty Acid Derivatives
to
Di Naphthenic Acid
Glycerine
Fatty Acid Amides
Batch Chemicals
Tannic Acid
Sodium Glutamate
Plasticizers
(Diethyl Phthalate)
Dyes
para-Nitro-Ani 1 i ne
Miscellaneous Dyes
Azo Dye
or t ho-N i tro-An i 1 i ne
Vanil lin
Citric Ac i d
lonone S- Methyl lonone
Citronellol Geraniol
Pigments
Flow
ga 1/1 000 Ib
7,900
440
1 ,450
7,650
1 ,230
354
1 ,070
15,200
550
688
4,760
5,450
2,250
9,560
1 ,200
8,030
78.3
3,930
4,680
221,000
26,200
32,200
15,900
57,100
1,370
1 ,220
37,500
Phenol
mg/l
.02
.55
1.19
.06
.45
37.6
.07
.33
.20
.54
8.57
10.6
.04
1.83
2.37
.05
.01
.63
7.15
16.9
7.49
7.97
147
.07
1.04
0.00
1.81
kg/kkg
.00138
.00202
.0144
.00383
.00461
. .112
.00059
.042
.00088
.00312
.341
.482
.00068
.19
.0238
.0035
.00001
.0205
.279
31.2
1.57
2.14
19.5
.0309
.0119
0.00
.565
NH^-N
mg/l
1.5
121
934
86.1
3.75
211.
4.2
40
.55
620
3.7
5.5
7,730
36.7
1.8
241
1.1
82.1
1,590
17.2
15.0
1 ,150
4.05
51.8
44.5
9.3
2.1
kg/kkg
.096
.447
11.30
5.50
.0364
.624
.0375
5.07
.0026
3.56
.147
.248
145
2.87
.0180
16.1
.00073
2.69
62.1
31.7
3.08
310
.536
24.7
.508
.0943
.66
TKN CN Sulfate
mg/l
4.6
147
2,430
87.6
21.2
223
13.4
109
15.5
640
6.3
980
7,890
53.7
350
458
3.9
126
1,830
27.9
32.3
7,340
181
91.2
53.2
11.8
13.9
kg/kkg mg/l
.303
.540
29.4
5.59
.218
.661 .078
.119
13.8
.071
3.67
.252 .02
44.5
148
4.16 .02
3.50 .0237
30.6
.00258 .04
4.14 .041
71.5
51.6 .432
6.63 .085
976
24.0
43.5 .026
.608 .023
.120 .020
4.33 .026
kg/kkg mg/l
33.6
1 ,400
1 ,860
280
456
.00023 914
192
960
640
1,640
.00079 3,230
4,200
2.4
.00154 1,220
.000303
279
.00003 2,030
.0014 548
92.5
.756 1,020
.018 442
103
5,330
.0123 2,070
.00026 3,980
.00020 40.8
.00814 564
kg/kkg
2.21
152
22.5
17.9
4.69
2.70
1.71
122
2.94
9.42
128
191
.045
98.6

18.7
1.33
18.0
3.61
578
90.7
27,700
33.5
986
45.3
0.414
176
Oi
mg/l
54
1,190
600
68
1,070
3
4,000
4,250
701
470
255
8
467
43.7

85
12,500
334
332
74
106
10
72
19
383
2,630
67
1
kg/kkg
3.56
4.36
7.25
4.34
11.0
.00753
35.7
540
3.22
2.70
10.12
.350
8.77
3.35

5.69
8,170
10.9
12.9
136
24.8
2,600
9.56
8.85
4.37
26.6
20.9
T-P
mg/l
.39
129
2.30
.10
9.53
.038
3.3
1.67
2.01
18.7
.194
2.48
.02
1.90
595
15.2
3.29
.142
.493
10.5
.53
.531
.087
.101
.293
.797
.309
kg/kkg
.026
.474
.0279
.00638
.0982
.000115
.029
.212
.0092
.107
.0077
.113
.00038
.156
5.96
1.02
.00215
.0047
.0193
19.4
0.113
.143
.0115
• 0484
.00335
.00808
.0967

-------
Product

Fatty Acids
Fatty Acids
Fatty Acids 6- Derivat.
Fatty Acids & Derivat.
Fatty Acids
Pentachloro Phenol
Esters from Fatty Acids
Methyl Esters
Fatty Acid Derivatives
Fatty Acid Derivatives
Naphthenic Acid
Glycerine
Fatty Acid Amides
Batch Chemicals
Tannic Acid
Sodium Glutamate
Plastic! zers
(Diethyl Phthalate)
Dyes
para-Nitro-Anal ine
Miscel laneous Dyes
Azo Dye
ortho-Nitro-Anal ine
Van! llin
Citric Acid
lonone & Methyl lonone
Citronellol Geraniol
Pigments


mq/l
.104
.755
.17
.31
.272
.66

.79
1.60
.302
.450

1.312
3.52

3.95
.413
.229
.580
.287
.068
.517
3.30
1.47
.317
.135

In
kg/kkg
.0069
.00913
.011
.0032
.00081
.0059

.00365
.0092
.0139
.021

.110
.0347

.00258
.0135
.00892
1.07
.0614
.0184
.0686
1.57
.0168
.00322
.0423

Cu
mg/l
.05
.075
.05
1.73
.185
.05

.22
.10
.05
.40

.587
.807

97.9
61.6
.11
.775
.941
.05
7.59
.25
9.31
.08
.26

kq/kkq
.0033
.00091
.0032
.0178
.00054
.00045

.00101
.00057
.002
.0182

.0442
.008

.0640
2.02
.00417
1.43
.192
.0142
1.00
.120
.106
.00081
.207

Table 6-5
(continued)
Miscellaneous RWL for Subcategory
Fe Cr-Total
mq/l
3.06
3.67
.01
2.85
2.69
21.4

2.71
2.13
9.23
11.2

9.05
28.6

4.49
5.62
5.48
7.62
4.58
2.79
17.2
2.09
25.0
.98
.85 .

kg/kkg
.202
.0445
.00064
.0294
.00796
.191

.0125
.012
.366
.509

.744
.287

.00293
.184
.214
14.1
.940
.751
2.28
.996
.286
.00996
.266

mg/l
.05
.65
.05
2.32
.107
.35

3.25
.05
.05
.05

1.15
.518

.076
.56
.147
12.6
.572
.05
.458
.055
.112
.062
.05
274
kg/kkg
.0033
.0079
.0032
.0240
.000315
.0031

.0149
.0029
.002
.0022

.0988
.00519

.00005
.0184
.00574
3.28
.136
.0135
.0607
.0264
.00128
.00063
.0157

Cd
mq/l
.05
.05
.05
.05
.15
.05

.05
.05
.05
.05

.05
.035

.151
.06
.073
.050
.049
.05
.186
.05
.090
.061
.05

kg/kkg
.0033
.00061
.0032
.00052
.00044
.00045

.00023
.00029
.002
.0022

.00383
.00035

.0001
.00197
.00287
.0924
.0100
.0135
.0247
.0238
.00102
.00062
.0157

TSS
mg/l
128
780
669
57
1 ,560
155
3,840
551
211
748
68.5
928
494
42.6

2,260 151
101
121
1 ,430

99.3
270
24.5
78
124
21
59

kq/kkq
8.44
2.86
8.10
3.64
16.0
.46
34.2
69.8
.970
4.29
2.72
42.2
9.27
3.28

,000
.0661
3.97
56.1

20.4
72.5
3.26
36.9
1.42
.211
18.4

TDS
mg/l
370
61,900
2,630
1,150
1,378
8,950
770
5,720
3,490
2,400
7,690
10,800

3,250
108,000
1 ,650
94,800
42,400
13,300

3,150
2,020
348,000
41,300
85 ,400
32,600
.,^0

kg/kkg
24.4
227
31.8
73.4
14.2
26.4
6.8?
726
16.0
13.9
305
4go

261
1,080
110
61.9
1,390
520

646
543
46,300
19,700
976
330
606

Cl"
mq/l
67
84
61.5
4,320
70
291,000
i 119
27
100
71
69
17
326
776

85
160
12,100
5,780

1,130
306
—
15,500
191
282
621

kq/kkq
4.40
.308
.074
275
.721
860
1.06
3.41
.651
.408
2.75
.791
6.12
61.4

5.68
.104
398
226

215
82.3
—
423
2.18
2.86i
194


-------
Oil, also called oil and grease, or hexane  solubles,  is  a
pollutant,  parameter  that  can  be  in  the wastes from the
organic chemicals industry.  Oil can form unsightly films on
the water, interfere with aquatic life,  disturb  biological
processes  in  sewage  treatment  plants,  and become a fire
hazard.  It also can be a food source for microorganisms and
exhibit an oxygen demand.  Oil emulsions may adhere  to  the
gills  of  fish or coat and destroy algae or other plankton.
Deposition of oil in  the  bottom  sediments  can  serve  to
prohibit  normal  benthic  growths,  thus  interrupting  the
aquatic  food  chain.   Soluble  and   emulsified   material
ingested  by  fish  may  taint the flavor of the fish flesh.
Water soluble components may exert  toxic  action  on  fish.
Floating oil may reduce the re-aeration of the water surface
and  in  conjunction  with emulsified oil may interfere with
photosynthesis.   Water  insoluble  components  damage   the
plumage  and  coats  of  fowls  and  water animals.  Oil and
grease  in  a  water  can  result  in   the   formation   of
objectionable  surface  slicks preventing the full aesthetic
enjoyment of the water.  Oil spills can damage  the  surface
of  boats  and  can destroy the aesthetic characteristics of
beaches and shorelines.

Oil RWL's for the major Subcategories A, B,  C,  and  D  are
presented  in  Tables 6-2 through 6-5.  Although some of the
raw waste loads show high concentrations  of  oil,  effluent
limitations  were  not  considered  to  be  warranted.   The
explanation for not limiting oil  discharges  is  that  this
pollutant  parameter  is  of  secondary  importance whenever
other primary pollutant parameters are  controlled  such  as
for BOD5 and TSS.

                          Nitrogen

Ammonia  nitrogen  in the raw waste is one of the many forms
of nitrogen in a waste stream.  Anaerobic  decomposition  of
protein,  which  contains  organic  nitrogen,  leads  to the
formation of ammonia.  Thus, anaerobic lagoons or  digesters
can  produce  increased  levels  of  ammonia.   Also, septic
(anaerobic)  conditions within the plant  in  traps,  basins,
etc., may lead to increased ammonia in the waste water.

Ammonia  is a common product of the decomposition of organic
matter.  Dead and decaying animals  and  plants  along  with
human and animal body wastes account for much of the ammonia
entering  the aquatic ecosystem.  Ammonia exists in its non-
ionized form only at higher pH levels and is the most toxic*
in  this  state.  The lower the pH, the more ionized ammonia
is formed and  its  toxicity  decreases.   Ammonia,  in  the
presence  of dissolved oxygen, is converted to nitrate (NO3)

*The term toxic or toxicity is used  herein  in  the  normal
scientific  sense  of the word and not as a specialized term
referring to Section 307(a) of the Act.
                             277

-------
by  nitrifying  bacteria.   Nitrite  (NO2),  which   is   an
intermediate  product between ammonia and nitrate, sometimes
occurs in  quantity  when  nitrification  is  not  complete.
Nitrification  may occur in an aerobic treatment process and
in streams.  Ammonia will deplete the  oxygen  supply  in  a
stream  and its oxidation products are nutrients for aquatic
growth.

Nitrates  are  considered  to   be   among   the   poisonous
ingredients  of  mineralized  waters, with potassium nitrate
being more poisonous than sodium nitrate.   Excess  nitrates
cause    irritation   of   the   mucous   linings   of   the
gastrointestinal tract and the bladder.   The  symptoms  are
diarrhea   and   diuresis.   Drinking  one  liter  of  water
containing 500 mg/1 of nitrate can cause such symptoms.

Infant methemoglobinemia, a disease characterized by certain
specific blood changes and cyanosis, may be caused  by  high
nitrate  concentrations  in  the  water  used  for preparing
feeding formulae.  While it is impossible to  state  precise
concentration  limits, water containing more than 10 mg/1 of
nitrate nitrogen (NOJ-N) is  not  recommended  for  infants.
Nitrates  are also harmful in fermentation processes and can
cause disagreeable tastes in beer.

In streams polluted with municipal sewage, up to one half of
the nitrogen in the sewage may be in the form  of  unionized
ammonia,  and  municipal  sewage  may carry up to 35 mg/1 of
total nitrogen.  It has been shown that at a  level  of  1.0
mg/1 unionized ammonia, the ability of hemoglobin to combine
with  oxygen  is  impaired and fish may suffocate.  Evidence
indicates that ammonia exerts a considerable toxic effect on
all aquatic life within a range of less than 1.0 mg/1 to  25
mg/1,  depending  on  the  pH  and  dissolved  oxygen  level
present.

Ammonia  can  add  to  the  problem  of  eutrophication   by
supplying  nitrogen  through  its  breakdown products.  Some
lakes in warmer climates, and others that are aging  quickly
are  sometimes  limited  by  the  nitrogen  available.   Any
increase will speed up the plant growth and decay process.

                  Kjeldahl Nitrogen  (TKN)

Kjeldahl Nitrogen (TKN) measures the amount of  ammonia  and
organic nitrogen.  When used in conjunction with the ammonia
nitrogen,  the  organic  nitrogen  can  be determined by the
difference.   Under  septic  conditions,  organic   nitrogen
decomposes  to  form  ammonia.   Kjeldahl nitrogen is a good
indicator of the crude protein in the waste water.  Kjeldahl
                             278

-------
nitrogen has not been a common parameter for regulation  and
is a much more useful parameter for raw waste than for final
effluent.

Ammonia and TKN RWJL data of major significance for Tables 6-
2 thru 6-5 are summarized below:

Subcategory        Product              RWL Concentration
                                        NH3	        TKN-N
                                        mg/1         mg/1

    B           Acrylonitrile           13,600       22,000
                Diphenylamine           15,500       16,700
                Hexamethylenediamine     7,630        9,170
    C           Hexamethylenetetramine   7,040        8,260
    D           Fatty Acids and
                 Derivatives           1-7,730      5-7,890

Effluent limitations were not established for TKN since as a
rule  those product processes with high TKN values also have
nigh BOD values.  The oxidation of the TKN would be at least
partially measured by the BOD  analysis.   Thus  limitations
based  upon  BOD  would  in  effect  control  the TKN in the
effluent.  Ammonia  limitations  were  not  established  for
these  product  processes.   It was determined that need for
such limitation should be established on a  plant  by  plant
basis  after  consideration  of the individual plants' total
waste load and/or water quality considerations in effect  at
the particular plant location.

                           Phenol

Phenols  and  phenolic  wastes  are  derived from petroleum,
coke,  and  chemical  industries;  wood  distillation;   and
domestic  and  animal  wastes.   Many phenolic compounds are
more toxic than pure phenol.  Their toxicity varies with the
combination and general nature of total wastes.  The  effect
of   combinations   of   different   phenolic  compounds  is
cumulative.

Phenols  and  phenolic  compounds  are  both   acutely   and
chronically  toxic to fish and other aquatic animals.  Also,
chlorophenols produce an unpleasant taste in fish flesh that
destroys their recreational and commercial value.

It is necessary to limit phenolic  compounds  in  raw  water
used  for drinking water supplies, as conventional treatment
methods used by water  supply  facilities  do  not  normally
remove  phenols.  The ingestion of concentrated solutions of
                            279

-------
phenols will result in severe pain, renal irritation,  shock
and possibly death.

Phenols  also  reduce  the  utility  of  water  for  certain
industrial uses, notably food and beverage processing, where
it creates unpleasant tastes and odors in the product.

Phenols can be removed in biological treatment  systems  and
reduce the problems described above.

                         Phosphorus

Phosphorus,  commonly  reported  as  P,  is  a  nutrient for
aquatic plant life and  can  therefore  cause  an  increased
eutrophication   rate   in  water  courses.   The  threshold
concentration of phosphorus in  receiving  bodies  that  can
lead  to  eutrophication  is about 0.01 mg/1.  Phosphorus in
raw waste from the organic chemical industry is a result  of
cleaning operation.  In some cases phosphorus is part of the
product  processes  formulation  and  would  enter the waste
water from spills and equipment wash down.

During the past 30 years, a formidable  case  has  developed
for  the  belief  that  increasing standing crops of aquatic
plant growths, which often interfere with water uses and are
nuisances  to  man,  frequently  are  caused  by  increasing
supplies  of phosphorus.  Such phenomena are associated with
a  condition  of  accelerated  eutrophication  or  aging  of
waters.  Phosphorus is not the sole cause of eutrophication,
but  there is evidence to substantiate that it is frequently
the key element  required  by  fresh  water  plants  and  is
generally  present  in  the  least  amount relative to need.
Therefore, an increase in phosphorus allows  use  of  other,
already present, nutrients for plant growths.  Phosphorus is
usually described, for this reasons, as a "limiting factor."

When  a  plant  population  is  stimulated in production and
attains a nuisance status, a large number of liabilities are
immediately apparent.  Dense populations of pond weeds  make
swimming  dangerous.  Boating and water skiing and sometimes
fishing may be eliminated because of the mass of  vegetation
that  serves  as  an physical impediment to such activities.
Plant populations have been  associated  with  stunted  fish
populations and with poor fishing.  Plant nuisances may emit
vile  stenches,  impart  tastes and odors to water supplies,
reduce the efficiency  of  industrial  and  municipal  water
treatment,  impair  aesthetic  beauty,  reduce  or  restrict
resort trade, lower waterfront property values,  cause  skin
rashes  to  man during water contact, and serve as a desired
substrate and breeding ground for flies.
                             280

-------
 Phosphorus  in the  elemental  form is  particularly toxic,   and
 subject   to bioaccumulation  in much  the  same way as  mercury.
 Colloidal  elemental   phosphorus  will   poison   marine   fish
 (causing  skin  tissue  breakdown and discoloration).  Also,
 phosphorus   is  capable  of   being  concentrated  and    will
 accumulate   in  organs  and   soft tissues.   Experiments  have
 shown  that  marine   fish  will  concentrate   phosphorus   from
 water  containing as little as 1 ug/1.

 Adequate  amounts   of  phosphorus must be in a waste  water to
 permit adequate  microbial growth in  a biological treatment
 system   and  hence   obtain  satisfactory   treatment  plant
 performance.   If inadequate  amounts  of phosphorus are not in
 a waste  water to achieve adequate biological treatment plant
 performance,  supplemental phosphorus will have  to be  added
 to the waste water of  the biological treatment  system.

 Effluent  limitation   for phosphorus were  not established
 because  in  general the concentrations in  the   waste  water
 were  too  low  to warrant specific  controls..  With  specific
 product/processes  phosphorus may have to be added,  rather
 than  removed,    to   assure  adequate   phosphorus  for   the
 biological  rreatment systems.

 Total  Dissolved  Solids, Chlorides, Sulfides

 In natural  waters  the  dissolved  solids   consist  mainly  of
 carbonates,  chlorides,  sulfates,  phosphates,  and  possibly
 nitrates of calcium, magnesium, sodium,  and potassium,   with
 traces of iron,  manganese and other  substances.

 Many communities in the United States and in other countries
.use water supplies containing 2000 to 4000  mg/1  of dissolved
 salts,  when  no better water is available.   Such waters are
 not palatable,  may not  quench  thirst,  and   may  have  a
 laxative action  on new users.  Waters  containing more  than
 4000 mg/1 of  total salts are generally considered unfit   for
 human  use,  although   in hot  climates such   higher   salt
 concentrations can be  tolerated whereas  they could not be in
 temperate climates.  Waters  containing 5000 mg/1 or  more are
 reported to be bitter  and act  as  bladder  and  intestinal
 irritants.     It   is    generally   agreed    that the   salt
 concentration of good,  palatable water should not exceed 500
 mg/1.

 Limiting concentrations of dissolved solids for   fresh-water
 fish  may  range  from  5,000  to 10,000 mg/1,  according to
 species  and prior  acclimatization.  Some fish are adapted to
 living in more saline  waters, and a  few   species  of  fresh-
 water  forms   have been found in natural waters with a  salt
                             281

-------
concentration of 15,000 to 20,000  mg/1.   Fish  can  slowly
become acclimatized to higher salinities, but fish in waters
of  low  salinity  cannot  survive  sudden  exposure to high
salinities, such as those resulting from discharges of  oil-
well brines.  Dissolved solids may influence the toxicity of
heavy metals and organic compounds to fish and other aquatic
life,  primarily  because  of  the  antagonistic  effect  of
hardness on metals.

Waters with  total  dissolved  solids  over  500  mg/1  have
decreasing utility as irrigation water.  At 5,000 mg/1 water
has little or no value for irrigation.

Dissolved  solids  in industrial waters can cause foaming in
boilers and cause interference  with  cleanness,  color,  or
taste of many finished products.  High contents of dissolved
solids also tend to accelerate corrosion.

Specific  conductance  is a measure of the capacity of water
to convey an electric current.  This property is related  to
the  total  concentration of ionized substances in water and
water temperature.  This property is frequently  used  as  a
substitute method of quickly estimating the dissolved solids
concentration.

                          Cyanide

Cyanides  in  water  derive  their  toxicity  primarily from
undissolved hydrogen cyanide  (HCN)  rather  than  from  the
cyanide ion (CN~).  HCN dissociates in water into H* and CN~
in  a  pH  dependent  reaction.   At a pH of 7 or below, less
than 1 percent of the cyanide is present as CN—; at a pH  of
8, 6.7 percent; at a pH of 9, 42 percent; and at a pH of 10,
87  percent  of the cyanide is dissociated.  The toxicity of
cyanides is also increased by increases in  temperature  and
reductions  in  oxygen tensions.  A temperature rise of 10°C
produced a two- to threefold increase in  the  rate  of  the
lethal action of cyanide.

Cyanide  has  been  shown  to  be  poisonous  to humans, and
amounts over 18 ppm can have adverse effects.

Trout and other aquatic organisms are extremely sensitive to
cyanide.  Amounts as small as 0.1 part per million can  kill
them.   Certain  metals,  such  as  nickel, may complex with
cyanide to reduce lethality especially at higher pH  values,
but  zinc  and  cadmium  cyanide  complexes  are exceedingly
toxic.
                              282

-------
When  fish  are  poisoned  by  cyanide,  the  gills   become
considerably  brighter  in  color than those of normal fish,
owing  to  the  inhibition  by  cyanide   of   the   oxidase
responsible  for  oxygen  transfer  from  the  blood  to the
tissues.

The  following  is  a  summary  of  cyanide  data  which  is
significant:

    Subcateqory          Product           RWL Concentration
                                                    mg/1

       B                 Adiponitrile               187
                         Hexamethylene Diamine       20
       C                 Acrylonitrile              270

The   cyanide  results  from  the  previous  processes  were
determined  using  Standard   Method's   Cyanide   Titration
Procedure  with  and  without preliminary distillation.  The
following is a comparison of results from one plant:

                                                        CN
                                                       mg/1

    Standard Method Titration Procedure                4,870
    Standard Method Distillation - Titration Procedure   940

It has been reported that aldehydes combine with HCN to form
cyanohydes  during  distillation  and  that   this   complex
interferes  with  the  titration  procedure.   Based on this
analytical experience,  it  is  recommended  that  only  the
titration procedure be used with these waste waters.

                        Heavy Metals

Heavy   metals  (such  as  zinc,  copper  and  cadmium)  are
inhibitory to microorganisms because of their ability to tie
up proteins in their key enzyme systems.

                          Cadmium

Cadmium in drinking water supplies is extremely hazardous to
humans, and conventional  treatment,  as  practiced  in  the
United States, does not remove it.  Cadmium is cumulative in
the liver, kidney, pancreas, and thyroid of humans and other
animals.   A  severe  bone  and kidney syndrome in Japan has
been associated with the  ingestion  of  as  little  as  600
ug/day of cadmium.
                                   283

-------
Cadmium  is  an  extremely  dangerous  cumulative  toxicant,
causing insidious progressive chronic poisoning in  mammals,
fish,  and  probably  other animals because the metal is not
excreted.  Cadmium could form organic compounds which  might
lead to mutagenic or tetratogenic effects.   Cadmium is known
to   have  marked  acute  and  chronic  effects  on  aquatic
organisms.

Cadmium acts synergistically with other metals.  Copper  and
zinc   substantially  increase  its  toxicity.    Cadmium  is
concentrated by  marine  organisms,  particularly  molluscs,
which  accumulate  cadmium  in calcareous tissues and in the
viscera.  A concentration factor of 1000 for cadmium in fish
muscle has been reported, as have concentration  factors  of
3000  in  marine  plants, and up to 29,600 in certain marine
animals.  The eggs and larvae of fish  are  apparently  more
sensitive  than  adult  fish  to  poisoning  by cadmium, and
crustaceans appear to be more sensitive than fish  eggs  and
larvae.

                          Chromium

Chromium,  in  its  various  valence states, is hazardous to
man.  It can produce lung tumors when  inhaled  and  induces
skin   sensitizations.    Large   doses  of  chromates  have
corrosive effects on the  intestinal  tract  and  can  cause
inflammation  of  the kidneys.  Levels of chrornate ions that
have no effect on man appear to be so  low  as  to  prohibit
determination to date.

The  toxicity  of  chromium salts toward aquatic life varies
widely with the species, temperature,  pH,  valence  of  the
chromium,   and   synergistic   or   antagonistic   effects,
especially that of hardness.  Fish are  relatively  tolerant
of  chromium  salts, but fish food organisms and other lower
forms of aquatic life  are  extremely  sensitive.   Chromium
also inhibits the growth of algae.

In  some  agricultural  crops,  chromium  can  cause reduced
growth or  death  of  the  crop.   Adverse  effects  of  low
concentrations  of chromium on corn, tobacco and sugar beets
have been documented.

                           Copper

Copper salts occur in natural surface waters only  in  trace
amounts,  up  to  about  0.05  mg/1,  so that their presence
generally is the result of pollution.  This is  attributable
to  the  corrosive  action  of the water on copper and brass
tubing, to industrial effluents, and frequently to  the  use
                               284

-------
of  copper compounds for the control of undesirable plankton
organisms.

Copper is not considered to be a cumulative systemic  poison
for  humans,  but  it can cause symptoms of gastroenteritis,
with nausea and intestinal irritations,  at  relatively  low
dosages.   The limiting factor in domestic water supplies is
taste.   Threshold  concentrations  for  taste   have   been
generally  reported  in the range of 1.0-2.0 mg/1 of copper,
while as much as  5-7.5  mg/1  makes  the  water  completely
unpalatable.

The   toxicity   of   copper  to  aquatic  organisms  varies
significantly, not only with the species, but also with  the
physical   and   chemical   characteristics  of  the  water,
including  temperature,  hardness,  turbidity,  and   carbon
dioxide  content.   In  hard  water,  the toxicity of copper
salts is reduced by the precipitation of copper carbonate or
other insoluble compounds.  The sulfates of copper and zinc,
and of copper and cadmium are  synergistic  in  their  toxic
effect on fish.

Copper concentrations less than 1 mg/1 have been reported to
be toxic, particularly in soft water, to many kinds of fish,
crustaceans,    mollusks,    insects,    phytoplankton   and
zooplankton.  Concentrations of  copper,  for  example,  are
detrimental  to some oysters above .1 ppm.  Oysters cultured
in sea water containing 0.13-0.5 ppm of copper deposited the
metal in their bodies and became unfit as a food substance.

                            Zinc

Occurring abundantly in rocks  and  ores,  zinc  is  readily
refined into a stable pure metal and is used extensively for
galvanizing, in alloys, for electrical purposes, in printing
plates,  for  dye-manufacture  and for dyeing processes, and
for many other industrial purposes.  Zinc salts are used  in
paint    pigments,    cosmetics,    Pharmaceuticals,   dyes,
insecticides,  and  other  products  too  numerous  to  list
herein.   Many  of these salts  (e.g., zinc chloride and zinc
sulfare) are highly soluble in water;  hence  it  is  to  be
expected  that  zinc  might occur in many industrial wastes.
On the other hand, some zinc  salts  (zinc  carbonate, zinc*
oxide, zinc suifide)  are insoluble in water and consequently
it  is to be expected that some zinc will precipitate and be
removed readily in most natural waters.

In zinc-mining areas, zinc  has  been  found  in  waters  in
concentrations  as  high  as  50  mg/1 and in effluents from
metal-plating works and small-arms ammunition plants it  may

*The term toxic or toxicity is used  herein  in  the  normal
scientific  sense  of the word and not as a specialized term
referring to Section 307(a)  of the Act.
                             285

-------
occur in significant concentrations.   In  most  surface  and
ground waters, it is present only in  trace amounts.

Concentrations of zinc in excess of 5 mg/1 in raw water used
for drinking water supplies cause an  undesirable taste which
persists  through  conventional treatment.  Zinc can have an
adverse effect on man and animals at  high concentrations.

In soft water, concentrations of zinc ranging  from   0.1  to
1.0  mg/1  have been reported to be lethal to fish.   Zinc is
thought to exert  its  toxic  action   by  forming insoluble
compounds  with  the mucous that covers the gills, by damage
to the gill epithelium, or possibly by acting as an  internal
poison.   The  sensitivity  of  fish   to  zinc  varies  with
species, age and condition, as well as with the physical and
chemical characteristics of the water.  Some acclimatization
to  the  presence  of  zinc  is  possible.  It has also been
observed that the effects of zinc poisoning may  not  become
apparent  immediately,  so  that  fish  removed  from  zinc-
contaminated water to zinc-free water (after  4-6 hours  of
exposure  to  zinc)  may die 48 hours  later.  The presence of
copper in water may increase the toxicity of zinc to aquatic
organisms, but the  presence  of  calcium  or  hardness  may
decrease the relative toxicity.

Observed values for the distribution of zinc in ocean waters
vary  widely.   The  major  concern  with  zinc compounds in
marine waters is not one of acute toxicity,  but  rather  of
the  long-term  sub-lethal effects of the metallic compounds
and complexes.   From  an  acute  toxicity  point of  view,
invertebrate  marine  animals  seem to be the most sensitive
organisms  tested.   The  growth  of  the  sea  urchin,  for
example, has been retarded by as little as 30 ug/1 of zinc.

Zinc  sulfate  has  also  been  found  to  be lethal to many
plants, and it could impair agricultural uses.  Due   to  its
potential  toxicity,  zinc  can  be  a  pollutant parameter
requiring the establishment of an effluent limitation.

The following  concentrations  of  heavy  metals  have  been
reported as being inhibitory to biological treatment:

           Pollutant                Inhibitory Concentration
                                                 mg/L

           Copper                                1.0
           Zinc                               5.0 -  10.0
           Cadmium                               0.02*
           Total Chromium                        3.0
           Iron                                  5.0*
                             286

-------
*Inhibitory to anaerobic sludge digestion.
The following is a summary of the metals data from Tables 6-
2 through Tables 6-5  which  is  considered  significant  in
regard to inhibition of biological treatment:
Subcategory
     B
  Product
Adiponitrile
Chloromethanes

Methyl Chloride
                  HMDA
                  Maleic Anhydride
                  Perchloroethylsne
                  Propylene Oxide
                  Saccharin
                  Hydrazine
                  Plasticizers
                  Dyes
                  Vanillin
                  Miscellaneous
Metal RWL Concentration
               mg/L

      48     - Copper
      14.3   - Iron
       7.7   - Total Chromium
      26.3   - Copper
       0.21  - Cadmium
      18.8   - Iron
      33.8   - Zinc
      74.5   - Zinc
       0.4   - Cadmium
       9.45  - Total Chromium
       0.1   - Cadmium
      23.9   - Iron
      26.9   - Zinc
      27.6   - Copper
       0.23  - Cadmium
      97.9   - Copper
      61.6   - Copper
      17.2   - Iron
      12.6   - Total Chromium
Effluent   limits   are   established  for  copper  for  the
manufacture of  plasticizers,  dyes,  pigments  and  toners.
Chromium  is  limited  for the manufacture of dyes, pigments
and toners.  These metals were considerably higher  in  load
based  on  Ibs  per  1000  Ibs  product  for  these  product
segments.  Therefore effluent limits  were  established  for
copper and chromium for these segments.

pH, Acidity and Alkalinity
                                 287

-------
Waters  with  pH outside the 6.0 to 9.0 range can affect the
survival of most organisms, particularly invertebrates.  The
usual pH for raw waste falls between 6.0 and 9.0.   This  pH
range  is  close  enough  to  neutrality  that  it  does not
significantly affect  treatment  effectiveness  or  effluent
quality.  However, some control may be required particularly
if  pH adjustment has been used in the production processes.
The pH of the waste water then should  be  returned  to  its
normal  range  before  discharge.   The  effect  of chemical
additions  for  pH   adjustment   should   be   taken   into
consideration, as new pollutants could result.

Acidity  and  alkalinity  are  reciprocal terms.  Acidity is
produced  by  substances  that  yield  hydrogen  ions   upon
hydrolysis  and  alkalinity  is  produced by substances that
yield hydroxyl ions.  The terms "total acidity"  and  "total
alkalinity" are often used to express the buffering capacity
of  a  solution.   Acidity  in  natural  waters is caused by
carbon dioxide, mineral acids, weakly dissociated acids, and
the salts of strong acids and  weak  bases.   Alkalinity  is
caused  by strong bases and the salts of strong alkalies and
weak acids.

The term pH is a logarithmic expression of the concentration
of hydrogen ions.  At a pH of 7, the hydrogen  and  hydroxyl
ion  concentrations  are  essentially equal and the water is
neutral.  Lower pH  values  indicate  acidity  while  higher
values indicate alKalanity.  The relationship between pH and
acidity or alkalinity is not linear or direct.

Waters  with  a  pH  below  6.0 are corrosive to water works
structures,  distribution  lines,  and  household   plumbing
fixtures  and  can  thus  add  such constituents to drinking
water as iron, copper, zinc, cadmium and lead.  The hydrogen
ion concentration can affect the "taste" of the water.  At a
low pH, water tastes "sour".   The  bactericidal  effect  of
chlorine  is  weakened  as  the  pH  increases,  and  it  is
advantageous to keep the  pH  close  to  7.   This  is  very
significant for providing safe drinking water.

Extremes  of  pH  or  rapid  pH  changes  can  exert  stress
conditions  or  kill  aquatic  life  outright.   Dead  fish,
associated  algal  blooms,  and  foul stenches are aesthetic
liabilities of any waterway.   Even  moderate  changes  from
"acceptable"  criteria  limits of pH are deleterious to some
species.  The relative toxicity  to  aquatic  life  of  many
materials   is   increased  by  changes  in  the  water  pH.
Metalocyanide complexes  can  increase  a  thousand-fold  in
toxicity  with  a drop of 1.5 pH units.  The availability of
                              288

-------
many nutrient substances  varies  with  the  alkalinity  and
acidity.  Ammonia is more lethal with a higher pH.

The   lacrimal   fluid   of  the  human  eye  has  a  pH  of
approximately 7.0 and a deviation of 0.1 pH  unit  from  the
norm   may   result  in  eye  irritation  for  the  swimmer.
Appreciable irritation will cause severe pain.

Effluent  limits  for  pH  have  been  established  for  all
subcategories to decrease the difficulties noted above.
                               289

-------

-------
                        SECTION VII

             CONTROL AND TREATMENT TECHNOLOGIES


The  waste  loads  discharged  from  the  organic  chemicals
industry to receiving streams  can  be  reduced  to  desired
levels,   including   no   discharge   of   pollutants,   by
conscientious water management including  recycle,  in-plant
waste  controls,  process 'revisions, and by the use of waste
treatment systems.

Control and treatment technologies which are  available  for
waste waters in the organic chemicals industry can encompass
the  entire  spectrum  of  waste water treatment technology.
The selection of a particular technology is dependent on the
technology economics and the desired magnitude of the  final
effluent,  concentration.   Control  and treatment technology
may be divided into two major groupings:

    1.   In-plant pollution abatement.
    2.   End-of-pipe treatment.

After discussing the available performance data, conclusions
will be made relative to the reduction of various pollutants
commensurate with the following distinct technology levels.

    1.   Best Practicable Control Technology Currently
         Available (BPCTCA).
    2.   Best Available Technology Economically Achievable
         (BATEA) .
    3.   Best Available Demonstrated Control Technology
         (BADCT) for New Source Performance Standards.

To assess the economic impact  of  these  proposed  effluent
limitations  on  the  industry, model treatment systems have
been proposed which are considered capable of attaining  the
recommended  RWL  reduction.   It  should  be noted that the
particular systems chosen for use in the  economic  analysis
are  not the only systems which are capable of attaining the
specified pollutant reductions.

There exist  many  alternate  systems  which,  either  taken
singly  or  in  combination,  are  capable  of attaining the
effluent  limitations  and  standards  recommended  in  this
report.  These alternate choices include:

    1.   Various types of end-of-pipe waste water treatment.
    2.   Various in-plant modifications and installation  of
         pollution control equipment.
                              291

-------
    3.   Various combinations of  end-of-pipe  and  in-plant
         technologies.

The  complexity  of  the Organic Chemicals Industry dictated
the use of only one treatment model for each effluent level.
The use of a single treatment model for these  waste  waters
is  done only to facilitate the economic analysis and should
not be inferred as the only feasible technology to meet  the
limitations.

The  individual  manufacturer  within  the Organic Chemicals
Industry must make the  ultimate  choice  of  what  specific
combination  of pollution control measures is best-suited to
his  situation  in  complying  with  the   limitations   and
standards presented in this report.

In-Plant Pollution Abatement

The  complexity  of the organic chemicals industry precludes
the possibility of providing  a  specific  list  of  process
modifications  or  control  measures which are applicable to
all of the Industry's processes.

The elimination or reduction of in-plant  pollution  depends
upon any one of the following factors:

    1.   Plant process selection to minimize pollution.

    Present corporate environmental awareness requires  that
    new  products  and processes be evaluated with regard to
    their environmental aspects.

    2.   The modification of process  equipment  to  improve
         product recovery or to minimize pollution.

    These  areas have been discussed thoroughly in the Phase
    I Development Document.

    3.   Maintenance   and   good   housekeeping   practices
         minimize pollution.

    The  competitive  nature  of the industry in conjunction
    with the  flammable  nature  of  many  of  its  products
    requires  most  producers to operate their plants in the
    most: efficient manner possible.  This necessitates  good
    maintenance  and housekeeping practices.  However, there
    are other segments of the industry that  have  minimized
    maintenance  expenditures  and whose management does not
    adequately fund their environmental  control  staff  nor
                              292

-------
    support   them   in   their   quest   to  enforce  rigid
    housekeeping regulations.

    4.   The age of the plant and process  equipment  as  it
         impacts on pollution.

    Poorly  maintained  process  equipment  does not warrant
    consideration under this age  consideration.   The  real
    problem is that older plants generally have larger waste
    water loads than newer plants.  In addition, older plant
    layouts often do not allow for economic modifications to
    the process equipment to minimize pollution and, in many
    cases,  make  segregation  of  storm  and process waters
    difficult but not impossible.

Tne following in-process controls will lessen the raw  waste
load to the treatment facility:

    1.   the substitution of noncontact heat exchangers
    for direct contact water cooling;
    2.   the use of nonaqueous quench media as a substitute
    for water where direct contact quench is required;
    3.   the recycle of process water, such as between
    absorber and stripper;
    4.   the reuse of process water (after treatment) as a
    make-up to evaporative cooling towers through which noncontact
    cooling water is circulated;
    5.   the use of process water to produce low pressure
    steam by noncontact heat exchangers in reflux condensers
    of distillation columns;
    6.   recycle cooling for contact water systems
    (barometric condensers);
    7.   the recovery of spent acids or caustic solutions
    for reuse;
    8.   the recovery and reuse of spent catalyst solutions;
    9.   the use of nonaqueous solvents for extraction of
    products with subsequent recovery of solvents; and
    10.  addition of demisters.

Guidelines  for  Prevention, Control and Reporting of Spills
have  been   developed   by   the   Manufacturing   Chemists
Association   (MCA)  for use in the organic chemicals industry
and other industries.  This 22 page document  notes  how  to
assess  tne  potential  of spills and how to prevent spills.
Plants in the organic  chemical  industry  should  use  such
guidelines  as part o± good practice in-plant waste control.
Numerous  articles  are   available   that   indicate   that
significant  in-plant  controls can be instituted in organic
chemical plants to decrease the waste output.
                                293

-------
The production of organic chemicals results in many types of
contaminated  waste  waters,  and  the   treatment   methods
employed cover the range of known practical techniques.  In-
plant  control  is  the  first step in instituting treatment
practices.  Such controls include the salvage  of  unreacted
chemicals, recovery of by-products, multiple reuse of water,
good housexeeping techniques to reduce leaks and spills, and
changes in processing methods.  These controls can result in
reducing   the   concentrations   of  almost  all  potential
pollutants and can, most importantly, reduce the volumes  of
waste waters requiring treatment.

Flow  equalization equipment can be an important part of in-
plant waste water control.  Equalization facilities  consist
of  a  holding tank and pumping equipment designed to reduce
the fluctuations  of  waste  water  flow  through  materials
recovery   and   waste   treatment  systems.   They  can  be
economically advantageous, whether the industry is  treating
its  own  wastes or discharging into a city sewer after some
pretreatment.  The equalizing tank  should  have  sufficient
capacity to provide for uniform flow to treatment facilities
throughout  a  24-hour  day.  The tank is characterized by a
varying flow input and a constant flow output.

The major advantages  of  equalization  are  that  treatment
systems  can  be  smaller since they can be designed for the
24-hour  average  rather  then  the  peak  flows,  and  many
secondary  waste  treatment systems operate much better when
not subjected to shock loads or variations in feed rate.

Many plants do not require any special tanks to achieve flow
equalization  because  of  the  manner  in  which  they  are
operated.  For example, plants with large continuous systems
or  a  number  of  batch  systems  (10 to 20) with staggered
cooling cycles that operate most of the day  are  inherently
achieving a near-constant flow of waste water.  Other plants
need  to  institute  procedures or equipment to achieve flow
and waste load equalization.

Drainage  or  spills  from  raw  materials  may   contribute
significantly  to  the  total raw waste load.  These sources
can be controlled  or  eliminated  by  containing  them  and
attempting  recovery  and  reuse or disposal in a non liquid
manner.

The  following  list  of  spill   prevention   and   control
techniques  that  are  commonly  found throughout the liquid
handling industries and apply equally well  to  the  organic
chemicals industry:
                               294

-------
1.   Diked areas around storage tanks.

For flammable substances these are required; however, as
a passive barrier to tank rupture,  and  tank  and  pipe
connection   leaks,   a   diked  tank  storage  area  is
considered the  first-line  barrier  to  containing  and
reducing the spread of large-volume spills.

2.   Tank level indicators and alarms.

The sounding of alarms at prescribed levels during  tank
filling   could  be  expected  to  minimize  the  common
occurrence  of  overflow  when  reliance  is  on  manual
gauging for control.

3.   Above-ground transfer lines.

Above-ground installation  permits  rapid  detection  of
pipeline  failures  and  minimizes  hazardous  polluting
substances  from  polluting  ground  waters.    Although
increasing  the  possible  mobility into surface waters,
long-term considerations are believed  to  favor  above-
ground transfer lines.

4.   Curbed process areas.

Spills from processing equipment must often  be  removed
rapidly  from  the  area  but  prevented  from spreading
widely in the immediate area; consequently, curbed areas
connected to collecting sewers are indicated.

5.   Area catchment basins or slop tanks.

For  containment  of  small  spills  and  leaks  in  the
immediate  area thereby effecting removal at the highest
concentrations,  local  catchment  basins  can   provide
significant   flexibility   in  preventing  spills  from
entering water courses.

6.   Holding lagoons for general plant area.

Lagoons which  can  be  used  to  segregate  spills  and
prevent  them  from  passing  as  slugs into waste water
treatment  plant  or  water  courses,  give  the   surge
capabilities  necessary  for  handling  large  volume or
highly toxic spills.

7.   Initial waste water treatment.
                            295

-------
    .For treatment of floating substances or for the chemical
    neutralization or destruction of spilled materials,  the
    initial waste water treatment plants serve to ameliorate
    the more drastic effects of spills in receiving waters.

    8.   Availability of spill cleanup equipment.

    Vacuum trucks, booms, neutralizing chemicals  and  other
    similar equipment represent obvious contingency planning
    to cope with spills.

    9.   Routine preventative maintenance schedule.

    10.  Spill control plan.

    The formalization of a plan for coping with  spills  and
    the  training  of personnel in courses of action similar
    to plant safety programs is a highly desirable  approach
    of  coping  with  spills  in  a manner which would avoid
    entry into water courses and sewers thereby avoiding the
    disruption of waste water treatment facilities.

The application of  ancillary  control  techniques  requires
judicious  planning of operational philosophy, organization,
and specific management and control measures.

Operational Philosophy

Each plant management needs to formulate a  "Spill  Exposure
Index"  which  will  reveal  potentially-serious problems in
connection  with  its  operation.   Once  the  problems  are
defined, remedies and the costs of implementing them are not
difficult  to  determine.   The  next  step  is establishing
priorities, a  budget,  and  a  commitment  to  capital  and
operating  expenditures.   As  new  production  projects are
proposed for a plant site, each should incorporate  adequate
measures  for  spill  prevention  as an integral part of its
design.  Capital  investment  in  this  category  should  be
considered  to  be  important  as  an  investment in process
equipment or, alternatively, in more elaborate  waste  water
handling procedures.

One  approach  is  the development of a classification index
(taking into consideration the  minimum  aquatic  biological
toxicity,  and  effect on waste treatment plant performance)
which establishes ratings of hazardous polluting  substances
and recommends the minimum acceptable containment measures.

Organization
                               296

-------
Since  most of the prevention and control measures represent
added inconvenience and costs  in  the  eyes  of  the  plant
operating   staff,   even   when   wholeheartedly  accepted,
establishment  of  an  independent  group,  with  a   direct
assignment to minimize spills and authorized to take action,
is especially desirable.

Specific Measures

In  a  facility  with  a  "high  spill exposure index" there
should  be  a  review  of  the  designs  and  conditions  to
determine  the potential consequences of spills and leaks in
an objective manner.  The review should consider the  design
of  the process and equipment and should involve a piece-by-
piece physical inspection.  In common with  most  successful
projects,  there  is  no substitute for careful attention to
details.  All possible accidents and departures from routine
should be considered and  then  analyzed  in  terms  of  the
hazard  and  the corrective action or control measures which
could be applied.

All plant facilities need to be included, both  process  and
service  units.   A number of potential sources of leaks and
spills   can   frequently   be   eliminated   without   real
inconvenience to the process.

In  the  process area, a number of spill exposure conditions
are often found.  One of the most serious is limited storage
between coupled process units which may not be  in  balanced
operation.   Intermediate storage of this type is most often
designed on the basis of surge volume provided.   But  often
operating rates are difficult to adjust, and overflow of the
surge tank results.  When spill prevention per se becomes an
important  criterion, a major revision in standard operating
procedure, and perhaps a revised standard for  the  size  of
storage  may be called for.  Small leaks at shafts of pumps,
agitators, and valve stems are frequently tolerated; and  in
the  case  of  rotating  equipment,  is  desirable for shaft
lubrication and cooling.  In the aggregate, such losses  may
be  significant spills and should be prevented or contained.
Sampling stations and procedures should also be reviewed  to
curtail  unnecessary  discard of small quantities of process
fluids.  Vent systems are  potential  points  of  accidental
spill  and, on hot service, may allow a continuous spill due
to vaporization and condensation.

The major hazard in storage areas is catastrophic failure of
the tank,  an  accident  which  on  economic  grounds  alone
justifies  careful attention to tank design, maintenance and
inspection.  Containment  of  a  large  spill  is  desirably
                              297

-------
provided  by  diking  or  curbing,  but  these  systems need
analysis as to proper operation both in standby  status  and
in  the  event  of  a spill; safety principles and operating
convenience can both be in conflict  with  spill  prevention
and  the  differences  must be reconciled.  Venting and tank
overflow problems can be severe because of the cyclic nature
of  storage  operations;  accessories  such  as  heating  or
cooling   systems,   agitators,  instrumentation,  and  fire
prevention control systems all can represent  potential  for
spill.

Loading, unloading, and transfer operations are particularly
accident  prone.  Where materials with obviously high hazard
are involved, a high degree of reliability of  the  transfer
system  is  achievable  at a cost which is reasonable.  This
reliability  can  be  achieved  by  provision  of   adequate
equipment  but  also in large measure by strict adherence to
well thought out procedures.  Carelessness and shortcuts  in
operation  can  often occur.  The same philosophy applied to
less dangerous materials can be fruitful.  Permanent piping,
swing  joint  systems  and  flexible  hoses  can   be   used
successfully  for transfer and each has its place.  Each has
inspection and maintenance problems as well.  The design  of
transfer  lines must consider such questions as leaving them
full or empty when  idle,  purging  before  and  after  use,
protection with check valves, and manifolding.  Multiple use
of  a  transfer line should be avoided but when necessary on
economic or other grounds the design should provide a  clear
indication  to  the  operator  that valves are properly set.
Remote setting of valves,  and  panel  indication  of  valve
position  are  practical  systems  that could be more widely
employed.

The emphasis on in-plant pollution control  technology  must
be  based equally on adequate, well-maintained equipment and
on operational  vigilance  and  supervision.   Attention  to
tnese  details  will  often result in reducing significantly
not only the total loads on  waste  water  treatment  plants
but, most importantly, reducing the variability of pollutant
flows  with  a  concomitant  improvement  in  the quality of
treated waste waters emitted to receiving bodies.

£nd-of-Pipe Treatment

Because of tJae scarcity of treatment plant performance data,
it was determined to be reasonable to combine  the  Phase.  I
and  II treatment technology data for this study.  A summary
of the types of treatment  technology  which  were  observed
during both phases is listed in Table 7-1.  During the Phase
XI  study, 70 individual plants were surveyed; however, 6 of
                                298

-------
                         Table 7-1
               Organic Chemicals Study
              Treatment Technology Survey
Type of Treatment or Disposal Facility          Number of Plants Observed
                                                Phase IPhase II
Activated Sludge                                   7               9
Activated Sludge-aerated lagoon                    2               0
Activated Sludge-polishing pond                    0               1
Activated Sludge-solar evaporation pond            0               1
Trickling Filter-activated sludge                  1               0
Aerated lagoon-settling pond                       3               1
Aerated lagoon-no solids separation                2               1
Facultative Anaerobic lagoon                       4               4
Stripping Tower                                    1               1
No current treatment -                             37
   system in planning stage
To Municipal Treatment Plant                       5              23
Deep-well disposal                                 2               6
Physical Treatment, e.g., API Separator            4               3
Activated Carbon                                   0               6
Incineration                                       0               1
             TOTAL                                34              64
                                  299

-------
the 70 plants were previously surveyed during  the  Phase  I
study.   Table 7-1 has been prepared taking this duplication
into consideration.  Of the  plants  surveyed  in  Phase  II
which  are  subcategorized  in A, B, C, or D over 80 percent
provide their  own  waste  treatment  facilities,  while  60
percent of the Subcategory D plants discharge to municipally
owned treatment facilities.

A description of the treatment technologies that may be used
with  the  wastes  from  this  industry  is  first presented
followed by data obtained  in  the  Phase  I  and  Phase  II
surveys.

Waste  water  treatment  technology in the organic chemicals
industry relies heavily upon the use of biological treatment
methods.  These  are  supplemented  by  appropriate  initial
treatment to insure that proper conditions, especially by pH
controls  and  equalization,  are present in the feed to the
biological system.

JnitiaJ. treatment for the removal of solids is not routinely
required in the industry and is  installed  on  a  selective
basis  where  the  quantity  of  solids would interfere with
subsequent treatment.   The  initial  step  in  waste  water
treatment  is  often  equalization basins for control of pH.
Consequently, the disposal of sludges or  solids  from  this
initial  treatment  step  is not the same type of problem as
encountered in municipal sewage systems.

Technologies for removal of pollutants from water have  been
investigated  for  many years.  The technologies that appear
applicable  to  the  waste  waters  of  this  industry   are
identified in the following paragraphs.

There  are  many  variations  of  the basic activated sludge
process that can be used with success.  There are also  many
variations   of  treatment  system  operation  that  can  be
incorporated to assist in meeting effluent limits and  there
are  many approaches to upgrading existing systems when they
fail  to  perform  effectively.   Specific  plants  in  this
industry have modified their operation and design to achieve
better  performance.   Reports  on such modifications can be
noted in the literature.   Manuals to improve the design and
performance of treatment  systems  are  available  from  the
Environmental  Protection  Agency.   The  available  design,
operational  and  upgrading  techniques   are   within   the
capability of the organic chemicals industry to consider and
apply.
                              300

-------
Oil Removal

For those waste waters having significant quantities of oil,
gravity   separators   are  particularly  useful.   The  API
separator is the most widely used  gravity  separator.   The
basic  design  is  a  long  rectangular  basin,  with enough
detention time for most of the oil to float to  the  surface
and  be  removed.  Most API separators are divided into more
than one bay to maintain laminar flow within the  separator,
making  the  separator  more  effective.  API separators are
usually equipped with  scrapers  to  move  the  oil  to  the
downstream  end  of the separator where the oil is collected
in a slotted pipe or on a drum.   On  their  return  to  the
upstream  end,  the  scrapers travel along the bottom moving
the solids to a collection trough.  Any sludge which settles
can be dewatered and either incinerated or  disposed  of  as
landfill.

The  gravity  separator  usually consists of a pre-separator
(grit chamber) and a main separator, usually rectangular  in
shape, provided with influent and effluent flow distribution
and  stilling  devices  and  with  oil  skimming  and sludge
collection equipment.  It is  essential  that  the  velocity
distribution  of the approach flow be as uniform as possible
before reaching the inlet distribution baffle.

Anotner type of separator that has been used  in  refineries
is  the  parallel plate separator.  The separator chamber is
subdivided by parallel plates set at a 45° angle, less  than
six  inches apart.  This increases the collection area while
decreasing the overall size of the unit.  As the water flows
through the separator, the  oil  droplets  coalesce  on  the
underside  of the plates and travel upwards where the oil is
collected.  The parallel plate separator can be used as  the
primary gravity separator, or following an API separator.

If  the  effluent  from  the  gravity  separators  is not of
sufficient quality  to  insure  effective  treatment  before
entering   the  biological  or  physical-chemical  treatment
system, other processes such as clarifiers and dissolved air
flotation units may be used to reduce  the  oil  and  solids
concentration.

Clarifiers use gravitational sedimentation to remove oil and
solids  from a waste water stream.  Often it is necessary to
use chemical coagulants such as alum  or  lime  to  aid  the
sedimentation   process.    These   clarifiers  are  usually
equipped  with  a  skimmer  to  remove  any  floating   oil.
Clarifiers  used  after  a biological system normally do not
have skimmers as there should be no floating  oils  at  that
                             301

-------
point.   The  sludge  from the clarifiers is usually treated
before final disposal.

Dissolved Air Flotation (DAF)

These systems are used to remove suspended material  with  a
specific  gravity close to that of water.  The dissolved air
system generates a supersaturated solution  of  waste  water
and   air   by  pressurizing  waste  water  and  introducing
compressed air, then mixing the two  in  a  detention  tank.
This "supersaturated" waste water flows to a large flotation
tank  where  the  pressure  is  released, thereby generating
numerous small air bubbles which effect the flotation of the
suspended organic material by one of  three  mechanisms:  1)
adhesion  of  the air bubbles to the particles of matter; 2)
trapping of  the  air  bubbles  in  the  floe  structure  of
suspended material as the bubbles rise; and 3) adsorption of
the  air  bubbles  as  the floe structure is formed from the
suspended organic matter.   In  most  cases,  bottom  sludge
removal facilities are also provided.

There  are  three  process  alternatives  that differ by the
proportion of the waste water stream that is pressurized and
into which the  compressed  air  is  mixed.   In  the  total
pressurization  process,  the  entire  waste water stream is
raised to full pressure for compressed air injection.

In partial pressurization only a part  of  the  waste  water
stream,  either  a  portion  of  the  influent  or  recycled
effluent, is raised to the pressure of  the  compressed  air
for  subsequent  mixing.   If  a  sidestream  of influent is
pressurized, the pumping required in the system is  reduced.
In the recycle pressurization process, treated effluent from
the  flotation  tank  is recycled and pressurized for mixing
with the compressed air and then, at the point  of  pressure
release,  is mixed with the influent waste water.  Operating
costs  may  vary  slightly,  but   performance   should   be
essentially equal among the alternatives.

Improved performance of the air flotation system is achieved
by  coagulation  of the suspended matter prior to treatment.
This is done by pH adjustment or the addition  of  coagulant
chemicals,  or  both.  Aluminum sulfate, iron sulfate, lime,
and polyelectrolytes are  used  as  coagulants  in  the  raw
waste.   These  chemicals are essentially totally removed in
the dissolved air unit, thereby adding little or no load  to
the   downstream  waste  treatment  systems.   However,  the
resulting float and sludge may become a less  desirable  raw
material  for  recycling as a result of chemical coagulation
addition.  A slow paddle mix will improve coagulation.   One
                               302

-------
of  tne  manufacturers  of dissolved air flotation equipment
indicated a 60 percent suspended solids removal and 80 to 90
percent grease removal without the  addition  of  chemicals.
With the addition of 300 to 400 mg/1 of inorganic coagulants
and  a  slow  mix  to  coagulate  the  organic  matter,  the
manufacturer indicated  that  90  percent  or  more  of  the
suspended  solids and more than 90 percent of the grease can
be removed.  Total nitrogen  reduction  between  35  and  70
percent  was  found  in  dissolved air units surveyed in the
meat packing industry.

The reliability of the dissolved air flotation  process  and
of the equipment is well established.  The usefulness of the
dissolved air process can be realized by proper installation
and operation.  The feed rate and process conditions must be
maintained  at the proper levels at all times to assure this
reliability.  This fact is not always understood,  and  thus
full benefit is frequently not achieved.

Anaerobic Processes

The  high  concentrations  of  organic  matter  in the waste
waters from  this  industry  make  these  wastes  suited  to
anaerobic     treatment.      Anaerobic    or    facultative
microorganisms, which function in the absence  of  dissolved
oxygen,  break down the organic wastes to intermediates such
as  organic  acids  and  alcohols.   Methane  bacteria  then
convert  the  intermediates  primarily to carbon dioxide and
methane.  Much  of  the  organic  nitrogen  present  in  the
influent  is  converted  to  ammonia  nitrogen.   If  sulfur
compounds are present, hydrogen sulfide will  be  generated.
Acid conditions are undesirable because methane formation is
suppressed  and  noxious odors develop.  Anaerobic processes
are economical because they provide high overall removal  of
BODJD  with  low  power  cost and low land requirements.  Two
types of anaerobic  processes  that  may  be  used  are  the
anaerobic lagoon and the anaerobic filter.

Anaerobic  lagoons  are not widely used in this industry but
could be used as the first step  in  a  secondary  treatment
sequence.   BOD  removal  efficiencies  of  over  50 percent
generally can be achieved in the lagoons.  These lagoons are
relatively deep (3 to 5 meters, or about 10 to 17 feet), low
surface area systems with typical waste loadings of  240  to
320 kg BOD5/1,000 cubic meters (15 to 20 Ib BOD5/1,000 cubic
feet) and detention times of five to ten days.  A scum layer
may be allowed to accumulate on the surface of the lagoon to
retard  heat  ioss,  to  ensure  anaerobic  conditions,  and
hopefully to retain  obnoxious  odors.   Plastic  covers  of
nylon-reinforced  Hypalon, polyvinyl chloride, and styrofoam
                               303

-------
have been used on occasion to reduce heat loss.   The  waste
water  flow  inlet  should  be located near, but not on, the
joottom of the lagoon.   In  some  installations,  sludge  is
recycled to ensure adequate anaerobic seed for the influent.
The  outlet  from  the  lagoon  should be located to prevent
short circuiting of the flow  and  carry-over  of  the  scum
layer.

For  best  operation,  the pH should be between 7.0 and 8.5.
At a lower pH, methane-forming bacteria  will  not  survive,
the  acid  formers  will predominate and the system will not
perform effectively.  At a high pH (above 8.5), acid-forming
bacteria will be suppressed and lower the lagoon efficiency.

Advantages of an anaerobic lagoon  system  are  initial  low
cost,  ease  of  operation,  and the ability to handle shock
waste   loads,   and   a   consistent   quality    effluent.
Disadvantages  of  an  anaerobic  lagoon  are  the  hydrogen
sulfide generated from  sulfate-containing  waters  and  the
increased  ammonia  concentrations in the effluent.  If acid
conditions develop, severe odor problems result.   Anaerobic
lagoons  used  as the first stage in secondary treatment are
usually followed by aerobic units.   Anaerobic  lagoons  are
not permitted in some states or areas where the ground water
is  high  or  the  soil  conditions  are  adverse  (e.g., too
porous), or because of odor problems.

The  anaerobic  filter  represents  the   newest   anaerobic
treatment  process.  The unit is useful for the treatment of
dilute soluble wastes and in denitrifying oxidized effluents
for nitrogen control.  The  filter  consists  of  a  bed  of
submerged  media  through  which  waste  flows  in an upward
direction.  The anaerobic organisms grow within the bed  and
either  cling to the media or grow in the voids.  The filter
aas a large capacity for retaining microorganisms.   Of  the
types  of  media  that  have  been  tested, one-inch rounded
stones appear to be the best.

wastes with COD concentrations of over 750 mg/1 appear  well
suited  for  this  process.  COD removal efficiencies of 90+
percent have been obtained with  hydraulic  detention  times
greater than 18 hr and with wastes having COD concentrations
up to 2,000 mg/1.

The  microorganisms  remain  in  the filter for a long time,
even though the  hydraulic  retention  time  is  short.   No
solids recycle is incorporated in the anaerobic filter.  The
filter  responds  to  changing  waste  loads  and  has  been
indicated to operate well on a periodic basis.
                              304

-------
Difficulties will be encountered with wastes that will  clog
the  filter  media  and therefore high solids wastes are not
appropriate unless solids  removal  precedes  the  anaerobic
filter.   The wastes must have adequate alkalinity to buffer
any pH reduction during treatment.  Initial start up  of  an
anaerobic  filter  should be done carefully to establish the
proper  organisms.    Once   the   methane   organisms   are
established,  oxidized conditions should not be permitted to
occur in the filter.

Aerobic Lagoons

Aerobic lagoons (stabilization lagoons or  oxidation  ponds)
are  large  surface  area, shallow lagoons, usually 1 to 2.3
meters (3 to 8 feet) deep, loaded at a BOD5 rate of 20 to 50
pounds per acre.  Detention times vary from about one  month
to  six or seven months; thus, aerobic lagoons require large
areas of land.

Aerobic  lagoons  serve  three  main  functions   in   waste
reduction:

         Allow solids to settle out;

         Equalize and control flow;

         Permit  stabilization  of organic matter by aerobic
         and facultative microorganisms.

If the pond is deep, 1.8 to 2.4 meters  (6 to  8  feet),  the
waste  water near the bottom may be void of dissolved oxygen
and anaerobic organisms may be present.  Therefore,  settled
solids  can  be  decomposed  into  inert and soluble organic
matter by  aerobic,  anaerobic,  or  facultative  organisms,
depending  upon  the lagoon conditions.  The soluble organic
matter  is  also  decomposed  by  microorganisms.    It   is
essential  to  maintain  aerobic  conditions in at least the
upper six to twelve inches in shallow lagoons, since aerobic
microorganisms cause the most complete  removal  of  organic
matter.   Wind action assists in carrying the upper layer of
liquid (aerated by air-water interface  and  photosynthesis)
into  the  deeper  portions.   The  anaerobic  decomposition
generally occurring in the bottom converts solids to  liquid
organics,   which  can  become  nutrients  for  the  aerobic
organisms in the upper zone.

Algae growth is common in aerobic lagoons.   This  currently
is  a  drawback  when  aerobic  lagoons  are  used for final
treatment because the algae appear as suspended  solids  and
contribute  BOD_5.   Algae added to receiving waters are thus
                                305

-------
considered a  pollutant.   Algae  in  the  effluent  may  be
reduced  by  drawing  off the lagoon effluent at least 30 cm
(about 14 inches) below the  surface,  where  concentrations
are  usually  lower,  maintenance  cleaning  of  the lagoon,
installation of a "polishing" clarifier  or  combination  of
these  actions.   Algae  in  the  lagoon,  however,  play an
important role an stabilization.  They  use  CO2f  sulfates,
nitrates, phosphates, water and sunlight to synthesize their
own organic cellular matter and give off oxygen.  The oxygen
may then be used by other microorganisms for their metabolic
processes.

The  effluent  quality  of  a  lagoon system can be affected
adversely during certain periods of the year  by  the  algae
generated  in  the  lagoons.   The  quantity of algae in the
lagoon effluent can be variable and result  in  difficulties
in meeting the effluent limitations.  These algae can settle
out  in  the  bottom  of a receiving stream or lake, undergo
death and degradation, exert an oxygen  demand  in  effluent
samples  and  in the stream, and will be measured as part of
the solids in the effluent.

There are, however, a variety of approaches that can be used
to control the quantity of solids in the effluent.  Most  of
these approaches either are in use or have been demonstrated
to  the  point  that  they  can be used where needed.  Under
specific design and operational  conditions,  each  approach
can  Joe  economical.  The more applicable approaches include
microstraining,  coalgulation-flocculation,  land  disposal,
granular   media   or  intermittent  sand  filtrations,  and
chemical control.

Microstrainers  have  been  used  successfully  in  numerous
applications  for  the  removal of algae and other suspended
material from water.  In a  series  of  nine  investigations
over  a period of years, an average removal of 89 percent of
net plankton was observed.  Microstraining  requires  little
maintenance  and  can  have  practical  application  for the
removal of algae from stabilization ponds or lagoons  on  an
as needed basis.

Coagulation-flocculation,  followed  by  sedimentation,  has
been applied extensively for the removal  of  suspended  and
colloidal  material  from  water.   Coagulation-flocculation
requires competent operating personnel and adequate disposal
of the sludge that will be produced.

Land disposal for all or a portion of the  lagoons  effluent
during  periods  when the effluent limitations are not being
met can be a feasible approach.   The  effluent  limitations
                               306

-------
are  in  mass units, thus a reduction in outflow to a stream
during periods of high algae content may compensate for  the
increased   solids   concentrations   and  permit  the  mass
limitations  to  be  attained.   Spray   irrigation   in   a
controlled  manner  onto  adjacent  land can be accomplished
without additional environmental problems.

In filtration, the suspended material is removed by physical
screening, sedimentation, and inter  particle  action.   For
separation  of  algae  cells from lagoon effluents, granular
media filtration can be economic and produce a  satisfactory
effluent.

Chemical measures for the control of excessive algae growths
in  lagoons  are  dependent  upon   the type, magnitude, and
frequency of growth, the local conditions, and the degree of
control that is necessary.

.Recommended chemicals have included copper sulfate for algal
control.  Additional chemicals have been used  with  varying
success.   Recommendations usually should be directed to the
specific problem within  a  specific  body  of  water.   For
maximum  effectiveness,  algal  control  measures  should be
undertaken before the development of the algal bloom.

Thus, there are many alternatives that can be used for algae
control and/or removal to assure that  the  lagoon  effluent
quality  meets  the  described limitations.  The approach of
choice at a specific location will be  a  function  of  land
availability,   available  operating  personnel,  degree  of
difficulty in meeting the  limitations,  and  overall  waste
management economics.

Ice   and   snow   cover   in  winter  reduces  the  overall
effectiveness of aerobic lagoons by reducing algae activity,
preventing mixing, and preventing reaeration by wind  action
and  diffusion.   This  cover,  if  present  for an extended
period, can result in  anaerobic  conditions.   The  adverse
effects  of  this condition can be substantially overcome by
supplemental aeration using submerged aerators.  When  there
is  no  ice  and  snow  cover on large aerobic lagoons, high
winds can develop a  wave  action  that  can  damage  dikes.
Riprap,  segmented  lagoons,  and  finger  dikes are used to
prevent  wave   damage.    Finger   dikes,   when   arranged
appropriately,  also  prevent  short circuiting of the waste
water through the lagoon.  Rodent and weed control, and dike
maintenance are all essential  for  good  operation  of  the
lagoons.
                                307

-------
Advantages  of  aerobic  lagoons  are  that  they reduce the
suspended solids  and  colloidal  matter,  and  oxidize  the
organic  matter  of  the  influent to the lagoon.  They also
permit flow control and waste water storage.   Disadvantages
are  reduced  effectiveness  during  winter  months that may
require supplemental aeration, increase design capacity, and
require possible provisions for no discharge for periods  of
three  months  or  more.   In addition, there are relatively
large land requirements, the potential algae growth  problem
leading  to higher suspended solids, and odor problems for a
short time in spring, after the ice  melts  and  before  the
lagoon becomes aerobic again.

Aerobic  lagoons  usually  are  the  last stage in secondary
treatment and frequently follow anaerobic or anaerobic-plus-
aerated lagoons.  Large  aerobic  lagoons  allow  plants  to
store waste waters for discharge during periods of high flow
in  the  receiving  body of water or for irrigation purposes
during the summer.  These lagoons are popular in rural areas
where land is available and relatively inexpensive.

Aerated Lagoons

The  aerated  lagoon  is  a  smaller,  deeper  aerobic  pond
equipped  with  mechanical  aerators  or diffused air units.
The addition of oxygen enables the aerated lagoon to have  a
higher  concentration  of  microbes than the oxidation pond.
The retention time in aerated lagoons  is  usually  shorter,
between  three  and  ten  days.   Many  aerated  lagoons are
operated  without  final  clarification.    As   a   result,
biological  solids  are  discharged in the effluent, causing
toe effluent to have high BODJ5  and  solids  concentrations.
As   the   effluent  standards  become  more  strict,  final
clarification will be increasing in use.

Aerated lagoons use  either  fixed  mechanical  turbine-type
aerators,  floating  propeller-type  aerators, or a diffused
air system for supplying oxygen to  the  waste  water.   The
lagoons  usually  are 2.4 to 4.6 meters  (8 to 15 feet) deep,
and have a detention time ranging from hours to days.   BOD5_
reductions  in  completely  mixed  aerated lagoons may range
from 40 to 60  percent,  with  little  or  no  reduction  in
suspended  solids.   Because  of  this,  aerated lagoons are
compared to extended aeration units without sludge recycle.

Advantages of this  system  are  that  it  can  rapidly  add
dissolved  oxygen  (DO)  to meet the oxygen demand, provides
BOI/5 reduction, and requires a relatively  small  amount  of
land.   Disadvantages include the power requirements and the
fact that the aerated lagoon, in itself,  usually  does  not
                               308

-------
reduce  tfODjj  and  suspended solids adequately to be used as
the final stage in a high performance secondary system.

Activated Sludge

Controlled biological treatment using  activated  sludge  or
one  of  its  modifications  can be used to treat the wastes
from the organic chemicals industry.   In  the  conventional
activated   sludge  process,  recycled  biologically  active
sludge or floe is mixed in  aerated  tanks  or  basins  with
waste  water.  The microorganisms in the floe adsorb organic
matter from the wastes and convert  it  by  oxidation-enzyme
systems  to  such  stable products as carbon dioxide, water,
and  sometimes  nitrates  and  sulfates  or   nitrogen   gas
(denitrification).  The detention time required for adequate
waste  stabilization  depends  on  the type of waste and its
concentration, but the average time is about six hours.  The
floe,  which  is  a  mixture  of  microorganisms   (bacteria,
protozoa,  and filamentous types), acquired waste, and inert
fractions,  can  assimilate  organic  matter  rapidly   when
properly  active;  hence, the name activated sludge.  Oxygen
is introduced by mechanical aerators, diffused air  systems,
or other means.

From the aeration tank, the mixed sludge and waste water, in
which  little  nitrification  generally has taken place, are
discharged  to  a  sedimentation  tank.   Here  the   sludge
settles,  producing  a  clear  effluent,  low in BODJ5, and a
settled  biologically  active  sludge.   A  portion  of  the
settled sludge, normally about 20-25 percent, is recycled to
serve  as  an  inoculum  and to maintain a high mixed liquor
suspended solids content.  Excess sludge is removed  (wasted)
from the system to thickeners and  anaerobic  digestion,  to
chemical   treatment   and   dewatering   by  filtration  or
centrifugation, or to land disposal  where  it  is  used  as
fertilizer  and  soil  conditioner  to  aid  secondary  crop
growth.

This conventional activated sludge process can  reduce  BODJ5
and  suspended  solids up to 95 percent.  However, it cannot
readily handle shock loads  and  widely  varying  flows  and
therefore might require upstream flow equalization.

Although the microorganisms remove almost all of the organic
matter  from  the waste being treated, much of the converted
organic  matter  remains  in  the  system  in  the  form  of
microbial cells.  These cells have a relatively high rate of
oxygen  demand  and  must  be removed from the treated waste
water  before  discharge.   Thus,  final  sedimentation  and
                               309

-------
recirculation of biological solids are important elements in
an activated sludge system.

Sludge  is  wasted on a continuous basis at a relatively low
rate to prevent build-up of excess activated sludge  in  the
aeration  tank.   Shock  organic  loads usually result in an
overloaded system and poor sludge settling  characteristics.
Effective   performance   of   activated  sludge  facilities
requires  pretreatment  to   remove   inhibiting   material.
Equalization  also  is useful to prevent shock loadings from
upsetting the aeration basin.  Because of the high rate  and
degree  of  organic  stabilization  possible  with activated
sludge, application of this  process  to  the  treatment  of
organic chemicals waste waters has been receiving increasing
attention.

Many   variations   of  the  activated  sludge  process  are
currently in use.  Examples include:  the  tapered  aeration
process,  which  has  greater  air  addition at the influent
where the oxygen demand is the highest; step aeration, which
introduces the influent waste water along the length of  the
aeration  tank;  and  contact  stabilization.   The  contact
stabilization process is useful where the oxygen  demand  is
in  the  suspended  or colloidal form.  The completely mixed
activated sludge plant uses large mechanical mixers  to  mix
the  influent  with  the  contents  of  the  aeration basin,
decreasing the possibility of upsets due to shock  loadings.
Tne  Pasveer  or  oxidation  ditch  is  a  variation  of the
completely mixed activated sludge  process  that  is  widely
used in Europe.  In this process, horizontal cage rotors are
used to provide aeration and mixing in a narrow oval ditch.

The  activated  sludge  process  has  several disadvantages.
Because of the amount of mechanical equipment involved,  its
operating  and  maintenance  costs  are  higher  than  other
biological systems such as aerated lagoons or aerobic ponds.
The small volume of the aeration  basin  makes  the  process
more  subject  to  upsets  than  either  oxidation  ponds or
aerated lagoons.

The activated sludge process is capable  of  achieving  very
low concentrations of BOD5, COD TSS, and oil, dependent upon
the  influent waste loading and the particular design basis.
Reported efficiencies for BODfj removal are in the  range  of
80 to 99 percent.

Filtration

A  variety  of filters can be used to remove the solids in a
treated waste water:  intermittent sand filters,  slow  sand
                             310

-------
filters,  rapid  sand filters and mixed media filters.  BOD5
removal occurs primarily as a  function  of  the  degree  of
solids  removal.   The  effluent  from the sand filter is of
high quality.  A summary of available information  indicates
that  effluent  suspended solids concentrations of less than
10 mg/1 can be met.  Although  the  performance  of  a  sand
filter is well known and documented, it is not in common use
in  the organic chemical industry because use of refinements
of this type has not been  needed  to  reach  current  waste
water standards.

Waste  water  filtration  technology  has  been  applied  to
biological  treatment  effluents  for  some  time  but  with
greater  rapidity  in  the  past decade.  Major use has been
with municipal waste waters but it has also  been  used  for
industrial  waste  waters.  A chemical plant in England used
sand filtration for effluent solids reduction prior to 1960.

Filtration has been applied to  biologically  treated  waste
waters  in  the  petroleum  refining industry.  A full scale
mixed media filtration system is presently operating at  the
Marathon  Oil  Company,  Robinson,  Illinois.  Review of the
self-reporting data from the facility after installation  of
the  filters  and after 20 months of operation indicated the
following removal efficiencies by the filter:  BOD-22X, TSS-
72%.  The average concentration of BOD and  TSS  applied  to
tne filters was 12.3 and 42 mg/1 respectively.

Knowledge   of   waste   water   filtration  technology  has
progressed to the point that design manuals and  information
are  readily  available.   There  is ample reason to believe
that  waste  water  filtration  can  be   applied   to   the
biologically  treated  wastes  from  the  organic  chemicals
industry.

A slow sand filter is a specially prepared bed  of  sand  or
other  mineral  fines  on  which  doses  of  waste water are
intermittently applied and from which effluent is removed by
an under-drainage system.

It removes solids primarily at the surface  of  the  filter.
The  rapid  sand  filter  is  operated  to  allow  a  deeper
penetration of  suspended  solids  into  the  sand  bed  and
thereby  achieve  solids  removal  through  a  greater cross
section of the bed.  The rate of  filtration  of  the  rapid
filter  is  up  to  100  times that of the slow sand filter.
Thus, the rapid sand filter requires substantially less area
than the slow sand filter; however, the cycle time  averages
about  24  hours in comparison with cycles of up to 30 to 60
days for a slow sand filter.  The larger area  required  for
                              311

-------
the latter means a higher first cost.  For small plants, the
slow  sand  filter  can  be used as tertiary treatment:.  The
rapid  sand  filter  can  be  applied  following   secondary
treatment.   If  a  rapid sand filter were used as secondary
treatment,  it  would  tend  to  clog  quickly  and  require
frequent  backwashing,  resulting in a high water use.  This
wash  would  also  need   treatment   prior   to   discharge
particularly if the rapid sand filter were used in secondary
treatment applications with only conventional solids removal
upstream  in the plant.  Thus its use generally occurs after
secondary treatment.

The rapid sand filters operate essentially  unattended  with
pressure  loss  controls  and piping installed for automatic
backwashing.  They are contained in concrete  structures  or
in steel tanks.

In  a  rapid  sand filter, as much as 80 percent of the head
loss can occur in the upper few inches of the  filter.   One
approach  to  increase the effective filter depth is the use
of more than one media in the filter.   Other  filter  media
have  included  coarse coal, heavy garnet or ilmenite media,
and sand.  There is no one mixed media design which will  be
optimum for all waste water filtration problems.

Although  a mixed media filter can tolerate higher suspended
solids loadings than  can  other  filtration  processes,  it
still  has  an  upper  limit  of applied suspended solids at
which  economically  long  runs  can  be  maintained.   With
activated sludge effluent suspended solids loadings of up to
120  mg/1,  filter runs of 15-24 hour at 5 gpm/ft* have been
maintained when operating to a terminal head loss of 15 feet
of water.

The  effluent  quality  produced  by  plain  filtration   of
secondary  effluents  is  essentially  independent of filter
rate within the range of 5-15 gpm/ft primarily  due  to  the
high strength of the biological floe.  The following quality
of  filter  effluents  is presented as general guides to the
suspended solids concentration which might be achieved  when
filtering   a  secondary  effluent  of  reasonable  quality,
without chemical coagulation:  high rate  trickling  filter,
10-20   mg/1,    two  stage  trickling  filter,  6-15  mg/1,
contract srablization, 6-15  mg/1,   conventional  activated
sludge  plant,  3-10 mg/1, and activated sludge plant with a
load factor less than 0.15,  1-5 mg/1.

The slow sand filter has been in use for 50 years and  more.
It  has  been  particularly  well suited to small cities and
isolated   treatment   systems   serving   hotels,   motels,
                              312

-------
hospitals, etc., where treatment of low flow is required and
land   and   sand   are   available.    Treatment  in  these
applications has been  of  sanitary  or  municipal-type  raw
waste.   Rapid  sand filters have received most attention as
the  principal  method  to  treat  water   supplies.    More
recently,  applications  as  a  tertiary  treatment mode for
municipal  and  joint   municipal-industrial   waste   water
facilities  have  proven  successfuly.   Multi-media filters
were developed for general use in  the  mid  1960's.   These
filters  also have been used for potable water treatment and
tertiary treatment of waste water since that time.

The reliability of all principal types of filters  seems  to
be  well  established.   When  the  sand  filter is operated
intermittently, there should be little danger  of  resultant
discharge  of  untreated  effluent or poor quality effluent.
The need for bed cleaning becomes evident with the reduction
in quality of the effluent or in the increased  cycle  time,
both of which are subject to monitoring and control.

With   larger   sized   slow  sand  filters,  the  labor  in
maintaining and cleaning the surface should receive adequate
consideration.  Cleaning of the rapid sand  filter  requires
bacJcwashing of the bed of sand.  Backwashing is an effective
cleaning  procedure  and  the only constraint is to minimize
the washwater required in backwashing, since  this  must  be
disposed  of in an appropriate manner other than discharging
a  stream.   Chlorination,  both  before  and   after   sand
filtration,  particularly in the use of rapid filters may be
desirable to minimize or eliminate potential  odor  problems
and slimes that may cause clogging.

The  rapid  sand  filter  has been used extensively in water
treatment  plants.   Its  use  ir,  tertiary   treatment   of
secondary treated effluents appears to be a practical method
of  reducing BOD5 and suspended solids to levels below those
expected from conventional secondary treatment.

Carbon Adsorption

Activated carbon can be used to reduce the pollutional  load
of  many  kinds  of  waste  waters.  It is particularly well
suited for removal of various dissolved  organic  materials.
Most  but  not  all  dissolved  organics  can be adsorbed by
carbon. The exact degree of removal from  the  liquid  phase
depends  upon  a  number of factors.  An important aspect of
carbon adsorption is its  capability  of  removing  organics
which  are not completely removed by conventional biological
treatment.   Since  some  biodegradable  organics  are  also
                               313

-------
adsorbable,  carbon  can  be used in either of two ways:  to
upgrade or to replace conventional biological treatment.

Carbon removes dissolved organics through the action of  two
distinctly  different  mechanisms.  The first is adsorption,
which removes the dissolved organics from solution.  Organic
molecules in solution are drawn to the porous surface of the
carbon granule by inter-molecular attraction  forces,  where
the  organics  become  substrates  for  biological activity.
Biodegradation is thus the second mechanism by which  carbon
improves   water   quality.   Adsorption  is  the  principal
mechanism by which the dissolved organics are  removed  from
solution.   Adsorption is probably predominant when a carbon
column is first put into service.   As  operation  proceeds,
however,  the  biological process grows in importance as the
numbers of microorganisms increase.

Waste water treatment with  activated  carbon  involves  two
major   and  separate  process  operations.   The  water  is
contacted with the carbon by passing  it  through  a  vessel
filled  either with carbon granules or with a carbon slurry.
Impurities are removed from the  water  by  adsorption  when
sufficient  contact  time  is  provided.   The carbon system
usually consists of a number of columns or  basins  used  as
contactors.  These are connected to a regeneration system.

After  a  period  of  use, the carbon adsorptive capacity is
exhausted.  The carbon must then be taken out of service and
regenerated  thermally  by   combustion   of   the   organic
adsorbate.  Fresh carbon is routinely added to the system to
replace   that   lost   during   hydraulic   transport   and
regeneration.  These losses include both  attrition  due  to
pnysical   deterioration   and  burning  during  the  actual
regeneration process.

The activated carbon process utilizes granular  or  powdered
activated carbon to adsorb pollutants from waste water.  The
adsorption  is a function of the molecular size and polarity
of the adsorbed substance.  Activated carbon  preferentially
adsorbs large organic molecules that are non polar.

Tne function of activated carbon is the removal of dissolved
organics.   However, while many organics are adsorbed, those
molecules which are small or highly polar  are  not  readily
captured.   Methanol,  formic  acid, or sugars, for example,
are not easily adsorbed.  Such readily biodegradable organic
chemicals can be removed  by  biological  treatment.   Where
such  chemicals  are  in  the  waste water, activated carbon
should be used after  biological  treatment.   An  important
aspect  of  carbon  adsorption is its capability of removing
                              314

-------
organics which are not completely  removed  by  conventional
biological treatment.

Unless the suspended solids content of the waste water to be
treated  is  low,  prehaps  less  than  50-65  mg/1,  it  is
advisable  to   employ   dual-media   filtration,   chemical
coagulation,  or other particulate removal techniques before
applying the waste  water  to  the  carbon  bed.   Activated
carbon  is  too  expensive  to be used primarily as a filter
medium.  Thus an activated carbon unit frequently follows  a
solids removal process, usually a sand filter which prevents
plugging  of  the  carbon pores.  From the filter, the water
can flow to a bank of carbon columns arranged in  series  or
parallel.   As  the  water  flows  through  the  columns the
pollutants are adsorbed by the carbon, gradually filling the
pores.  At intervals, portions of the carbon are removed  to
a  furnace where the adsorbed substances are burnt off.  The
regenerated carbon is  reused  in  the  columns,  with  some
makeup added, because of handling and efficiency losses.

Detailed evaluation of carbon adsorption as a possible waste
water  treatment  technology began in 1960-61 as part of the
mandate of Congress  (PL 87-88)  to investigate advanced waste
treatment technology.

In recent years, many carbon  adsorption  applications  have
been  evaluated  on  a  full  scale.  These include granular
activated  carbon,   powdered   activated   carbon,   carbon
adsorption  as  the  entire  waste  water treatment process,
carbon added  to  existing  activated  sludge  systems,  and
carbon   adsorption  following  biological  treatment.   The
latter appears to be the most applicable for the wastes from
the organic chemicals industry.  Activated carbon technology
has been demonstrated and shown to be feasible in  a  number
of   applications   of  granular  activated  carbon  systems
currently in use by industry.

Process designs for carbon adsorption  systems  are  readily
available  from  consultants  and  equipment  manufacturers.
Process design procedures are available  in  the  literature
and  a  design  manual  is  available from the Environmental
Protection  Agency.   Several  of  the  companies  producing
organic  chemicals have subsidiaries or components that have
developed  significant  practical   experience   on   carbon
adsorption  and  are attempting to market that experience by
providing services to other industries in the  treatment  of
their wastes.

The   effluent   quality  obtainable  from  granular  carbon
treatment depends on the character of the waste water  being
                               315

-------
treated.   Therefore,  in  documenting the probable effluent
quality of carbon plants, the nature of the raw waste  water
and the type of pretreatment is important.

Other Technology

Among  the available waste water treatment technologies, the
following have reached a  reasonable  stage  of  development
and/or  can  be transferred from other industries when their
unique capabilities are required.
                                 316

-------
Ammonia Stripping

The removal of ammonia from alkaline solution is  the  major
potential  application  for  air  stripping.   Although  the
process  has   been   demonstrated   in   moderately   large
operations, its selection will depend upon the nature of the
waste waters and requirements for the removal of nitrogenous
substances.   Scale  formation  in  equipment,  typical of a
cooling tower configuration, can cause operational  problems
or  demand close control of the chemistry of the system.  In
addition, air stripping of ammonia is temperature sensitive,
proceeding at slow rates at low temperatures.  The  stripped
substances  are usually in such low concentrations that they
are not considered to be air pollutants.

Chemical Oxidation

Chemicals such as chlorine, permanganate, hypochlorite,  and
ozone  may  be  used  to chemically oxidize some pollutants.
Breakpoint  chlorination  for  destruction  of  ammonia   in
treated  waters  from  municipal sewage plants has long been
recognized and ozone has been  used  for  the  treatment  of
potable  water.   The  application  of  oxidative  chemicals
requires  that  specific  determination  be  made  of  their
effectiveness in removing the pollutants, and in particular,
to  determine  if the reaction products are innocuous.  As a
particular example, the chloramines produced by chlorine and
ammonia are more toxic to aquatic  life  than  the  ammonia.
Similarly,  the  toxic  aspects  of  the  chemicals  must be
carefully evaluated to insure that the removal of  one  type
of  pollution  does  not  result in creating a different or,
perhaps, even more severe pollution problem.  It is expected
that  chemical  oxidation  will  be  employed  on  a  highly
selective  basis such as in the destruction of cyanide where
its overall effectiveness is assured.

Foam Separation

Surfactants added to a waste water followed by air  diffused
in the liquid to produce a foam can effect the concentration
of various substances often found in waste waters.  However,
successful  development  above the pilot plant scale has not
been  demonstrated  and  its  usefulness  as   a   treatment
technology will be limited.

Algal Systems

Nutrient  removal  by  the  growing  of algae is well known;
however, it has not achieved any significant acceptance  due
                               317

-------
primarily  to  (1)  the necessity of having a relatively warm
climate  with  high  incidence  of  sunshine  and  (2)    the
difficulties  of  removing  the  algae  from the waste water
before discharge.

Incineration

Destruction of pollutants by combustion or  incineration  is
technically feasible regardless of the concentration insofar
as the products of combustion do not create an air pollution
problem.   At the present time, incineration of concentrated
liquid  wastes  containing  phenolic  compounds   is   being
practiced.     Equipment    is   available   for   achieving
incineration of virtually any type of  waste;  however,  the
use of supplementary fuel is usually required.  Incineration
is  not  frequently used because of the high cost of energy.
In some instances where the removal of pollutants cannot  be
achieved  in a less costly manner or because disposal of the
removed  pollutants  still  presents   a   severe   problem,
incineration may be an appropriate method of water pollution
control

Wet Air Oxidation

The  oxidation  of  organic pollutants by introducing air or
oxygen into water under pressures of from 300 to  1800  psig
has been primarily used for the destruction of sludges.  For
the  oxidation to proceed autogenously, it is necessary that
a  sufficient  concentration  of  oxidizable  substances  be
present  to  provide  the  exothermic  energy  necessary  to
maintain the required temperatures.   Partial  oxidation  of
concentrated  biological  streams  such  as the sludges from
initial and biological treatment  results  in  a  stabilized
solid  which  can  be  used  as a soil conditioner.   Wet air
oxidation will continue to be considered primarily  for  the
destruction  of  concentrated pollutants such as slurries or
sludges.

Liquid-Liquid Extraction

The transfer of mass between two immiscible phases,  known as
liquid-liquid extraction, is often capable of achieving high
degrees of removal and recovery of selected components.  The
technology has been  well  developed  in  the  chemical  and
nuclear fuel industries but has been infrequently applied to
the   treatment   of  waste  water  streams.   Liquid-liquid
extraction would be employed to remove a relatively valuable
component or a particular noxious  substance  from  a  waste
water  stream  prior  to  additional  treatment.   A typical
example is the recovery of phenolic compounds.  Loss of  the
                               318

-------
extracting  liquid  to  the  water stream must be considered
since it may then be  a  pollutant  which  requires  further
removal before discharge of the treated waste water.

Ion-Exchange

The  removal  of  ions from water by the use of ion-exchange
resans has been well  established  in  the  field  of  water
treatment.   Man-made resins or naturally occurring minerals
such as zeolites or  clinoptilolite  have  been  used.   The
removal  of  zinc  from viscose rayon wastes by ion-exchange
has  been  demonstrated;   however,   successful   long-time
operation has not been achieved.  Ion exchange has been used
for  the  removal  of  nitrates, and clinoptilolite has been
shown to be effective in the removal of  ammonium  ion  from
waste  waters.   Although  ion  exchange can be an effective
method for the removal of ionic  species  from  waters,  the
economic  necessity  for  regeneration  of  the ion-exchange
media results in a  concentrated  liquid  stream  for  which
further  disposal  must  be  considered.   The  use  of  ion
exchange in waste water treatment would be  limited  to  the
selective  removal  or concentration of pollutants for which
more  economically  effective  methods  are  not  available.
Since  ion-exchange  regenerates  added  mass  to  the waste
stream  from  the   regeneration,   ultimate   disposal   of
concentrated  streams from ion-exchange systems will contain
more total dissolved solids  than  removed  from  the  waste
waters.

Reverse Osmosis

Desalination  research  and  development  efforts  have been
responsible for the development  of  reverse  osmosis  as  a
method  for  removal  of  ionic  species  from waste waters.
Nonionic species also can be removed;  however,  control  of
membrane  fouling  must be given special consideration.  The
major process advantage of reverse osmosis is its low energy
demand when compared with evaporation  and  electrodialysis;
however,  the  costs  of  replacement  membranes  may  be an
offsetting  factor  to  the   total   cost   picture.    The
applicability  of  reverse osmosis to the treatment of waste
water streams can only be determined by laboratory and pilot
plant tests on the waste water of concern.  As in  the  case
of  ion  exchange,  reverse  osmosis produces a concentrated
stream containing the removed pollutants  and  further  con-
sideration must be given to its disposal.

Evaporation
                              319

-------
Evaporation  has been well developed and widely used for the
desalination  of  seawater.   Furthermore,  it  is  a   well
developed  operation  in  the  chemical  process industries.
Direct evaporation is the most energy consuming of the water
removal processes; therefore, elaborate multi-stage  systems
are  required  to effect energy economy.  Its application to
the  concentration  of  selected  waste  water  streams   is
established;   however,   evaporation  is  usually  used  in
conjunction with other process operations where  the  energy
demands   and   resulting   concentrated  solutions  can  be
justified on the basis of most economic overall performance.

This approach can be expected to continue  in  the  face  of
rising  energy  costs and increasingly stringent limitations
on waste water discharges.   The  technical  feasibility  of
evaporation   will   have  to  be  determined  for  specific
situations since a highly concentrated waste water may cause
fouling of heat transfer substances.  Also, volatile species
which can be removed by  the  steam  stripping  action  and,
consequently,  appear  in  the condensate would mean further
treatment before reuse or discharge.  The disposal of highly
concentrated streams of pollutants must be considered.

Electrodialysis

Developed for the desalination of water, electrodialysis  is
a  separation  technique  that  would be expected to compete
with ion exchange, reverse osmosis, freezing and evaporation
for the removal of pollutants from waste water streams.   As
in the case of all of these, electrodialysis for waste water
treatment  must  be  chosen  on  the  basis of achieving the
necessary performance under required operating conditions.

                    PLANT SURVEY PROGRAM
             Single-stage Biological Treatment

During  the  plant  survey  program,  historic  waste  water
treatment   plant   performance   data  were  obtained  when
available.  The data were statistically analyzed, and,  when
possible,  the  individual  plant  performance was evaluated
with respect to the original design  basis.   Subsequent  to
this  evaluation,  a  group  of plants was selected as being
exemplary in performance as indicated  by  effectiveness  of
BODj>   removal.    These  particular  exemplary  plants  are
indicated in Table 7-2, which is a summary  of  all  of  the
historic performance data made available by industry for the
purposes  of  the study.  The amount of analytical data used
in the statistical analyses are indicated in the "data  base
column"  of  Table  7-2.   The following is a summary of the
average reductions capable of exemplary treatment plants:
                              320

-------
                                                                                    Table 7-2
                                                                      Historic Treatment Plant Performance
                                                                          50% Probability of Occurrence
                                                 COD
                                                                             BOD
                                                                                                         TOC
                                                                                                                                      SS
                                                                                                                                                                Data Base
Plant
No.
11
21.2
31
41
51.2
6
7
81
9'
101
,,1.2
12
13
14
15
16'
171
18
19'
201
Exemplary
Exemp la ry
Treatment
System
AL
AS-AL
AS
AS
TF-AS
AL
AL
AL
AS
AS
AS-AL
AS
AS
AS
AL
AS
AS
AS
AS
AS
Plant Average
Single Stage
Category °i
D
C
D
B
B
B-C
C
B
C
B
C
A-B
B-C
B

D
D
D
D
C
>
Plants - Average
i Removal
75
96.4
63
64.2
73.5
~
-
-
-
74.5
-
85
—
—
—
—
67
25.4
-
~
74
69
Effluent
320
470
200
120
83
~
165
75
-
80
-
97
610
—
226
—
1 ,760
1,520
--
296
378

% Removal
97
-
93.5
-
—
~
--
-
83
90.1
99.7
-
—
73
-
82.5
—
63.6
97.6
98.8
93
92
Effluent „. D , Effluent
,. % Removal ,,
10
„
16
15
-
291
9.9
23.5
152 60 170
20
20 97 100
59
294 — 295
410 42 780
63
362
—
303
157
46.9
82.2 79 135
60
o/ „ i Effluent
% Remova 1 , ,
—
163
55
—
-
665
81
24.3
130
-
-370 145
..
189
280
-
289
_.
480
-
„
134
-
Durat i on
(months)
6(Sept-Feb)
12
12
14
14
12
12
12
7(Aug-Feb)
12
12
12
14
14
6(July-Dec)
S(Aug-Mar)
6(June-Oct)
12
5(June-Sept)
5 (June-Sept)


Performance
Pe r i od
dai ly average
dai ly average
monthly average
monthly average
monthly average
weekly average
monthly average
monthly average
dai ly average
weekly average
dai ly average
monthly average
monthly average
monthly average
weekly average
monthly average
dai ly average
weekly average
monthly average
weekly average


 Plants considered to be exemplary in performance.
 Multiple-stage biological  treatment.


^Plant 16 is not included in average.

-------
                                                                                      Table 7-3
                                                                          Treatment Plant Survey Data
Plant No.
   11

o  13

^  162

   172


   18

   192

   202

   21

   22

   23

 Average

 1
                AS-AL

                 AS

                 AS

                TF-AS

                 AL

                 AL

                 AS

                AS-AL

                 AS

                 AS

                 AS


                 AS

                 AS

                 AS

                 AL

                 AS

                 AS
                                B

                               B-C
COD
% Removal

64
71
57
59
66
69
75
94
65
54.8
60.0
77.3
22.1
59.5
96.2
62
16.1
95.^
72
Effluent
mg/L
2,300
284
214
133
980
92
595
337
940
1 ,650
1 ,400
1 ,000
2,680
5,100
317
600
1 ,370
147

Total
% Remova 1

90
73
82
92
73
84
92
99
90
82.1
81.4
90.0
16.7
69.8
99.5
78
47.5
92.6
87
BOD
Effluent
mg/L
427
74
13
12
235
6
75
16
177
300
240
310
650
1 ,800
19
27
210
41

TOC
% Removal
mg/L
32
71
35
43
1 1
26
69
27
64
80.8
63.4
76.8
-
55.8
96.6
66
8.3
95.4
58
Effluent
mg/L
2,710
132
80
61
573
52
242
343
470
280
410
360
1 ,025
1 ,700
114
47
550
35

TSS
% Removal

Negative
Negative
40
97
Negat i ve
99
Negative
Negat i ve
120
43.6
Negative
42.9
Negat i ve
Negat i ve
89
53.4
Negat i ve

Effluent
mg/L
4,700
62
14
44
362
3
50
145
338
552
1 ,300
732
1 ,170
2,500
100
30
82
37

TDS
Effluent
mg/L
2,300
3,100
2,900
1 ,430
3,000
690
3,810
2,690
1 ,520
10,990
3,750
4,060
2,050
8,360
1,950
9,800
15,400
580

Oi 1 £- Grease
Effluent
mg/L
-
13
43
23
113
-
,23
,3
63
2264
22k
1064
-
194
-
<.034
21*

 Based on 24 hrs composite samples.
^Plants considered to be exemplary in performance based on  historical data.
.Oil and grease are reported as carbon tetachloride extractables.
 Oil and grease are reported as Freon extractables.
-"Includes exemplary plants as well as Plant 23.

-------
                         COD       BOD       TOC     Effluent
                       Removal   Removal   Removal     TSS	
                       percent   percent   percent     mg/1

Exemplary Single- and
Multiple-Stage Plants     74        93        79       134

Exemplary Single-stage
Plants                    69        92        60        65

Major differences in performance data were observed for  TOC
removals   because   only  two  historic  data  points  were
available.

During the survey program, 24-hour  composite  samples  were
obtained  in  order to verify the plant historic performance
data, as well as to provide  a  more  complete  waste  water
analytical profile.  These results are presented in Table 7-
3.   The  following  is  a summary of the average reductions
capable of being attained by exemplary treatment as verified
by composite sampling:

                                  COD       BOD        TOC
                                Removal   Removal    Removal
                                percent   percent    percent

    Exemplary Treatment Plants   72        87         58

The results of the composite sampling program compared  well
with  the  historic data, thus, verifying the historic plant
information.  The TOC(removal of 58 percent  would  seem  to
substantiate  the  lower  value  of 60 percent as previously
indicated (Table 7-2).  As  indicated  by  the  TSS  removal
data,  9 of the 17 plants surveyed had negative TSS removal.
Over 75 percent of the plants had inadequate solids handling
facilities.

There are very wide variations in the suspended solids  data
obtained  in  the  verification sampling (Table 7-3).  These
variations are beyond the normal variations  experienced  at
well  designed  and operated biological treatment plants.  A
major  problem  was  that  the  biological  sludge  in  many
facilities  is  not  wasted, thereby increasing TSS effluent
levels.   Unless  one  is  thoroughly  familiar   with   the
operation  of the particular plant surveyed, it is difficult
to interpret TSS data, much less  use  it  to  set  effluent
limits.  For this reason, recommendations concerning TSS for
the  technology  levels  BATEA  and  BADCT were based on the
performance  experience   of   adequately   designed   units
functioning in other industries.
                                323

-------
    Multiple-Stage Biological Treatment

During  the  course  of the plant surveys, three plants were
observed to have multiple-stage biological treatment.  Plant
5 (see Table 7-2)  required two-stage  treatment  for  phenol
removal,  while  Plants  2  and  11  required  it because of
relatively high raw waste  loads  and  rigid  water  quality
criteria.   Multiple  biological  treatment is being used in
the industry and can achieve high pollutant  removals.   The
Phase   I   recommendation   that  biological  treatment  be
considered BPCTCA is further substantiated by the  Phase  II
survey data.

    Performance of Industry Treatment Systems

As  part  of  the  survey  conducted  for  this phase of the
industry, no waste water treatment technology was found that
was  unique  to  the  organic   chemicals   industry.    The
application   of   end-of-pipeline   waste  water  treatment
technology  throughout   the   industry   includes   similar
operational  steps.   The  waste  water treatment technology
presently used  in  the  industry  is  generally  applicable
across all industry subcategories.

End-of-pipe   treatment   technology   is  based  upon  well
established methods, such as biological treatment, which can
be carried out in various types of  equipment  and  under  a
wide variety of operating conditions.  The treatment systems
for  the  organic  chemicals  industry  can  be  affected by
intermittent, highly concentrated waste  loads  due  to  the
nature  of  certain  pollutant  generating  operations or to
inadvertent spills and leaks.  The effective control methods
for such intermittent loads are to prevent  their  occurence
or  provide  sufficient  volumetric capacity in equalization
basins to ameliorate their effect.

A combination of methods may  be  used  depending  upon  the
nature  of the process operations, safety requirements  (such
as the dumping of reactors to prevent runway  reactions  and
possible  explosions), and the availability of land area for
the construction of  equalization  basins.   For  presently-
operating   plants,  the  most  practical  solution  is  the
installation of an equalization basin of  sufficient  volume
and  residence time to insure that any "slugs" of pollutants
can  be  mixed  into  larger  volumes.   This  will  usually
guarantee that concentration levels are lowered to the point
where the operability of the ensuing treatment step, usually
the  biological  system,  will not be overly affected unless
the pollutants are highly toxic to the microorganisms.
                                324

-------
The importance of equalization prior to biological treatment
cannot be overstressed when the potential exists  for  large
variations in either flow or concentrations of waste waters.
Equalization basin design may vary from simple basins, which
prevent  short circuiting of inlet waste waters to the basin
outlet going into  the   waste  water  treatment  plant,  to
basins  which  are  equipped with mixers to insure rapid and
even mixing of influent waste water  flows  with  the  basin
volume.   In either case, the operability and reliability of
an  equalization  basin  should   be   high   with   minimal
expenditure  of  operating labor and power.  The results are
well-designed and  well-operated  equalization  basins  that
insure that the subsequent treatment steps, especially those
steps  sensitive to fluctuating conditions  (i.e., biological
treatment),  are  not   confronted   with   widely   varying
conditions which may drastically affecc overall performance.

The  operability,  reliability and consistency of biological
waste water treatment systems  are  subject  to  a  host  of
variables.   Some  of  the most important are the nature and
variability  of  both  the  flow   and   the   waste   water
composition.   The  best  overall  performance of biological
treatment systems is realized when the  highest  consistency
of  flow  and waste water composition occurs.  While it must
be recognized that no waste water stream can be expected  to
have  constant  flow at constant composition, it is possible
to insure that these effects are ameliorated by equalization
basins.  Equalization, coupled with attention to such  items
as   the   possible   occurrence   of   chemicals  toxic  to
microorganisms, is  the  basis  for  achieving  the  maximum
potential  in  operability,  reliability, and consistency of
biological systems.  Although in-line  instrumentation  such
as  pH,  dissolved oxygen and total organic carbon analyzers
are available, their usage, except for pH and, infrequently,
dissolved oxygen,  for  in-line  control  is  minimal.   The
reliability  of some in-line instrumentation for control has
not been developed to a degree where it is frequently  used.
Control  of  the  biological  waste  water treatment process
relies  principally  on  adequate  designs   and   judicious
attention  to  the  physical  aspects  of  the plant.  Well-
trained,  conscientious  operators  are  most  important  in
achieving  the maximum potential reliability and consistency
in biological treatment plants.

Achieving a high degree of operability and consistency in  a
waste   water   treatment   plant  is  contingent  upon  the
application of good process  design  considerations  and  an
effective maintenance program.  The most important factor is
the   incorporation   of  dual  pieces  of  equipment  where
historical experience indicates  that  high  maintenance  or
                              325

-------
equipment,  modification  is  apt  to  occur.    Although  the
highest degree of performance reliability would be  achieved
by   installing   two   independent  waste  water  treatment
facilities, each capable of handling the entire waste  water
load, practical installations and operating costs as well as
the well-demonstrated operability of waste treatment plants,
indicate  that  a  judicious  blend  of  parallelism,  surge
capacity, and spare equipment are the major  factors  to  be
considered.   Some  of  the  most  critical  parameters that
should  be  incorporated  in  the  design  of  waste   water
treatment for the organic chemicals industry are as follows:

    1.   Provision  for  surge  capacities  in  equalization
    basins  or special receiving basins to permit repair and
    maintenance of equipment.

    2.   Installation  of  excess  treatment   capacity   or
    provisions  for  rapidly  overcoming  effects  which may
    destroy  or  drastically  reduce  the   performance   of
    biologically based treatment systems.

    3.   Installation of spare equipment, such as pumps  and
    compressors,   or   multiple   units,  such  as  surface
    aerators, so that operations can be continued at  either
    full or reduced capacity.

    4.   Layout of equipment and selection of equipment  for
    ease of maintenance.

    Filtration

Supplemental  organic  pollutant and solids removal is being
practiced within the industry in one particular case using a
polishing pond.  One major problem during summer periods  is
algal  blooms  which, if unchecked, can drastically increase
the  TSS  and  COD  of  the  polishing  pond  effluent.   In
addition,  the acreage requirements of this system limit its
potential uniform application.

As described earlier, filtration can do an excellent job  of
removing  particulate matter from the effluent of biological
treatment systems.  Where appropriate  technology,  such  as
filtration, is not routinely used in the industry and hence,
operaring   treatment  plant  data  is  not  available,  the
following approaches  would  be  used  in  deciding  whether
filtration technology was appropriate for consideration: (a)
utilize   performance   data   from  waste  water  treatment
situations where filtration had been used,   (b)  attempt  to
obtain  reasonable  estimates  using  samples  of biological
                              326

-------
treatment plant effluent, or  (c)  a  combination  of  these
options.  The combination option  was investigated.

To  quantify  the  effectiveness  of effluent filtration for
this industry, the following steps were taken.   First,  the
existing literature and data on filtration of effluents from
biological waste treatment plants were reviewed to ascertain
the  general  performance  that  could be expected.  Second,
samples of the effluents from  biological  treatment  plants
treating  organic  chemical  waste  waters were tested using
laboratory filter tests to see if the results of such  tests
appeared  reasonable  as  compared to the results from other
situations described in the  literature.   The  results  are
presented  in  Table 7-4.  Average percent COD, BOD, and TOG
removals associated with filtration  are  20,  17,  and  20,
respectively.   Comparison  of the laboratory and literature
data revealed that filtration was a feasible technology  for
this industry.

    Carbon Adsorption

Granular  activated  carbon technology is continuously being
developed  and  is  beginning  to  compete   actively   with
biological treatment as a viable treatment alternative or as
a  biological  treatment effluent polishing process for some
industrial wastes.  This technology has been applied to  the
waste of the organic chemicals industry.  The technology has
been  used with other waste waters and has been demonstrated
at the pilot plant and full scale plant levels.  To identify
whether carbon adsorption can be used with the waste  waters
from  this  industry,  plants  using  activated  carbon were
surveyed and carbon adsorption isotherms  were  run  on  the
effluent  from  biological  waste  treatment plants treating
organic chemical industry wastes.

During the plant survey program, 6 activated  carbon  plants
treating raw waste waters were surveyed, and the results are
presented  in  Table 7-5.  The most interesting fact is that
domestic waste water  treatment  experience  indicates  that
efficient  treatment  is provided with contact times between
10 and 50 minutes, while the design contact times  in  Table
7-5  vary between 22 and 660 minutes (calculated on an empty
column basis).  These  higher  contact  times  are  required
because  of  the  much  higher  raw waste loads generated by
industry.

The major problems encountered in trying to  compare  design
criteria  and  present  performance  of carbon plants are as
follows:
                              327

-------
                                     Table 7-4
                           Effectiveness of Filtration Tests on
                           Biological Treatment Plant Effluents
        Plant
          3
         15
         15
         14
          9
          9
         13
          4
         24
         12
         21
         16
         25
         20
         35
         26
         27
         18
         17
         19
Average of selected data
Average of all data
Percent Removal
COD
9
87
85
24
11
10
32
None
8
21
3
84.3
39.3
8.5
51.4
26.2
***
86.8
88.4
33.3
data 20
42
BOD
4
56
*
28
None
None
36
None
2
None
None
57.8
**
17.2
***
71.4
12.5
72.1
55.6
***
17
26
38****
TOC
3
78
82
14
5
17
8
None
20
7
8
75.9
39.4
33.0
27 .7
41.2
25.0
90.6
91.6
66.0
20
37
       Average does not include plants 15,  16,  17,  18,  and  26,  since  these  plants  have
        excessively high effluent TSS.   These high effluent  TSS  values are the  result of
        poor performance of the final  clarifiers.  The purpose of the filtration tests
        was to quantify the effectiveness of filtration  on typical  effluents from a
        properly designed and operated biological  plant, the data from  atypical
        effluents are excluded.
        *   Error in control BOD value
        **  No initial BOD determination.
        *** Data not available.
        ****Average of samples excluding indeterminate answers.
                                     328

-------
    1.   In most cases, design loadings,  both  organic  and
         hydraulic,  have not yet been attained.  This means
         the new plants are sometimes grossly under-loaded.

    2.   Thermal carbon regeneration  is  presently  an  art
         which   is  acquired  only  with  actual  operating
         experience.  For this reason, start-up problems are
         often extended, and  it  is  not  unusual  for  the
         pollutant  concentrations  of  the activated carbon
         effluent to be higher than the design value.   This
         situation continues until the carbon is regenerated
         thoroughly.

    3.   Plants with insufficient  spill  protection  and/or
         inadequate  housekeeping  practices  may  discharge
         specific low molecular  weight  hydrocarbons  which
         are  not  amenable  to  adsorption.  This situation
         results in an erratic plant performance.

The carbon adsorption isotherm is widely used to screen  the
applicability  of  different activated carbons, to calculate
theoretical  exhaustion  rates,  and  determine  if   carbon
adsorption  technology  can  be  applied  to  specific waste
waters.  The comparison of isotherm  and  design  exhaustion
rates  for  Plant  29 in Table 7-5 further substantiates the
fact that isotherm data are preliminary and  should  not  be
used  for design purposes.  However, carbon isotherm data do
indicate relative amenability of the particular waste  water
to treatment by carbon adsorption and to identify reasonable
removal  efficiencies.  In addition, several existing plants
in this and other industries use carbon in combination  with
activated sludge systems for industrial waste treatment.

To  investigate  the  possibility  of using activated carbon
technology on the effluents from biological treatment plants
treating organic chemical waste  waters,  series  of  carbon
isotherms  were  run  at standard conditions using a contact
time of 30  minutes.   The  results  of  the  isotherms  are
presented  in  Tables 7-6 and 7-7.  BOD carbon isotherm data
performed  on  the  biological  treatment  plant   effluents
yielded  only  two  usable data points.  Average performance
values are presented hereafter.  Table 7-8 contains TOC  and
COD  carbon  exhaustion  data  from  a recent survey made of
plants in this and other industries.
                             329

-------
                Table  7-5
    Organic Chemical Plants Using
Activated Carbon to Treat Raw Wastewaters
Plant
28
29
30
31
32
33
Removal Ef f iciencies-%
Pretreatment Design Present
Solids Removal and 	 Polyol-11
Equalization 9-hr
detention time
Equalization 150- TOC-94 TOC -89
day detention time
Equalization, Neu- Phenol-89 Phenol-94
tral ization and
solids removal
Equalization and 	 TOC-91
Neut ra 1 i zat ion
Equalization and Phenoi-99.9 Phenol-95
Neut ra 1 i zat i on
Equalization, Neu- Color-90 	
tral i zat ion and
solids removal
Hydraulic Loading
Flows-gpd gpm/sq.ft. Contact Time-minutes Carbon Exhaustion Rate
Design Present Design Present Design Present Design
100,000 55,000 5.6 3.0 22 40 0.4 lb^j>olyol
Ib. carbon
20,000 7,000 0,49 0.17 540 1,550 0.07 Ib. TOC
Ib. carbon
750,000 500,000 4.6 3.1 69 104 .028 ib. phenol
Ib. carbon
30,000 20,000 	 	 660 912 	
72,000 22,000 2.0 0.6 215 75 	
800,000 	 7.7 	 27 	 5.4 Ibs. color
Ib. carbon
1 sotherm
0.19 Ib. TOC
Ib. carbon

-------
                                                Table 7-6


                                    Summary COD Carbon  Isotherm  Data
                           (Performed on Biological Treatment  Plant Effluent)

                             Carbon Exhaustion  Rate

Plant No.
lit
15
15
3
9
9
13
13
4
2k
12
21
16
20
26
. Q
23
07
17
Average1
Ibs COD Removed
Ib Carbon
0.035
0.8
0.2
1.35
0.30
0.36
0.42
0.36
0.51
0.34
^. 5
0.11
.12
4.0
.1+5
.069
0.094
.41
Ibs Carbon
1 ,000 qal 'ons
232
8.9
28.6
1.87
13.9
13.3
10.6
12.6
2.2
32.2
0.27
21 .4
29.5
.25
2.0
3.9
44.3
15.7
Max. Soluble
COD Removal (%)
22
87
87
87
7^
84
79
75

70
57
69
87
3
50.2
C7 R
41.6
42 4
72.8
83 4
63.6
on L.
93.9
69.0

Category
B

D
C

B-C
B
B
B
C
D
C
B-C
A
D
B
D

The average does not include Plants No. 12, I1*, 20 and 21.

                                                  331

-------
                                                  Table 7-7

                                      Summary TOC Carbon Isotherm Data
                               (Performed on Biological Treatment Plant Effluent)
to
Plant

16
25
20
35
26
18
23
27
17
19
Influent TOC
(soluble)
mg/L
87
43
28
34
20
104

6
148

Effluent TOC
(Soluble)
mg/L
58
5
12
4
2
19

3
20

TOC
Removal
%
33.4
88.4
37.2
88.3
90.0
81.6

50.0
86.6

Carbon Exhaustion
Ibs. TOC Removed
Ib. Carbon
—
.01
—
.13
1.35
.0036
—
—
.0485

Ibs. Carbon
1,000 gal
—
35.9
—
2.25
.12
241
—
—
25.4

     Average
             1
87
,063
21.77
     Average includes Plant Nos.  17,  25, and 35.

-------
                                                         Table 7-8
                                           Summary of TOC and COD Carbon  Exhaustion  Rate
Wastewater Practical
TOC Carbon Exhaustion Rate Influent Effluent
Plant Pounds Per 1,000 Gallons* Concentration(TOC) Objective
A
B
C
D
E
F
F
OJ
**•
LJ G
H
I
J
Mean
Standard
Deviation
1.8
2.1
1.9
6.2
14.0
4.5
8.4
4.6
3.6
9.2
5.6
3.9
18
22
186
100
200
19
105
82
60
114
91
65
3
2
37
15
6
2
15
3
5
9
10
11
%TOC Removal
@
Objective
83
90
80
85
97
89
86
96
92
92
89
6
COD Carbon Exhaustion Wastewater Practical % COD Removal
Exhaustion Rate Pounds Influent con- Effluent @
Per 1000 Gallons* centration(COD)Objective Objective
3.5
2.0
11.8
9.7
5.6
2.4
4.4
2.6
7.3
18.8
6.8
5.3
47
75
520
275
405
50
290
220
190
215
229
154
<10
<10
22
10
35
•CIO
<10
17
60
<:10
19
16
>89
>87
96
96
91
>80
>96
92
68
>95
89
9
*Mim'mum theoretical exhaustion rate based on use of two-stage fixed bed contacting system.

-------
                                              Soluble
                                             Pollutant
    Parameter       Carbon Exhaustion Rate     Removal
                    Ibs removed/lb carbon      percent

        COD               0.41                   69
        BOD               0.03                   89
        TOC               0.06                   87

Inspection of the specific data in Tables  7-6  through  7-8
indicates  that  carbon  adsorption  has  varying degrees of
amenability  with  regard  to  cost  effective  waste  water
treatment.    However,   the   data   does   indicate   that
biologically treated waste waters from the organic chemicals
industry  are  readily  treatable  using  activated  carbon.
Following  identification of the feasibility, typical design
data for carbon adsorption systems were  used  to  establish
the  design  of  model  BAT  treatment  systems  for costing
purposes.  The laboratory data were not  used  to  establish
the  design.   The  actual  design  data  are  identified in
Chapter IX.

BPCTCA Treatment Systems

The review of the industry historic treatment plant data was
to quantify BPCTCA reduction factors, which  would  then  be
applied to BPCTCA raw waste load values for each subcategory
in order to generate recommended effluent limitation.  Based
on  the  previous  discussions  of biological treatment, the
following  pollutant  reduction   factors   are   considered
achievable with BPCTCA treatment technology:

         Percent Reduction Factors    Minimum Average
         Applied to Average BPCTCA    Effluent Concentration
Parameter      Range	Average     	mg/1	

   BOD1        83-99         93                   20

   COD                       74

   TSS                                            30
IControlling Parameter

The  BPCTCA effluent discharge recommendations are made only
for BOD and TSS.

To evaluate the economic  effects  of  the  BPCTCA  effluent
limitations  on  the  organic  chemicals  industry,  it  was
necessary to formulate a BPCTCA treatment model.  The  model
selected  was single stage activated sludge.  (See Figure 7-
1.) It is  recognized  that  specific  industry  plants  may
choose other biological treatment systems to meet the BPCTCA
limitations.   Since it is impossible to anticipate the cost

                                                  v
                           334

-------
 O
 (0
 1)
 I.
in
ID
u
a.
to
                                                       335

-------
                                                                     Figure  1-2


                                                          BATEA  Waste  Treatment Model
RIOLOtlCAL TREAT1ENT j i
                -cxh
                            **•
                   RACR MSN
                   HOLDINC TANK
PLWT EFFLUENT
                    FILTER INLET
                    Kll
K—-n..^,,..]
"T^Tfe^giia
TtS^
                                                                FILTER UTER
                                                                HOLDINC TtNK
                                              t~
                                                      •—(XH
                                                      «—OO-
                                      DUAL
                                      CMVITf FILTERS
                                                                          •O*-
                                                                          URBON coium
                                                                          FEED PIMPS
                                                          RACK IASH
                                                          PWS
                                                                                          RECENERATEO CARRON
                                                                                          STtRACE TANK
                                                                                                  PLANT EFFLUENT
PULSED
RED
CARRON
coium
                                                                                                 TRANSFER
                                                                                                 TANK
                                                                                                                               NTINC TMR
                                                                                                       tj
                        .

                        I  I Mf STOItCE TNW


                         T
                                                                                                                      L
                                                                                                                                     SCMI FEEKR
                                                                                                                                         KCUEMTIM FMMCI
                                                                                                                               OIENCH TANK
                                VIRCIN
                                CARHN
                                STORACI

-------
of every possible treatment system that  could  be  used,  a
common  system  was  chosen,  single stage activated sludge.
Tne model serves the  function  of  representing  a  maximum
effluent    treatment   cost   which   might   actually   be
significantly lower due to in-process modifications or other
methods of effluent treatment.

BATEA Treatment Systems

Based on the previous performance data  from  multiple-stage
biological   treatment  plants,  existing  carbon  treatment
plants and various carbon isotherms, it has been possible to
formulate waste  reduction  factors  commensurate  as  BATEA
treatment technology:

            Percent Reduction Factors
            Applied to BPCTCA        Minimum Average
Parameter  Effluent Limitation	    Effluent Concentration

   BOD              89                              10

   COD              69                              50

   TSS                                              15

The  BATEA  effluent  discharge  limitations  will  have two
controlling  parameters,  i.e.,  BOD  and  COD.   The  major
emphasis,  however, should be on COD removal since the major
portion  of  the  carbonaceous  oxygen  demanding  materials
should have been removed with BPCTCA technology.

The  BATEA  treatment  model used for economic evaluation of
the proposed limitations includes the BPCTCA treatment model
followed by dual media filtration and carbon adsorption.   A
typical  flow  diagram  is  shown  in Figure 7-2.  The BATEA
design basis and the unit sizing criteria are  discussed  in
the  Phase 1 study.  The carbon regeneration facilities were
sized using 0.41 Ib COD  removed/lb  carbon,  which  is  the
average result as determined from the carbon isotherm data.

BADCT Treatment Systems

Based  on the previous filtration data, it has been possible
to formulate waste reduction factors commensurate  as  BADCT
treatment technology:
                               337

-------
            Percent Reduction Factors        Minimum
                Applied to BPCTCA            Average Effluent
    Parameter   Effluent Limitation          Concentration
                                                mg/1

       BOD               17

       COD               20

       TSS                                           15

The  BADCT  treatment  model used for economic evaluation of
the proposed limitations includes the BPCTCA treatment model
followed by dual media filtration.

Although  dual  media  filtration  of  biologically  treated
wastewaters  has not been practiced on a plant scale in this
industry,  at  least  one  other  industry,  the   petroleum
refining industry, does successfully employ this technology.
However, rather than adopt performance requirements based on
results  obtained  in  other  industries,  the  removals  of
pollutants observed in the laboratory filtration tests  were
used to establish removal factors.

filtration
                              >
Laboratory  experiments  were conducted with the recognition
that results were not actual operating data, but rather that
the results  would  allow  a  comparison  to  be  made  with
existing   data   resulting   from   filtration   of   other
biologically treated effluents.   The laboratory  experiments
therefore  did  provide  reasonable  results, as compared to
data in  the  literature.   In  adopting  filtration  as  an
appropriate  technology  for  this  industry  in  the  above
manner, the judgement was made that such technology has been
adequately demonstrated, if not routinely applied.

In using the average removals from the laboratory filtration
studies to establish the BADCT limitations,  a  conservative
approach  was  taken.   Available data from other situations
indicates that higher percent removals can be achieved.   In
determining   the  average  percent  removals  (Table  7-4),
certain data were not included (plants 15, 16, 17,  18,  and
26)  because  it  was  felt  that the data from these plants
would bias the results, i.e., could indicate higher  results
than  otherwise  might  occur.   If all of the data had been
used the average percent removals would have been: COD  42%;
BOD 26*; and TOG 31%.  These removals are about double those
chosen as representative.
                               338

-------
In  choosing  the values that were used as indicative of the
results  of  filtration,  reasonable  conservative   percent
removals were chosen.  Such a choice used the best available
technical judgement and an evaluation of results obtained by
filtration  in  other  waste water situations.  Reliance was
not placed solely on the laboratory filtration tests.
                             339

-------

-------
                        SECTION VIII

         COST, ENERGY AND NONWATER QUALITY ASPECTS

Cost

Tiiis section provides quantitative cost information relative
to assessing the economic impact of  the  proposed  effluent
limitations  on the organic chemicals industry.  In order to
evaluate the economic impact on a uniform  treatment  basis,
end-of-pipe   treatment  models  were  proposed  which  will
provide the desired level of treatment as follows:

          Technology Level               Treatment Model

            BPCTCA           Single-stage Activated Sludge.

            BADCT            Activated Sludge and Filtration.

            BATEA            Activated Sludge, Filtration, and
                             Carbon Adsorption.

The method used to attain the effluent  limitations  whether
through  in-plant  controls  or  by end-of-pipe treatment is
left up to the individual manufacturer as to  which  is  the
most attractive economically.

Extensive  annual  and  capital cost estimates were prepared
for  numerous  end-of-pipe  treatment  models,  which   were
presented in the Phase 1 study.  As an expedient, these cost
estimates  were linearly extrapolated to include the similar
Pnase 2 treatment models.

The capital and  annual  cost  for  BPCTCA,  BATEA  and  New
Sources  are presented in Table 8-1 for each product/process
segment.  It is noted that these costs reflect treatment  of
wastes  from a single product plant situation.  The relevant
flow and production rates are also included in Table 8-1 for
each situation.  These rates were based upon those which are
typical for each process.

These costs are presented with the understanding  that  most
plants in this industry are multi-product plants which treat
a  mixture  of waste waters.  Thus, in some cases, costs are
larger than actual costs for the multi-product plant due  to
economies  of  scale.   In evaluating the economic impact of
the costs of treatment, the costs presented in Table 8-1 may
need to be adjusted to account for the economy of scale  for
the particular plant's actual flow.
                              341

-------
                     Table  8-1
    ORGANIC CHEMICALS  INDUSTRY (PHASE  II)
          ECONOMICS SUMMARY
(All Costs Shown Are Cumulative Totals)


Cumene
Para-Xy lene
BTX Aromatlcs
Chlorotoluene.
Chloromethanes
Chlorobenzene
D i pheny 1 ami ne
Perchloroethylene
Phthal ic Anhydride
Tri cresyl Phosphate
Methyl ethyl Ketone
Hexane thy 1 ened i ami ne
Hexarethy t ened I ami ne
Adi poni tai le
Benzoic Acid
Methylchloride
Maleic Anhydr ide
Ethyl Acetate
Propyl Acetate
Oxalic Acid
Fornic Acid
OJ Cyclohexanone Oxime
•^ 1 sopropanol
Cal ci U.TI Stearate
Hexane thy lene let ram me
Hydraz 1 ne
Isobutylene
Sel -Butyl Alcohol
Acryloni trt 1 e
Synthetic Cresols
Caprolactam
Para-Ani nophenol
Propylene Oxide
Pentaerythr itol
Sacchar i n
Ortho-Ni troani 1 i ne
Para-tJ i troani 1 i ne
Pentachlorophenol
Fatty Acids
Fatty Acid Derivatives
lonone & Methyl lonone
Methyl Sal icylate
Misc. Batch Chemicals
Cltronellol & Gerantol
Plasticizers
Dyes & Dye Intermediates
Toner Pi gments
Lake Pigments
Citric Acid
Naphthenic Acid
Monosodium Glutamate
Tanntc Acid
Vanillin
Pro-
ducti on
Lbs/Oav
822,000
550,000
1 ,041 ,000
30,000
356,000
300,000
100,000
50,000
342,000
50,000
274,000
548,000
548,000
548,000
164,000
82,000
137,000
503,000
197,000
500 ooo
27,400
50,000
150,000
1 ,370.000
80,000
22,000
6,000
137,000
218,000
658,000
50,000
685,000
50,000
548,000
68,500
25,000
50,000
65,000
50,000
150,000
150,000
600
10,000
1,000,000
1 ,400
50,000
10,000
10,000
10,000
100,000
22,000
33,000
55,000
10,000
Waste-
Water
Gal/Dav
33
2,900
5,800
436,000
120,000
1,800
6,300
32,000
24,000
168,000
43,000
66,000
72,000
642,000
56,000
118,000
38,000
78,000
28,000
330 ,000
939! ooo
1 ,710,000
40 , 000
366,000
519,000
80,000
2,300
335,000
16,400
353,000
2,000
2,390,000
75,600
4,180.000
83,800
807,000
1,610,000
305,000
16,100
504,000
116,000
675
20,800
9,450,000
1,700
3,900
1,138,000
375,000
1 ,200,000
5,720,000
99,700
246,200
661 ,000
160,730
5
Capital
Cost
Zero
383,000
454,000
953,000
583,000
386,000
411 ,000
424,000
505,000
762,000
1,660,000
3,600,000
3,350,000
10,700,000
5,640,000
1 ,670,000
.7'! ,000
539,000
RWL
RWL
1 ,410,000
RWL
$ Per
S 1000
Per Year Gal.
3,600
148,000
160,000
281 ,000
190,000
14; ,000
153,000
160,000
171,000
725,000
498,000
916,000
805,000
2,800,000
1,490,000
470,000
691 ,000
182,000
RWL
RWL
402,000
RWL
300
135
72.8
1.77
4.35
217
64.6
13.7
19.5
3.64
31.7
38.1
30.6
11.9
72.8
10.9
49.8
6.41
RWL
RWL
1.17
RWL
$ Per
1000
Lbs.
0.012
0.72
0.41
25.7
1.47
1.31
4.08
8.87
1-37
12.2
4.98
4.58
4.04
14.0
24.8
15.7
13.7
1.00
RWL
RWL
40.0
RWL
S
Capital
Cost
Zero
398,000
479,000
1 ,150,000
676,000
401,000
436,000
468,000
544,000
880,000
1 ,710,000
3,670,000
3,420,000
11 ,000,000
5,700,000
i , 760 , ooo
711 ,000
629,000
RWL
RWL
1 ,750,000
RWL
S
Per
	 Year
3,600
151 ,000
164,000
314,000
206,000
156,000
158,000
167,000
178,000
245,000
507,000
928,000
817,000
2,850,000
1,500,000
485,000
691 ,000
198,0/JO
RWL
RWL
467,000
RWL

S Per $ Per
1000 1000
Gal. Lbs.
300
138
74.8
1.98
4.71
237
66.4
14.3
20.3
3.97
32.3
38.6
31.1
12.1
73.3
11.3
49.8
6.94
RWL
RWL
1.36
RWL
0.012
0.73
0.50
28.8
1.59
1.42
4.19.
9.28
l.43
13.3
5.07
4.64
4.10
14.2
25.0
16.2
13.7
1.08
RWL
RWL
46.5
RWL
$
Capital
Cost 	
Zero
413,000
495,000
1,400,000
839,000
416,000
519,000
536,000
577,000
1,100,000
1,840,000
4,360,000
3,890,000
12,800,000
6,080,000
2,150,000
711 ,000
BADCT
RWL
RWL
2,230,000
RWL
	 — BATEA
$
Per
Year 	
3,600
1 76 , 000
193,000
383,000
257,000
182,000
171 ,000
203 ,000
222^000
308,000
530,000
1,160,000
960,000
3,780,000
1,620,000
603,000
691 ,000
BADCT
RWL
RWL
576,000
RWL

$ Per
1000
Gal.
300
162
88.8
2.41
5.88
277
72.4
17 4
i ( .*
25.3
H.99
35.0
48.2
36.5
16.1
79.1
14.0
49.8
BADCT
RWL
RWL
1.68
RWL

$ Per
1000
Lbs.
0.012
0.86
0.58
35.0
1.99
1 66
4^57
11 I
,6.f
5.50
5.81
4.82
18.9
27.0
20.2
13.7
BAOCT
RWL
57.4
RWL
SEE CAPROLACTAM
1 ,070,000
1 ,390,000
850,000
522,000
1 ,560,000
1,900,000
2,400,000
203,000
22,700,000
2,820,000
11 ,100,000
1 ,270,000
3,640,000
1 ,530,000
911,000
503,000
1,760,000
1,500,000
Zero
655,000
6,180,000
86 , 1 00
1 43 , 000
1 ,260,000
1,960,000
4,890,000
5,480,000
1,480,000
1,090,000
1,240,000
5,000,000
293,000
365,000
241 ,000
179,000
389,000
557,000
677,000
124,000
5,610,000
632,000
12,490,000
1,390,000
1,010,000
446,000
259,000
168,000
488,000
389,000
73,900
102,000
1,910,000
15,800
26,100
431 ,000
548,000
1,260,000
1 ,570,000
414,000
291 ,000
320,000
1,310,000
2.20
1.93
8.24
213
3.18
93.1
5.25
170
6.43
22.9
1.62
45.4
3.44
0.76
2.32
28.5
2.65
9.17
300
13.5
0.56
25.5
18.3
1 .04
4.00
2.88
0.75
11.4
3.24
13.3
22.2
0.62
12.0
30.0
8J.7
8.22
7.38
3.18
6.^?
22.4
32.4
12.7
55.6
111
24.7
10.9
9.2
8.91
7.06
337
2.81
5.31
30.9
1.43
118
150

43.0
51.6
24.2
15.9
359
1 ,270,000
640,000
940,000
558,000
1 ,740,000
1,950,000
2,600,000
203,000
23,200,000
2,890,000
11 ,800,000
1,270,000
3,910,000
1 ,950,000
1,110,000
546,000
2,000,000
1,610,000
Zero
908,000
7,380,000
90,700
151 ,000
1,620,000
2,160,000
5,280,000
5,650,000
1,570,000
1,240,000
1,310,000
5,110,000
328,000
408,000
256,000
185,000
420,000
565,000
715,000
124,000
5,710,000
644,000
2,630,000
1,390,000
1,060,000
522,000
293 ,000
175,000
530,000
402,000
73,900
109,000
2,150,000
16,800
27,500
395,000
583,000
1,330,000
1,740,000
429,000
317,000
332,000
i ,330,000
2.46
2.16
8.75
220
3.43
04 s
5*52
170
6.55
23.3
.1.71
45.4
3.60
0.89
2.63
29.8
2.87
9.47
300
14.3
0.63
27.0
19.4
1.19
4.26
3.04
0.83
11.8
3.52
16.2
22.5
0.69
13.5
32.0
84 5
8] 84
7 48
3:3?
6.82
22.8
33.0
13.4
55.6
116
28.6
12.3
9.59
9.65
7.29
337
2.98
5.97
32.7
1.52
135
160
364
Ve
53.4
11.3
19.4
364
1 ,730,000
2 , 1 40 , 000
1 ,290,000
574,000
2,450,000
2,530,000
6,430,000
203,000
26,800,000
3.220,000
13,600,000
1,270,000
5 ,2tO ,000
2,910,000
1,740,000
572,000
2,660,000
2,180,000
Zero
704,000
12,900,000
134,000
223,000
2,780.000
3,220,000
8,090,000
9,840,000
2,080,000
1,640,000
1,710,000
10,600,000
446,000
525,000
358,000
218,000
624,000
741,000
2,040.000
124,000
6,760,000
740,000
3.000.000
1,390,000
1,460,000
752 000
455,000
255,000
700,000
481 ,000
73,900
139,000
3,700.000
27,900
46,100
1,260,000
911,000
2,180,000
2,970.000
573,000
420,000
442,000
3.330,000
3.35
2.78
12.2
260
5.1
124
15.8
170
7-75
26.8
1.96
45.4
4.96
1 27
4. '09
43.4
3.79
11.4
300
18.3
1.08
44.8
32.4
1.91
6.66
4 °S
1.42
K o
V.'67
20.8
56.6
0.93
17.5
44.7
99-5
12.9
9.69
8.86
6.82
27.0
37.9
15.3
55.6
160
40.8
19. '2
14.0
12.7
8.75
337
3.81
10.2
54.3
2.54
217
250

81 .2
O
34'. 9
24.9
911

-------
Energy

The  BPCTCA  treatment,  models were designed assuming sludge
dewatering using vacuum filtration with sludge cake disposal
to a sanitary  landfill.   An  alternative  sludge  disposal
method  is  incineration, which oxidizes the sludge organics
and evaporates the  water  in  the  sludge.   The  remaining
inorganic  ash  is  10  percent of the original volume.  The
offsetting  factor  is  the  substantial  amount  of  energy
required to realize this volume reduction.

Since  the  previous  cost  tables are computed using August
1971 dollars, the recent energy crisis has not  impacted  on
these  figures.   The  future  availability  and  pricing of
energy will play an ever increasing role in the selection of
waste  water  treatment  processes   and   sludge   handling
alternatives.

Nonwater Quality Aspects

The  major  nonwater  quality  consideration  which  may  be
associated with.in-process control measures is  the  use  of
alternative  means of ultimate disposal.  As the process RWL
is reduced in volume, alternate disposal techniques (such as
incineration, ocean discharge, and deep-well injection)  may
become  feasible.   Recent  regulations are tending to limit
the applicability of ocean discharge and deep-well injection
because  of  the  potential  long-term  detrimental  effects
associated  with these disposal procedures.  Incineration is
a  viable  alternative  for  concentrated   waste   streams,
particularly    those   associated   with   Subcategory   C.
Associated air pollution and the need  for  auxiliary  fuel,
depending   on   the   heating   value  of  the  waste,  are
considerations which must  be  evaluated  on  an  individual
basis for each use.

Other  nonwater  quality aspects, such as noise levels, will
not be perceptibly affected.  Most chemical plants  generate
fairly  high  noise  levels  —  85-95  dB (a)   — within the
battery  limits  because  of  equipment   such   as   pumps,
compressors,  steam  jets, flare stacks, etc.   Equipment as-
sociated with  in-process  or  end-of-pipe  control  systems
would not add significantly to these levels.
                              343

-------

-------
                         SECTION IX

            BEST PRACTICABLE CONTROL TECHNOLOGY
                CURRENTLY AVAILABLE  (BPCTCA)

The  application  of  best  practicable  control  technology
currently  available   (BPCTCA)   for  the  secondary  organic
products  segment  of  the  organic  chemicals manufacturing
point source category should include the utilization of both
in-process controls  as  well  as  end-of-process  treatment
technologies.   The  goal of these controls and technologies
is the reduction and eventual elimination of pollutants from
all discharges.  These pollutants are responsible  for  most
of the degradation this industry presently inflicts upon the
aquatic environment.  The following discussions describe the
pollution  control technologies commensurate with BPCTCA and
the  procedure  used  to  establish   effluent   limitations
guidelines.

The  nature  of  the  specific  manufacturing  process  will
determine  the   combination   of   process   controls   and
modifications  which  are  best  suited  for at-source water
pollution control.  However, some  practices  are  generally
applicable  to  all  process plants within this point source
category.

The  first  of  these  is  the  implementation  of   process
observation and sampling programs to determine the identity,
location,  quantity,  and composition of all aqueous streams
within the plant.  Monitoring  should  include  all  aqueous
process  streams as well as storage tank drainage, flare and
pump seal waters, storm runoff, and waste  water  associated
with  support  activities  such  as  laboratories, materials
receiving  and  shipment,  and  intake   waters   treatment.
Although  not  considered  as  major  sources of pollutants,
utility waters and steam condensate from noncontact  cooling
and heating should also be included in any such survey.  The
flows  and  loadings  developed  should  be allocated to the
different processes in the plant  in  terms  of  production-
based  ratios.   This  provides  a clear understanding as to
which specific products require high  water  utilization  or
generate  large  amounts  of water-borne pollutants.  At the
present time, this information has been developed by only  a
very few manufacturers within this industry.

Waste  characterisation  studies of this type logically lead
to the selection of various streams for segregation  or  the
application   of  at-source  controls.   Exemplary  chemical
process plants  segregate  all  waste  waters  which  become
                              345

-------
contaminated  with organic chemical pollutants.   These waste
waters include contact wastes which flow  continuously  from
within  the  process  battery limits as well as  intermittent
waste  waters  which  have  contacted  chemicals  in   other
sections  of  the  plant.   The segregation and collection of
these contaminated wastes from noncontaminated streams  such
as  noncontact  cooling waters appreciably reduce the volume
of waste water to be treated in a  centralized  waste  water
treatment plant.

In most chemical manufacturing processes, the volume of non-
contact  cooling  water  required is between 3 and 100 times
greater than the water which contacts chemicals   within  the
process.   The  exact  ratio  depends upon whether the plant
uses once-through cooling water or  a  recirculating  system
with  cooling  towers.   However, the quantity of pollutants
present in these waters generally is less than  one  percent
of  that  present  in  contact waters.  The major pollutants
associated with noncontact waters are inorganic   anions  and
cations  existing  as  dissolved  solids  and  chemicals  to
control slimes, algae, and corrosion.   These  materials  do
not  normally  affect  dissolved  oxygen levels  in receiving
waters.

In exemplary  plants  where  contact  waters  are  collected
separately  from noncontact waters, it is possible to design
and operate a treatment system which has been sized to treat
the optimum hydraulic and organic  pollutant  loadings  from
the  manufacturing  operations.   Fluctuations  in  influent
concentration can be reduced by equalization of  the  wastes.
This   practice  also  serves  to  smooth  out  shock  loads
resulting from process upsets.  Such shock loads can  result
in  conditions  which  could  cause  the treatment system to
perform at less than design efficiency due to  hydraulic  or
organic overlaods or to toxic or inhibitory conditions.

One  of  the  most  common  at-source  controls   utilized by
organic chemical plants  is  the  separation  and  selective
burning  of  hydrocarbon  by-products.   These materials are
invariably formed because very few  chemical  reactions  are
100  percent  selective  in  the  formation  of   the desired
product.  In almost every plant surveyed for the  production
of  secondary organic products, some waste organic chemicals
are disposed of by burning or hauling to landfill  disposal.
Although they may not be significant on a flow volume basis,
these  materials,  if flammable, should not be discharged to
the sewer and if not flammable would increase the quantities
of hydrocarbons present in  waste  waters  by  an  order  of
magnitude if they were combined with aqueous process wastes.
                               346

-------
The  devices  used  for burning may range from simple flares
(for materials with high vapor pressures) to complex  liquid
waste  incinerators or pyrolysis furnaces with extensive air
pollution control equipment.  In many cases,  waste  organic
by-products are suitable as auxiliary boiler fuel.  Although
the  continuation  of  this  practice should be evaluated to
insure that  adequate  air  pollution  control  devices  are
utilized,  it  represents  a significant contribution to the
reduction of hydrocarbons present in the waste  waters  from
most  plants surveyed.  For this reason, it is considered as
one of the generally applicable in-process control practices
that should be considered for BPCTCA.

A second  practice  involves  the  separation  of  insoluble
organic chemicals from process waste waters.  In many cases,
this can be accomplished by simple gravity separation or the
use  of  flotation  systems.  The fatty acid product/process
grouping  uses  this  technique  to  advantage.    Insoluble
hydrocarbon   skimmings   are   collected   and  treated  by
filtration and sulfuric acid addition  to  increase  product
yields.

Process  modifications  consistent  with  BPCTCA include the
regeneration and reuse of  aqueous  working  fluids  in  the
process.   This  is  normally  done  by  vacuum evaporation.
Typical examples include the regeneration of  sulfuric  acid
in  processes  to  produce  isobutylene  and secondary butyl
alcohol.

Other modifications include the direct recycle of a  working
aqueous  fluid  such  as  the absorbent in a gas scrubber or
water used in barometric condensers.  These  techniques  are
utilized  in  the  processes to manufacture benzoic acid and
hexamethylenetetramine.   In  these  cases,  the  volume  of
contact  water  discharged  is  reduced  from a once-through
operation to  tne  blowdown  from  a  recirculating  system.
Because  of the diverse nature of even the limited number of
processes examined in this study,  it  is  not  possible  to
generalize  beyond  practices  such as sewer segregation and
nonaqueous disposal of specific organic chemical waste water
components.  For this reason,  BPCTCA  effluent  limitations
guidelines  were  calculated  based  upon  an end-of-process
treatment model.  However, it is expected that the  industry
will  incorporate  in-process  controls whenever possible to
reduce waste water discharges.

End-of-process  treatment  technologies  commensurate   with
BPCTCA  are  based  on the utilization of biological systems
such as the activated  sludge  process,  extended  aeration,
aerated   lagoons,  trickling  filters,  and  anaerobic  and
                               347

-------
facultative lagoons.  These systems may  include  additional
treatment  operations  such as equalization, neutralization,
primary clarification with separation of insoluble material,
and nutrient addition.  Final removal of suspended solids is
accomplished by clarification.

Although the activated sludge process is considered  as  the
treatment  system  most  generally  applicable  to  the wide
variety of wastes generated by this  industry,  it  must  be
recognized  that  many  specific  processes  generate wastes
which, if directly treated, would be toxic or inhibitory  to
a  biological  system accepting only those wastes.  However,
most of these wastes become noninhibitory  if  the  influent
concentrations  are  reduced  from the extremely high values
existing in the raw waste.  This has  been  demonstrated  in
biological  systems  treating  chlorinated hydrocarbons from
the manufacture of ethylene dichloride  and  vinyl  chloride
and  in systems which treat the combined wastes from a batch
chemical plant where the treatability  of  individual  batch
wastes may vary widely.

BPCTCA  does  not  preclude  the use of carbon adsorption or
other types of physical/chemical treatment to achieve BPCTCA
effluent limitations guidelines if such  treatment  is  more
appropriate or cost effective.

At  the  present  time,  most  manufacturers have elected to
dispose of toxic, inhibitory, or difficult wastes  by  means
other  than  waste water treatment systems, such as by deep-
well injection or ocean dumping.  The geographic location of
many plants manufacturing these materials has  made  this  a
rather  common  practice.   If  deep-well injection or ocean
dumping were considered as  viable  alternatives  consistent
with  BPCTCA,  some of the process plants surveyed would not
discharge any process wastes to receiving waters.   However,
because  of  the  potential danger of underground leakage or
contamination  inherent  in  the   practice   of   deep-well
disposal,   effluent   limitations   guidelines   have  been
developed  as  if  these  wastes  were  to  be  treated  for
discharge to surface waters.

The   effluent   limitations   guidelines  for  BPCTCA  were
developed using  a  step-wise  approach  starting  with  the
process  raw  waste  load   (RWL).   The  process  RWL is the
production-based  ratio  relating  pollutants  to   specific
products  manufactured  by  specific  processes.  During the
field sampling program, the process RWL  was  developed  for
different   manufacturing  operations  by  sampling  contact
process waste waters.  The RWL is the necessary link between
the wide diversity of products and manufacturing  operations
                               348

-------
existing  in this industry and the production-based effluent
linu.rations guidelines.

A single set of RWL values was first established for each of
the secondary product-product groups covered in Phase II  of
this  study.   It  was necessary to develop single numerical
values for flow as well as values  for  each  of  the  three
waste  load  parameters despite the fact that field sampling
data indicated that  significant  variation  exists  between
sampling  periods for a single process and between different
manufacturers operating nominally the same process.

The single set  of  values  assigned  to  each  process  was
designated  as  the  RWL  which  can be obtained through the
application of in-process pollution control practices  which
are   commensurate   with   BPCTCA.   These  practices  were
discussed previously in this section.  The actual RWL values
were  indicated  with   each   of   the   separate   process
descriptions presented in Section IV.

It  should be noted that the lowest observed values were not
arbitrarily chosen as  RWL  for  BPCTCA.   Factors  such  as
process  plant age, size, geographic location, and method of
discharge (to surface waters or  to  a  municipal  treatment
plant)  were  considered when drastically differing RWL were
obtained for the same process.

There were many cases where only a  single  value  from  one
sampling period could be developed for the process, or where
the  RWL  varied  drastically  between  sampling  periods or
between manufacturers for no apparent reason.  In such cases
it was necessary to use  either  the  single  value  or  the
arithmetic mean as the RWL assigned to the process.

In  some of the batch or semi-batch manufacturing operations
associated  with  the  batch  and  semi-continous  processes
subcategory, it was not possible to develop individual RWL1s
for  each  of  the  hundreds  of specific batch processes in
operation.   However,  commodities  such  as  dyes  and  dye
intermediates,  fatty  acids,  primary  derivatives of fatty
acids,  plasticizers,  and  pigments  were   considered   as
subgroups of materials whose manufacturing operations can be
considered  as  a segment of the industry for which effluent
limitations and standards can be applied.

The RWL values assigned to each of the 55 secondary  organic
product-product  groupings  were  then  placed  in the major
process subcategories  described  in  Section  IV  (Industry
Categorization).    Consideration   of  differences  in  the
feedstocks, unit operations,  and  chemical  conversions  is
                              349

-------
implicit in this method of subcategorization as discussed in
Section IV.

Tables 5-1 through 5-U, show the raw waste loads for each of
the  55 product/process segments investigated in this study.
Only 29  product/process  segments  were  selected  for  the
application of effluent limitations and guidelines.  The raw
waste    loads   and   applicable   reduction   factors /  or
concentrations  are  presented  in  Table  9-1  for  the  29
product/processes.

Although  the effluent limitations guidelines for BPCTCA may
be obtained by whatever combination of in-process  and  end-
of-process   means   is   best   suited  to  the  individual
manufacturers, the numerical values for the guidelines  were
calculated   through  the  application  of  waste  reduction
factors based upon the use of a biological treatment system.
The waste reduction factors used for calculating the  BPCTCA
effluent   limitations   guidelines  for  the  BOD  and  COD
parameters are listed as follows:

    BOD       range 83-99 percent reduction
              (93 percent average)

    COD       74 percent reduction

These factors are based upon the performance  of  biological
treatment  systems  described  in  Section VII - Control and
Treatment  Technologies.   The  performance  data  used   to
develop  these  factors, in many cases, were obtained over a
full  year's  operation  and  are  indicative  of  treatment
systems  which  accept  a  wide variety of wastes.  For this
reason, these same reduction factors  were  applied  to  the
BPCTCA  mean  RWL  for  each  subcategory  in  the following
manner:

     (1)  The reduction factor of 93 percent was  applied  to
         the  subcategory  mean  raw waste load whenever the
         effluent concentration  for  the  subcategory  mean
         flow, gallons per 1000 Ib product is between 20 and
         30 mg/1.

     (2)  Whenever the resultant concentration  is  below  20
         mg/1   after  applying  the  93  percent  reduction
         factor, a less  stringent  effluent  reduction  was
         determined  based  on  the  concentration  limiting
         basis of 20 mg/1.

     (3)  Whenever the resultant  effluent  concentration  is
         above  30  mg/1  with 93 percent reduction a higher
                               350

-------
         reduction is required based on 30 mg/1 effluent  up
         to a maximum reduction of 99 percent.

It  is  noted  that  BOD  should  be used as the controlling
parameter for BPCTCA effluent  limitation  guidelines.   The
values specified for COD should only be used where it can be
demonstrated  through  the  use  of  biological treatability
studies that the  waste  (even  after  dilution  with  other
wastes  from  the plant) can not be effectively reduced in a
biological system.  In such cases  it  is  anticipated  that
some  combination  of in-process controls, coupled with end-
of-process  systems  such  as  activated  carbon  adsorption
applied  to  any  of  the  29 product-product groupings, can
provide the  required  74  percent  reduction  of  COD.   In
addition,  the  74  percent represents an overall efficiency
and therefore can be related to the end-of-process treatment
facilities in which some product/process having  greater  or
less  than  this  volume  will be treated. It should also be
noted that compliance with both the  BOD  and  COD  effluent
limitations is not required.  Reduction of the BOD to levels
developed   through   the  application  of  the  93  percent
reductions is considered generally for BPCTCA end-of-process
reduction of the principal  pollutant,  BOD5.   Due  to  the
extremely   high   waste   load  observed  in  some  of  the
subcategory groups, and the need for in-process controls  to
assure  that  these  wastes are treatable, reduction factors
higher than 93 percent were recommended for specific cases.

The remaining two general  pollutant  parameters  for  which
BPCTCA  effluent  limitations  guidelines  are specified are
total suspended solids  (TSS) and pH.  The  basis  for  these
limitations guidelines are as follows:

    TSS     60 mg/1 (30 day maximum average)
           135 mg/1 (maximum daily limitation)

    pH      6-9

The  long  term  TSS  concentration  from  which  the  above
limitations were derived is 30 mg/1.  Variability factors of
2.1 and 3.9 were then applied to the long term concentration
of 30 mg/1 in order to obtain the 30 day maximum average and
the daily maximum limitations.

BPCTCA effluent values for the BOD and COD  parameters  were
obtained  in  the manner indicated previously.  These values
shown as the BPCTCA effluent should not be directly  applied
as  effluent  limitations  guidelines.   They  must be first
multiplied by adjustment factors based  on  treatment  plant
performance developed in Section XIII.  The last two columns
                              351

-------
in  Table  9-1  indicate  the  actual  effluent  limitations
guidelines for BPCTCA which have been adjusted for:

    1.   The maximum average of daily values for any  period
         of 30 consecutive days = 2.1 x long term average.

    2.   The maximum value for any one day = 3.9 x long term
average.

The total effluent  limitation  for  a  multi-process  plant
would   be   the  summation  of  these  values  relating  to
individual processes.  Limitations for TSS and pH relate  to
the  entire  facility  and  should  be applied in the manner
shown in Table 9-1.

Finally,  effluent  limitations   for   specific   pollutant
parameters  which are applicable to specific product/process
segments  were  determined  to  be  applicable  to   BPCTCA.
Cyanide   limitations   are   also   established  for  HMDA,
acryionitrile and adiponitrile product/processes based  upon
the  achievement  of  effluent concentrations below 0.5 mg/1
and 1.0 mg/1 for the average of 30 consecutive days and  the
daily  maximum  respectively.   Heavy metals limitations for
the  plasticizers  segment   (Cu)    were   based   upon   the
achievability  of  less  than  1  mg/1  concentration (daily
maximum basis and 0.5 mg/1/30 day maximum average).
                              352

-------
                                                                     TABLE 9-1

                                                        DEVELOPMENT OF BPCTCA EFFLUENT LIMITATIONS
                                                 SIGNIFICANT ORGANIC PRODUCTS SEGMENT OF THE ORGANIC CHEMICALS
                                                          MANUFACTURING POINT SOURCE  CATEGORY
SUBCATEGORY
FLOW
L/kkg
Nonaqueous Process - Subcategory A
BTX Aromatics 46.7
Cumene
p-xylene 44.3
RAW WASTE LOAD

gal/1000 Ib

6.6
Negligible
5.3
Process With Process Water Contact Only as Steam Diluent,
Chloromethanes 2800
Diphenylamine 526
Phthalic Anhydride 593
(oxidation of o-xylene)
Hexamethylenediamine(2) 1,010
(adiponitrile process)
Hexamethylenediamirie(2) 1,100
(hexanediol process)
Methyl ethyl ketone 1,310
Adiponitrile(2) 9,770
Benzoic Acid &Benzaldehyde 2,840
Maleic Anhydride 2,300
335
63
71

121

132

157
1,170
340
274
BOOS COD
lb/1000 Ib or kg/kkg(mg/l)

0.015(32 ) 0.053(113 )
Negligible
0.01 (238) 0.025(580)
Quench or Vent Gas Absorbent -
0.22 (77) 0.94 (335)
0.087(164) 0.31 (600)
0.13(215) 0.64(1,080)

3.97(3,930) 21(20,900)

4.0(3.630) 11.7(10,600)

3.9(3,000) 2.1(1,630)
19.2(1,970) 135(13,800)
25.6(9,010) 51(17,900)
108(47,000) 287(126,000)
BASIS for BPCTCA
LIMITS


93% (23 mg/1)
N/A
20 mg/1 (91*)
Subcategory B
20 mg/1 (74*)
20 mg/1 (88*)
20 mg/1 (91*)

99% (39 mg/1)

99% (36 mg/1 )

30 mg/1 (99*)
30 mg/1 (98.5%)
99% (90 mg/1 )
99% (470 mg/1 )
Aqueous Liquid Phase Reaction Systems - Subcategory C
Ethyl Acetate 1,290
Isopropanol 2,540
Calcium Stearate 54,100
Hydrazine 30,300
Isobutylene 20,400
Sec Butyl Alcohol 626
Acrylonitrile(2) 4,470
p aminophenol 12,600
Batch and Semi -Continuous Process -
o-nitroaniline 269,000
p-nitroaniline 39,100
lonone and Methyl ionone 9,370
Methyl Sallcylate 1,735
Citronellol and Geraniol 10,000
Plasticizers (3) 650
Tannic Acid 10,000
155
304
6,460
3,630
2,440
75
536
1,510
Subcategory D
32,200
4,680
1,120
208
1,199
78
1,200
0.049(38) 0.1(79)
0.99 (393) 2.99 (1,127)
13.8(255) 32.8(605)
9.09 (300) 115 (3800)
13.6(670) 64.1(3,150)
14.2(22,800) 38.8(62,000)
38.7(8,620) 133 (32,800)
41.6(3,300) 73.7(5,850)

16 (61) 105(390)
2.55(65) 79.1(2,030)
24 (2,60(1) 94 (10,000)
22 (12.680) 93.9(54,100)
58 (5,810) HI (11,000)
54 (82,600) 83 (127,000)
153 (15,300) 1,070(107,000)
20 mg/1 (47*)
93% (27 mg/1)
20 mg/1 (92*)
21 mg/1 (93*)
30 mg/1 (96*)
99% (228 mg/1 )
99% (87 mg/1)
99% (33 mg/1 )

20 mg/1 (67*
20 mg/1 (69*
30 m /I (99%
99% 126 mg/1)
99% 58 mg/1)
99* 826 mg/i )
99% 153 mg/lj
BODS
LIHITQ )

0.0010
Negligible
0.00090
0.056
0.010
0.012
0.040
0.040
0.039
0.29
0.26
1.1
0.026
0.069
1.1
0.64
0.61
0.14
0.39
0.42
5.4
0.78
0.28
0.22
0.58
0.54
1.5
TSS
LIRIIMl
(a 30 mg/1
0.0014
Negligible
0.0013
0.084
0.016
0.018
0.030
0.033
0.039
0.29
0.085
0.069
0.039
0.076
1.6
0.91
0.61
0.019
0.13
0.38
8.1
1.2
0.28
0.052
0.30
0.020
0.30
(1)  Variability factors applicable for the daily maximum and 30 day  maximum  average  are  3.9  x  and 2.1  x (  mean  limit)  respectively
ill  L]mltajlons/or- cyanide established on the basis of 1.0 mg/1  and 0.5  mg/1  for  the  daily  maximum and 30 day  maximum average limitation.
(.i)  Limitation for total copper established on the basis of 1.0 mg/1  and  0.5 mg/1  for  the  daily maximum and 30  day maximum average limitation.

-------

-------
                         SECTION X

           BEST AVAILABLE TECHNOLOGY ECONOMICALLY
                     ACHIEVABLE  (BATEA)

Best available technology  economically  achievable   (BATEA)
for  the Secondary Products segment of the organic chemicals
point source category  is  based  upon  the  most  exemplary
combination  of  in-process and end-of-process treatment and
control technologies.

In-process practices include those mentioned previously  for
BPCTCA as well as the following:

    1.   The reuse of aqueous waste streams from one process
         in another so that the discharge is eliminated.

    2.   The  recycle  of  waste  streams  from   one   unit
         operation  within  a  process  to  another with the
         subsequent recovery of a product or co-product.

    3.   The concentration and disposal of waste  waters  by
         means which eliminate the discharge entirely.

Process  modifications  for  BATEA go beyond those described
for BPCTCA in that they would require changes to major  unit
operations  or chemical conversions within the process.  For
example,  recycle  of  aqueous  waste  streams  for  product
recovery  might involve replacement of existing distillation
columns or reactors.

Other examples of practices consistent with  BATEA  include:
the  reuse  of  aqueous  hydrochloric  acid  streams  in the
manufacture of different chlorinated methanes;  the  recycle
of  aqueous  waste  streams  for  product  recovery  in  the
manufacture of hexamethylene diamine, maleic anhydride,  and
methyl   ethyl   Jcetone;  and  the  use  of  evaporators  or
incinerators  to  completely  eliminate  discharges  in  the
manufacture of phthalic anhydride and p-aminophenol.

The  wide  diversity  of the organic chemicals industry pre-
vents prescribing a concise list  of  process  modifications
which  are applicable to the industry as a whole (or even to
the small fraction of its products covered in both phases of
this study).  This problem is aggravated by  the  fact  that
tne   industry  as  a  whole  zealously  guards  information
relating to the nature of specific manufacturing  processes.
This  secrecy  may  or  may  not  be  warranted  in order to
maintain a competitive positions.  However, it is  difficult
to develop effluent limitations guidelines based solely upon
                             355

-------
the  application  of  in-process  technologies.   Therefore,
although the use of in-process techniques  may  represent  a
viable   alternative  for  specific  manufacturers,  general
effluent  limitations  guidelines  for   BATEA   have   been
developed  based  upon the application of additional end-of-
process treatment technologies.

Treatment commensurate with BATEA requires  the  application
of  activated  carbon  adsorption  or  the use of additional
biological systems in series with the  treatment  previously
described  for  BPCTCA.  The specific choice of which system
should be utilized depends  upon  the  specific  process  or
group of processes in operation at any given facility.

Tne   performance   of  these  treatment  systems  has  been
discussed  in  Section   VII   -   Control   and   Treatment
Technologies.   The  incremental waste reductions associated
with these technologies is indicated as follows for the  BOD
and COD parameters:

    BOD  89  percent reduction (BATEA effluent is 11 percent
         of BPCTCA effluent).

    COD 69 percent reduction (BATEA effluent is  31  percent
         of BPCTCA effluent) .

Effluent limitations guidelines for BATEA were calculated by
applying  these  reduction  factors  to average effluent for
BPCTCA shown in Table 9-1.

There are specific subcategories where  the  direct  use  of
these  reduction  factors  will  still  result  in  effluent
concentrations which  are  below  the  capabilities  of  the
control systems considered as BATEA.  In this case, effluent
limitations  for  BATEA  were  obtained  by applying minimum
concentration of 10 mg/1 BOD5_ and 50 mg/1 COD from the  mean
waste water flow from each subcategory group.

Cyanide  limits  for  HMDA,  adiponitrile  and acrylonitrile
products are based on achievable concentration of  0.5  mg/1
and  0.25  mg/1  for  the  daily  maximum and 30 day maximum
average limitations respectively.  Copper  (Cu)  limitations
for plasticizers are also based on achievable concentrations
of 0.5 mg/1 and 0.25 mg/1 respectively.

It,  is  also  noted that the BATEA requires suspended solids
removal to an average concentration of 15 mg/1  through  the
use  o±  filtration  or  other  treatment technique which is
equally effective.
                             356

-------
The effluent limitation guidelines for BATEA  are  presented
in Table 10-1.  The BOD, COD and TSS values specified as the
average  effluent  for  BATEA. should not be directly applied
before  adjustment  for  variations   in   treatment   plant
performance.   The  factors  used  here  are the same as for
BPCTCA and are discussed in  Section  XIII  -  Variation  in
Treatment Plant Performance.
                              357

-------
                                                                    TABLE 10-1

                                                      DEVELOPMENT OF BATEA EFFLUENT LIMITATION FOR THE
                                               SIGNIFICANT ORGANIC PRODUCTS SEGMENT OF THE ORGANIC CHEMICALS
                                                        MANUFACTURING POINT SOURCE CATEGORY
BPCTCA
EFFLUENT LIMITATION
FLOW
BODS
COD
L/kkg lb/1000 Ib or kg/kkg (mg/1)
Nonaqueous Process - Subcategory A
BTX Aromatlcs 46.7
Cumene No Discharge
p-xylene 44.3
Process With Process Water Contact Only
Chloromethanes 2800
D1phenylam1ne 526
Phthalic Anhydride 593
(oxidation of o-xylene)
Hexamethylenediamine 1,010
(adiponitHle process)(3)
Hexamethylenediamine 1,100
(hexanediol process) (3)
Methyl ethyl ketone 1,310
Adiponitrile(3) 9,770
Benzole Acid & Benzaldehyde 2,840
Maleic Anhydride 2,300

0.0010(23)
No Discharge
0.00090(20)
as Steam Diluent
0.056(20)
0.010(20)
0.012(20)

0.040(39)

0.040(36)

0.039(30)
0.29(30)
0.26(90)
1.1(470)

0.04
No Discharge
0.0065
BODS BATEA (1 )
EFFLUENT LIMITATION
BASIS LIMITATION
mg/1 or % lb/1000 Ib or kg/kkg(mg/l)

10 mg/1 (57%)
No Discharge
10 mg/1 (50%)

0.00047

0.00045
COD BATEA (2) TSS (1)
EFFLUENT LIMITATION LIMIT ? 15 mg/1
BASIS
LIMITATION lb/1000 Ib or
mg/1 or % lb/1000 Ib or kg/kkg

69%
No
69%
kg/kkg
0.0042
discharge
0.0022

0.00070
No Discharge
0.00066
, Quench or Vent Gas Absorbent - Subcategory B
0.24
0.081
0.17

5.5

3.0

0.55
35
13
75
10 mg/1 (50%)
10 mg/1 (50%)
10 mg/1 (50%)

10 mg/1 (74%)

10 mg/1 (72%)

10 mg/1 (67%)
10 mg/1 (67%)
10 mg/1 (89%)
89% (50 mg/1 )
0.028
0.053
0.0060

0.010

0.011

0.013
0.10
0.028
0.12
50 mg/1
50 mg/1
69%

69%

69%

69%
69%
69%
69%
0.14
0.26
0.050

1.7

0.94

0.17
11
4.1
23
0.042
0.0080
0.0090

0.015

0.016

0.020
0.14
0.042
0.035
Aqueous Liquid Phase Reaction Systems - Subcategory C
Ethyl Acetate
Isopropanol
Calcium Stearate
Hydrazine
Isobutylene
Sec Butyl Alcohol
Acrylonitr1le(3)
p aminophenol
                1,290
                2,540
               54,100
               30,300
               20,400
                  626
                4,470
               12,600
0.026 (20)
0.069(27)
1.1(20)
0.64 (21)
0.61(30)
0.14(228)
0.39(87)
0.42(33)
0.065
0.78
8.5
30
17
10
35
19
10 mg/1 (50%)
10 mg/1 (63%
10 mg/1 (50%
10 mg/1 (50%
10 mg/1 (67%
89% (25 mg/1
10 mg/1 (89%)
10 mg/1 (70%]
0.013
0.025
0.54
0.3
0.20
0.016
0.045
0.13
                                                                                                                  50 mg/1
                                                                                                                  69%
                                                                                                                  50 mg/1
                                                                                                                  69%
                                                                                                                  69%
                                                                                                                  69%
                                                                                                                  69%
                                                                                                                  69%
                                                                                                                             0.065
                                                                                                                             0.24
                                                                                                                             2.7
                                                                                                                             9.2
                                                                                                                             5.1
                                                                                                                             3.1
                                                                                                                              11
                                                                                                                             5.9
                                                                                                                   0.020
                                                                                                                   0.038
                                                                                                                   0.81
                                                                                                                   0.45
                                                                                                                   0.30
                                                                                                                   0.0095
                                                                                                                   0.067
                                                                                                                   0.19
Batch and Semi-Continuous Process - Subcategory D

                                            4(20)
o-nitroaniline
p-nitroaniline
lonone and Methylionone
Methyl Sal icylate
Citronellol and Geraniol
Plasticizers (4)
Tannic Acid
269,000
 39,100
  9,370
  1,735
 10,000
    650
 10,000
                                          0.78(20)
                                          0.28(30)
                                          0.22(126)
                                          0.58(58)
                                          0.54(826)
                                          1.5(t53)
 27
 20
 25
 24
 29
 22
278
50%)
50%)
67%)
10 mg/1
10 mg/1
10 mg/1  „,»,
89% (14 mg/1)
10 mg/1 (83%)
89% (91 mg/1)
89% (17 mg/1)
2.7
0.39
0.094
0.024
0.10
0.059
0.17
                                                                                                                 50 mg/1
                                                                                                                 69%
                                                                                                                 69%
                                                                                                                 69%
                                                                                                                 69%
                                                                                                                 69%
                                                                                                                 69%
                                                                                                                 13
                                                                                                                6.3
                                                                                                                7.8
                                                                                                                7.5
                                                                                                                8.9
                                                                                                                6.6
                                                                                                                 86
                                            4.0
                                            0.59
                                            0.14
                                            0.026
                                            0.15
                                            0.0095
                                            0.15
        (4
Effluent limits for daily maximum and 30 day maximum average are  based on  variability factors 3.9 x and 2.1 x  (mean  limit).
COD values are not limitations on BPCTCA but are utilized as 74%  reduction basis  for BATEA  limitations.
Limitation for cyanide established on the basis of 0.5 mg/1 and 0.25 mg/1  for  the daily maximum and 30 day maximum average.
Limitation for copper established on the basis of 0.5 mg/1 and 0.25 mg/1 for the  daily maximum and 30 day maximum average.

-------
                         SECTION XI

              NEW SOURCE PERFORMANCE STANDARDS

Determination  of  the  best  available demonstrated control
technology  (BADCT) for new sources of the 29 product/process
segments involves the evaluation of the most  exemplary  in-
process   control  measures  with  exemplary  end-of-process
treatment.  Some major in-process controls which were  fully
described  in  Section  VII are applicable to new sources as
follows:

     (1)  The substitution of noncontact heat exchanger using
         air, water or refrigerants for direct contact water
         cooling equipment (barometric condensers);

     (2)  The use of nonaqueous quench media, e.g.,  such  as
         furnace  oil,  as  a  substitute  for  water, where
         direct contact quench is required;

     (3)  The recycle  of  process  water,  such  as  between
         absorber and stripper;

     (4)  The reuse of process  water  (after  treatment)   as
         make-up to evaporative cooling towers through which
         noncontact cooling water is circulated;

     (5)  The reuse of process water to produce low  pressure
         steam  by  noncontact  heat  exchangers  in  reflex
         condensers or distillation columns;

     (6)  Recycle   cooling   for   contact   water   systems
          (barometric condensers);

     (7)  The recovery of spent acid or caustic solutions for
         reuse;

     (8)  The recovery and reuse of spent catalyst solutions;

     (9)  The use of nonaqueous solvents  for  extraction  of
         products with subsequent recovery of solvent; and

     (10) Addition of demisters.

Although these control measures are generally applicable, no
attempt was made to identify all of these or any single  one
as   universally   applicable.    There  are  other  equally
appropriate  control  measures  which  should  be  carefully
explored and utilized by new plants in this industry.
                             359

-------
The end-of-process treatment model has been determined to be
biological  treatment  with  the additional suspended solids
removal by clarification, sedimentation,  sand  and/or  dual
media filtration.

Although  biological  treatment  has  been  described as the
basis for the BADCT, it is recognized that chemical-physical
systems such as activated carbon may also be employed as  an
end-of-process  technology or as an in-process or by-product
recovery system.  It may also be necessary to remove certain
wastes which are toxic to or interfere with biological waste
treatment systems by  in-process  chemical-physical  control
processes.

The  BODJ5  reductions  that  were  used to develop the BADCT
limitations  are  discussed  in  Section  VII,  Control  and
Treatment  Technology.  These reductions were applied to the
effluent obtained from BPCTCA and are listed as follows:

    BOD5 17* reduction (BADCT  effluent  is  83X  of  BPCTCA
    effluent) .

    COD  20% reduction (BADCT  effluent  is  80*  of  BPCTCA
    effluent) .

As  with BPCTCA, the major oxygen demand pollutant parameter
is  BOD5  for  which  effluent  limitations  guidelines  are
established.   TSS  limitations are based upon an achievable
concentration of 15 mg/liter.  Cyanide limitations for HMDA,
acrylonitrile and adiponitrile products, as well  as  copper
limits   for   plasticizers,   were   based  upon  the  same
technologies and achievable limits as BPCTCA (Section IX).

The variability associated with the  BADCT  model  treatment
process was assumed to be nearly the same as that for BPCTCA
since both systems are identical except for filtration which
is added to the biological system for BADCT.

Standards  of  performance  for new sources are presented in
Table 11-1.
                               360

-------
                                                                    TABLE 11-1

                                                     DEVELOPMENT OF STANDARDS OF PERFORMANCE FOR THE
                                               SIGNIFICANT ORGANIC PRODUCTS SEGMENT OF THE ORGANIC CHEMICALS
                                                        MANUFACTURING POINT SOURCE CATEGORY
 SUBCATEGORY
                                      FLOW
                                                RPC.Tr.A  EFFLUFNT
                                                          BODS
                                      L/kkglb/1000 Ib or kg/kkg (mg/1)
                                                                                  BODS LIMITATION
                                                                                kg/kkq or  lb/1000  Ib
                                                                                                       NSPS    EFFLUENT  fl]
                               TSS LIMITATION
                               kg/kkg or Ib/lOOO
                                                                                                                                    (at 15
 Nonaqueous Process - Subcategory A

 BTX Aromatics                        46.7                0.0010(23)
 Cumene                               No Discharge        No Discharge
 p-xylene                             44.3                0.00090(20)
                                                                                 0.00083
                                                                                 No Discharge
                                                                                 0.00075
 Process With Process Water Contact Only as Steam Diluent, Quench or Vent Gas Absorbent - Subcategory B
                                       0.00070
                                       No  Discharge
                                       0.00066
 Chloromethanes                     2,800
 Diphenylamlne                        526
 Phthalic Anhydride                   593
 (oxidation of p-xylene)
 Hexamethylenediamine               1,010
  (adiponitrile process)(2)
 Hexamethylenediamine               1,100
  (hexanediol process)(2)
 Methyl ethyl ketone                1,310
 Ad1pon1trile (2)                    9,770
 Benzole Acid and Benzaldehyde      2,840
 Maleic Anhydride                   2,300

 Aqueous Liquid Phase Reaction Systems - Subcategory C
 Ethyl Acetate
 Isopropanol
 Calcium Stearate
 Hydrazine
 Isobutylene
 Sec Butyl Alcohol
 Acrylonitrile(2)
 p-aminophenol
                               1,290
                               2,540
                              54,100
                              30,300
                              20,400
                                 626
                               4,470
                              12,600
                                                     0.056(20)
                                                     0.010(20)
                                                     0.012 (20)

                                                     0.040(39)

                                                     0.040(36)

                                                     0.039(30)
                                                     0.29(30)
                                                     0.26(90)
                                                     1.1(470)
0.026(20)
0.069(27)
0.64 (21)
0.61(30)
0.14
0.39
0.42
228)
87)
33)
 0.046
 0.0083
 0.010

 0.033

 0.033

 0.032
 0.24
 0.22
 0.91
 0.022
 0.057
 0.91
 0.53
 0.51
 0.12
 0.32
 0.35
0.042
0.0080
0.0090

0.015

0.016

0.020
0.14
0.042
0.035
0.020
0.038
0.81
0.45
0.30
0.0095
0.067
0.19
Batch and Semi-Continuous Process - Subcategory D

o-nitroaniline                   269,000
p-nitroaniHne                    39,100
lonone and Methylionone            9,370
Methyl Salicylate                  1,735
Citronellol and Geraniol          10,000
Plasticizers (3)                     650
Tannic Acid                       10,000
                                                    5.4(20)
0.78
0.28
0.22
0.58
0.54
1.5(1
20)
30)
126)
58)
826)
53)
4.5
0.65
0.23
0.18
0.48
0.45
1.2
                                                                                                                      4.0
                                                                                                                      0.59
                                                                                                                      0.14
                                                                                                                      0.026
                                                                                                                      0.15
                                                                                                                      0.0095
                                                                                                                      0.15
(1)  Effluent limitation for the daily maximum and 30 day maximum average are based on variability factors
     3.9 x and  2.1x (mean limit).
(2)
(3)
Limitation for cyanide established on the basis of 1.0 mg/1  and 0.5 mg/1  for the daily maximum and 30 day maximum average.
Limitation for copper established on the basis of 1.0 mg/1  and 0.5 r-g/1  for the daily maximum arid 30 day maximum average.
                                                                         361

-------

-------
                        SECTION XII

                  P&ETREATMENT GUIDELINES

Pollutants  from  specific  processes  within  the   organic
chemicals   industry   may   interfere  with,  pass  through
inadequately treated, or otherwise be  incompatible  with  a
publicly  owned  treatment  works.   The  following  section
examines the general  waste  water  characteristics  of  the
industry  and  tne pretreatment unit operations which may be
applicable.

A review of the waste water characteristics  indicated  that
certain  products  can  be  grouped together on the basis of
pollutants   requiring   pretreatment.    Accordingly,   the
previously  determined  subcategories  were divided into two
Sub-Groups as follows:

            Subgroup 1        Subgroup 2

           Subcategory A          Subcategory C

           Subcategory B          Subcategory D

The principal difference in the general  characteristics  of
the  process  waste waters from the manufacture of chemicals
in these two Subgroups is that the waste waters of  Subgroup
1 are more likely to include significant amounts of free and
emulsified oils (petroleum origin), whereas the waste waters
of Subgroup 2 are more likely to include significant amounts
of heavy metals.  Detailed analyses for specific products in
the industry are presented in Section IV.

The  types  and  amounts  of heavy metals in the waste water
depend primarily on the manufacturing  process  and  on  the
amounts  and types of catalysts lost from the process.  Most
catalysts are expensive, and  therefore  are  recovered  for
reuse.  Only recoverable catalysts (heavy metals), generally
in  small  concentrations,  appear  in the waste water.  The
products and processes in Subgroup 2 are most likely to have
heavy  metals  in  their  waste  water,  and  waste   waters
associated  with dye/pigment production (Subcategory D) also
may  have  high  heavy  metal  concentrations  due  to   the
production  of  metallic  dyes.   Fatty  acid  waste  waters
(Subcategory D)  contain free and emulsified oil  (animal  and
vegetable origin)  of significance.

The  manufacture of acrylonitrile (Subcategory C) produces a
highly  toxic  waste  water  which  is  difficult  to  treat
Biologically   unless   adequate  provisions  are  made  for
                              363

-------
pretreatment of  these  waste  waters  for  removal  of  the
cyanide  pollutant.   The toxicity characteristics have been
attributed to the presence of hydrogen cyanide in  excessive
quantities  (200  mg/1).   In  addition,  the waste water is
generally  acidic  (pH   4   to   6)    and   contains   high
concentrations of organic carbon (TOC = 18,500 mg/1).  These
waste  waters  are  generally  segregated from other process
wastes  and  are  disposed   of   by   other   means   (e.g.
incineration);   they   are   not  generally  discharged  to
municipal  collection  systems.   For  these  reasons,   the
pretreatment  unit  operations  developed  in  the following
section do not include the process  waste  waters  from  the
manufacture of acrylonitrile.

Tafcle  12-1 shows the pretreatment unit operations which may
be  necessary  to  protect  joint  waste   water   treatment
processes.

Oil  separation  may  be  required  when  the oil (petroleum
origin) content of the waste water exceeds 100 mg/1.  Animal
and vegetable oils in the fatty acid waste waters should  be
segregated  in  order to minimize solids separation problems
in the waste water treatment facility.

The heavy metals present in organic chemical wastes  are  in
many cases so low in concentration that heavy metals removal
is   not   required  from  the  standpoint  of  treatability
characteristics.   However,  the  effluent  limitations  for
toxic   pollutants   may   require  additional  pretreatment
(chemical precipitation) for removal of these materials.

The  pretreatment  unit  operations  generally  consist   of
equalization,   neutralization,   and  oil  separation.   In
addition,   phenol   recovery   (to   reduce   the    phenol
concentrations)   and  spill  protection  for spent acids and
spent caustics may be required in some cases.

Biological Treatment Inhibition

The scope of  this  study  did  not  allow  for  a  specific
toxicity  evaluation  of  individual  product  waste waters.
However, the completeness of the  RWL  analytical  data  did
provide  a  waste  water  profile  which  could  be  used to
evaluate  possible  biological  inhibition.   The  list  and
concentrations  of  inhibitory  pollutants  in EPA's Federal
Guidelines - Pretreatment of  Discharge  to  Publicly  Owned
Treatment  Works  were  examined,   and specific comments are
presented in Section VI.  This previous list was amended  in
the Phase I report to include phenol and iron:

                Inhibition to           Inhibition to
 Parameter     Biological Treatment   Anaerobic Sludge Digestion

 Phenol              50  mg/1                	

 Iron                	                    5 mg/1
                               364

-------
                                              Table 12-1

                                 Pretreatment Unit Operations For the
                                   Organic Chemicals Industry
    Pretreatment
     Sub-Group

         1
OJ
cr\
 Suspended Growth
Biological System

Oi 1  Separat i on +
Equa1i zation +
Neutralization +
Spi11  Protection +
Chemical Precipita-
  tion '
  Fixed Growth
Biological System

Oi 1  Separati on +
Equali zation +
Neutra1i zation +
Spi11 Protect!on +
Chemical  Precipita-
  tion'
Independent Physical -
   Chemical System

Oi1  Separation +
Equa1i zatton +
Neutra1i zat ion +
Chemical  Precipitation
                                                                                                     1
                        Equa1i zation +
                        Neutra1i zati on +
                        Spi11 Protection +
                        Chemical Precipita-
                          tion'
                           Equa1i zation +
                           Neutra1i zati on
                           Equa1i zation +
                           Neutra1i zation
    1
     Need for chemical precipitation depends on extent of catalyst  recovery.
    "Oil separation may be required for the fatty acid industry.

-------

-------
                        SECTION XIII

  ALLOWANCE FOR VARIABILITY IN TREATMENT PLANT PERFORMANCE

Variabilty in Biological Waste Treatment Systems

In  the past, effluent requirements for wastewater treatment
plants have been related to the  achievement  of  a  desired
treatment  efficiency based on long term performance.  There
are, however, factors that affect the performance and  hence
the  effluent quality or treatment efficiency over the short
term, such that short term performance  requirements  cannot
be  taken  directly from the longer term data.  Knowledge of
these factors must be incorporated  in  the  development  of
effluent limitations and in decisions of whether a treatment
plant is in compliance with the limitations.

The effluent limitations promulgated by EPA and developed in
this  Document  include values that limit both long term and
short  term  waste  discharges.   These   restrictions   are
necessary  to  assure  that  deterioration  of  the nation1s
waters does not occur on a short term  basis  due  to  heavy
intermittent  discharges,  even though an annual average may
be attained.

Most of the factors that bring about variations in treatment
plant performance can be minimized through proper dosing and
operation.  Some of the controllable causes  of  variability
and  techniques  that  can  be used to minimize their effect
include:

    A.   Storm Runoff

    Storm water holding or diversion  facilities  should  be
    designed on the basis of rainfall history and area being
    drained.  The collected storm runoff can be drawn off at
    a  constant rate to the treatment system.  The volume of
    this  contaminated  storm  runoff  should  be  minimized
    through segregation and the prevention of contamination.
    Storm  runoff  from  outside  the plant area, as well as
    uncontaminated runoff, should  be  diverted  around  the
    plant or contaminated area.

    B.   Flow Variations

    Products-process upsets and raw waste variations can  be
    reduced    by   properly   sized   equalization   units.
    Equalization is a retention of the wastes in a  suitably
    designed  and operated holding system to average out the
    influent before allowing it into the treatment system.
                              367

-------
C.   Spills

Spills of certain materials in the  plant  can  cause  a
heavy loading on the treatment system for a short period
of  time.   A  spill  may not only cause higher effluent
levels as it goes through the system, but may inhibit  a
biological  treatment  system  and therefore have longer
term effects.  Equalization helps to lessen the  effects
of spills.  However, long term reliable control can only
be  attained  by  an  aggressive  spill  prevention  and
maintenance  program  including  training  of  operating
personnel.    Industrial   associations   such   as  the
Manufacturing  Chemists   Association   have   developed
guidelines  for  prevention,  control  and  reporting of
spills.  These note how to assess the potential of spill
occurrence and how to prevent spills.   Each  industrial
organic chemical plant should be aware of the MCA report
and  institute  a  program of spill prevention using the
principles described in the report.  If every plant were
to use such guidelines as part of plant waste management
control  programs,  its  raw  waste  load  and  effluent
variations would be decreased.

D.   Start-up and Shut-down

These periods should be reduced to a minimum  and  their
effect   dampened   through   the  use  of  equalization
facilities and by  proper  scheduling  of  manufacturing
cycles.

E.   Climatic Effects

The design and choice of  type  of  a  treatment  system
should  be based on the climate at the plant location so
that this effect can  be  minimized.   Where  there  are
severe   seasonal  climatic  conditions,  the  treatment
system should be  designed  and  sufficient  operational
flexibility  should  be available so that the system can
function effectively.

F.   Treatment Process Inhibition

Chemicals likely  to  inhibit  the  treatment  processes
should  be  identified and prudent measures taken to see
that they do not enter the wastewater in  concentrations
that  may  result in treatment process inhibition.  Such
measures include the diking of a chemical  use  area  to
contain  spills  and  contaminated wash water, using dry
instead of wet clean-up of equipment,  and  changing  to
non-inhibiting chemicals.
                          368

-------
The common indicator of the pollution characteristics of the
discharge  from  a plant historically has been the long-term
average  of  the  effluent  load.   However,  the  long-term
(yearly)  average is not the only parameter on which to base
an effluent limitation.   Shorter  term  averages  also  are
needed,  both  as  an  indication  of  performance  and  for
enforcement purposes.

Wherever possible, the best approach to develop  the  annual
and  shorter term limitations is to use historical data from
the industry or product-process line in question.  If enough
data is available,  the  shorter  term  limitations  can  be
developed  from  a  detailed  analysis of the hourly, daily,
weekly, or monthly  data.   Rarely,  however,  is  there  an
adequate  amount  of  short  term data.  However, using data
which show the variability in the effluent load, statistical
analyses can be used to compute short term  limits  (30  day
average  or  daily)   which should be attained, provided that
the plant is designed and run in the proper way  to  achieve
the  desired  long term average load.  These analyses can be
used  to  establish   variability   factors   for   effluent
limitations  or  to  check  those  factors  that  have  been
developed.

During the industry survey, EPA tried to use all  historical
performance  data  that were available.  Unfortunately, data
were  available  only  for  four  plants,   Amoco,   Joliet,
Illinois;  Amoco,  Decatur,  Alabama;  DuPont,  Belle,  West
Virginia; and Union Carbide  at  Institute,  West  Virginia.
The Agency used long term performance information from these
facilities  to  establish  the  variability  factors for the
Phase I regulations.  The counsel for  industry  petitioners
in challenges to the Phase I regulations vigorously objected
to  the use of these data points, or said that if these data
were to be used, much higher variability factors  should  be
derived.

For  the Significant Organic Products Segment of the Organic
Chemicals Manufacturing Point Source Category EPA has used a
data base consisting of 21 organic chemicals,  plastics  and
petrochemical  plant  performance  data,  to establish daily
maximum and  monthly  average  variability  factors.   While
these   plants  make  different  products.  Agency  analysis
revealed that they can  be  grouped  because  the  treatment
plant  characteristics  and response to flow and constituent
variables,  for  example,  are  similar.   Plants   examined
include  the  Amoco,  Decatur,  Alabama,  Yorktown,  Va. and
Joliet, Illinois plants; B.F. Goodrich,  Fredricktown,  N.J.
facility;  B.W.  Marlion, Ottawa, Illinois; Borden Chemical,
Illiopolis,  Illinois;  Celanese  Fiber,  Rock  Hill,  S.C.;
                             369

-------
F.M.C.  Corporation,  Fredricksburg,  Va.; Fiber Industries,
Salisbury, N.C.; Champlin, Corpus Christi, Texas;  Marathon, /
Texas  City,  Texas;  Shell,  Houston,  Texas  and Martinez,
California; and several oil refineries about which data were
supplied by the American Petroleum Institute.

The BODS variability from these plants has  been  calculated
in  the  following  way:  it is known from the properties of
normal  distribution  that  99  percent  of   all   effluent
observations will have a value less than ;u + 2.3270 and that
C29/C5J)  =        1Q2.327 x cr .  The relationship between the
average value, median value and standard  deviation  of  the
logarithm  of  a  log   normally distributed variable can be
expressed: A = joP+(2.303 a2)  * 2 and C50  =  Kr" ,  therefore,
CSjO/A  =  !Q-(2.303 a2) *  2  •   Using  these  bases, the daily
maximum variability factor  (C9_9_/A)  equals 2.10.   These  are
the  factors  that  have  been  used  to  generate  effluent
regulations  for  the  product-processes  covered  by   this
Document.

The data base upon which EPAfs variability factors are based
is  the  most  extensive available.  Commenters on these and
prior EPA Development  Documents  have  suggested  no  other
source  of  information  on  which  to base BODS, TSS or COD
variability factor calculation.  While it is known that  the
behavior  of  waste  characteristics such as COD and TSS are
not precisely the same as BODS in  variations  of  effluent,
and  that  use  of  different treatment techniques can alter
expected variations, there are  not  data  sources  for  COD
which  can be used to generate separate variability numbers.
While  there  is  slight  information   available   on   TSS
variability, it is not enough upon which to rely solely, and
appears  to be consistent with the BODS variability factors.
If anyone has more  or  better  information  available,  the
Agency will readily consider it.  For these reasons, EPA has
used  factors  of  2.1 and 3.9 for all pollutant parameters,
for regulations covering existing plants and new sources.
                              370

-------
                        SECTION XIV

                      ACKNOWLEDGMENTS

This report was prepared for  the  Environmental  Protection
Agency by the staff of Roy F. Weston Co. under the direction
of  Mr.  James  Dougherty,  Project Director.  The following
individuals  of  the  staff  of  Roy  F.  Weston  Co.   made
significant, contributions to this effort:

    Mr. David Smallwood, Project Manager
    Mr. Charles Mangan, Project Engineer
    Mr. Kent Patterson, Project Engineer
    Mr. James Weaver, Project Engineer
    Dr. Sun-nan Hong, Project Engineer

Mr.  John  A. Nardella, Project Officer, Effluent Guidelines
Division, contributed to the  overall  supervision  of  this
study and preparation of the draft report.

Mr. Allen Cywin, Director, Effluent Guidelines Division, and
Mr.  Walter  J. Hunt, Chief, Effluent Guidelines Development
Branch, offered guidance and helpful  suggestions.   Members
of  the Working Group/Steering Committee who coordinated the
internal EPA review are acknowledged:

    Mr. Walter J. Hunt, Effluent Guidelines Division, Chairman
    Mr. John A. Nardella, Effluent Guidelines Division,
    Project officer
    Mr. George Rey, Office of Research and Development
    Dr. Thomas Short, Ada Laboratory, Office of Research
    and Development
    Mr. Davxd G. Davis, Office of Planning and Evaluation
    Mr. James Rogers, Office of General Counsel
    Mr. Wayne Smith, NFIC, Denver
    Mr. John Lank, Region IV, Atlanta
    Mr. Joseph Davis, Region III, Philadelphia
    Mr. Ray George, Region III, Philadelphia
    Mr. Albert Hayes, Office of Solid Waste Management
    Mr. Frank Kover, Office of Toxic Substances

Special appreciation is given to Dr. Raymond Loehr, Effluent
Guidelines Division Program Advisor, Dr. Robert  Swank,  EPA
Athens,   Georgia  Laboratory,  and  Dr.  W.  Lamar  Miller,
Effluent Guidelines Division, for  reviewing  this  document
and suggesting technical and editorial improvements.

Acknowledgement  and  appreciation  is  also  given  to  the
secretarial staffs of both Effluent Guidelines Division  and
Roy F. Weston Co. for their efforts in the typing of drafts,
                              371

-------
necessary  revisions,  and final preparation of the effluent
guidelines document.  Appreciation is  especially  given  to
the following:

    Ms. Kay Starr, Effluent Guidelines Division
    Ms. Brenda Holmone, Effluent Guidelines Division
    Ms. Nancy Zrubek, Effluent Guidelines Division

Appreciation  is  also  extended  to  both the Manufacturing
Chemists' Association and  the  Synthetic  Organic  Chemical
Manufacturers'  Association  for the valuable assistance and
cooperation given to this  program.   Appreciation  is  also
extended  to  those  companies  which  participated  in this
study:

    Accent International, Inc.
    Allied Chemical Corporation
    American Cyanamid Company
    Armak Chemcial Company
    BASF - Wyandotte Company
    Benzeroid Organics, Inc.
    Borg Warner Chemicals, Inc.
    Ceianese Chemical Company
    Conoco Chemicals, Inc.
    E.I. DuPont de Nemours, Inc.
    Emery Industries, Inc.
    Exxon Chemical Company, U.S.A.
    General Mills, Inc.
    Givaudan Corporation
    Glyco Chemicals, Inc.
    A. Gross & Company
    Hercules, Inc.
    Hooker Chemical Corporation
    Jefferson Chemical Company
    Kraftco Corporation
    Mallinckrodt Chemical company
    Monsanto, Inc
    Olin Corporation
    Petro - Tex Chemical Corporation
    Pfizer, Inc.
    Pit - Consol Chemical Company
    Roma Chemicals, Inc.
    Rubicon Chemicals, Inc.
    shell Chemical Corporation
    Sherwin - Williams Corporation
    Stepan Chemical Company
    Sun Oil Company
    Tenneco Chemicals, Inc.
    Union Carbide Corporation
    Vulcan Materials Company
    USS Chemicals, Inc.
    Vistron Corporation

                               372

-------
                         SECTION XV

                        BIBLIOGRAPHY

This  bibliography   supplements   the   main   bibliography
previously presented in the Phase I study.

     Development  Document for Proposed Effluent Limitations
Guidelines and New  Source  Performance  Standards  for  the
Major  Organic  Products.  U^.  S.  Environmental  Protection
Agency.! EPA 440/1-73/009; December, 1973
         oEment Document for Effluent Limitations Guidelines
and Standards of Performance - Organic Chemicals Industry
Draft.   Prepared  by Prepared by_ Roy F. Westgn^ Inc. for U._
S. Environmental Protection Agency ; Contract No. 68-01-1509^
JuneA 19.73^

    Hager,  Donald.   "A  Survey  of  Industrial  Wastewater
Treatment  by  Granular Activated Carbon."  Presented at the
4th  Joint  Chemical  Engineering   Conference;   Vancouver,
British Columbia; September 10, 1973.

     Kennedy,  D.  C. ,  and  others.   "A New Adsorption/ Ion
Exchange Process for Treating Dye  Waste  Effluents."   Rohm
and Haas Company; Philadelphia, Pennsylvania.

     Pattison,  E.  Scott,  editor.   Fatty  Acids and Their
Industrial Applications.  New York:   Marcel  Dekker,  Inc. ,
1968.
                                 373

-------
     Bibliography From the Phase I Development Document
Albright,  P.N.,  "The  Present  Status  of   Phenol   Waste
Treatment"  Public  Works,  Vol. 98, No. 6  (June 1967), 124-
127.

"Are  You  Drinking  Biorefractories   Too?"   Envi ronmenta1
Science and Technology, Vol. 7 No.l  (January 1973), 14-15.

Bengly,  M., "The Disposal of Liquid and Solid Effluents and
Oil  Refineries."  Proceedings  of  21st  Industrial   Waste
Conference, Purdue University (May 1966), 759-767.

Beychok,    M.R.,    "Wastewater   Treatment."   Hydrocarbon
Processing, Vol. 50, No. 12 (December 1971), 109-112.

Black, G.M., and Schoonman, W., "Save  Water:  Air  Condense
Steam."  Hydro-carbon  Processing,  Vol. 49, No. 10 (October
1970), 101-103.

Borkowski, B., "The Catalytic Oxidation of Phenols and Other
Impurities in Evaporated Effluents." Water Research, Vol.  1
(Pergamon Press, 1967), 367-385.

Browning,  J.E.,  ed., "Activated Carbon Bids for Wastewater
Treatment  Jobs."  Chemical  Engineering,  Vol.   77,   No.9
(September 1970), 32-34.

Games,  A.,  Eller,  J.M.,  and  Martin,  J.C. ,  "Reuse  of
Refinery and Petrochemical  Wastewaters."  Industrial  Water
Engineering, Vol. 9, No. 3 (June/July 1972), 25-29.

lDonal  Hager,  "A Survey of Industrial Wastewater Treatment
by Granular Activated Carbon" Presented  at  the  4th  Joint
Chemical    Engineering   Conference;   Vancouver,   British
Columbia; Sept. 10, 1973.

Dorris,  T.C.,  Patterson,  D.,  and  Copeland,  B.J.,  "Oil
Refinery  Effluent Treatment in Ponds." Journal of the Water
Pollution Control Federation, Vol. 35, No.  7  (July  1963) ,
932-939.

Easthagen, J.H., Skrylov, V., and Purvis, A.L., "Development
of  Refinery Wastewater Control at Pascagoula, Mississippi."
Journal of Water Pollution Control Federation, Vol. 37,  No.
12  (December 1965), 1671-1678.
                                 374

-------
Eisenhauer, H.R., "Increased Rate and Efficiency of Phenolic
Waste  Ozonization."  Journal  of  Water  Pollution  Control
Federation, Vol. 43, No. 2  (February 1971), 200-202.

Elkin,  H.F.,  "Activated  Sludge  Process  Applications  to
Refinery  Effluent  Waters."  sewage  and Industrial Wastes,
Vol. 28, No. 9  (September 1956), 1122-1129.

Emery, R.M., Welch, E.B., and Christman,  R.F.,  "The  Total
Organic   Carbon  Analyzer  and  Its  Application  to  Water
Research." Journal of Water  Pollution  Control  Federation,
Vol. 43, No. 9  (September 1971), 1834-1844.

Ewing,  R.C.,  "Modern  Waste  Treatment Plant," Oil and Gas
Journal, Vol. 68, No.  9  (September  1970),  66-69.    (June
1960), 377-379.

Figueroa,  L.O., "Water Pollution Control at Phillips Puerto
Rico Petrochemical Complex." Chemical Engineering, Vol.  67,
No. 6  (June 1960), 377-379

Franzen,  A.E., Shogan, V.G., and Grutsch, J.F., "Successful
Tertiary Treatment at American." Oil and Gas  Journal,  Vol.
70, No. 4 (April 1972), 48-49.

Gilliam,  A.S.,  and Anderegy, F.C., "Biological Disposal of
Refinery  Wastes."  Proceedings  of  14th  Industrial  Waste
Conference, Purdue University  (May 1959), 145-154.

Gloyna,  E.F.,  Brady,  S.O., and Lyles, H., "Use of Aerated
Lagoons and Ponds in Refinery and Chemical Waste Treatment."
Journal of Water Pollution Control Federation, Vol. 41,  No.
3  (March 1969), 429-438.

Gloyna,  E.F.,  Ford,  D.L.,  and Eller, J., "Water Reuse in
Industry." Journal of Water  Pollution  Control  Federation,
Vol. 42, No. 2  (February 1970), 237-242.

Gazzi,   L.,   and  Pasero,  R.,  "Selection."   Hydrocarbon
Processing, Vol. 49, No. 10 (October 1970), 83-90.

Harris, A.J., "Water Pollution  Control  Activities  of  the
Central  Ontario  Lakeshore  Refineries."   Journal of Water
Pollution Control Federation,  Vol.  35,  No.  9   (September
1963), 1154-1165.

Hart,  J.A.,  "Air Flotation Treatment and Reuse of Refinery
Waste  Water."   Proceedings  of   25th   Industrial   Waste
Conference, Purdue University  (May 1970), 1-14.
                                375

-------
Hart,  J.A.,  "On Improving Wastewater Quality."  Industrial
Water Engineering, Vol. 7, No. 8  (September/October  1970),
20-26.

Henshaw,  T.B.,  "Adsorption/Filtration  Plant  Cuts Phenols
from Effluent." Chemical Engineering, Vol. 78,  No.  5   (May
1971), 47-55.

Hovious,  J.C.,  Conway,  R.A.,  and Garze, C.W., "Anaerobic
Lagoon Pretreatment of Petrochemical  Wastes."   Journal  of
Water  Pollution Control Federation, Vol. 45, No. 1  (January
1973), 71-84.

Jaeschke,  L.,  and  Trobisch,   K.,   "Treat   HPI   Wastes
Biologically."  Hydrocarbon Processing, Vol. 46, No. 7  (July
1967), 11-115.

Kent, J.A., Industrial Chemistry, Reinhold Publishing Corp.,
New York  (1962).

Kumke,  G.W.,  Conway,  R.A.,  and  Creagh,  J.P.,  "Compact
Activated   Sludge   Treatment   of  combined  Petrochemical
Municipal Waste." Water and Wastes Engineering, Vol. 9,  No.
11  (November 1972), 342-351.

Lewis,   W.L.,   "New   Process   To   Remove  Phenols   from
Wastewater." Journal of Water Pollution Control  Federation,
Vol. 40, No. 5  (May 1968), 869-872.

Lund,  H.F.,  ed.,  Industrial  Pollution  Control Handbook;
McGraw-Hill, Inc. New York  (1971).

Mapstone,   G.E.,   "Control   Cooling   Tower    Slowdown."
Hydrocarbon  Processing, Vol. 46, No. 1  (January 1967),  155-
160.

McKinney, R.E., "Biological Treatment Systems  for  Refinery
Wastes." Journal of Water Pollution Control Federation,  Vol.
36, No. 3  (March 1967), 346-359.

McPhee, W.T., and Smith, A.R., "From Refinery Wastes to Pure
Water."  Proceedings  of  16th  Industrial Waste Conference,
Purdue University  (May 1961), 311-326.

"Methods  for  Chemical  Analysis  of  Water  and   Wastes."
Environmental   Protection  Agency,  National  Environmental
Research  Center,  Analytical  Quality  Control  Laboratory,
Cincinnati, Ohio  (1971) .
                                 376

-------
Morissey,   A.J.,   and   LaRocca,  S.A.,  "Wastewater  Load
Evaluated  at  a  MultiProduct   Organic    Chemical  Plant."
Industrial Water Engineering, Vol. 7, No. 5  (May 1970), 173-
178.

Mytelka,  A.I.,  and Manganelli, R., "Energy-Induced Changes
in an Azo Dyesstuff  Waste."   journal  of  Water  Pollution
Control Federation, Vol. 40, No. 2 (February 1968), 260-268.

1972-73  OPD  Chemical  Buyers Directory, Chemical Marketing
Reporter.  Schnell Publishing Co., Inc., New York  (1973).

Parmelley, C.S., and Fox, R.D.,  "Reuse  Comes  our  Ahead."
Water  and  Wastes  Engineering,  Vol.  9,  No. 11  (November
1972).

Paulson, E.G., "The War on Pollution." Oil and Gas  Journal,
Vol. 68, No. 6  (June 1970), 85-92.

Perry, J.H., Chemical Engineer's Handbook, McGraw-Hill, Inc.
New York  (1963).

Polss,  P.,  "What  Additives Do for Gasoline."  Hydrocarbon
Processing, Vol. 52, No. 2  (February 1973), 61-68.

Prather,  V.,  "Advanced  Treatment  of  Petroleum  Refinery
Wastewater  by  Autoxidation."   Journal  of Water Pollution
Control Federation, Vol. 42, No. 4 (April 1970), 596-603.

Pursell, W.L., and Miller R.B., "Waste Treatment  of  Shelly
Oil  Company's  ElDorado,  Kansas Refinery."  Proceedings of
16th Industrial Waste  Conference,  Purdue  University   (May
1961), 292-303.

Rainbow,    C.A. ,    "Industrial   Wastewater   Reclamation."
Proceedings of  23rd  Industrial  Waste  Conference,  Purdue
University  (May 1968), 1-9.

Rey, G., Lacy, W.I., and Cywin, A., "Industrial Water Reuse;
Future   Pollution  Solution."   Environmental  Science  and
Technology, Vol. 5, No. 9  (September 1971), 842-845.

Rose, B.A., "Water Conservation Reduces  Load."   Industrial
Water Engineering, Vol. 6, No. 9  (September 1969), 4-8.

Rose,  W.L., Gorringe, G.E., "Activated Sludge Plant Handles
Loading Variations."  Oil and Gas Journal, Vol. 70,  No.  10
(October 1972), 62-65.
                                 377

-------
Ross,  W.K.,  and  Sheppard,  A.A., "Biological Oxidation of
Petroleum  Phenolic  Waste  Waters."   Proceedings  of  10th
Industrial  Waste  Conference, Purdue Univeraity  (May 1955),
106-119.

Santoleri, J.J., "Chlorinated  Hydrocarbon Waste."   Chemical
Engineering Process, Vol. 69, No. 1 (January 1973) , 68-74.

Sawyer,  G.N.,  "Fertilization  of  Lakes by Agriculture and
Urban  Drainage."   Journal  of  New  England  Water   Works
Association, (1949).

"Sequential  Gasification."   Oil  and Gas Journal, Vol. 70,
No. 10  (October 1972) , 116-117.

Shreve, R.N.,  Chemical Process Industries,  third  edition;
McGraw-Hill, Inc., New York  (1956).

Smallwood,   D.S.,  Ramanathan,  M.,  and  Dougherty,  J.H.,
"Reference  Effluent   Guidelines   for   Organic   Chemical
Industries, Process Narratives."  Roy F. Weston, Inc. report
to   Environmental   Protection  Agency,  Washington,  D.C.,
Contract No. 14-12-963,  (Unpublished).

Snoeyink, V.L., Weber, W.J., and Mark,  H.B.,  "Sorption  of
Phenol  and  Nitrophenol  by  Active Carbon."  Environmental
Science and Technology, Vol. 3, No. 10  (October 1969),  918-
926.

"Sohio  Uses  Sewage-Plant Effluent as Stop Feedwater."  Oil
and Gas Journal, Vol. 70, No. 2  (February 1972), 80-82.

"Standard  Methods  for  the  Examination   of   Water   and
Wastewater."  American  Public Health Association, Inc., New
York (1971) .

Steck,  W.,  "The  treatment  of  Refinery  Wastewater  with
Particular  consideration of Phenolic Streams."  Proceedings
of 21st Industrial Waste conference, Purdue University  (May
1966), 783-790.

Stroud,  P.W.,  Sorg,  L.V.,  Lamkin, J.C., "The First Large
Industrial Waste Treatment Plant  on  the  Missouri  River."
Proceedings  of  18th  Industrial  Waste  Conference, Purdue
University  (May 1963), 460-475.

Taras, M.J., ed., Standards Methods for the  Examination  of
Water  and  Wastewater  American  Public  Health Assocation,
Washington, D.C.,  (1971).
                                 378

-------
Thompson, C.S.,  Stock,  J.,  and  Mehta,  D.L.,  "Cost  and
Operating  Factors  for Treatment of Oily Waste Water."  Oil
and Gas Journal, Vol. 70, No. 11 (November 1972), 53-56.

Thompson, S.J.,  "Techniques  for  Reducing  Refinery  Waste
Water." Oil and Gas Journal, Vol. 68, No. 10 (October 1970),
93-98.
Vania,  G.B.,  Bhatla,  M.N.,  Thompson, A.F., and Bralston,
C.W.,   "Process   Development,   Design,   and   Full-Scale
Operational  Experience  at  a  Petrochemical  Manufacturing
Wastewater Treatment Plant." Proceedings of 44th  Conference
of the Water Pollution Control Conference  (October 1971), 1-
25.

Water;  Atmospheric  Analysis,  Part 23, "Standard Method of
Test for Bio-Chemical Oxygen Demand of Industrial Water  and
Industrial   Waste   Water."    1970  Annual  Book  of  ASTM
Standards,  American  Society  for  Testing  and  Materials,
Philadelphia, Pennsylvania  (1970).

"Water Quality Criteria." State Water Quality Control board.
Publication No. 3-A, Sacramento, California  (1963).

Wigren,   A.A.,   and  Burton,  F.L.,  "Refinery  Wastewater
Control." Journal of  Water  Pollution  Control  Federation,
Vol. 44, No. 1 (January 1972), 117-128.
                                 379

-------
             Summary of EPA Research Development and
           Demonstration Projects Utilizing Activated
                  Carbon Adsorption Technology
EPA Advanced Wastewater Treatment Demonstration
Grant No. 17080 EDV, "Tertiory Treatment by Lime
Addition at Santee, California, "Santee County
Water District, Santee, California, January 12, 1966.

EPA Advanced Wastewater Treatment Demonstration Grant
No. 802719, "Interim Wastewater Treatment Plant
Demonstration, Covington Kentucky, "Campbell and Kenton
Counties Sanitation District, July 23, 1973.

EPA Advanced Wastewater Treatment Demonstration
Grant No. 80266, "Physical Chemical Treatment Evaluation",
Metropolitan Sewer Board Minneapolis, St. Paul Minn.,
January 1, 1974.

EPA Storm and Combined Sewer Research Grant No. 802433
Rice University, Houston, Texas, "Maximum Utilization of
Water Resources in a Planned Community, July 16, 1973.

EPA Industrial Research Grant No. 17020 EPF, "Adsorption
from Aqueaus Solution", University of Michigan, Ann Arbor
Michigan, October 1, 1969.

EPA Industrial Demonstration Grant No. 12050GXE, "Treatment
of Oil Refinery Wastewaters for Reuse Using a Sand Filter
Activated Carbon System, B.P. Oil Company, Marcus Hook,
Pennsylvania January 1, 1971.

EPA Industrial Demonstration Grant No. 12020EAS "Recondition
and Reuse of Organically Contaminated Waste Sodium Chloride
Brines, Dow Chemical Company, Midland, Michigan, January 6, 1969,

EPA Advanced Wastewater Treatment Demonstration Grant No.
11060 EGP, "Advanced Waste Treatment at Painesville, Ohio,
City of Painesville, Ohio, December 15, 1969.

EPA Research Grant No. 12040 HPK, "Organic compounds
in Pulp Mill Lagoon Discharge", University of Washington.
                                380

-------
EPA Research Study No. 21ACU07, "Development of Analog
Chemical Treatment", EPA NERC Cincinnati, Ohio, January 7, 1972

EPA Research STudy No. 21 ABD 06, "Process Modification
to Enhance Removal of Heavy Metals, NERC Cincinnati, Ohio
January Ht 1973.

EPA Advanced Wastewater Treatment Demonstration Grant
No. 11010 EHI, "Teritory Treatment of Combined Storm
Water Sanitary Relief Discharge and Sewage Treatment
Plant Effluent", Sanitary District of East Chicago,
January 12, 1966.

EPA Advanced Waste Treatment Demo Grant No. 11010 DAB,
"Chemical Clarification and Carbon Filtration and Adsorption
as Secondary Treatment for Rocky River Wastewater Treatment
Plant, Cuyahoga County, Ohio Sewer District, August 16, 1968.

EPA Industrial Demonstration Grant No. 801U31, "An Activated
Carbon Secondary Treatment System for Purification of a
Chemical Plant Wastewater for maximum Reuse, "Hercules, Inc.,
January 3, 1973.

EPA Demonstration Grant No. 80055U, "Carbon Adsorption and
Regeneration for Petrochemical Waste Treatment", University
of Missouri, Columbia, Missouri, January 6, 1972.

EPA Research Contract No. 68-01-0183 "Physical Chemical
Treatment of Municipal Waste", Envirotech Corporation
Salt Lake City, Utah, July t, 1972.

EPA Research Contract No. 68-01-0137, "Development
and Demonstration of Device for on Board Treatment
of Wastes from Vessels," AWT Systems Inc., Wilmington
Delaware, March 6, 1971

EPA Research Contract No. 68-01-0130, "Device for on
Board Treatment of Wastes from Vessels", Fairs banks
Morse, Inc., Beloit, Wisconsin, March 6, 1971.

EPA Research Contract No. 68-01-0099, "Development of
Modular Transportable Prototype System for Treating
Spilled Hazardous Materials", Hernord, Inc., Milwaukee,
Wisconsin, June 29, 1971.
                                381

-------
EPA Research Contract No. 68-01-0077, "Process for
Housing and Community Development Industries", Levitt
and Son, Nassau County, New York, June 15, 1971.

EPA Research Contract No. 68-01-0013, "Waste Heat
Utilization in Waste Water Treatment", URS Research
Company, San Mateo, California, December 31, 1970.

EPA Research Contract No. 58-01-0901, "Study of
Improvements in Granular Carbon Adsorption Process",
FMC Corporation, Princeton, New Jersey, June 26, 1970.

EPA Advanced Waste Treatment Contract No. 58-01-0441,
"Carbon Adsorption and Electro dialipes for Demineralization
at Santee California," Santee Coutny Water District,
Santee California, June 29, 1968.

EPA Research Contract No. 58-01-0400, "Activated Carbon
Powder Treatment in Slurry Clarifiers", Infilco, Fullers
Company, Tucson, Arizona, June 9, 1968.

EPA Research Contract No. 58-01-0075, "Study of Powdered
Carbons for Waste Water Treatment, "West Virginia Pulp
and Paper Company, Covington, Virginia, June 29, 1967.

EPA Research Study No. 21ABK-31, "Treatability of Organic
Compounds", EPA NERC Cincinnati, Ohio January 7, 1973.

EPA Research Study No. 21 ABK 16, "Treatability of Organic

EPA Research Study No. 21 ACP 09, "Removal of Toxi Metals
in Physical Chemical Pilot Plant", EPA NERC Cincinnati, Ohio
January 1, 1972.

EPA Research Study No. 16 ACG-05, "Identify Pollutants
in Physical Chemical Treated Wastes", EPA NERC Corvallis,
Oregon, January 8, 1971.

EPA Advanced Waste Treatment Demonstration Grant No. 800685,
"A Demonstration of Enhancement of Effluent from Trickling
Filter Plant", City of Richardson, Texas, December 24, 1971.

EPA Advanced Waste Treatment Demonstration Grant No. 801026,
"Removal of Heavy Metals by Waste Water Treatment Processes",
City of Dallas, Texas, January 2, 1972.
                                    382

-------
EPA Advanced Waste Treatment Demonstration Grant No. 801401,
"Piscataway Model Advanced Waste Treatment Plant", Washington
Suburban Sanitary Commission, Hyattsville, Maryland, January
1, 1967.

EPA Research Grant No. 800661, "Oxidation Mechanisms on
Supported Chromia Catalysts, "Purdue Research Foundation,
Lafayette, Indiana, January 6, 1970.

EPA Research Grant No. 12130 DRO, "Deep Water Pilot Plant
Treatability Study", Delaware River Basin Commission,
Trenton, New Jersey, July, 1971.
                                 383

-------

-------
                         SECTION  XVI


                 GLOSSARY AND ABBREVIATIONS




Act

The Federal Water Pollution Act Amendments of  1972.
In the presence of oxygen.
Living or active in absence of  free oxygen.

Aguatic_Li f e

All living forms in natural waters, including plants,   fish,
shellfish, and lower forms of animal life.
Hydrogen   compounds  involving  a  6-carbon,   benzene   ring
structure.

Best^Available_Technoj,ogY_EconomicallY_Achievable_iBATEA).

Treatment required by July 1, 1983 for industrial   discharge
to  surface  waters as defined by section 301  (b)  (2)  (A) of
the Act.

Best_Pra^icable_Contrgl_Technglog^_CurrentlY_Achievable_JBPCTCAX

Treatment required by July 1, 1977 for industrial   dsicharge
to  surface  waters as defined by section 301  (b)  (1)  (A) of
the Act.

Best Available_Demonstrated_Technology JBADT^

Treatment required for new source as defined by section  306
of the Act.
Oxygen used by bacteria in consuming a waste substance.
                                 385

-------
Slowdown

A  discharge from a system, designed to prevent a buildup of
some material, as in boiler and  cooling  tower  to  control
dissolved solids.
Material  which,  if  recovered,  would accrue some economic
benefit, but not necessarily enough to  cover  the  cost  of
recovery.

Capj.tal_Cgsts

Financial  charges which are computed as the cost of capital
times the capital expenditures for pollution control.

Catalyst

A  substance  which  can  change  the  rate  of  a  chemical
reaction, but which is not itself involved in the reaction.

CateggrY_and_Subcategory

Divisions of a particular industry which processed different
traits which affect water quality and treatability.

Chemical_Oxy.gen_Demand __ (COD).

Oxygen consumed through chemical oxidation of a waste.

Clarification

The process of removing undissolved materials from a liquid.
Specifically,  removal  of  solids  either  by  settling  or
filtration.

Effluent

The flow  of  waste  waters  from  a  plant  or  wash  water
treatment plant
The  cost  reflecting  the  deterioration of a capital asset
over its useful life.

End-of-Pipe Treatment
                                    386

-------
Treatment of overall refinery wastes, as distinguished  from
treatment of individual processing units.

Filtration

Removal of solid particules or liquids from other liquids or
gas  streams  by  passing the liquid or gas stream through a
filter media.

Industrial^ Waste

All wastes streams within a plant.  Included are contact and
noncontact  waters.   No  included  are   wastes   typically
considered to be sanitary wastes.

Investment_Costs

The  capital expenditures required to bring the treatment of
control  technology  into  operation.   These  include   the
traditional  expenditures  such  as design; purchase of land
and   materials;   site   preparation;   construction    and
installation; etc., plus any additional expenses required to
bring  the  technology into operation including expenditures
to establish related necessary solid waste disposal.

New_Source

Any building, structure, facility or investment  from  which
there  is  or  may  be  a  discharge of pollutants and whose
contribution is commercial after publication of the proposed
regulation.

EH

A measure of the relative acidity or alkalinity of water.  A
pH of 7.0 indicates  a  neutral  condition.   A  greater  pH
indicates  alkalinity  and a lower pH indicates acidity.   A
one unit change in pH indicates 10 fold  change  in  acidity
and alkalinity.

Pretreatment

Treatment  proved  prior  to  discharge  to a publicly owned
treatment works.

Process_Effluent_or_Discharge

The volume of water emerging from a particular  use  in  the
plant.
                                387

-------
PI ant ^Ef fluent or Discharge After^Treatment

The  volume  of  waste  water  discharge from the industrial
plant.  In this definition, any waste  treatment  device  is
considered part of the industrial plant.
   ^ Waste _ Load

Untreated waste effluent or waste effluents.
Biological treatment provided beyond primary clarification.

Sludge

The   settled   solids   from   a  thickener  or  clarifier.
Generally, almost any flocculated settled mass.

Sur f ace^Wat er s

Navigable  waters.   The  waters  of  the   United   States,
including the territorial seas.

Total_Susjeended_Sglids_j[TSSl,

Any  solids  found  in waste water or in the stream which in
most cases can be removed  by  filtration.   The  origin  of
suspended  matter  may be man-made wastes or natural sources
such as silt from erosion.

Waste Discharged

The amount (usually expressed as weight)  of  some  residual
substance generated by a plant process or the plant as whole
and which is suspended or dissolved in water.  This quantity
is measured before treatment.
Total  amount of pollutant substance, generally expressed as
pounds per day.
                                 388

-------
Abbreviations





AL - Aerated Lagoon



AS - Activated Sludge



BADT - Best Available Demonstrated Technology



BATEA - Best Available Technology Economically Achievable



BPCTCA - Best Practicable Control Technology Currently Available



BOD - Biochemical Oxygen Demand



BTX - Benzene-Toluene-Xylene mixture



COD - Chemical Oxygen Demand



cu m - cubic meter(s)



DAF - Dissolved Air Flotation



DO - Dissolved Oxygen



gpm - Gallons per minute



k - thousand(e.g., thousand cubic meters)



kg - Kilogram(s)



1 - liter



Ib - pound (s)



LPG - Liguified Petroleum Gas



M - Thousand (e.g., thousand barrels)



mgd - Millions gallons per day



mg/1 - Milligrams per liter (parts per million)



MM - Million (e.g., million pounds)



psig - pounds per sguare inch, gauge  (above 14.7 psig)



RWL - Raw Waste Load



sec - Second-unit of time
                                389

-------
scf - Standard cubic feet of gas at 60°F and 14.7 psig



SIC - Standard Industrial Classification



SS - Suspended Solids





TOC - Total Organic Carbon



TSS - Total Suspended Solids



VSS - Volatile Suspended Solids
                                  390

-------
                                   METRIC  TABLE
                                 CONVERSION  TABLE
MULTIPLY (ENGLISH UNITS)

    ENGLISH UNIT      ABBREVIATION
acre                    ac
acre - feet             ac ft
British Thermal
  Unit                  BTU
British Thermal
  Unit/pound            BTU/It
cubic feet/minute       cfm
cubic feet/second       cfs
cubic feet              cu ft
cubic feet              cu ft
cubic inches            cu in
degree Fahrenheit       °F
feet                    ft
gallon                  gal
gall en/minute           gpm
horsepower              hp
inches                  in
inches ct mercury       in Hg
pounds                  Ib
million gallons/day     mgd
mile                    mi
pound/square
  inch (gauge)          psig
square feet             sq ft
square inches           sq in
ton (short)             ton
yard                    yd
* Actual conversion,, not a multiplier
     by                TO OBTAIN (METRIC UNITS)

CONVERSION   ABBREVIATION   METRIC UNIT
                            hectares
                            cubic meters

                            kilogram - calories

                            ki 1 ograni co "iori es/ki 1 ogram
                            cubic meters/miriute
                            cubic meters/minute
                            cubic meters
                            1i ters
                            cubic centimeters
                            degree Centigrade
                            meters
                            liters
                            1i tors/second
                            ki1lowatts
                            centimeters
                            atmospheres
                            kilograms
                            cubic meters/day
                            kilometer

                            atmospheres (absolute)
                            square meters
                            square centimeters
                            metric ton (1000 kilograms)
                            meter
0.405
1233.5
0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(*F-32)*
0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.509
(0.06805 osig +1)*
0.0929
6.452
0.907
0.9144
ha
cu rn
kg ca.1
kg cal/k.g
cu m/mi n
cu m/min
cu m
1
cu cm
°C
m
1
I/sec
kw
cm
atm
kg
cu rn/day
krn
atm
sq m
sq cm
kkg
m
                                        391

-------

-------

-------

-------

-------
U.S. ENVIRONMENTAL PROTECTION AGENCY (A-107)
WASHINGTON, D.C. 20460
           POSTAGE AND FEES PAID
ENVIRONMENTAL PROTECTION AGENCY
                        EPA-335

-------