WASTES FROM MANUFACTURE OF
           AZO DYES AND PIGMENTS
  (Excluding Benzidine and Its  Congeners)
                     By

              D. C. Bomberger
               R.  L.  Boughton
             SRI International
           333 Ravenswood Avenue
           Menlo Park, CA  94025
            Contract 68-03-2944
             Task 1, Subtask 2
              Project Officer

             Mr. Mark Stutsman
    Industrial Pollution Control Division
Industrial Environmental Research Laboratory
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
     OFFICE OF RESEARCH AND DEVELOPMENT
    U.S. ENVIRONMENTAL PROTECTION AGENCY
           CINCINNATI,  OHIO   45268

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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
= ORT NO. 2.
"LE AND SUBTITLE
iSTES FROM MANUFACTURE OF AZO DYES AND PIGMENTS.
:XCLUDING BENZIDINE AND ITS CONGENERS)
JTHOR(S)
,C. Bomberger & R.L. Boughton
.RFORMING ORGANIZATION NAME AND ADDRESS
RI International
33 Ravenswood Ave.
enlo Park, CA 94025
SPONSORING AGENCY NAME AND ADDRESS
ndustrial Environmental Research Laboratory
iff ice of Research & Development
I.S. Environmental Protection Agency
lincinnati , OH 45268
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-2944
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA/600/12
**#
SUPPLEMENTARY NOTES
!
  .ABSTRACT
  In a study of the manufacture of azo dyes and pigments, several solid wastes that coul
  contain hazardous material were identified.  These solid wastes included filter cake
  from clarifying operations, wastewater treatment solids, intermediates on discarded
  shipping containers, and fines collected in baghouses used in grinding and drying oper
  tions.  An aqueous waste stream containing process wastewater and mother liquor that
  could contain hazardous material was also identified.  The major components in the sol
  and liquid streams were identified, and the amounts produced were estimated.  These
  estimates were made on an individual dye basis and summarized on an industry-wide basi;
  The major potential discharges of dye, unreacted intermediates, and reaction by-produc
  were in the mother liquor after dye or pigment transferred to wastewater treatment
  solids.  Other major sources of solid residues included dye and pigments on baghouses
  fines, intermediate in discharged shipping containers, and filter cake solids.  Pigment
  manufacture represented the most important source of wastes because of its large volurn*
  relative to dyes.  The emissions showed that on an industry-wide basis 2-naphthol and
  3-hydroxy-2-naphthoic acid account  for nearly 50% of the intermediates estimated to be
  in the combined aqueous-solid stream [650 metric tons/year (mt/yr)].  This stream is
  also estimated to contain 350 mt/yr of dyes and pigments and 640 mt/yr of reaction by-
  products on an industry-wide basis.  The total amount of dye or pigment in the solid
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
-
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
b. IDENTIFIERS/OPEN ENDED TERMS
>k
19. SECURITY CLASS (This Report)
UNCLASSIFIED
20. SECURITY CLASS (This page)
IINH ASSTFTFH
c. COSATI Field/Croup

21. NO. OF PAGES
22. PRICE '
EPA Form 2220-1 (R»v. 4-77)   PREVIOUS EDITION it OBSOLETE

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

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                                   FOREWORD
     When  energy  and material  resources  are extracted, processed, converted,
and used,  the  related pollutional impacts  on our environment and even on  our
health  often  require  that  new  and  increasingly  more  efficient  pollution
control methods  be used.   The  Industrial Environmental Research Laboratory  -
Cincinnati  (lERL-Ci)  assists  in developing and demonstrating new and  improved
methodologies  that will  meet  these needs  both efficiently  and economically.

     This  report  is  one  of a series  of preliminary studies  of segments of  the
dye and pigment manufacturing industry conducted  for  the Organic and Inorganic
Chemicals  and  Products  Branch  of the Industrial Pollution Control Division.
The objective  of  these studies  was to determine if process  waste streams might
contain hazardous material  and to  recommend sites  where  a sampling program
could be used  to  confirm the  nature  of any  hazards that were identified.
                                                 David G. Stephan
                                                     Director
                                   Industrial Environmental Research Laboratory
                                                    Cincinnati

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                                   ABSTRACT
     In  a  study  of  the manufacture  of  azo dyes  and  pigments, several .solid
wastes  that  could contain  hazardous material  were identified.   These  solid
wastes  included  filter cake  from  clarifying operations, wastewater  treatment
solids,  intermediates  on discarded shipping  containers,  and  fines  collected  in
baghouses  used  in grinding  and drying  operations.   An aqueous waste  stream
containing process  wastewater and mother  liquor  that  could contain  hazardous
material was also identified.

     The major components in  the solid and liquid  streams were  identified, and
the  amounts  produced  were  estimated.    These   estimates  were  made  on  an
individual  dye  basis  and summarized  on an industry-wide   basis.   The major
potential discharges of dye,  unreacted intermediates,  and reaction by-products
were  in the  mother  liquor   after  dye  or  pigment  transferred to wastewater
treatment  solids.   Other major  sources of solid  residues  included dye and
pigments on  baghouses fines,  intermediates  in discarded shipping containers,
and filter cake solids (which could  contain  unreacted  intermediates,  partially
coupled  dye molecules, and N-nitrosamines).

     Pigment  manufacture  represented  the  most   important  source  of  wastes
because  of its  large volume  relative to dyes.  The emissions estimates  showed
that  on  an  industry-wide  basis  2-naphthol  and  3-hydroxy-2-naphthoic  acid
account  for  nearly  50% of  the intermediates  estimated  to  be  in the  combined
aqueous-solid  stream  [650  metric  tons/year (mt/yr)].   This  stream is  also
estimated  to  contain 350  mt/yr of  dyes and  pigments and 640 mt/yr of reaction
by-products on an industry-wide  basis.   The total  amount of dye or pigment  in
the solid  residue from azo  dye and  pigment manufacturing  is  estimated to  be
550 mt/yr, which  makes the dyes and pigments themselves the more significant
synthetic  organic component   of  the total  solid  residue.   Sampling at six
representative  manufacturing   is estimated   to be  550  mt/yr, which  makes the
dyues and pigments themselves the more significant synthetic organic  component
of the  total solid residue.   Sampling a  six  representative manufacturing sites
was recommended to determine  actual  waste  composition  and amount.

    'This  report  was  submitted  in  fulfillment of  Contract  No. 68-03-2944  by
SRI International under the  sponsorship  of  the U.S.  Environmental Protection
Agency.  This  report  covers  the period  February 1981  to March 1982,  and  work
was completed as  of  August 1983.
                                      IV

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                                   CONTENTS


FOREWORD o	    iii

ABSTRACT	     iv

TABLES	     vi

L.   INTRODUCTION	      1

2.   SUMMARY AND CONCLUSIONS	     22

3.   PROCESS CHEMISTRY	     24

       Introduction	     24
       Diazotization	     25
       Coupling	     28
       Other Reactions	     40
       Chemistry of Azoic Compounds	     43

4.   DYE INTERMEDIATES	     45

5.   SOURCES OF WASTE DISCHARGES DURING AZO DYE AND PIGMENT
       MANUFACTURE	     59

       Overview of Azo Dye and Pigment Production Processes	     60
       Raw Material Receiving and Handling	     62
       Dye Synthesis	     65
       Product Filtration	     67
       Drying, Grinding, Standardization, Blending
         and Packaging	     70
       Summary of Aqueous and Solid Waste Emission Estimates	     71
       Wastewater Treatment	     74

6.   SOLID AND AQUEOUS WASTE PRODUCTION	     79

REFERENCES	    194

APPENDICES
  A.   Example of Multistage Process  for a Complex Dye	    198
  B.   Estimation of By-Products and  Unreacted  Intermediates
       Produced by Dye and Pigment Manufacture	    202

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                                    TABLES
Number                                                                 Page
1.   Azo Dyes and Pigments Included in this Study...	     2
2.   Azo Dyes and Pigments for Which no Structure Information
     was Available	•	    16
3.   Azoic Coupling Components and Azoic Diazo Components
     Included in this Study	    21
4.   Colour Index Descriptions of Monazo Dye and
     Pigment Subclasses	    30
5.   Colour Index Classification of the Azo Colouring Matters	    33
6.   Colour Index Descriptions of  the Disazo Dye and
     Figment Subclasses	    34
7.   Colour Index Descriptions of  the Trisazo Dye and
     Pigment Subclasses	    37
8.   Organic Intermediates and Other Chemicals used  in Azo Dye
     and Pigment Manufacture for which Physical Property Data
     were Found	    46
9.   Organic Intermediates for which no Physical Property
     Data were Found	    52
10.  Summary of the Estimated Aqueous Wastes and Solid Residue
     Produced by Water  Soluble Dye Manufacturing Operations	    72
11.  Summary of the Estimated Aqueous Waste and Solid Residue
     Produced by Pigment and Solvent and Disperse Dye
     Manufacturing Operations	    73
12.  Estimated Wastes Produced in Manufacturing Azo  Dyes and
     Pigments Other Than Those Based on Benzidine and
     Its Congeners	    82
13.  Intermediates Used in Table 12 that have Common Names	   170
14.  Directory of Azo Dye and Organic Pigment Manufacturers, 1978	   172
15.  Producers of Monoazo Dyes and Pigments	   174
16.  Producers of Disazo Dyes and Pigments	   184
17.  Producers of Trisazo, Tetrakisazo
     and Polyazo Dyes and Pigments	   188
18.  Producers of Azoic Diazo Components	   189
                                      VI

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                              TABLES (Concluded)
19.  Producers of Azoic Coupling Components	  190

20.  Estimated Total Quantity of Organic Intermediates
     in Solid and Aqueous-Solid Wastes from the Manufacture
     of Azo Dyes and Pigments other than Those Based on
     Benzidine and Its Congeners	  191

B-l. Example Estimation of By-Products and Unreacted
     Intermediates from Production of Acid Black 1	  203

B-2. Results of By-Product Estimation from Azo Dye Synthesis	  205
                                     Vll

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                                   SECTION 1

                                 INTRODUCTION
     The Resource Conservation and Recovery Act  (RCRA) requires that hazardous
solid wastes  produced by manufacturing operations  be identified and disposed
in  a   manner  that  limits  the  release   of  hazardous  materials  to   the
environment.    To  date,  many  specific  waste  streams  from  manufacturing
processes have  been listed  in regulations  as being hazardous because of their
chemical  composition.   The objective  of  this  preliminary  study  is  to help
determine  if  wastes  produced by  the manufacture of  dyes  and  pigments in  the
United  States might  require  listing  as hazardous  materials.   An analysis of
both  the  chemistry  and  the physical  processing involved in  dye and pigment
manufacturing will  be used to identify  all wastes that may contain significant
chemical  hazards.    An analysis  of  the  industry  will  be used  to determine
specific  manufacturers  where  the  candidate  wastes  are  produced.    This
information  will help  the  U.S.  Environmental  Protection Agency,  Office of
Solid Wastes, to design a sampling and  analysis program to confirm or disprove
the  presence  of  hazardous  materials  in  .the candidate  wastes  and  thereby.
develop a  basis for listing dye and  pigment  manufacturing wastes under RCRA.
This  report  deals  with  the  wastes  from  the  manufacture  of  azo  dyes   and
pigments based  on intermediates other  than benzidine  and its congeners.

     Among  the  commonly recognized  structural classes of dyes  and pigments,
the most  important  commercially  in  the  United  States  are  the  azo  dyes   and
pigments.  The  1978 U.S. production of  azo dyes and pigments was approximately
41,000 metric tons  or about  35% of all  U.S. dye and pigment production.  These
dyes and pigments are characterized  by the presence  of one or more azo groups
(-N=N-)  in  the  molecule.    Consequently,   the  class  can  be   divided  into
subclasses  (monoazo,  disazo, trisazo,  tetrakisazo,  and polyazo).   A special
subclass  consists   of  azoic compounds;  the  azoic  coupling  components,  azoic
compositions,  and  azoic diazo  components,  that  are  reacted on  the  fiber to
produce  azo  dyes.    The  azo  dyes,   pigments,  and azoic  compounds  based on
benzidine  and its   congeners were  studied  separately as  described in another
report.  This study deals with the remaining  azo  dyes, pigments, and azoics.

     The azo  dyes and pigments produced in commercial quantities  in the United
States  were  selected  as  the  subject  of  this study because  of  the current
concerns  about  their  possible  adverse effects  on  the  environment  and human
health.  The  Colour Index  (The  Society of  Dyers  and  Colourists,  1980) numbers
and names of  the  dyes and  pigments for which  chemical composition  information
was available  are  shown  in  Table  1.   The   dyes  and pigments  are  listed in
subgroups according to manufacturing chemistry.   (These subgroups  and  the  C.I.
number ranges are described  in Section  3.)  The 1978  U.S.  production  levels of

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                                Table  1
               AZO DYES AND PIGMENTS INCLUDED  IN THIS  STUDY
                     (1978 Production Figures from  the
                   U.S. International  Trade Commission)
C.I. Subgroup

Monoazo Dyes and
 Pigments

  11000-11435
                   C.I. No.
11000
11005
11014
11021
11043
11052
11055
11056
11077

11085
11087
11100
11110
11115
11116
11117
11119

11150
11152
11154
11160
11210
11215
11227
11228
11270
11320
11365
                 C.I. Dye Name
Solvent Yellow 1
Disperse Orange 3
Basic Red 30
Solvent Yellow 56
Basic Violet 18
Basic Blue 54
Basic Red 22
Basic Orange 24
Disperse Blue 165
Disperse Blue 79
Basic Red  18
Basic Yellow  15
Disperse Orange  5
Disperse Red  1
Disperse Red  13
Disperse Red  73
Disperse Red  90
Disperse Orange  30
Disperse Red  54
Disperse Red  7
Disperse Brown  1
Basic  Blue 41
Solvent Yellow  3
Disperse Red  17
Disperse Red  5
Disperse Orange  25
Disperse Red  65
Basic  Orange  2
Basic  Orange  1
Disperse Black  1
  2
                         Production
                           (mt/yr)
>  2.3
  21.4
>  2.3
>  4.5
>  2.3
>  6.8
>  2.3
>  2.3
>  6.8
1284
  147.3
>  2.3
>  4.5
  174.1
>  6.8
>  4.5
>  2.3
>  6.8
 > 4.5
 > 2.3
   18.2
 > 4.5
 > 14a
   77.3
   36.4
  325.5
  104.5
  283.6

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                          Table 1 (Continued)
C.I.  Subgroup
  11440-11630
  11640-11770
C.I. No.
11460
11480
11660
11670
11680
11710
11720
11725
11727
11730
11738
11740
11741
11765
11767
11770
C.I. Dye Name
Basic Red 29
Basic Yellow 24
Pigment Yellow 5
Pigment Yellow 6
Pigment Yellow 1
Pigment Yellow 3
Pigment Yellow 9
Pigment Orange 1
Pigment Yellow 98
Pigment Yellow 2
Pigment Yellow 73
Pigment Yellow 65
Pigment Yellow 74
Pigment Yellow 49
Pigment Yellow 97
Pigment Yellow 75
Production
(mt/yr)
> 5a
> 4.5
> 0.9
> 0.5
199.5
66.4
> 0.5
> 0.9
> 0.5
> 0.5
245.5
>50a"
588.2
> 0.5
> 0.5
> 0.5
  11800-11975
11855
                                  Disperse Yellow 3
>95
  12050-12211
12055
12060
12070
12075
12085
12090
12100
12120
                                  Solvent Yellow 14
                                  Pigment Orange 2
                                  Pigment Red 1
                                  Pigment Orange 5
                                  Pigment Red 4
                                  Pigment Red 6
                                  Solvent Orange 2
                                  Pigment Red 3
 173.2
>  5a
>  2.7
 309.1
  49.5
  10.5
>  2.3
 485.9

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                          Table 1 (Continued)
C.I.  Subgroup
C.I. No.
  C.I. Dye Name
Production
  (mt/yr)
  12050-12211
  (Continued)
 12140
 12150
 12156
Solvent Orange 7
Solvent Red 1
Solvent Red 80
   > 6.8
   > 2.3
   > 2.3
  12300-12505
 12300
 12310
 12315
 12320
 12355
 12360
 12367
 12370
 12390
 12395
 12420
 12460
 12465
 12467
 12475
 12476
 12480
 12485
 12490
Pigment Red 21
Pigment Red 2
Pigment Red 22
Pigment Red 32
Pigment Red 23
Pigment Red 31
Pigment Orange 38
Pigment Red 112
Pigment Red 17
Pigment Red 13
Pigment Red 7
Pigment Red 9
Pigment Red 15
Pigment Red 188
Pigment Red 170
Disperse Red 220
Pigment Brown 1
Pigment Red 146
Pigment Red 5
   > 5°
    23.2
    35.5
   > 0.9
   200
   > 0.9
   > 0.5
   > 0.9
    41.4
   > 0.9
   > 0.9
   >10a
   > 0.5
   > 0.5
   > 0.9
   > 2.3
   > 0.5
   > 5a
    25.9
   12600-12875
 12700
 12705
 12715
 12770
 12775
Solvent Yellow 16
Pigment Yellow 60
Solvent Red 8
Disperse Yellow 4
Pigment Greeen 10
  4
                                                              > 2.3
                                                              > 0.9
                                                              > 2.3
                                                              > 2.3
                                                              > 0.9

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                           Table I  (Continued)
C.I. Subgroup
   13010-13710
   13890-13970
   13990-14155

C.I. No.
13025
13065
13080
13091
13095
13150
13190
13245
13250
13265
13361
13390
13900
13906
13950
14025
14030
14110
14155

C.I. Dye Name
Acid Orange 52
Acid Yellow 36
Acid Orange 5
Acid Orange 1
Acid Yellow 63
Acid Orange 50
Reactive Yellow 4
Reactive Yellow 3
Mordant Brown 33
Mordant Brown 70
Acid Green 35
Acid Blue 92
Acid Yellow 99
Acid Yellow 151
Direct Yellow 27
Mordant Yellow 1
Mordant Orange 1
Mordant Yellow 20
Direct Green 28
Production
(mt/yr)
> 2.3
> 6.8
> 2.3
> 2.3
> 2.3
> 2.3
> 2.3
> 2.3
> 4.5
> 2.3
> 2.3
> 9a
> 9.1
1620.9
> 2.3
> 2.3
> 4.5
> 2.3
> 2.3
  14160-14345
14170
                                  Acid Yellow 65
                                             4.5

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C.I. Subgroup
C.I. No.
                           Table 1 (Continued)
C.I. Dye Name
Production
  (mt/yr)
  14600-15085
 14645
 14700
 14710
 14720
 14830
 14880
 15050
Mordant Black 11
Food Red 1
Acid Red 4
Acid Red 14
Acid Red 20
Acid Blue 158
Acid Blue 158:1
  > 45
  >  4.5
    19.5
  > 25.5
  >  0.5
  >  4.5
  >  4.5
  15500-16315
 15510
 15575
 15585
 15602
 15620
 15630
 15670
 15705
 15711
 15800
 15825
 15850
 15860
 15865
 15880
 15970
 15985
 16035
 16105:1
 16105
 16150
 16185
 16230
 16255
Acid Orange 7
Acid Orange 8
Pigment Red 53
Pigment Orange 46
Acid Red 88
Pigment Red 49
Mordant Violet 5
Mordant Black 17
Acid Black 52
Pigment Brown 5
Pigment Red 58
Pigment Red 57
Pigment Red 52
Pigment Red 48
Pigment Red 63
Acid Orange 12
Food Yellow 3
Food Red 17
Pigment Red 60 :1
Mordant Red 9
Acid Red 26
Acid Red 27
Acid Orange 10
Acid Red 18
  6
   206.8
   142.2
  1800
  >  0.5
    40.0
  3150
  >  2.3
  >  4.5
   40.6.8
  >  1.8
  >  0.9
  1550
   798.6
  1135.5
    25.9
  >  2.3
   488.2
   867.3
   136.2
  >  2.3
  >  2.3
  >  2.3
    65.9
  >  ^.5

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                           Table 1 (Continued)
C.I.  Subgroup
C.I. No.
C.I. Dye Name
Production
  (mt/yr)
  16500-16730
                   16580
                Acid Violet 3
                                                                6.8
   17000-17260
 17025
 17045
 17053
 17100
 17101
 17200
Acid Violet 1
Acid Red 37
Acid Red 57
Acid Brown 90
Acid Red 266
Acid Red 33
Acid Red 337
      2.3
      4.5
      4.5
      2.3
      9.1
      4.5
    794.
   17750-18245
 17755
 17757
 17590
 17907
 17908
 18050
 18055
 18075
 18097
 18158
 18165
 18200
Acid Red 137
Reactive Orange  16
Mordant Brown 40
Reactive Orange  1
Reactive Red 8
Acid Red 1
Acid Violet 7
Acid Violet 12
Reactive Violet 5
Reactive Red 1
Acid Black 60
Reactive Red 2
     41.8
      2.3
      2.3
      2.3
      2.3
    154.1
      4.5
      2.3
      2.3
      2.3
      2.3
      4.5
   13260-1G270
 18260
 18270
                                  Reactive Orange 4
                                  Reactive Orange 13
                              4.5
                              2.3

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                             Table 1 (Continued)
C.I. Subgroup
  18670-19245
  19300-19610
C.I. No.
18690
18732
18740
18745
18760
18810
18820
18821
18835
18852
18890
18900
18930
18950
18965
18967
18971
18972
19005
19010
19140
19351
19555
C.I. Dye Name
Acid Yellow 121
Acid Orange 60
Acid Orange 72
Acid Orange 74
Mordant Red 7
Acid Red 186
Acid Yellow 11
Mordant Yellow 8
Acid Yellow 25
Reactive Yellow 17
Acid Yellow 34
Acid Yellow 29
Acid Yellow 200
Acid Yellow 40
Acid Yellow 17
Acid Yellow 19
Reactive Yellow 1
Reactive Yellow 2
Acid Yellow 127
Acid Yellow 54
Acid Yellow 23
Acid Red 179
Direct Yellow 28
Production
(mt/yr)
> 2.3
298.6
> 2.3
> 4.5
> 9.1
> 2.3
> 2.3
> 2.3
> 2.3
> 2.3
> 4.5
> 2.3
> 2.3
> 6.8.
84.1
> 9.1
> 2.3
> 2.3
> 2.3
> 4.5
730
> 2.3
25.9

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                         Table 1  (Continued)
 C.I.  Subgroup     C.I.  No.
            C.I.  Dye Name
                            Production
                              (mt/yr)
Disazo Dyes and Pigments
  Disazo Dyes I
    20000-20045
20040
Pigment Yellow 16
0.4
    20070-20140
20110
Mordant Brown 1
4.5
    20150-20305      20150      Mordant Brown 18
                     20170      Acid Orange 24
                     20177      Acid Brown 354
                     20195      Acid Brown 14
                     20250      Acid Brown 83
                                          >  2.3
                                          > 13.6
                                          >  2.3
                                           106.4
                                          >  2.3
    20310-20540      20460      Acid Blue 29
                     20470      Acid Black 1
                     20480      Acid Black 41
                     20495      Acid Green 20
                     20505      Reactive Black 5
                                           >  2.3
                                           169.1
                                           >  2.3
                                           >  9.1
                                           >  2.3
  Disazo Dyes II
     21000-21030
                     21000      Basic Brown 1
                     21010      Basic Brown 4
                     21030      Basic Brown 2
                                            41.8
                                            110
                                              2.3

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                       Table 1 (Continued)
C.I.  Subgroup     C.I.  No.
     C.I. Name
Production
  (mt/yr)
 21230-21280      21230
                  21240
                  21250
Solvent Yellow 29
Solvent Yellow 30
Solvent Red 22
 > 4.5
 > 2.3
 > 2.3
  24750-24840     24810
Acid Red 134
 > 2.3
  24850-24920     24890       Direct Yellow 4
                  24895       Direct Yellow 12
                             300.4
                             > 6.8
  25080-25135     25100       Mordant Yellow 16
                  25135       Acid Yellow 38
                             > 2.3
                             > 2.3
  25200-25450     25200
                  25380
Direct Orange 73
Direct Red    75
 > 2.3
 > 2.3
Disazo Dyes III
   26006-26150    26050       Solvent Red 19
                  26070       Disperse Yellow 23
                  26077       Disperse Orange 29
                  26100       Solvent Red 23
                  26105       Solvent Red 24
                  26120       Solvent Red 26
                  26125       Solvent Red 27
                             > 2.3
                             217.7
                             196.8
                             > 2.3
                             > 9.1
                             > 4.5
                             > 2.3
   26200-26440     26360       Acid Blue 113
                  26370       Acid Black 24
                                  10

-------
                            Table 1 (Continued)
C.I. Subgroup    C.I. No.
              C.I. Dye Name
                                                       Production
                                                         (mt/yr)
  26200-26440
  (Continued)
26410      Acid Blue 118
26440      Reactive Brown 1
                                                         >  2.3
                                                         >  2.3
  26500-26580      26520
                   26550
           Mordant Orange 6
           Acid Orange 51
                                                        >  9.1
                                                        >  2.3
   26900-27311      26900      Acid Red 151
                   26905      Acid Red 66
                   27200      Acid Red 115
                   27290      Acid Red 73
                   27291      Solvent Red 30
                                        > 15.9
                                        >  2.3
                                        >  4.5'a
                                          74.5
                                        >  2.3
27600-27790      27680
                              Direct Red 16
                                        >  4.5
   27850-27990     27855
                   27885
                   27925
           Direct Violet 7
           Direct Violet 9
           Direct Blue 67
                                                         >   2.3
                                                         >   4.5
                                                         >   2.3
   28100-28500     28160      Direct Red 81
                   28255      Direct Oranse 74
                                        1066.4
                                              a
                                        >  4.5
 Disazo Dyes IV
   29000-29090     29000
                   29025
                   29030
           Direct Yellow 44
           Direct Yellow 50
           Direct Yellow 51
                                                         >  6.8
                                                          102.3
                                                         >  2.3
                                   11

-------
Table 1 (Continued)
I. Subgroup
29000-29090
(Continued)
29100-29130



29150-29232










C.I. No.
29042
29058
29060
29065
29100
29105
29110
29120
29155
29156
29160
29165
29175
29180
29185
29190
29200
29210
29225
C.I. Dye Name
Direct Yellow 118
Direct Orange 72
Direct Yellow 34
Direct Red 79
Direct Red 31
Direct Violet 14
Direct Red 149
Direct Violet 66
Direct Orange 29
Direct Orange 102
Direct Red 23
Direct Red 4
Direct Red 62
Direct Red 73
Direct Red 24
Direct Red 26
Direct Red 72
Direct Red 122
Direct Red 83
Production
(mt/yr)
> 2.3
> 6.8
> 6.8
> 4.5
> 4.5
> 2.3
> 2.3
> 4.5
> 2.3
192.3
65.4
> 2.3
> 4.5
> 2.3
94.1
> 2.3
266.4
> 2.3
67.3
        12

-------
C.I. Subgroup     C.I.
Trisazo Dyes and Pigments
  Trisazo I
                             Table 1 (Continued)
             C.I. Dye Name
                           Production
                             (mt/yr)
    30000-30030      30015      Direct Black 78
                                           > 2.3
  Trisazo II
    31500-32055      31600      Direct Black 80
                                           > 9.5
  Trisazo IV
    34005-34025      34010      Direct Blue 126
                                           > 2.3
    34040-34060      34045      Direct Green 26
                                           > 2.3
    34080-34100      34085
                     34090
           Direct Blue 120
           Direct Blue 120A
                                > 4.5
                                > 4.5
    34200-34230      34200
                     34220
           Direct Blue 78
           Direct Blue 75
                                > 2.3
                                > 2.3
    34260
34260
Direct Green 51
> 2.3
                                     13

-------
C.I. Subgroup
Tetrakisazo
Dyes and
Pigments
  35000-35900
                    Table 1 (Concluded)
 C.I. No.
35005
35255
35435
35780
 C.I. Dye Name
Production
  (mt/yr) .
Direct Brown 44
Direct Black 19
Direct Black 22
Direct Red 80
>  4.5'
>  2.3
> 11.4
 200.9
 1977 production range minimum from CICIS.
                                14

-------
the marketed product  (including  inert  salts and other material used to produce
a standardized  product)  are also shown in  this  table.   The data in this table
were taken from the Organic Dyes  and Pigments  Data Base, which was prepared by
SRI  International  (Swett,  et  al.,   1983).    For   some   dyes  and  pigments,
production is shown only  as greater than  a minimum number.  These are dyes and
pigments  produced  by three or fewer manufacturers  so  that  public  sources do
not list  specific  production  amounts.   The CICIS  data base lists production
ranges for some of  these dyes and pigments  in  its nonconfidential files.  The
production ranges cover  an  order  of magnitude  that does not always overlap the
1978 values derived  from the U.S. International Trade  Commission (1979) which
was the basis of  the  production amounts  in  the  Organic Dyes and Pigments Data
Base.   The CICIS  values  are shown in Table 1  when  they  exceeded  the minimum
U.S. International  Trade Commission values.  It is  important to note that the
CICIS production values  are for  the unstandardized material and do not include
the  inert  ingredients   used   to   standardize   the   product.    In  addition,
production claimed confidential  is  not  included.   This  means that,  since Table
1  is  based  primarily on  standardized products,  the  minimums for  the  CICIS
production range values  are definitely  only a  lower  bound on production.

     The  azo dyes  and pigments that have  proprietary structures and that have
not been  assigned  C.I.  numbers  by  the  Society of Dyers and Colourists  (1980)
are  listed  in  Table   2.     Because   no  information  is  available  on  the
intermediates used to produce  these dyes,  no waste production estimates  can be
made; therefore, these dyes and  pigments  are not discussed in this  report.

     In 1972, the  azoic  compounds,  shown in Table 3,  accounted for about 4650
metric  tons  (mt)  of  product  (U.S.   Tariff   Commission,   1975).    The  1972
production of each subclass was  as  follows:

       	Azoic Compound	    mt


     Azoic diazo components                        2180

     Azoic coupling components                     1320

     Azoic compositions                             1146

Because  the  compounds  involved  in  producing  these  azoics  are identical  to
intermediates that  are  used for  dye  synthesis, no waste  production estimates
were made  for azoics.

     In the following sections of  this  report  the  process chemistry of the azo
dyes  and  pigments  and   the  sources   of  waste  during  azo  dye  and  pigment
manufacture  are discussed  in  detail.   The  final  section  gives  the estimated
amounts  of  solid   and   aqueous  wastes produced  during azo  dye and  pigment
manufacture developed from  the engineering analysis  of Section 5.
 Chemicals  in  Commerce  Information System (CICIS)  (Nonconfidential files of
 the TSCA Inventory).   U.S.  Environmental Protection Agency;  Office of
 Pesticides  and  Toxic Substances,  Washington,  D.C.
                                       15

-------
                               Table 2
AZO DYES AND PIGMENTS FOR WHICH NO STRUCTURE INFORMATION WAS AVAILABLE
    Monoazo Dyes
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
      C.I. Acid
     o
      C.I. Acid
      C.I. Acid
      C.I. Acid
 and  Pigments
Black 107
Black 172
Brown 31
Brown 223
Green 70
Orange 64
Orange 119
Red  132
Red  194
Red  211
Red  257
Red  278
Red  309
Red  324
Red  361
Red  384
Yellow 128
Yellow 129
Yellow 169
Yellow 174
Yellow 221
      C.I. Basic Orange 26
      C.I. Basic Orange 28
      C.I. Basic Orange 31
      C.I. Basic Orange 39
      C.I. Basic Red 17
      C.I. Basic Red 23
      C.I. Basic Red 73
      C.I. Basic Red 101
C.I. Direct Yellow 127
C.I. Direct Yellow 137
C.I. Direct Yellow 147
C.I. Disperse Blue 94
C.I. Disperse Blue 102
C.I. Disperse Blue 122
C.I. Disperse Blue 125
C.I. Disperse Blue 148
C.I. Disperse Blue 174
C.I. Disperse Blue 200
C.I. Disperse Blue 283
C.I. Disperse Blue 322
C.I. Disperse Brown 2
C.I. Disperse Brown 5
C.I. Disperse Orange 17
C.I. Disperse Orange 31
C.I. Disperse Orange 37
C.I. Disperse Orange 41
C.I. Disperse Orange 44
C.I. Disperse Orange 53
C.I. Disperse Orange 56
C.I. Disperse Orange 62
C.I. Disperse Orange 77
C.I. Disperse Orange 78
C.I. Disperse Orange 79
C.I. Disperse Orange 89
C.I. Disperse Orange 90
C.I. Disperse Orange 98
C.I. Disperse Orange 125
C.I. Disperse Red 30
C.I. Disperse Red 35
                                  16

-------
                   Table 2 (Continued)
Disazo Dyes and Pigments
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Red
Red
Red
Red
Red
Red
Red
Red
Red
Red
Red
Red
Red
Red
Red
Red
50
76
32
88
105
106
108
109
117
135
137
140
193
271
273
316
Violet 33
C.
C.
C.
C.
C.
C.
C.
C.
C.
C.
C.
C.
C.
C.
C.
C.
C.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Orange
Red 5
Red 21
Red 29
Red 40
Red 41
Red 43
Red 49
Red 123
Yellow
Yellow
Yellow
Yellow
Yellow
Yellow
Yellow
Yellow
78








6
15
18
22
24
25
27
42
Violet 40
Violet 43
C.
I.
Solvent
Red 210

Yellow 74
Yellow 136
Yellow 138
Yellow 143
Yellow 198
   C.I. Mordant Brown  50
   C.I. Mordant Orange 8

   C.I. Reactive Blue  13
   C.I. Reactive Brown 10
   C.I. Reactive Orange 12
   C.I. Reactive Qror.^e 14
                            17

-------
                       Table 2  (Continued)
Disazo Dyes and Pigments (Continued)
  C.I.  Acid  Yellow 159
  C.I.  Acid  Yellow 219
  C.I.  Acid  Orange 116
  C.I.  Acid  Orange 128
  C.I.  Acid  Orange 132
  C.I.  Acid  Orange 152
  C.I.  Acid  Orange 156
  C.I.  Acid  Red  119
  C.I.  Acid  Red  299
  C.I.  Acid  Brown  158

  C.I.  Basic Yellow  83

  C.I.  Direct Yellow 84
  C.I.  Direct Yellow 107
  C.I.  Direct Yellow 132
  C.I.  Direct Yellow 139
  C.I.  Direct Orange 80
  C.I.  Direct Orange 118
  C.I.  Direct Red  236
  C.I.  Direct Red  238
  C.I.  Direct Red  239
  C.I.  Direct Blue 191
  C.I.  Direct Blue 260
  C.I.  Direct Blue 263
  C.I.  Direct Blue 279
C.I.
C.I.
C.I.
C.I.
C.I.

C.I.
C.I.
C.I.
C.I.
C.I.
C.I.
C.I.
C.I.
C.I.
C.I.

C.I.
C.I.
C.I.

C.I,
C.I.
C.I.
C.I.
C.T.
Disperse Orange 66
Disperse Orange 75
Disperse Red 161
Disperse Red 219
Disperse Blue 194
Pigment
Pigment
Pigment
Pigment
Pigment
Pigment
Pigment
Pigment
Pigment
Pigment
Yellow 93
Yellow 95
Yellow 126
Yellow 128
Orange 31
Red 144
Red 166
Red 220
Red 221
Brown 23
Reactive Blue 173
Reactive Brown 18
Reactive Black 9

Solvent Yellow 87
Solvent Red 33
Solvent Red 74
Solvent Red 164
Solvent Red 165
  C.I.  Disperse  Yellow  56
  C.I.  Disperse  Orange  38
                            18

-------
            Table  2  (Continued)
and Higher Azo Dyes and Pigments
Trisazo
   C.I.  Acid  Yellow 59
   C.I.  Acid  Yellow 114
   C.I.  Acid  Yellow 135
   C.I.  Acid  Yellow 199
   C.I.  Acid  Yellow 216
   C.I.  Acid  Orange 161
   C.I.  Acid  Brown 97
   C.I.  Acid  Brown 98
   C.I.  Acid  Brown 239
   C.I.  Acid  Black 29
   C.I.  Acid  Black 92
   C.I.  Acid  Black 194

   C.I.  Basic Yellow 41
   C.I.  Basic Orange 40
   C.I.  Basic Red 51
   C.I.  Basic Blue 76
   C.I.  Basic Blue 78

   C.I.  Direct Red 209
   C.I.  Direct Red 212
   C.I.  Direct Red 251
   C.I.  Direct Green 27
   C.I.  Direct Green 47
   C.I.  Direct Green 69

   C.I.  Disperse Yellow 96
   C.I.  Disperse Yellow 114
   C.I.  Disperse Yellow 126
   C.I.  Disperse Yellow 219
   C.I.  Disperse Orange 21
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
                             C.I.
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Orange 55
Orange 57
Orange 58
Orange 73
Orange 88
Orange 94
Orange 129
Orange 136
Red 118
Red 128
Red 136
Red 153
Red 163
Red 167
Red 177
Red 179
Red 195
Red 214
Red 274
Red 275
Red 278
Red 305
Red 309
Red 313
Red 319
Red 333
Violet 42
Violet 60
Blue  121
Blue  138
Blue  139
                      19

-------
                     Table 2 (Concluded)
Trisazo and Higher Azo Dyes and Pigments
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
c.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
I.
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Disperse
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Reactive
Blue 175 C.I
Blue 177 C.I
Blue 281 C.I
Blue 284 C.I
Blue 291 C.I
Blue 317 C.I
Green
Brown
Brown
Black
Black
Yellow
Yellow
Yellow
Yellow
Yellow
Orange
Orange
Orange
Orange
Red 11
Red 31
Red 33
Red 58
9 C.I
10 C.I
18
9
33.
7
86
132
133
135
64
70
84
86




Red 120
Violet
1
Blue 89
Blue 109
Brown
17
(continued)
Solvent Yellow 13
Solvent Yellow 71
Solvent Yellow 72
Solvent Orange 20
Solvent Orange 73
Solvent Orange 74
Solvent Red 105
Solvent Red 173
                            20

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                    Table 3

AZOIC COUPLING COMPONENTS AND AZOIC DIAZO COMPONENTS
                INCLUDED IN THIS STUDY
C.I.
No.
37000
37010
37025
37040
37050
37085
37096
'37100
37105
37110
37120
37125
37130
37135
37150
37151
37175
Azoic
Diazo
Component
44
3
6
9
49
11
32
34
12
8
10
5
13
1
42
14
20
Production
(mt/yr)
>2.3
>4.5
>2.3
>6.8
>2.3
>2.3
>2.3
>2.3
>2.3
>4.5
>6.8
>6.8
>6.8
>6.8
>2.3
>2.3
>2.3
C.I.
No.
37505
37510
37515
.37520
37525
37526
37527
37530
37531
37535
37545
37550
37558
37565
37600
37615
—
Azoic
Coupling
Component
2
10
17
18
8
21
29
20
34
11
19
12
14
7
15
35
43
Production
(mt/yr)
>2.3
>2.3
>2.3
>4.5
>2.3
>4.5
>4.5
>4.5
>4.5
>4.5
>2.3
>2.3
>4.5
>4.5
>2.3
>2.3
>4.5
                       21

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                                   SECTION  2

                            SUMMARY AND  CONCLUSIONS
     In this preliminary  study  of azo dyes  and  pigments,  the following solid
residues were identified that might contain hazardous material:

    »  Filter  cake   from  clarifying  operation   after   diatozation  and/or
       coupling.    The cake  could contain unreacted  intermediates,  partially
       coupled dye molecules,  and N-nitrosamines.    If  the  filter  cake  is
       treated with  hypochlorite, as  is  the  case  at some  plants,  the total
       amount of  organic  material may be  reduced,  but additional chlorinated
       aromatics  may  be created.   There was  not  enough  information available
       to quantify this residue.
    •  Discarded   shipping  containers.  These would  be  paper bags  and fiber
       drums  used  to transport  dye  and  pigment  intermediates,   and  would
       contain a  residual amount of intermediate when emptied.

    «  Wastewater  treatment  solids.   The evidence suggests  that  the solids
       will  be  contaminated with low levels  of  all  of  the  dye  and pigment
       intermediates  as  well as  the  dyes  and pigments  themselves  and  some
       reaction  by-products.   If  these   solids  are  placed  in a  landfill,
       intermediates  may  be  released as  a-  result of reduction of  the  azo
       linkages under the anaerobic conditions prevailing in the landfill.

    •  Baghouse   fines.     The   fines   are   generated  during   the  drying,
       standardizing, and packaging of the dyes  and pigments.   The  fines will
       be  principally the  dyes  and  pigments  and  inert  salts.    Anaerobic
       conditions in  a disposal site  could cause  intermediates to be  released
       from these fines.

     On  an industry-wide  basis,   the major  sources   of  waste  emissions  are
associated with  azo  pigment  manufacture  rather  than dye  manufacture simply
because  pigments  are the  major products  produced.   At any  given  plant,  the
major  source of  discharges  of  organic  chemicals  is  probably the  process
wastewater rather than the solid  residue  stream since, at many locations, the
process  wastewater   includes   the   mother  liquor  that  contains  unreacted
intermediates  and  by-products  in  potentially  high  concentration.   Actual
emissions  will,  however,   be quite  site-specific,  because  emissions  will be
affected  by the  disposition  of   the mother  liquor,  specific  treatment  of
individual process  step wastewaters,  the  overall wastewater treatment  system,
and the  treatment  of  the  filter cakes.   The  intermediate, by-product,  and dye
and pigment  emissions that  were  summarized  in  Section 6  (Tables  12 and 20)
ignored these site-specific factors.


                                      22

-------
     The  information  on  the  production  patterns  for  dyes  and  pigments
contained in  Section 6  (Tables  12  and 15 through  19)  was  analyzed to choose
representative manufacturers  where  a  sampling program might  be conducted  to
confirm  the  composition and  the  magnitude  of  the  estimated waste emissions.
Companies  that  manufacture  the  major  volume  azo  dyes  and  pigments  were
recommended.  There was no way, using public sources, to determine exactly how
much of  each  dye  or  pigment  was made at each manufacturing  site; therefore  it
was  assumed  that  each  company producing  a  major  dye  or pigment  produced a
significant fraction of  the  total amount  produced.   The six companies are the
American  Color  and Chemical  Corp.,  American Cyanamid  Co.,  Atlantic Chemical
Corp., E.  I.  DuPont de  Nemours & Co., Inc.,  Harshaw Chemical  Co.,  and Toms
River Chemical Corp.

     The  six  companies  that  are  recommended  for  a sampling  program should
yield  samples   from   facilities   using  different   manufacturing  and  waste
treatment practices.   Since there is  considerable  overlap  in the actual dyes
or  pigments  that  they  make,  the  six-company  sampling program  increases  the
chances  of identifying  material  in  the waste streams that may be sensitive  to
plant practices.
                                       23

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                                   SECTION 3

                               PROCESS  CHEMISTRY
INTRODUCTION

     A discussion of the process steps required to synthesize  the azo dyes  and
pigments will aid  in formulating the emission  estimates  developed in  Section
5.   The first part  of  this section  describes  the azo dyes  and pigments  use
classes as background.  The  remainder of this section is devoted largely to  a
discussion  of  the  process  chemistry  of  the  two   key   steps  required  to
synthesize these  dyes  and pigments,  diazotization and coupling,  with  special
attention given to the starting materials, intermediates, reaction conditions,
and  potential by-products.   The recipe  for  an azo dye is  shown  in detail in
Appendix A.   Some azo dyes  and  pigments are produced by reactions other than
diazotization and coupling, and these reactions are briefly discussed.

     The  majority   of  the   commercially  produced   azo  dyes  and  pigments
considered in this report fall into the  following classes:

    •  Direct dyes

    •  Acid dyes
                                                   o
    •  Disperse  dyes

    «  Reactive  dyes

    «  Solvent dyes

    •  Pigments.

In addition,  small amounts of azoic components  (azoic  coupling
components,  azoic diazo components, and  azoic compositions) are produced.

     The  class   of  direct   dyes   consists  of  anionic  dyes  substantive  to
cellulose  when   applied  from  an   aqueous  bath  containing   an  electrolyte.
Chemically,  the azo  direct  dyes are  mostly  di-,  tri-, and polyazo compounds,
with only a few  monazo compounds.

     Acid dyes  are water-soluble anionic  dyes  applied to nitrogeneous  fibers
(e.g.,  wool,  silk,  nylon, and  modified  acrylics) that  function  by virtue of
the  presence  of  one or  more  sulfonic  acid  or  other  acidic groups  in  the
molecule.
                                       24

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     Disperse dyes have been  specially  developed to dye cellulose acetate  and
some  of  the  synthetic fibers.  The  class may  be  broadly divided  into  two
general  groups:  insoluble  simple  azo  dyes  and  insoluble aminoanthraquinone
dyes  (the  anthraquinone  dyes are  discussed  in a  separate report).   Both  are
highly dispersed  and capable of  penetrating  fibers, and  both general  groups
usually contain the  ethanolamine  side chain, -NHCH2CH2OH,  or  a similar  group
to increase dispersibility in water.

     Reactive  dyes,  which  link chemically to  cellulosic  fibers,  are  water-
soluble compounds  that contain  reactive groups  capable  of combining with  the
hydroxyl  groups  of  cellulose  under  alkaline  conditions.  The wet-fastness
properties of these dyeings is high.

     Solvent, or spirit-soluble, dyes are  frequently simple azos used to  color
oils, waxes, varnishes, shoe dressings, lipsticks, and gasoline.

     Included  in  organic  pigments are substances  (usually soluble in organic
solvents)  that  impart a  positive  color  to  another substance  (as  opposed to
whiting agents, extenders, and fillers).

     The  class  of azoic  compounds includes  those materials used  to produce
insoluble  azo dyes  in-situ,  usually  on a  textile substrate.   This   class
consists of  three  subclasses:  the azoic  diazo  components,  the azoic coupling
components, and the  azoic compositions, which are mechanical  mixtures of  the
first  two  in which  the azoic diazo component has  been stabilized to prevent
coupling before application.  The  azoic  diazo components consist of diazonium
salts  (or  their parent amines when the  dyer performs the diazotization)  based
on  aromatic   amines.     Any  primary  aromatic  amine  that  is  capable  of
diazotization  and   coupling  and   that   is   free  from  sulfonic  and   other
solublizing groups may, in principle, be used as an azoic diazo component,  but
the number of amines actually used is limited to about 50.  The azoic coupling
components  are   principally  beta-naphthol   derivatives,   but  also  include
arylamides.    The  anilide  of  beta-naphthol  carboxylic   acid  is  the  most
frequently used.
DIAZOTIZATION

     As  applied  in  dye  chemistry,  diazotization  is  the  conversion  of   an
aromatic amine to the corresponding diazonium chloride using nitrous acid:*
              ArNH2 + NaN02 4-  2HC1  - *-ArN=NCl  + NaCl
              Aromatic                    Diazonium
              amine                        chloride
 Since nitrous acid is unstable, it is produced as needed from  the  reaction  of
 aqueous solutions of sodium nitrite and hydrochloric acid at 0°C.
                                      25

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     The mechanism  of  the diazotization  reaction  was  elucidated by Hughes  et
al. (1958).   Nitrous  acid reacts with  the primary amine by attachment  of  the
nitroso group to the nitrogen with  the  elimination of water:
                                           H
                                       H   0
                HONO +  ArNH2  	»-Ar-N...N=0 	J»-Ar-N-N=0
                                       H                 H

The product is unstable and isomerizes  to  a diazotic acid:

                          Ar-N-N=0 	J—Ar-N=H-OH
                             H
The diazotic  acid  is  also unstable  in neutral or acid  solution and usually
decomposes rapidly to a diazonium salt:

                       Ar-N=N-OH -
     When  diazotization is  applied to  diamines  such  as  m-phenylenediamine,
both  amino groups  are  diazotized,  so  the  process,  termed  tetrazotization,
produces a tetrazonium  chloride.

                 2  HONO + H2N-Ar-NH2  HC1 ». Cl~l"N=N-Ar-N=N+Cl~

     The azotization reaction is generally  conducted at 0°  to  5°C  (to
retard  decomposition  of  the  diazonium  salts  formed)  for  one to three  hours
using  a molar ratio  of diamine:sodium  nitrite:hydrochloric  acid of  1:1:2.5.
The reaction product is an aqueous solution containing approximately 15  wt% of
the diazotized material and 7 wt% sodium chloride.

     Sodium nitrite is employed in the  theoretical quantity,  but excess  acid
must  be  used  to   prevent  partial  diazotization  and   condensation   of  the
diazonium  salt with the undiazotized amine  to  form the diazoamino  compound.

                                 Ar-N=N-Ar-NH2

Excess  mineral  acid   also  stablizes  the   diazonium  salt  by  inhibition  of
decomposition due to other secondary reactions  (Venkataraman,  1952).

     The  diazotization reportedly  gives high  yields (Abrahart,  1968;  Lubs,
1955),  so  very  little  of the  starting   amine  is believed to  be  left  in  the
reaction product.  However,  some undecomposed  diazotic acid (Ar-N=N-OH)  may be
present.   In  addition  to  the  diazoamine  by-products   mentioned  above,  one
source  (Roberts  and Caserio,  1964)  has  indicated  that the  use of  hydrochloric
acid  may  result in  the  formation  of   aryl  chlorides  as a  result  of  the
decomposition  of the  diazonium  salt  to   nitrogen gas  and a carbonium  ion  and
reaction of the  latter  with  chloride ion:

                 Ar-N=N+Cl~ 	»-N0 +  Ar+ + Cl~ 	»
                                       26

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The aryl chlorides are  considered  "terminated"  by-products because they cannot
be converted  to  the  desired azo  compounds  in subsequent  coupling steps.  They
are not  completely  inert,  however,  and  may react  with  the  original  primary
amine  starting  material to  form  secondary amines,  which  in  turn,  may  be
converted  by  the  nitrous  acid  to  their  N-nitroso  derivatives  (Rys  and
Zollinger, 1972):
                ArCl  + ArNH,.
-»-HCl + Ar NH
                                                 HONO_
             N-N=0
N-nitrosamines  are  very  weak  bases  and  are  characteristically  yellow  or
orange-yellow insoluble  liquids  or  solids that separate from  solution.   If an
N-nitroso compound  is  formed during a diazotization reaction, the  liquor  may
require  clarification  by filtration before  transfer to the coupling  reactor.
This  operation  may be   done  only  as  required,  although  clarification  is
specifically called for  in some  dye recipes  (BIOS,  1945)

     Free aryl  radicals  formed  during  breakdown of  diazonium salts  to  yield
nitrogen gas may react with  (among others) diazonium cations with  formation of
a symmetrical azo  compound Ar-N=N-Ar or  the  radicals may attack  undecomposed
covalent diazo  compounds  with  formation of  a diazo  biaryl  compound,  Ar-Ar-
N=N Cl~,  which  eventually   yields   polyaryls   or  combines   to   form   an
arylazobiaryl, Ar-Ar-N=N-Ar  (Saunders and Waters, 1946).
     Snow  (1932)  measured  the rate  of  decomposition  of  diazonium  chlorides
based on  various  amines at 20 °C  and  has  arranged them in the  following  order
of decreasing stability:
      p-Chloroaniline

      m-Nitroaniline

      l-Amino-2,4-dimethyl-6-nitrobenzene

      o-Nitroaniline

      o-Anisidine

      p-Nitroaniline

      p-Phenetidine

      5-Aminosalicylic acid

      p-Toluidine

      Aminoazobenzene

      p-Aminophenol

      p-Phenylenediamine (diazotized)

      Picramic acid

      Sulfanilic acid

      p-Aminobenzoic acid
cc-Naphthylamine

p-Anisidine

p-Naphthylamine

l-Amino-2,4-dimethylbenzene

Anthranilic acid

Aminoazotoluene

m-Aminobenzoic acid

l-Amino-3,4-dimethylbenzene
l-Amino-2,3-dimethyIbenzene

Aniline

o-Toluidine

m-Toluidine

m-Anisidine

l-Amino-2,6-dimethylbenzene

p-Phenylenediamine (tetrazotized)
                                      27

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Electronegative  substitution  of  the  amine  increases  the  stability  of  the
diazonium salt.  Substitution by chlorine,  carboxyl,  sulfonic,  or nitro groups
and by methyl, hydroxyl,  methoxy,  or phenyl groups may  increase  the stability
of  the  diazonium salt  (Crossley et al.,  1940).   Diazonium  sulfates are  more
stable and the acetates less stable  than  the chlorides.
COUPLING

     As  applied  in azo  dye  manufacture,  coupling is  the  conversion  of  a
diazonium  salt  (the diazo  component)  to  an  azo  compound by  reaction  with  an
aromatic  compound  (the  coupling  component),  which  generally  has  a  strong
electron-donating  substituent  on the  aromatic  ring (e.g., a  phenolic,  amino,
or substituted amino group):

                                                           HC1
AT W— M PI -1
Diazo
Component
U A t _TI
Coupling
Component

Azo
Compound
     For  the tetrazonium  chlorides made  from diamines,  the initial  desired
reaction  may be  either- coupling  of  both diazonium  chlorides or  coupling  of
only one.  In the latter case,  the  resultant  product  may  be  coupled again with
a  different  coupling  component.    The  final  products  from  the  two  different
procedures are the  symmetrical  and  unsymmetrical  disazo compounds.

               Ar ' -N=N-Ar-N=N-Ar '             Ar ' -N=N-Ar-N=N-Ar "

     A  variety  of  coupling  components  are  used  to  produce  the  commercially
significant  azo dyes and pigments.  The  specific chemicals used for  each of the
azo dyes  and pigments  included  in  this  study  are  enumerated  in Section 6.  The
structures of the coupling components used depend on  the  color desired and the
type  of  dye  desired.   For   direct  and acid   dyes,  the  molecules  contain
solubilizing groups  such  as  hydroxyl,  sulfonic acid,  or  carboxylic  acid
groups,  whereas  for pigments  and  for  solvent  and disperse dyes these groups
are usually  absent.  The direct  dye  molecule is  designed to  be  long and have
aromatic  components that  are coplanar,  whereas  the acid  dye  molecule is more
compact .

     The  structure  of  the  coupling component has  a complex  effect  on the rate
of  the coupling  reaction  and  the  products   formed.   In  general,  the phenols
couple   very  readily   in   alkaline  media   at   both   their  ortho  and  para
positions.    If  excess  diazo  component is  present, multiple   couplings  are
possible  and di-  and   triazo  phenols   may result.   The  anilines  couple less
readily  than the  phenols  and  only in  the  para   position.    Both  coupling  of
phenols  and anilines  is impeded  by  electron-attracting substituents   (e.g.,
nitro,  sulfonic)  and   facilitated by   electron-donating  substituents   (e.g.,
methyl,  methoxy).

     The  structure  of  the diazonium salt also affects the rate of the coupling
reaction  and the  formation  of  by-products.   In general,  diazonium salts  of
negatively substituted  amines,  such as  nitroanilines , nitrochloroanilines , and
                                       28

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the aniline  sulfonic  acids,  couple rapidly.   Coupling is generally  conducted
under mildly alkaline conditions at 0°C to  5°C  for  4  to 24 hours,  using almost
a 1:1 molar ratio of diazonium salt to coupling component.   Coupling  reactions
are  performed  in  a  medium  in  which  the  equilibria  of  the diazo  and  the
coupling  component  lies  as  far  as possible  toward the  coupled product  and
where  the coupling  rates are  fast.    The  rate  of  the  coupling reaction  of
amines,  for  example, increases  with increasing  pH.   However,  a lower pH  is
used to  suppress  the decomposition of the  diazonium compound and to  suppress
the formation of triazene compounds.
                       i   —             OH
                Ar-N=N  Cl + Ar'NH--^  ° ^- Ar-N=N-N-Ar'  + HC1
                                       H            H
There  is  an optimum pH  range  for  coupling reactions for each combination  of
diazo and coupling components.  This range  is about pH 4  to  9  for anilines  and
other  aromatic  amines,  7 to 9 for  enols, and  8.5 to 9.5  for  phenols.   The  pH
is commonly  adjusted  using  soda ash so  that  the hydrochloric acid by-product
from the  coupling is converted to sodium chloride.

     At  the  temperatures used  for  coupling, the reaction is  reported  to give
good yields  (90%-99%)  of the  desired  azo  compound (Rys  and  Zollinger,  1972;
Lubs,   1955).   i  However,  because  of  side   reactions   that   occur   during
diazotization  (such as  decomposition  reactions),  impurities may already  be
present  in  the diazonium chloride  that  decrease  the overall apparent  yield,
and these impurities may  also react to form additional side  products.

     If  the  diazonium chloride  decomposes  to  nitrogen gas and a  carbonium  ion
before  the  coupling  reaction takes  place (in the basic medium),  the  carboniu'm
ion may  react with hydroxyl  ion to  form phenols:

             Ar-N=N+Cl~  	»~N2 + (Ar+ + Cl")   Na°V ArOH + NaCl

These  phenols  are considered "terminated"  by-products  because they cannot  be
converted  to the  desired azo  compounds  and may  occur  during any step  of  the
dye synthesis.

     Any  diazotic  acid  formed  in  the  diazotization  step  that   does   not
decompose  to the  desired diazonium chloride  may  react  in the basic  solution
used for  most coupling reactions to form stable diazotate  salts:

                    Ar-N=N-OH + NaOH 	»-Ar-N-N=0 + H~0
                                                 Na
These  salts  are insoluble in water and may require  that  the  coupling  reaction
liquor  be clarified by filtration before proceeding to the next  process.

     Table  4  shows  the  Colour  Index descriptions  of  the  monoazo  dye  and
pigment  subclasses.  The  subclasses are arranged  in two sections  consisting of
dyes essentially  insoluble  in  water and dyes  soluble in water,  respectively.
Within  each  section  the items  are  arranged  in  a  succession  based  on  the
coupling  component.  Also shown  in Table 4 are  the number of  dyes included in
this study and  the cumulative approximate U.S.  production for  each subclass.
                                      29

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                                                          Table 4
                              COLOUR INDEX DESCRIPTIONS OF MONAZO DYE  AND PIGMENT SUBCLASSES
                                                                                    Number
  C.I. Numbers
                 Nature of Coupling Components
Water-Insoluble Dyes (dyes without -CQOll, -S03H, or SC^NH^ groups)
  11000-11435    Arylamlnes
  11440-11630
  11640-11770    Acetoacetyl compounds
  11800-11975    Phenols
  12000-12020    1-Naphthol
  12050-12211    2-Naphthol
  12300-12505    3-Hydroxy-2-naphthanUides
  12600-12825    Heterocyclic hydroxy compounds
Water-Soluble Dyes (dyes with -COOH, SO H. or SO NH  groups)
  13000-13001    Dyes without auxochromlc groups
                 Arylamlnes
                 Acetoacetarylamides
                 Salicylic acid
                 Other phenol derivatives
13010-13710
13890-13970
13990-14155
14160- 14345
14600-15085
                 1-Naphthol and 1-naphthol
                  sulfonic acids
  15500-16315    2-Naphthol and 2-naphthol
                  sulfonic acids
  16500-16730    Naphthalenediols and dihydroxy-
                  naphthalene sulfonic acids
  17000-17260    Aminonaphthol sulfonic acids
  17500-17670    N-alkyl(or aryl)aminonaphthol
                  sulfonic acids
Malor Application
r SO_NU. groups)
Solvent and disperse
—
Pigment
Mordant , disperse, and solvent
Solvent
Pigment and solvent
Pigment
Disperse, pigment, and solvent
H- groups)
Acid
Acid and mordant
Direct
Mordant
Acid and mordant
Acid and mordant
Acid and mordant
Acid and mordant
Acid
of Dyes
Included
in thia
Study

30
2
14
1
0
11
19
5

0
12
3
4
1
6
23
1
7
Subclass
Approximate Average
1978 U.S. . % Mole
Production (mt) Excess0

2638 7 cc
7 8 cc
1106 4 cc
14
- -
1046 8 cc
339 10' cc
9

- -
36 3 azo
1632 9 cc
11 3 cc
4
59 10 'cc
10837 5 cc
7 -
821 4 cc
                                                 Mordant

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                                                    Table 4  (Concluded)
                                                                                  Number,
C.I. Number     Nature of Coupling Components
] 7750-1.8245   Acylamlnonaphtholsulfonic acids      Direct

18260-18270

18670-19245   Pyrazolones

19300-19610   Other heterocyclic liydroxy
               compounds


    Total
Major Application
groups) (Continued)
Direct

Acid and mordant
Acid, mordant, and direct
of Dyes
Included
In This
Study

12
2
21
2
Approximate
1978 U.S.
Production (mt)

223
7
1179
28
Subclass
Average
% Mole
„ c
Excess



6 cc
6 cc
172
                                                                                                   20,000
 for which CI numbers are available.

 Many production values are reported as a lower limiti thus the

 subclass production values are approximate.
c
 cc " coupling component added in excessj azo • azo component added in excess
d
 Hounded.

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     A review  of dye  recipes  given in the  BIOS  reports (1945) shows  that  in
many  cases  excess  ingredients  are  called   for.     The   amount   of   excess
ingredients used in  the  synthesis  of a. dye  or  pigment  is used  to  estimate the
losses of intermediates during dye  manufacture  (Section 5).

     The BIOS recipes  found for the monoazo  dyes  and  pigments  (49 with  recipes
out of  172  dyes and  pigments  with  known  ingredients included in this  study)
were used to calculate the  molar  addition of the  coupling  component and diazo
component for each batch  of  dye  produced.    These  values were  then compared  to
find  the molar  excess of  component added  (if  any).   These  excess  amounts
ranged from  12%  excess diazo component  (Pigment  Orange 1,  C.I. 11725)  to 20%
excess coupling  component  (Disperse Orange 3,  C.I. 11100) based on  the amine.
Using the classification  scheme  for monazo  dyes  and pigments  from  the  Colour
Index (The  Society of Dyers  and  Colourists, 1980),  we compared these  excess
addition  values  on  a subclass  basis  to  see  if   dyes  based  on   different
components  required  common  amounts  of  excess  components.     The subclass
averages appear  in Table  4.   The  majority of the  subclasses show  the addition
of  excess coupling components ranging from  about 3 to 10%.  However,  many  of
the subclasses did not have enough  recipes to give confidence  that the  pattern
has been identified  properly.   Table  4  shows  that subclass C.I.  15500-16315,
derived   from   2-naphthol   (and   2-naphthol   sulfonic  acids)  as  coupling
components,  is  estimated  to  account for  approximately 54%  of the  estimated
production  of  the  monoazo  dyes   and  pigments  for  which  information was
available.     Within  this  subclass   the  top   two  pigments  account  for
approximately 25%  of  the entire production  estimated for monoazo class.  The
average  value  for this subclass  of 5%  excess  coupling component should  then
have  a  major influence on the entire  monoazo  class average.   This  was  indeed
found  to be  the case  since the  entire  monoazo  class average  was about  5%
excess coupling  component from the  information  available.

     Table  5 summarizes  the Colour Index  classification  scheme for  disazo,
trisazo, and the higher  azo  dyes.   The table also indicates schematically the
type  of  coupling reactions  used  to generate the dyes  in-each  subclass.   These
reactions and the  by-product  formation in each subclass are discussed  in more
detail below.

     Table  6 shows  more  of the  details  of the  subclassification  scheme for
disazo   dyes,   in   particular   identifying  the   specific   type  of coupling
components  used and  the  nature  of the  azo product.   The   excess ingredients
required  in  each  subclasss  were  estimated   from   the  BIOS  recipes.   The
resulting  estimates  are  not  definitive because  only  12 recipes  were  found,
although there are 75  dyes in this  class with known  intermediates.

     The Disazo  I  subclass  is  characterized by the coupling of two  diazotized
arylamines (often dissimilar) to a  single  coupling component.   Several  recipes
called   for   excess   diazo  component   of  3   to  8%,  whereas   others  were
stoichiometric.  No recipes called  for excess coupling components.

     The Disazo  II subclass is characterized  by  the use of a  diamine  that  is
tetrazotized  and  coupled  to  two  coupling  components  (often  dissimilar).
Recipes  found  for  this  subclass  called  for   addition  of  0  to   10%  excess
coupling component based  on  the araine.
                                       32

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                        Table 5

COLOUR INDEX CLASSIFICATION OF THE AZO COLOURING MATTERS
Class of Azo
Compound
Disazo



Trisazo



I
II
III
IV
I
II
III
IV
A -+
E -<-
A +
A -»•
E -s-
E «-
A ->•
A ->•
General
Formula
Z
D
M
Z
D
D
Z
M
+- A'
-> E'
-> E
•X- Z -f- A'
-s- Z -f- A
-> M -> E'
-*- M -«- A'
->• M'-" E
C.I. Range
20000-20999
21000-25999
26000-28999
29000-29999
30000-31499
31500-33499
33500-33999
34000-34899
        V

Tetrakisazo
and higher
polyazo
                      "   "  -A"

                      Extensions
                      of above
                                         34900-34999
35000-36999
       Symbol key:

           A, a diazo component
           D, a tetrazo component
           E, a coupling component end group
           M, an amine  that can be diazotized after coupling
              with a diazo component
           Z, a coupling component that can be coupled with
              two (or more) molecules of a diazo component
              (often dissimilar)
           Z-X-Z, a bihuclear coupling component capable of
              coupling with two molecules of a diazo com-
              ponent (s)
           ->, diazotized and coupled with
                            33

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                                                          Table 6

                          COLOUR TNDEX DESCRIPTIONS OF THE DISA20  DYE AND PIGMENT SUBCLASSES
    C.I.  Number
                    Nature of Coupling Component
Disazo I (general formula A-Z*-A)

    20000-20045    Dyes without COOH, SO-jH or
                  S02NH2  salt-forming  groups

    20070-20140    m-Arylenediamines

    20150-20305    Phenol,  reaorclnol and
                   1-naphthol

    20320-20540    Aminonaphthol sulfonic acid
    C.I.  Number    Nature  of  Tetrazotisable  Diamine
                                                      Major  Application



                                                 Various


                                                 Acid and mordant

                                                 Acid and mordant


                                                 Acid and mordant




                                                      Major  Application
Disazo II (general formula &-D-E')

  Water-Insoluble Dyes (dyes without COOH, SO^l, or S02NH2 groups)

    21000-21030   m-Arylenediamines                 Basic and solvent

    21050-21220   Benzidine and derivatives0        Pigment

    21230-21280   Diamines                          Solvent
                                 Number of  Dyes
                                     Included
                                  in  This Study
  Approximate 1978
U.S. Production (mt)
                                                                   0.4
1
5
5
4.5
126.9
185.1
                                                                                                        Subtotal    317
                                 Number of Dyes
                             Included  in this  Study
    Approximate
U.S. Production (mt)
                                                                                                                  154.6
                                                                                                                    9.1
Water-Soluble Dyes (dyes with COOH, S03H, or SC

  21500-21725   Arylenediaminea
                                         c
  22000-24500   Ucnzldine and derivatives

  24550-24565   (4,4'-Dianino-3,3-biphenylene-
                 dioxy) dlacetic acid

  24750-25735   Binuclear diamines
!H  groups)

 Direct

 Direct, acid, and mordant


 Direct

 Direct
                                                                                          0

                                                                                          0

                                                                                          0
                                                                                                                    337

                                                                                                          Subtotal   496

-------
    C. t. Number
   Nature  of  Second
  Coupling Component
                                                     Table  6  (Concluded)
                                                         Major Application
 Uiaazo  III  (general  formula  A—M-*E)
Number of Days
   Included
in Tills Study3
Approximate 1978 U.S.
  Production (mt)
  Water-Insoluble Dyea  (dyes without COOH, SO H, or  SO.Nll-  groups)

      26000-26150   Various                         Disperse and solvent
                                                                                          431
  Water-Soluble Dyes  (dyes with COOH, SO H,  or  SO^NH«  groups)
                                        J         t-   i
26200-26440
26500-26580
26650-26785
26900-27311
27500-27560
27600-27790
27350-27990
28100-28500
Arylamines
Phenol, resorcinol, or
derivatives
1-Naphtholsul fonic acid
2-Naphthol or
2-naphthol sulfonic acid
Dihydroxy naphthalene sulfonic
acid
Aminonaphtho] sulfonic acid
Arylaminonaohthola
Acylamino (or aroylamino)
Acid and direct
Mordant and direct
Acid and direct
Acid and direct
Acid
Direct
Direct
Direct
4
2
0
5
0
1
3
2
11.4
11.4
—
97.3
—
4.5
9.1
1068.7
                    naphthol sulfonic acids
      28650-28725   Pyrazolone or heterocyclic
                    compounds
Disazo IV (general formula A-«Z• X• &-A' )
                                Direct
                                                                                                 Subtotal     1633
      29000-29090   Diphenylurea residue from
                     phosgenation of simple
                     aminouzo compound
      29100-29130   6,6'  Iminobis-1-naphthol-
                     3-sulfonic acid
      29150-29232   6,6'-Ureylenebis-l-naphthol-\  Direct
                     3-sulfonic acid
      29250-29275
Bis ureas or amides from
 diamines
     29290-29295    Diphenylurea  from phosgena-
                     tion of  aminophenyl-
                     pyrazolone azo dye
       4

      11

       0

       0
                                                                                                  Subtotal
                                                                                          131.8


                                                                                           13.6

                                                                                          701.5
                                                                                                    Total   3293
       Kur  which C.I.  numbers were available.                                                	
       Many production values arc reported as lower limits ; thus the subclass production values  are  approximate.
      CA/.o  flvij^  ami  nli'ninnlH h;ispd nn hpn?. IH I ni» and Irn dfrivnrfveR nrp nor Inoludpd 1n this studv.

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     The  Disazo   III   subclass,   which   is  characterized   by   successive
diazotization  and  coupling  steps,  accounts  for  about  50%  of   the   total
estimated disazo  dye  and pigment production.   Three of  the available recipes
for this subclass called  for  no  excess components.  This included  the largest
volume disazo dye (Direct  Red 81;C.I.28160),  which accounted  for about  30%  of
the total estimated production volume  for the disazo class.

     The majority of the dyes in the Disazo IV  subclass are formed  by treating
2  moles  of  an aminoazo  compound  with phosgene,  producing   a  twice coupled
binuclear component. No BIOS  recipes were found for  this  subclass.

     From the  limited  number  of  recipes available for  the disazo class  it  is
difficult to find an average  value  for excess components  added.  The 5%  figure
may, in many cases, overestimate the  excess value; however, because the  total
estimated disazo  class  production  is  small  compared with the  monoazo class,  a
value of 5% excess coupling component  is assumed for each coupling  step.

     Table  7  shows  the  details  of the subclassification  scheme  for trisazo
dyes, identifying  the type of  coupling component used and  the nature of  the
azo  product.    Because  of  the  coupling  sequence  and  types   of   coupling
components  used,  none  of  these  is  likely  to  be  the   homogeneous  product
indicated.   The polyazo dyes must,  in many cases,  be mixed products and  the
dye  structure  given  by  the Colour  Index  represents no more  than a  probable
major component.   Only one BIOS  recipe was found for  the 13  tris and higher
azo  dyes  and  pigments  with  known  intermediates that are  included  in this
study.    It  is  therefore  difficult to  assign  an  excess  ingredient value.
However, because these  classes  are small compared with the monoazo dye class,
a value of 5% excess  coupling component has  been  assumed during dye or pigment
synthesis.

     Because of  the many azo dyes  for  which no recipes were found (197),  the
choice  of  5% excess  could  be  in  error  on a basis  of  the number of  azo dyes
studied  (259).    However,  the  individual  dye  recipes of  the  four monoazo
pigments with the highest estimated  production volume  (Pigment Red 53, 49,  57,
and  48),  which  together  account  for 36%  of the estimated  total monoazo  dye
production  volume,   called  for  3,  7,  4,  and  6% excess  coupling component,
respectively.   The large fraction of the  estimated total azo dye production
that has  approximately 5%  excess  coupling components  called  for in  the BIOS
recipes leads  to the conclusion that the  entire  azo class may be represented
by this value of 5%.

     The  reactions  that yield undesirable couplings  and  by-products  have
different impacts on  the  waste  produced when dyes and pigments in the various
subgroups are synthesized.  These  differences are discussed  below.

     The  monazo  class  should  be  the  "cleanest"  with  respect  to by-products
because  only one  diazo compound  is used and  only  one coupling reaction  is
required.    For  the  most   part,  only  terminated  azo  compound  and  unreacted
coupling  component  are  expected  as  by-products.     Smaller  amounts   of
miscouplings, disazo  compounds, and  polyaryls may also  be  found.
                                      36

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                                                     Table 7
   C.I.  Number
                  COLOUR INDEX DESCRIPTIONS OF THE TRISAZO DYE AND PIGMENT SUBCLASSES

                                                                    Number of Dyes
                       Nature of Tetrazo Component	     Included in This Study
Triaazo  I  (general  formula
  30000-30030
  30035-30400
                     p-Phenylenediamine
                     Benzidine and its congeners

Trisazo II (general formula E-MJ-ttt+E')
  31500-32055
                     Phenylenediamine and its derivatives
                     Benzidine and its congeners0
                       Nature of Twice Coupled Component

Trisazo III (general formula A-»-Z+W*-A')

  33500-33999        m-Phenylenediamine and resorcinol

                       Nature of End Component
                                                                         1

                                                                         0
Approximate 1978
U.S. Production
     (rot)"
                                                                                                 >  2.3
                                                                                                 > 9.1
Triaazo IV (general
34005-34025
34035
34040-34060
34080-34100
34120-34180
34200-34230
34250-34255
34260
34270-34280
34285
34290-34300
formula A->M+M'-i-E)
2,5-Xylidlne, cresidine, and ra-diarainea
Phenol
Salicylic acid, and resorcinol
Naphthol Bulfonlc acid
J-acid, and Gamma acid
N-Phenyl- J-acid
N-Carbamoyl-J-acido
N-m-Aminubenzoyl- J-acid
N-Acetyl-H-acld , and 2-methylinJole
2,4-Quinolinediol
Pyrazolones

1
0
1
2
0
2
0
1
0
0
0

> 2.

> 2.
9
-
> 4.
—
> 2.
-
-
-

3

3


5

3




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                                       Table 7 (Concluded)

            COLOUR INDEX DESCRIPTIONS OF THE TRISAZO DYE AND PIGMENT SUBCLASSES



                                                                                    Approximate 1973
                                                            Number of Dyes3         U.S. Production
  C.I. Number          Nature of Tetrazo Component       Included in This Study     	(mt)k


Trisazo V (general formula .A+Z-t-A1 and T + E"


  34900-34999      Various components                               0


Tetrakis and Polyazo (combinations of above)

  3500-36999       Various components                               4                      216
 For which C.I. numbers were available.

 Many production values are reported as lower limits; thus the subclass
 production values are approximate.

 Azo dyes and pigments based on benzidine and its derivatives are not included in this study.

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     The  Disazo  I  subclass  is an  extension of  the monoazo  class  because  a
monoazocompoundformedduring  the first  coupling reaction  is  coupled  with
another  diazo  compound.   This  sequence  is  thus  equivalent  to  two  monazo
coupling  reactions  in  series.    The  by-products  would  be similar  to  those
encountered during monoazo dye manufacture.  The  reaction  conditions  favor the
disazo product; however, some monoazo compounds may remain.

     The  Disazo  II  subclass  represents   those  dyes  made  from diaminoaryl
compounds that are  tetrazotized.   The major  by-product from this subclass  is
the terminated  first-coupled product (or monoazo compound) that is  incapable
of  coupling  further.    Also polyazo  compounds  could  form from  some  diazo
components.

     The Disazo III subclass represents dyes made by successive diazotizations
and couplings  of  arylamino compounds.   Thus,  initially,  a coupling  component
with  an  amine or reducible  nitro group is coupled to a  disazo  component  to
form a monoazo compound.   The  amine group  is then  diazotized and coupled to  a
second coupling component.  This sequence of reactions  would lead to  a  greater
chance of nitrosamine  formation  from the terminated diazo  component  remaining
from  the first  coupling  reaction,  because under  the  diazotization  reaction
conditions,  the  aryl  chloride  (or  terminated by-product)  may react  with  a
primary  amine,  giving  a  secondary amine  that  could  then form  a  secondary
nitrosamine.   The  other types  of by-products  could be the terminated  coupled
product  (monoazo  compound)  as  well as the  primary  nitrosamines and  polyaryls
discussed previously.

     The  Disazo  IV subclass is  similar  to Disazo  I in the coupling  reaction
sequences and would also be similar in the  type of  by-products formed.

     The Trisazo I  subclass  is made up of  dyes similar to  Disazo II  dyes that
have been  coupled  again on one of  the  end  components of the disazo  compound.
The by-products from this category  should be of the same type as  the  Disazo  II
subclass  with  the possible addition of  some miscouplings  between  the  excess
coupling  components added  during  the  first two coupling  reactions  and  the
diazo component added during the final coupling reaction.

     The Trisazo II  and IV subclasses  both require diazotization of  a  monoazo
or  disazo  product  before  the  next  coupling reaction.   In each subclass  then
the conditions  exist  (similar  to Disazo III)  for producing nitrosamines  from
terminated products that remain from the previous couplings.

     Trisazo  III  subclass  dyes are similar to the Disazo I subclass  where  a
diazo component is  coupled  to  the disazo compound.   The by-products  should  be
similar  to the Disazo I subclass with the addition  of miscouplings such as may
occur between the final diazo component and any excess  uncoupled  or  terminated
disazo compound remaining in solution.

     The  Trisazo  V  subclass  is  unique  in that  a  single coupling  component
capable  of coupling  in  three positions  is   coupled  with three diazo  components
(often  dissimilar).    The  possible  by-products would  include  incompletely
coupled  products   (similar  to  Disazo  I)   and  coupling  components  that  had
coupled  twice with  the  same diazo component.


                                      39

-------
     The  Tetrakis  and  Polyazo  classes  include,  in general,  products  from
further  coupling  on  trisazo  compounds  although   some   dyes   are   made  by
condensation  of  two  disazo  compounds  with phosgene.   The  by-products  from
tetrakis and polyazo  dye  and  pigment production are expected to  be similar  to
the other azo dye classes.

     The  dye  and pigment subclasses  that  would be  most   likely  to  have by-
products other than terminated  couplings  or miscouplings (which are common  to
all  subclasses)   are  the  Disazo  III, Trisazo  II,  IV,  and  all  higher azo
classes.   This  is  due  to  the  conditions  during  subsequent   diazotization
reactions and the possible formation of nitrosamines.

     Several dyes and pigments  require further steps to complete synthesis  of
the active color molecule.  One such reaction  is  termed  premetallization,  when
the dye molecule  is complexed with metals such as chromium (III).  Other  dyes
are completed by  the  condensation reactions of  terminal hydroxyl groups  with
aryl sulfonyl chlorides to yield  sulfonyl esters.  These reactions and  others
are discussed below.
OTHER REACTIONS

Phosgenation Reactions

     Several of  the disazo and  higher azo  dyes  (many in the  direct dye use
class) are  made  by reacting  two moles of monoazo  compound  containing a free
amino  group with   phosgene   (carbonyl  chloride).   This  provides  a  way   of
preparing the higher azo dyes and pigments that are symmetrical.

     The reaction  takes  place in  two  steps that produce  an isocyanate as  an
intermediate.

                 Ar-NH2   +    COC12  	*-Ar-N=C=0   + 2HC1

                 Monoazo      Phosgene      Isocyanate


The isocyanate  reacts with any amine present to form a substituted urea.

                                                     0
                   Ar-N=C=0   +  Ar-NH  	>*~Ar-NH-C-NH-Ar

                  Isocyanate     Amine            Disazo
                                                 Compound

The reactions  are  conducted  by  bubbling  phosgene-enriched  air  into the dye
manufacturing vessel and monitoring the disappearance of amine.  When water  is
present,  as  it is  in  an azo  dye manufacturing  operation,  isocyanates yield
substituted carbamic acids,  which decarboxylate with extreme ease to  yield the
original  amine.     The  amine can  then   react   with  isocyanate  to  give   a
symmetrically substituted urea.  Consequently, it is very difficult to  produce
an unsymmetrical  dye or pigment by phosgenation.
                                      40

-------
     The phosgenation  reaction is not  likely  to produce a significant  amount
of hazardous  waste.   It is  assumed that  phosgene was  added  with the  amine
always in  excess  and  that  the phosgenation reactions  are complete (i.e.,  no
free amines  remain in  the  reaction liquor).   The  major organic reaction  by-
products are  assumed  to be  the compounds  produced by  the  reaction  between
phosgene  and  any  unreacted   coupling  component   (containing  a  free  amine)
remaining  after  previous  coupling   reactions.   The  resulting  isocyanate  can
further react with any of the  amines present to  form  substituted  ureas.

Condensation Reactions of Cyanuric Chloride

     Several  monoazo  dyes  (many  in   the  reactive  dye  class)  are  made  by
condensation  reactions  with cyanuric chloride.   Cyanuric chloride will  react
with an aryl  amino  group in the partial dye molecule.  Hydrogen  chloride is a.
by-product of the reaction:
                                                             +  HC1
                                 Cl
             Arylamine   Cyanuric
                         chloride
The chlorine atoms  in  cyanuric chloride are as highly  reactive  as  in ordinary
acid chlorides, but at 0°C no  hydrolysis by water  occurs  in  12 hours.

     Aniline and its ring—substituted  derivatives  react with cyanuric chloride
to form primary, secondary, and tertiary condensation products.   However,  more
complex  amines undergo  the third  condensation with  difficulty.    If  water-
soluble amines, such as the sodium  salts of arylamine sulfonic acids  are used,
the  condensation  may  be  affected  in  aqueous  solution  at  0°C.     Higher
temperatures  (30-90 C)  are necessary  for the  second  and third  replacements,
or the third chlorine atom can be replaced by  a hydroxyl  or  amino group.

     These  reactions were not  studied  in detail because  the dyes involved are
relatively  minor  and not likely  to produce  significant  amounts of  hazardous
wastes.  It was assumed that no excess  cyanuric chloride  was required and that
chloride  with excess   aryl   amine  from  previous  from   previous   coupling
reactions.

Esterification Reactions
     The  synthesis  of  five  azo  dyes  included  in  this  study  is  completed
 through  an esterification  reaction  instead  of  another  coupling  via an  azo
 group.  They are:  Acid  Yellow  65,  Acid  Yellow  40,  Acid Yellow 38,  Acid Orange
 51,  and  Direct  Yellow  12.    p-Toluene  sulfonyl  chloride,  benzene  sulfonyl
                                       41

-------
chloride, or  ethyl  chloride react with  the hydroxyl group on  the  partial dye
molecule.  Hydrogen chloride is a by-product  of  the  reaction:
ArS02Cl  +  Ar'OH
                                                         HC1
     This  reaction  was  not  studied in  detail because  the dyes  involved  are
relatively minor  and not  likely  to produce  significant amounts  of  hazardous
wastes.  It was assumed  that no excess esterifying  component  was  required  and
that  the  major   reaction by-product  was  the  condensation  product  of  the
esterifying component  with  excess  coupling  component,  containing a  hydroxyl
group, from previous coupling steps.

Metal Complexes

     Azo  dyes  can -form  complexes with  metal ions.   In forming  the  complex,
unpaired electrons  in  parts  of the  molecule  interact with coordination  sites
on  the metal  ion.  These  unpaired  electron sites are called  ligand  groups in
the  following  discussion.   Many azo dyes  have two or more ligand groups that
are   close  together.     These  ligand   groups   can  interact  with   several
coordination sites  on  a  single  metal ion.  For example,  bifunctional azo dyes
with  salicylic acid  as  the  coupling  component  have  two ligand groups,  a
hydroxide  group and a carboxylic  acid group  and  can form 1:1  complexes (one
metal ion  to one  dye molecule)  with copper (II) or  nickel  (II)  ions  that have
four  coordination sites.   These dyes  also  form 1:2 (one metal  ion to  two  dye
molecules) complexes with chromium  (III) and cobalt (III) ions that  have  six
coordination sites  as  illustrated below;
                          Cr
                            .+3
                                                              + 2H
     Trifunctional  azo  dyes with  three  ligand groups  have amino  or  hydroxyl
groups on both sides of the azo linkage.   o,o'-Dihydroxyazo dyes  are important
members  of  this  class.   These  dyes  form 1:1 complexes with copper and nickel
and  1:1  or  1:2  complexes  with  chromium or  cobalt.    The  formation of  a  1:1
complex with chromium is illustrated below.
                                     -2H+
                                                                3H20
                                       42

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     The  metal  ion  coordination  sites  that  do  not  interact with  the  dye
molecule  can  interact  with water  or ligand  groups  such as hydroxyl  or  amine
groups on  the  fabric.   The formation  of the metal complex  stabilizes  the  dye
molecule,  making  it  more  resistant  to  degradation and   sometimes  aids  in
binding the dye to fabrics.

     Several different  procedures  can  be  used to  form  the dye-metal  complex
(metallized dye):

     •  Precipitation and  filtration of the  organic  dye followed by  reaction
        of the diluted  filter cake with metal salts.  The  metallized  dye  may
        be prepared for final processing by drying  the entire  reaction mixture
        rather than reprecipitation and filtering.

     •  Reaction  of  the metal with  the organic dye  molecule directly in  the
        mother liquor before  the product is precipitated  and filtered.

     •  Some  1:2  complexes  are prepared  by reacting  the 1:1  complex  from
        either of  the above two routes with unmetallized  dye.

     The  commonly used metal salts in  these  reactions  are the sulfates  and
formates  although fluorides  and  acetates  are  also used.   Based  on  the BIOS
recipes,  these salts  may  be  formed in  situ  from the  metal  oxides  and  the
appropriate  acid.   The metalization  reactions are  most  often  conducted  in
aqueous  solutions although  organics  such as  ethylene  glycol  and formamide
(Abrahart,  1968)  are  sometimes  present.     Autoclaves  are  used   for   the
metalization reactions because temperatures of  up to  130°C  may  be used.

CHEMISTRY OF AZOIC COMPOUNDS

     The azoic compounds, which include azoic diazo components, azoic  coupling
components,  and  azoic   compositions,  are  dye intermediates that  are  used  to
produce colors directly on fibers.

     Azoic  diazo  components  are  either  diazonium salts  or  aromatic  amines
substituted  by  electronegative groups  but free from water-solublizing  groups
that can  be  converted  to  diazonium salts  in  the dye  bath and  coupled  to  other
aromatic molecules to produce the  dye.  The first amine  used as an  azoic  diazo
component was p-nitroaniline.

     Azoic coupling  components  react with diazonium  salts  in the  dye bath or
on the fibers  to  form  dyes.   The majority of the azoic  coupling components in
use today are the  substituted arylamides of 3-hydroxy-2-naphthoic  acid.   These
coupling components are prepared generally by the condensation  of  3-hydroxy-2-
naphthoic acid (or its  sodium salt)  with  the appropriate arylamine  in boiling
toluene with phosphorus trichloride as a condensing agent.

     The azoic compositions are mixtures of diazonium salts and azote  coupling
components.  The  mixture  Itself  is placed in  the dye bath,  where  the  coupling
reactions to produce a dye occur.
                                      43

-------
     For the  azoic  coupling and diazo  components  included in this  study,  the
chemistry  involved  in  the  preparation of  the  components  does  not  include
reactions  such  as  diazotization and  coupling.  They  are made using  the  same
kind  of  chemical  reactions  that  are  used to  make  the other  intermediates
(which  are  used to  manufacture  azo  dyes and  pigments).    These  chemical
reactions and the residuals  they  produce were  not included in this  discussion
because they were too varied to discuss in any significant manner.   The  azoic
compounds  are considered  to  be  purchased  as is  or transferred  from  other
manufacturing facilities at  the dye and  pigment manufacturing  site.
                                      44

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                                   SECTION 4

                              DYE  INTERMEDIATES

     A list of  the  intermediates used in  manufacturing azo dyes and pigments
in the United  States was  compiled from information  in the Colour Index  (The
Society of  Dyers and  Colourists,  1980).   Intermediates used  to manufacture
dyes and  pigments whose  ingredients  were  not  published in  the Colour Index
could not  be  included in  the  list.   Table  8  lists  the organic  intermediates
for  which  some  physical  property data were  found  in OHMTADS   and  Hansch
(1978).   (These  physical  properties are  listed because they are  used later  in
this  report  to  discuss  the  emissions  of  intermediates  during  the  dye
manufacturing process.)

     All the intermediates listed  in Table 8, except  the liquids, aniline, and
some  substituted anilines,  have  melting points  above  ambient temperature,
which means  that they will  be  solids when  received  at the dye  manufacturing
site.  Nearly all the  intermediates are  estimated to have  low vapor pressures
(<1  mm  Hg  at  ambient  temperatures).    Some are reported  to  have substantial
vapor  pressures  at  high  temperatures,  but  when the vapor  pressure  versus
temperature data is extrapolated  to  ambient  temperatures, the  result  is  an
insignificant  vapor pressure.    Thus,   even  though   2-naphthol  has a  vapor
pressure  of 100  mm  Hg  at  206°C,  its  vapor pressure will be far  less than  1  mm
Hg at 20  °C.  The low  vapor  pressures are mirrored in the  high  boiling points
for most of the  compounds.

     The  low vapor  pressures mean that  vapor  losses  from manufacturing steps
at ambient  temperature will be  minor.   Even at 100°C,  most  of  the compounds
have vapor  pressures  far  less   than  water.   Any  of   these low—vapor-pressure
unreacted  intermediates  that  accompany  precipitated  and  filtered   dye  or
pigment will volatilize  much more slowly  than  water  during the  final product
drying step.   They  will  therefore remain on the  dye or pigment solids after
all of the water has evaporated.

     Table  8 also  gives  the log of the  octanol-water  partition  coefficients.
In general, these values are low,  indicating that  the  compounds  are  not likely
to   concentrate   in  lipid  materials.     Another  environmentally  important
parameter is K   , which indicates  the tendency of  organic chemicals  to adsorb
*
 OHMTADS is an online data system that  is a  component  of  the  Chemical
 Information System (CIS) operated by the National  Institute  of  Health and the
 U.S. Environmental Protection Agency.
                                      45

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                           Table 8
    ORGANLC INTERMEDIATES AND OTHER CHEMICALS USED IN AZO DYE
AND PIGMENT MANUFACTURE FOR WHICH PHYSICAL PROPERTY DATA WERE  FOUND2
Vapor
Pressure
Intermediate (mm Hg, °C)
Solubility
in Water
(ppm at 25°C)
Log
Octanol-
Water
Partition
Coefficient
MP
SubstJLuted Naphthalene  Compounds
  ].-Aminonaphthalene                           1    104
  l-!lydroxynaphthalene                        <0.1   20
  2-Hydroxynaphthalene                        100    206

  7-Ain i no-1 ,3-naphthalene  disulfonic  acid      —   —
  l-Ami no 8-hydroxy-3,6-naphthalene
    disulfonic acid                             —   —
  2-llyd roxy-3 , 6-naphthalene  disulfonic  acid     —   —
  2-llydroxy-6,8-naphthalene  disulfonic  acid     —   —
  4 , 5-I) i.liydroxy-2, 7-naphthalene  disulfonic   ,
    acid                                        —   —
  2-Amino-l-naphthalene  sulfonic acid          —   —
  4-Arn ino-1-naphthalene  sulfonic acid          —   —
  1-llydroxy-4-naphthalene  sulfonic  acid        —   —
  L-lIydroxy-5-naphthal ene  sulfonic  acid        —   —
  I -llydroxy-8-naphthalene  sulfonic  acid
  2-llydroxy-6-naphthalene  sulfonic  acid
  3-llycl roxy-2-naphthalene  carboxylic  acid      —   —

Siibst i.Lutcd AnilLne  Compounds
  AnjI ine                                     <1      25
  p-N i troani.li.ne                              101     106
  2,4-l)iaminotol uene                            1     100
  m-l'henylenediamine                            1     100
  Crcsidine (3-amino-4-methoxytoluene)          —   —
  4,4'-Thiouianiline
  2,4-Thiodianiline
                                  Soluble
                                  Insoluble
                                  1,000

                                  Soluble

                                  Slightly
                                  Very
                                  Very

                                  Soluble
                                  Slightly
                                  Insoluble
                                  Very
                                  Soluble
                                  Very
                                  Very
                                  Insoluble
                                  35,000
                                  800
                                  Very
                                  3 x 105
                                  Slightly
                                  Slightly
                                  Slightly
 2.25
 2.6
 2.8
-0.44
-0.17
 0.92
 1.39
                                                                             BP
 50
 95
122

273
301
150
288
220

   b
170b
120
107
125
220
-6
148
99
63
93
108
62
184
322
292
287
235
—
—

-------
Table 8 (Continued)
Vapor
Pressure
Intermediate
o-l'hcny 1 azoaniline
2, 4-1) Lchl oroaniline
m-Ani Inobenzoic acid
p-Aminobenzoic acid
o-An Is Ldine (2-methoxyaniline)
2-Nitro-p-anisidine
4-Nitro-o-anisidine
5-Nitro-o-anisidine
2 , 4-1) i am Lno toluene
2, 6-1) iamlno toluene
o-To 1 uidine (2-amino toluene)
m-Toluidine (3— aminotoluene)
4-Chloro-o-toluidine
2-N i tro-p-toluidine
5-N i Lro-o-toluid ine
o-Ch 1 oroaniline
p-Chloroaniline
2-Chloro-4-nitroaniline
4- ('111 oro-2-nitroaniline
2 , 5-0 ich.l oroaniline
2 , ft-Oich 1 oro-4-nitroaniline
N,N-l)Letliylaniline
N, N-Oimethy] aniline
2,4-Din.I troaniline
2 , 4 , 5-Trichloroaniline
o-N i troan L.I. ine
iii-N i Lroan LI Ine
(mm H£,
	
> 0.1
—
—
1
—
—
—
1
1
! 1
1
	
	
	
1
1
	
	
< n.i
«.01
i
i
—
—
i
—
°0
	
20
—
—
61
—
—
—
106
106
44
41
—
—
—
46
59
—
—
20
20
50
29
—
—
104
—
Solubility
in Water
(ppm at 25°C)
Slightly
Slightly
Slightly
Slightly
Insoluble
Soluble
—
Slightly
Soluble
Soluble
15,000
Slightly
—
Slightly
Slightly
Insoluble
Slightly
Slightly
—
Slightly
Insoluble
14,000
insoluble
Insoluble
—
4,700
1,100
Log
Octanol-
Water
Partition
Coefficient
__
2.6
0.28
0.46
0.95
—
—
—
—
—
1.3
1.4
—
—
—
1.9
1.7
—
—
2.5
—
3.3
2.3
i
3.27
1.8
1.37

MP
(°C)
128
63
174
187
5
123
140
118
94
105
-16
-30
29
117
107
-14
71
104
115
20
191
-38
2.4
170
96
71
114

BP
(°C)
>360
245
—
—
220
—
—
—
280
—
200
203
241
—
—
209
231
—
—
251
—
216
193
—
270
284
306

-------
Table 8 (Continued)

lermedJ.a te

Vapor
Pressure
(mmHg, °C)

Solubility
in Water
(ppm at 25°C)
Log
Octanol-
Water
Partition
Coef f icieni
                                          MP
            BP
p-Am.inophonol                              <0.1  20      5,600
2-Amino-5-nitrophenol                       —    —        —
2-Amino benzene sulfonic acid               —    —      Slightly
  (ortlifinilic acid)
4-AmLno benzene sulfonic acid               —    —      10,000
  (sulfanilic acid)
4-AmLno-6-nJtro-4-phenol sulfonic acid      —    —      Slightly
2-Amino-4-phenol sulfonic acid              —    —      Slightly
5-Aniino-2,4-xylene sulfonic acid            —    —      Slightly
4-Amlno-3-toluene sulfonic acid             —    —      Slightly
2-Amino benzene carboxylic acid             —    —      Slightly
  (unthraniLie acid)
4-Amino benzamide                           —    —      Slightly
Diphenvl amine                               1    108     Insoluble
2,4-;;ylidLne                               <0.1  20      Slightly
2,5-XyJ.idine                                .14   20      Slightly
N-(3-Amlnophenyl) acetamide                 —    —      Very
N-Kthy.l-N-phenyl benzylamine                —    —      Insoluble
2-Am.i no-4,6-d Lnitro -phenol                  —    —      650
                           0.04
                           1.2

                           0.02
                           3.5
186
201
325b

288b
                                       155
                                       290b
                                                   284b
145
183
54
16
15
87
—
310
215
214
—
                                                    285
                           0.93
169

-------
                                               Table 8 (Concluded)
              Intermediate
Other Intermediates
  p-Cyu]ohexylphcnol
  p-Nitrobenzoyl chloride
  CyanurJc chloride
  2-(N~Hc-thylanilino) ethanol
  p-Aminoacetanilide
  Acetoacetaniltcle
  p-Cresol
  o-Cre.sol
  3-Methyl-L-phenyl-5-pyrazolone
  3-HeL'ayl-l-(p-sulfophenyl)-5-pyrazolone
  Benzenesulfonyl chloride
  l-Methyl-2-phenyl-l-H-indole
  2-Ilydroxybenzoic acid

  1) kizoaminobenzene
  Kcsorcinol
  Phenol

Solvents and Reagents

  'iLhano 1
  'hosgenc
  ''or ma.I cl ohyde
  'yridiae
  'oui'iarniJe
Vapor

Pressure
(mmHg,
—
2
—
0.01
1
1
—
—
1
1
	
20
GO
40
1180
10
20
29
°C)
—
70
—
20
50
38
—
—
66
114
—
168
86
19
20
-88
25
129
Solubility
in Water
(ppm at 25°C)
Decomposes
Insoluble
Slightly
Slightly
24
31
Slightly
Slightly
Insoluble
2,000
Insoluble
100,000
67,000
Miscible
Slightly
555,000
Miscible
Miscible
    Lo<5
 Octanol-
   Water
 Partition
Coefficient3
      4.2
      0.08

      1.95
      1.95
                                                                                            MP
                                                                                                    BP
      2.3
      0.78
      1.5
     -0.3
      0.62
     -1.51
120
75
150
—
162
85
, 36
31
127,
V,
290D
14
98
157
98
111
43
-115
-118
-92
-42
2.5

202
194
150
—
b
201
190
287

—
251b
200
b
b
281
182
78
: 8
-19
115
210
  ^Source:   OHMTADS,  Kirk-Othmer (1978), Hansch (1978) for partition coefficients.
   Decomposes,

-------
to the organic material in soils and sediments  (Smith  et  al.,  1977,  1978).   It
has been shown that for organic chemicals the overall  potential  for  adsorption
to soil  and  sediment is  the  product of  KQC and  the  fraction of the  soil  or
sediment that  is  organic  (Kenaga and  Goring,   1978).   KQC  values  have  been
measured for  many  pesticides  and  common organic  chemicals.   This work  has
shown that KQC  and the octanol-water  partition  coefficient  (&_„) values  are
related.   Mabey  et al.  (1981)  present  the relationship  log K^c  =  log  KQW
-0.21, which was derived statistically, to predict Koc values  from Kow-  Based
on this relationship it can be  predicted that few of  the chemicals  in  Table 8
with  known Kow  values  would  have  KOC values  much  greater  than  100.    Our
experience (Smith  et al.,  1977,  1978)  indicates that  sorption to the  organic
material in soils and sediments is not significant for compounds  with such  low
values for KQC.

     The solubility data  in  Table 8 are  hard to interpret because it  was  not
possible,  given  the  scope  of  this  study, to review  the  individual  data
sources.   It  is assumed,  however,  that  "slightly"  indicates solubilities  of
about 100 ppm and that  "soluble" indicates solubilities of about  1000 ppm.   Of
the   intermediates  listed,   aniline,   resorcinol,  2,4-diamino   toluene,   m-
phenylenediamine, and some of  the  substituted naphthalene sulfonic acids have
substantial solubilities.

     Included  in  Table  8  are  solvents  and  other  chemicals  that  are  not
considered intermediates  but  are  added during  the  synthesis  of  several  dyes.
These compounds have significant  vapor  pressures at 20 C, low melting  points,
and appreciable solubility in water.  With the  exception  of phosgene, which  is
a gas, they are all liquids.

     The high vapor pressures  of  these  compounds will lead to vapor  losses  in
all  phases of  the dye manufacturing  operation in which  they  are  employed.
Phosgene is so volatile that it is not expected  to remain in  the  mother liquor
at all.   The  others will persist  to some degree  in the  mother liquor.   When
the dye  or pigment product is dried,  any that  is carried in  entrained mother
liquor will volatilize and be carried into the  air pollution  control  system.

     Several  workers  have  shown   that  solubility  and  K     are   inversely
related.   Figure  1, which is from  a review of  solubility relationships  (Mill
et  al.,  1980),  shows that  compounds that  are  soluble in water, such as  the
liquid  solvents  and  reagents,  are  likely  to  have  low K   values.   Even
formaldehyde, which is  the least  soluble,   has  a molar soluollity  of  greater
than  1  and is  predicted  to  have  a K    value  of  less  than  1.   Thus,  these
materials will not  sorb strongly to  soils and sediments when  released.

     Table 9  lists  the  more highly  substituted organic intermediates  used  in
the  United  States  to  manufacture  azo  dyes  and  pigments.   The  names  in
parenthesis are  common  names  that are  often used.  No physical  property data
were  found  for  these compounds in  the  sources  searched.  They  are  assumed to
have  properties  similar  to the majority  of  those in  Table 8, i.e.,  low vapor
pressure,  solid  at ambient temperature,  and not strongly adsorbed  to  organic
material or soils and sediments. Because  many of these compounds  have multiple
sulfonic acid and/or hydroxyl functional  groups,  they  may be  more soluble than
the intermediates  listed in Table 8.
                                       50

-------
   108 e=
   10?
f-
z


y

LL
LL
UJ
O
O

z
o
   105
CC

<
Q.
   1Q3
   102
   10'
= i i mini  i i mini  i i mini  mimd  iimiid  i mind  iiiniid  irsjnd
                                                                           11
                                                                            ^
     10-9    ID'8    TO'7    1CT6    ID'5     1Cr4     10~3    10'2     1Q-1

                              SOLUBILITY — moles liter1
SOURCE: T. Mill et al.. 1980.
                                                                      SA-4396-85B
       FIGURE 1  SOIL OR SEDIMENT PARTITION COEFFICIENT OF CHEMICALS VERSUS

                SOLUBILITY IN WATER
                                      51

-------
                                  Table 9
                     ORGANIC INTERMEDIATES FOR WHICH
                  NO PHYSICAL PROPERTY DATA WERE FOUND
Substituted Naphthalene Disulfonic Acid Compounds
  2-Amino-l,5-naphthalene  disulfonic acid
  3-Amino-l,5-naphthalene  disulfonic acid
  4--Amino-5-liydro'xy-l, 3-naplithalene disulfonic
    acid
  4,3-Dianino-2,6-naphthalene disulfonic acid
  l-Hydroxy-3,6-naphthalene  disulfonic acid
  l-Hydroxy-3,C-naphthalene  disulfonic acid
  H-Acetyl-l-amino-8-hydroxy-3,6-naphthalene
    disulfonic acid
  o-Phenylsulfonyl-l-amino-8-hydroxy-3,6-
    naphthalene disulfonic acid
  o-Tolylsulfonyl-l-amino-G-hydroxy-3,6
    naphthalene disulfonic acid
  o-Phenylsulfonyl-2-amino-8-hydroxy-3,6-
    naphthalene disulfonic acid
(Chicago acid)
(N-Acetyl H acid)
(o-Phenylsulfonyl H acid)
(o-Tolylsulfonyl H acid)
(o-Phenylsulfonyl 2 R acid)
Substituted Naphthalene Sulfonic Acid Compounds
  l-Aniino-4-naphthalene sulfonic acid
  1-Amino-6-naphthalene sulfonic acid
  l-Amino-7-naphthalene sulfonic acid
(Naphthionic acid)
(1,6-Cleves acid)
(1,7-Cleve's acid)
                                     52

-------
                           Table 9 (Continued)

  l-Amino-2-hydroxy-4-naphthalene sulfonic acid
  l-Amino-8-hydroxy-4-naphthalene sulfonic acid
  l-Amino-2-hydroxy-6-nitro-4-naphthalene
    sulfonic  acid
  2-Amino-6-naphthalene  sulfonic acid
  5-Amino-l-naphthalene  sulfonic acid
  5-Amino-6-ethoxy-2-naphthalene sulfonic
    acid
  6-Amino-4-hydroxy-2-naphthalene sulfonic
    acid
  7-Amino-4-hydroxy-2-naphthalene
    sulfonic  acid
(S acid)
(Bronners acid)
(Gamma acid)


(J acid)
  4,6-Dihydroxy-2-naphthalene  sulfonic  acid
  6,6'Iminobis-l-hydroxy-3-naphthalene
    sulfonic  acid
  N-Acetyl-2-amino-5-hydroxy-7-naphthalene
    sulfonic  acid

  N-Acetyl-7-amino-l-hydroxy-3-naphthalene
    sulfonic  acid
  N-Phenyl-l-amino-8-naphthalene
    sulfonic  acid

  N-Phenyl-2-amino-8-hydroxy-6-naphthalene
    sulfonic  acid
  N-Phenyl-7-amino-4-hydroxy-2-naphthalene
    sulfonic  acid

  N-Benzoyl-7-amino-4-hydroxy-2-naphthalene
    sulfonic  acid

  N-m-Aminobenzoyl-7-amino-4-hydroxy-2-
    naphthalene  sulfonic  acid

  N-p-Aminobenzoyl-7-amino-4-hydroxy-2-
    naphthalene  sulfonic  acid

  N-p-Tolyl-l-amino-8-naphthalene  sulfonic
    acid
(N-Acetyl-J acid)
(N-Acetyl Gamma acid)
(N-Phenyl Peri acid)
(N-Phenyl Gamma acid)
(N-Phenyl J acid)
(N-Benzoyl J acid)
(N-m-Aminobenzoyl J acid)
(N-p-Aminobenzoyl J acid)
(N-p-Tolyl Peri acid)
Substituted Naphthalene  Compounds


  3-Hydroxy-2-naphthalene  carboxylic  acid

  3-Hydroxy-2-naphthalene-o-anisidide
                                    53

-------
                          Table 9 (Continued)

  3-Hydroxy-2-naphthalene-o-toluidide
  4'-Chloro-3-hydroxy-2-naphthalene-o-toluidide
  3-Hydroxy-2-naphthanilide
  3-Hydroxy-2',5'-dimethoxy-2-naphthanilide
  3-Hydroxy-3' -nitro-2-naphthanilide
  4'-Acetamido-3-hydroxy-2-naphthanilide
  4'-Chloro-3-hydroxy-2',5'-dimethoxy-2-naphthanilide
  5'-Chloro-3-hydroxy-2',4'-dimethoxy-2-naphthanilide
  N-Ethyl-2-aminonaphthalene
  N-(7-Hydroxy-l-naphthyl)acetamide
Substituted Pyrazolone Compounds

  3-Methyl-l-p-tolyl-5-pyrazolone
  3-Carbethoxy-l-phenyl-5-pyrazolone
  3-Carboxy-l-(m-nitrophenyl)-5-pyrazolone
  3-Carboxy-l-(p-sulfophenyl)-5-pyrazolone
  l-(4-Chloro-2-sulfophenyl)-3-methyl-5-pyrazolone
  l-(2-Chloro-5-sulfophenyl)-3-methyl-5-pyrazolone
  1-(2,5-Dichloro-4-sulfophenyl)-3-methyl-5-pyrazolone
  3-Methyl-l-(2,4-dichloro-4-sulfophenyl)-5-pyrazolone
  3-Ilethyl-l-(m-sulf ophenyl)-5-pyrazolone
  3-Methy1-1-(4-sulfo-o-tolyl)-5-pyrazolone
  l-(6-Chloro-o-tolyl)-3-methyl-5-pyrazolone
Substituted Benzene Sulfonic Acid Compounds

  2-Amino-5-nitrobenzene sulfonic acid
  2-Amino-l-hydroxy-4-benzene  sulfonic acid
  2-Amino-5-chloro-4-ethyl benzene  sulfonic acid
  2-Amino-5- methoxybenzene sulfonic acid
                                     54

-------
                            Table 9 (continued)

  2-Amino-4-(3-chloro-l-oxido-l,2,4-benzotriazene-7-
    carboxamide)  benzene  sulfonic  acid
  2-Amino-5-(4-amino-3-sulfo-l-anthraquinonylamino)
    benzene sulfonic  acid
  2,4-Dianinobenzene  sulfonic  acid
  3-Amino-4-methoxybenzene sulfonic acid
  5-Amino-2-(p-aminoaniline) benzene sulfonic  acid
  6-Amino-4-chloro-l-hydroxy-2-benzene  sulfonic acid
  6-Amino-4-nitro-l-hydroxy-2-benzene sulfonic acid

  6-Amino-3,4'-azodibenzene: sulfonic acid
  (2-(p-Aminoaniliao)-5-nitrobenzene sulfonic
    acid
  5-Acetamide-2-aninobenzene sulfonic acid
  p-(p-Aminophenylazo)-benzene sulfonic  acid
  5,5'-Ureylenebis(2-aninobenzene sulfonic acid)
  2-Amino-5-chloro-p-toluene sulfonic acid
  4-Amino-5-methoxy-o-toluene  sulfonic  acid
  6-amino-4-chloro-m-toluene sulfonic acid
  6-Amino-m-toluene sulfonic acid
  p-Amino-a-toluene sulfonic acid
  4,6-Diamino-m-toluene sulfonic acid
  2-Amino-3,5-xylene  sulfonic  acid

Substituted  Acetoacetic Amides

  o-Acetoacetotoluidide
  p-Acetoacetotoluidide
  o-Acetoacetanisidine
  4'-Chloro-o-acetoacetotoluidide
  4,4'-Bi-o-Acetoacetotoludine
  2,4-Acetoacetoxylidide
  p-Acetoacetophenetidide
  o-Chloroacetoacetanilide
  4'-Chloro-2 ' , 5 ' - diaethoxyacetoacetanilide
  2,4-Acetoacetoxylidine
  4 '-Chloro-2',5'-dimethoxyacetoccetanilide

                                    55

-------
                           Table 9 (Continued)
Other Compounds
  m-Aminoformanilide
  5-Amino-l,4-dimethyl-lH-l,2,4-triazole
  2-Amino-3-methylthiazole
  2-Amino-6-methoxy-3-methylbenzothiazole
  2-Amino-N-methyl-l-phenol-4-sulfonamide
  2-Amino-l-phenol-4-sulfonaiaide
  2-(N-Ethylanilino)ethanol
  2-(4-Amino-3,6-dimethoxyphenylsulfonyl)ethanol sulfate ester
  2-(4-Amino-3-methoxyphenylsulfonyl)ethanol sulfate ester
  2-(p-Aminophenylsulfonyl)ethanol sulfate ester
  2,2'-(m-Tolylimino)diethanol
  2,2'-(m-Chlorophenylimino)diethanol
  3-Hydroxy-2-naphtho-o-phenetidide

  2,5-Dimethoxyaniline
  N-Methyl-N-(2,3-dimethoxypropyl)aniline
  m-Diethylaminoacetanilide
  3-Amino-p-anisanilide
  Methanilic acid
  2-Amino-N-ethylbenzenesulfonanilide
  4-Amino-2,5-dimethoxybenzenesulfonanilide
  5-Amino-o-toluenesulfonanilide
  3-(2-Chloroanilino)propionitrile
  3-(N-2-Cyanoethylanilino)propionic acid methyl ester
  3-(N-Ethylanilino)propionitrile
  3-(N-Ethyl-m-toluidino)propionitrile
  3-(N-2-Hydroxyethylanilino)propionitrile, acetate ester
  3-(N-Methylanilino)propionitrile
  Anilinomethanesulfonic acid
  o-Toluidinomethanesulfonic acid
  dihydrothio-p-toluidinesulfonic acid
  Sodium dihydrothio-p-toluidinesulfonate
                                     56

-------
                           Table 9  (Continued)

Ethyl acetoacetate
p-Phenylazoaniline
2,5-Xylidine
2,4-Dichloroaniline
o-Toluidide
m-Aminoformanilide
p-Aminooxanilic acid
3-Methyl-2-hydroxybenzoic acid                     (2,3-Cresotic  acid)
4-Sulfoanthranilic acid
2,4-Quinolinediol
2-Amino-N-methylpyridinium salt
l-Naphthol-8-sulfonamide
N,N-Diethyl-4-methoxymetanilamide

2-5-Dichlorosulfanilic acid
3-Amino-4-chlorobenzamide
5-(p-Aminophenylazo)-salicylic acid
N-(3-Amino-4-sulfophenyl)glycine
Xylylazoxylidine
p-Toluenesulfonyl chloride

4,4'-Benzylidenedi-2,5-xylidine
4,4'-(o-Chlorobenzylidene)di-2,5-xylidine
4 ,4 '-Cyclohexylidenedi-o-anisidine
4,4'-Diamino-2,2'-stilbene disulfonic  acid
6, 6'-Thiodenet'aanilic acid
3,3'-Diaminobenzanilide
4-o-Tolyazo-o-toluidine
4-Nitro-m-phenylenediamine.1Diazotized
Toluene-2,4-diamine hydrochloride
4-L-iethoxy-m-phenylenediamine
                                   57

-------
                           Table 9  (Concluded)

m-Phenylenediamine
p-Nonylphenol
4,4'-Cyclohexylidenedi-o-toluidine

2-Amino-5-tiitrobenzonitrile
[2-(N-Ethylanilino)ethyl]trimethylammonium salt
2-Amino-4-(2,5-dichlorophenylcarbamoyl)benzoic acid methyl ester
(p-Aminobenzoylmethyl)trimethylanmionium chloride
2-Amino-5-nitroisophthalonitrile
6-Chlorometanilic acid
2-Bromo-4,6-dinitroaniline
4-Chloro-a,a,a-trifluoro-o-toluidine
a,a,a-trifluoro-o-toluidine
m-Dieth anolamino-p-methoxyacetanilide
3-(N-2-Hydroxyethylanilino)-propionitrile, acetate  ester
                                   58

-------
                                   SECTION 5

                      SOURCES OF WASTE DISCHARGES DURING
                       AZO DYE  AND PIGMENT MANUFACTURE
     The  wide  range  of  azo dye  and  pigment  production processes  and  the
specific  plant   characteristics  and   process   control   capabilities  make
estimation of  material  losses  during dye  manufacture a  difficult  task.   In
general,  though,  the  most  significant  material  losses  will be  intermediates
that  do  not  react   and   by-products,   such  as  incomplete   dye or   pigment
molecules.  The intermediates and by-products  from dye manufacture are  present
either  in  the  product  or  in the  solid waste  streams  regulated under RCRA—
wastewater,  solid residues,  or  the vapor and dust emissions.  The material in
the wastewater may be discharged in  the plant effluent  (although some  will be
destroyed by  treatment  as  described below),  and some  will  be  discharged  on
wastewater treatment  solids.

     Published information and  industry contacts concerning  the presence  of
organic  materials in  the wastewaters  of  several  unit  operations   of  dye
production (e.g.,  Steadman et  al.,  1977;  Lapp  et  al.,  1979; Abrahart,  1968;
Boeniger,  1980)  were  used  to   develop  materials  release   estimates   for
intermediates,  by-products,  and dyes and pigments  in the azo dye and  pigment
manufacturing processes.

     This  section first   gives  a  general   overview  of  azo  dye  and   pigment
production  processes   and  then  describes   the  bases  used  for   developing
estimates of  the  amounts   of  material lost  (expressed  as  a percentage of  the
finished  and  standardized  dye  or pigment).   The losses  from  both  dye  and
pigment manufacture are discussed  below according to the  stages  of  production
in  which  they  would   occur  (i.e.,  raw material  receiving, synthesis,   drying,
grinding, standardization, blending,  and packaging).

     The solid residues are  assumed  to  be placed in  a  landfill,  either on  the
manufacturing property  or  at a commercial  facility.   The process wastewaters
are processed through a wastewater treatment  system that may  include physical,
chemical and/or biological  treatment of all or  just  some  of  the effluent.   In
some  cases,  the   wastewater  treatment system  may discharge partially  treated
wastewater to municipal treatment systems.   Concentrated aqueous waste  streams
may  also  be  concentrated  further  and  landfilled.    The actual  environmental
releases that occur after wastewater  treatment  are  discussed  at  the  end of  the
section.
                                      59

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OVERVIEW OF AZO DYE AND PIGMENT PRODUCTION  PROCESSES
     Figure 2 illustrates  the  dye and pigment manufacturing  process  and  shows
where the losses of materials  occur.  The  dye  manufacturing  equipment required
to produce  azo dyes  and pigments  consists of  well-stirred tanks,  plate  and
frame filter presses, dryers,  grinders,  and blenders.

     A dye or pigment is usually  prepared  in batches,  and  the plants  typically
contain   several   reactor  trains.     Each   train   includes  at  least   one
diazotization reactor,  one coupling  reactor,  and one  filter press.    Complex
dyes and  pigments  may  require use of  several reactor trains.  Production of
colors is usually rotated by set  schedules  from  light- to  dark-colored dyes or
a train may be used exclusively for production of  one  color  or one  dye.

     After  diazotization,  coupling,   and  any  other  chemical  reactions  are
completed  as  described in  Section  3,  the  water-soluble  acid,  direct,  and
reactive  dye materials  are precipitated  (salted out)  by  the  addition of  salt
to give a final brine concentration of  up  to 20% weight  by volume  (BIOS,  1945;
Abrahart, 1968).   The  resulting  slurry is filtered using a  filter press,  and
air is blown through  the presscake to remove as  much mother  liquor  as possible
(Kent, 1974).  The  cake is removed from the press and dried in an  atmospheric
tunnel dryer or a vacuum tray  dryer.  The  dye  is then  ground in a  swing hammer
mill and  thoroughly mixed in a blender.

     Often sodium chloride  or  Glauber's salt  (sodium  sulfate)  is added to  the
blender to  reduce  the water-soluble  dye  concentration to a  standard strength
(so-called standardization).   The amount  of salt added to  a  dye depends on  the
dye  and  the   producer   and  may  even  vary  among  dye batches  at  a single
facility.   Various  estimates  of the percentage of inert salt in the final,
marketed, water—soluble dye product included in  this study are as  follows:

                  <75%             (Gerber, 1980)*

                   50%-92%         (Steadman et  al., 1977)
                   50%             (Shreeve and  Brink,  1977)

                   45%-65%         (DETO,  1980)

An inert  salt  level  of 50% has  been assumed  in the  discussion that follows.
(An  estimate  of  the  salt  content  of   the  standardized  final  product  is
necessary  in  discussing  actual  waste  amounts  produced  by  dye manufacturers
because  the  majority of  available production data are  for  the  standardized
dye.)
 Personal communication,  S.  Gerber,  American Cyanainid Company;  Sept.  8,
 1980.
                                       60

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p
Was




Air Pollution
Control
1
Solid Waste

Material
Receiving
and
Weighing
1 1









\
Wastewater

Dye
* Synthesis
1 1






Filtration

1 Solid Waste 1 Solid Waste
-ocess Process '
tewater Wastewater Mother
1
Solid
Liquor




Drying
1 1



Waste^ 1 Solid Waste'
Process P
Wastewater Was
1
Air Pollution
Control
j

1
C
1 r
Wastewat
Grinding,
Blending,
Standard! zatio
and
Packaging
T
roces
tewa




jolid Waste
er
n, . . .,„
Product

Solid Waste
s
ter
                                                                         JA-1106-1A
FIGURE 2  PRODUCTION OPERATIONS THAT ARE SOURCES OF WASTE
         EMISSIONS IN DYE AND PIGMENT MANUFACTURE

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     Pigments and  disperse and solvent  dyes  are insoluble and do  not  require
salting out.  After filtration from the  mother  liquor, 45%  of  all  pigments  are
dried, ground, and sold without dilution (Lapp  et  al., 1979).  Another  40%  are
flushed  (dispersed into  an oil  phase).   On  the  basis of  information  from
Steadman  (1977),  we have  assumed that  flushing adds 65%  inert  ingredients.
The remaining  15%  of all  pigments  are  sold  as  wet  filter press cake  without
processing.  This  means  that,  on  the average,  27.5% of  the final  product  sold
is inert  ingredients:   (45% x 0%  inert  salt) +  (40%  x  65% oil) +  (15% x  10%
water in press cake) = 27.5% inert ingredients.

     The  disperse  dyes  may  be   sold  as  100%  product  or  flushed  with  a
dispersing  agent   (sulfonated  oil)  and   a  surfactant.   This may  add  10-25%
inerts.

     The solvent dyes are  generally sold as 100%  product  (i.e., dried,  ground,
and sold without dilution).

     It was  assumed  that the. water-insoluble dyes  (solvent and disperse)  and
pigments  contain   25%  inert  ingredients.    The release  estimates  for each
process  step are  developed separately   for  the  water-soluble  dyes  and  the
water-  insoluble  dyes  and pigments.    An  average diluent value  of  25%  was
chosen  to encompass  the water insoluble dyes  and  pigments  and  50% for  the
water-soluble dyes.
RAW MATERIAL RECEIVING AND HANDLING

     Dye  intermediates  are received  either  from other chemical manufacturing
sites or  from manufacturing  operations at  the dye  manufacturing  site.   The
physical  properties  of  the chemical  intermediates for which  data were  found
(see  Table   8)   indicate  that  they   are   almost  all  solids  at   ambient
temperatures.  The intermediates  for  which no data were found were  assumed to
be solids  also  because  they are  chemically  similar to the intermediates  with
known properties  and often of  higher molecular weight.   Therefore,  material
from other manufacturing  sites  is  likely to  arrive in fiber  drums  or  paper
bags.   Material  from  the  same site  may  arrive  the  same way  or  in  some
container  such  as a tote  box designed  for  transfer  and  temporary  storage  of
solids.    The intermediates are  weighed and  transferred  into the appropriate
vessels  in the dye reactor train.
Solid Residues
     Most  solid  residues from material  receiving will be shipping  containers
contaminated  by  chemicals  that  stick  to  the  walls  or   fill  cracks  and
crevices.   It  has  been  estimated  that  0.1%  of such solids  remains in  the
shipping container.  Very few data are available  to  indicate  the  disposition
                                       62

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of  this  material.    One  industry  contact   stated  that  his  company  which
manufactures azo  dyes  and pigments, sends  about  one truckload  of  fiber  drums
and paper waste  to  a dump every  day.   Thus  any  chemicals  in the  drums  or on
the paper  would  be  transferred to  the dump  site.   Manufacturing  operations
that receive material  in temporary storage and transportation  containers from
their own chemical manfuacturing  operation may wash the containers  and return
them to  duty  so  that any chemicals  remaining in the containers would  then go
into the process wastewater treatment system.

     To  indicate  the   order   of  magnitude   of  the  potential  solid  residue
disposal required  by azo dye  and pigment  manfuacturing,  it has been  assumed
that all intermediates arrive  in fiber  drums  or bags,  which  are  later disposed
of in a landfill.

     We have estimated  that 0.1%  of the material in a  bag or  drum  is retained
in  cracks  or  as  a  coating on wall surfaces when  the container is  emptied.
This would  represent only 0.05  Ib of  material  in a  50—Ib  bag and  less than
0.25 Ib in a 30-gallon drum.

     Because the water-soluble dyes have been assumed  to be  50%  inert salts,  a
0.1% loss of the delivered intermediates is equivalent  to a  total intermediate
loss of  0.05% on  a  final marketed product basis.  Thus the  manufacture of 100
pounds of a standardized monoazo  dye would result in a total  of 0.05 pound of
intermediates in discarded drums and  bags.    However, because monoazo  dyes
require  two  intermediates,   there  would   be   only   0.025  pound  of   each
intermediate if  we  assume that  all the intermediates  all have  approximately
the  same molecular weight.    (Because  of  the assumptions used  to   obtain the
0.05% estimate for material loss from material handling, it  was  not  considered
reasonable  to  correct  for  molecular  weight   differences when estimating  the
residue  production for  each dye).   Disazo dyes require three  intermediates so
that the loss of each intermediate would be only  0.017  pound.   In general, the
solid  residue  associated  with  each intermediate  is  determined  by  dividing
0.05% by the number of intermediates used  to  build the  dye molecule.  For dyes
that are premetallized,  the metal is considered as an  additional intermediate.

     The assumption  of  similar molecular weights  for all intermediates is not
unreasonable even when  metals  are  included  in  the  dye.   A common  source of
chrome  for  dyes  is  chromium formate, which has  a molecular weight  of  187, or
chrome  oxide,  which has a molecular weight  of  152,  compared to a molecular
weight of 93 for  aniline or  144 for 8-naphthol, which  are both  common organic
intermediates in  azo dye production.   The chromium  in the  dye might  have an
equivalent molecular weight of 87.5  or 123 because of  the chlorides necessary
to make  a neutral salt when the dye precipitates.  Metals may  actually be lost
in  their  oxide  form because the  metal  formate is often made  in  situ from the
oxide.
*
 Personal communication  M. B. Bochner,  Atlantic  Chemical Corporation, Sept,
 10, 1980.
                                       63

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     The same  general procedure  was followed  for pigments  and disperse  and
solvent dyes, which are  assumed  to  be 75% active  ingredients.   For  these dyes
the total amount  of  intermediate in  the  solid residue stream would  be  0.075%
of  the  final marketed  product.   This  amount was  divided by  the  number  of
intermediates to determine the loss for each  intermediate.

     In  this procedure  for  calculating  intermediate solid  residue  losses,
several special  cases  need to  be treated.   Some  dyes use phosgene  to  couple
two aromatic amines  together.    Phosgene is  not  counted  as  an  intermediate
because  its  total  weight contribution  to  the final product  is  very  small
(equivalent  to urea).  Phosgene  is  generated on-site  from  gaseous ingredients
(such as  carbon monoxide  and chlorine),  and its use would not  result in  a
solid residue.  Cyanuric  chloride,  which is  used  for  various dyes,  is  counted
as  an  intermediate  but   is  not  included in the  solid  residue  stream  from
materials handling.    It  is  made,  on-site from  gaseous  and  volatile  liquid
components (such as HCN,  chloroform and chlorine).
Process Wastewater
     The material from spills during transfer operations and  residual  material
in temporary storage  and  transfer containers may  be washed away.  The  amount
of water required and  the  frequency  of cleaning is  difficult  to  quantify,  and
no quantitative estimates have been made.
Vapor and Dust Losses

     Vapor  losses  during  chemical  intermediate  transferring  and weighing
operations  are  expected  to  be  small  because  most  of  the  chemicals   are
estimated to  have low vapor  pressures  and to  be  solids atQroom  temperature.
The loss  of  solid material from dusts may occur during handling.   The vapors
and dusts at  the weighing  and  tranfer operations  at  some facilities will  be
vented  to a  scrubber unit  (DETO,  1980;  Keinath,  1976).   In  this  study,  the
vapor and dust  losses  of intermediates are  not estimated separately, but  are
included in the estimates  of  the  vapor  losses that occur  during  dye synthesis
and product  filtering.

     Most of the  chemicals  with high vapor pressures at  room  temperature  (see
Section 3) are  chemicals used as  solvents  or reaction aids.   These materials
are  not  incorporated   into  the   dye   molecule  and   are  not   truly   dye
intermediates.  In  general,  these chemicals  have  low melting  points and  will
be transferred as liquids.  The scrubber  blowdown from  the  material receiving
and handling area could  contain these materials and may be  a  logical sampling
point for chemicals of interest (such as formaldehyde).  No  estimate of  losses
of these  compounds  was  made because  it was  difficult to quantify  the amounts
of material  used.
                                      64

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DYE SYNTHESIS

Solid Residues

     The major  solid residue  produced during dye  synthesis  is the  discharge
from a  filter press if  one  is used to  clarify  the diazonium salts  and  other
incomplete dye  liquors.  Keinath (1976)  reported  an example of  this  filtering
operation at  the Fabricolor  facility in Patterson, New Jersey.  A  filter cake
from clarifying a  liquor  containing  benzidine  tetrazonium salts   (Celite  and
carbon are used to form the  cake)  is  washed with water,  and the washings  are
transferred to  the coupling vessel  where  the next synthesis step  will  occur.
A  sodium  hypochlorite solution is  added  to the filter  press  to   oxidize  and
bleach any organic material  on the filter cake, and the  resulting  solution is
discharged  to  the  process   sewer.    The  filter  cake   is  then  removed  and
transported to  a  landfill.    Although the  Fabricolor  facility was  producing
dyes based on benzidine  that are not  covered in this report, filtration might
be required for any azo  dye  because  the  reactions  that result in insoluble  by-
products are  not restricted  to benzidine dyes.

     If  the   above filtering  procedure  were  followed   for  other  diazotized
amines, the water  washing  step would probably  remove  some organic  and  water
soluble material  from the  filter  cake, although  some  may remain  adsorbed  to
the  carbon.   The  materials  that  remain  on this   filter  cake  material  after
water washings  are probably  the by-products  and  the azo decomposition products
(e.g.,  as indicated in the previous  discussion of  dye chemistry, some of  these
by-products may be N-nitrosamines and polyaryls).   If  the washed  filter cake
were removed  without further treatment,  it might be  considered   a  hazardous
material.  The  sodium hypochlorite  solution that  is used  to treat the  filter
cake  at Fabricolor probably  oxidizes  some of  the organics,  but  may  also
produce  soluble   chlorinated   aromatics,   some   of  which  may   have   toxic
qualities.  Only a small amount of residual  organic material  is  expected to be
sorbed to the cake material  after  this treatment.

     Occasionally,   a   clarification   step   is   required  after   a   coupling
reaction.   If  the decontamination  procedure for  the  filter  is  the same  as
described above (washing,  followed by oxidation with hypochlorite),  the  solid
residue produced  may have  little  residual  organic content.   However,  if  the
hypochlorite  oxidation step  is not used, the filter cake material  may contain
insoluble by-products  of the  coupling reactions,  including N-nitrosamines  and
polyaryl compounds.

     The solid  residues  produced by  these  filtering operations  are  expected to
be small, and have not  been quantified.  They should, however,  be  sampled and
chemically analyzed to determine if  they represent  a significant hazard.
Process Wastewater
     Process  wastewater  is  produced  when  reactors  are  cleaned between  dye
syntheses.     This   cleanup  water   would   contain  detergents,   unreacted
intermediates, by-products,  and  dye.   However,  cleanup may not  occur  between
                                       65

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every synthesis,  because   the dyes  are  sometimes produced in a  light-to-dark
sequence, which  would disguise  any carryover  from  uncleaned or  incompletely
cleaned equipment.  Also, for a major dye or pigment, a  train of  equipment  may
be exclusively  used for  that  dye.  Thus cleaning frequency may  be  decreased.
Because  there  was  no information  on cleanup  frequency  and no  data  on  the
chemical  content of  cleanup  waters,  the  loss  of  materials  from  equipment
cleanup was not  quantified  separately,  but  instead was  included  in  an  overall
loss estimate.

     Other  sources  of wastewater  from dye synthesis  include floor  washdown,
laundry,  worker  showers  (Keinath,  1976),  and  blowdown  from scrubbers.    The
amount  of  material  in  the  combined process  wastewater  has  not  been well
determined.  Lapp's  (1979)  estimate  of  a 1% loss based on the  raw  materials
added to  the  process was  used to  estimate  the  loss of intermediates  to  the
process  wastewater.    These  losses  would  be  in  the   form   of   unreacted
intermediates,  by-products,  and  dye.   Because  the final product  is  assumed to
be  50%  inert  salt  for  a  water-soluble dye  and 25%   inert  ingredients  for
pigments, disperse  dyes, and solvent dyes, these  losses  are equivalent  to 0.5%
and  0.75%,  respectively,  based  on final product.   Because  the losses could
occur before  significant  reaction had  occurred or  after completion  of  the
synthesis  or  anywhere  in  between,  it  is  assumed  that  one-third  of   the
intermediates were  lost as intermediates, that  one-third were lost in the form
of by-products,  which include  incomplete  couplings, and  that  one-third were
lost in the form of the  final dye or pigment product.   The one-third share of
these  losses  assigned  to  intermediates  was  divided  by  three  to  obtain  an
estimate  for  individual  intermediates  because  three  is a  typical  number  of
intermediates.    A  more  rigorous  approach  would be  to  choose  the  number  of
intermediates for each class or  dye (i.e.,  two for monoazo,  three for  disazo,
and  so forth) instead of  using the "average"'  of  three.  However,  the emission
factor  is small compared with  other sources of  emission,  and  it was  assumed
that the  above method was satisfactory.

     If  nitrous  acid  treatment  of  the   process   wastewater,   such  as   was
practiced  by  the  Allied  Chemical  Co.  when it  was  producing  benzidine dyes
(Keinath, 1976),  is used, the estimated loss  of intermediates  in the  process
wastewater  is   probably   an  overestimate  of   the   amount   of  the  actual
intermediates,   by-products,  and  dye released  to the process  sewer,  because
chemical  changes  will occur during  treatment.    Nitrous oxide  treatment will
convert amines  to  diazonium salts,  which  will  then  decay to the by-products
discussed in Section 3,  including replacement  of the  amine with hydroxide or
chloride.   Nitrosamines may also  be formed.   The value  may be a  reasonable
estimate  of  the  total  amount  of  organic  material,  however,  because  nitrous
acid  treatment  was  not  reported  to completely  oxidize organics  to C0~  and
water.  Because  the extent to which all manufacturers chemically  treat  process
wastewaters  was  not  known,  chemical  treatment was   not  assumed for   the
industry.   The  overall waste emission estimate for  the entire dye  or  pigment
manufacturing  process  is not  sensitive  to   these  assumptions  because  much
larger losses occur later in the process.
                                       66

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Vapor Losses

     During dye  and  pigment synthesis,  vapor  losses  are expected  to  be  small
because the reaction  temperatures  are low and because the physical properties
of  the  chemical intermediates  for which  data were  found  indicate that  they
have  low  vapor  pressures.   The  vapor pressures  for  intermediates  and  by-
products  for  which no  data were found  are  assumed to  be  low also.   Several
materials  used  during  dye  manufacture do  have significant  vapor pressures
(such as  phosgene, formaldehyde,  pyridine,  and  formamide).   Many  facilities
have vents at  process vessels  that lead to a  scrubbing  system (Keinath,  1979;
DETO, 1980).   Again,  the  scrubber  blowdown  should  be sampled for  these  types
of  chemicals  if  they are  of concern.   The vapor losses of intermediates  were
not  quantified  separately,  but were  combined with  the vapor  losses during
materials handling and  filtration.
PRODUCT FILTRATION

Solid Residues

     The solid residues produced  during  product  filtration  are  dye  solids  that
are  spilled during  transfer of  the press  cake  to  the drying  operation  or
remain  as  a residual in  the filter press.  In  keeping with the estimates  of
Lapp  (1979),  total  losses  of  dye  or  pigment  are  assumed  to be  1%  of  the
organic dye or pigment, which converts to  0.5% on  a  final standardized  product
basis  for  the  water-soluble  dyes  and  0.75%  for  pigments and  solvent  and
disperse  dyes.    Metal  losses  are  estimated as  10%  of  the  dye  or  pigment
losses.   These  solid materials  are assumed  to  be  washed  into  the  process
wastewater  system  so  that product filtration does not  produce  a solid  residue
directly, although solid  residues  may result from  wastewater treatment.
Process Wastewater
     The   major   contributors  to   potential  discharges  of  material   from
filtration  operations  are  the  mother  liquor  and  process  wastewater  from
filtration  equipment washwaters.    The mother liquor  will contain  unreacted
intermediates,  terminated coupling  products, other  by-products  (see  Section
3),  and  dye.    To   calculate  the amounts  of these  materials  that  might  be
present,  we  assumed  that 5%  excess  (molar  basis)  of each  coupling component,
with  respect  to  the   diazo  component,  is  used  during   dye   or  pigment
manufacturing. Five  percent of  the  diazo component  in each coupling  step  is
assumed  to go to  by-products, with terminated  couplings  being the  dominant
species.   Hence,  the yield of  desired product from each coupling  reaction  is
95%, based on the diazo  component.

     The  extent  of   precipitation and  efficiency  of filtration will  determine
the amount of dye remaining  in the  mother liquor.  We  have assumed that 2%  of
a  soluble dye (standardized  dye  product basis) remains  in the mother liquor
because salting out  will  not  make it completely insoluble.   This  is equivalent
to  the  estimates of  l%-3%  made by  Lapp  (1979).   Since pigments and disperse
                                       67

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and solvent dyes are  insoluble  in water, it has been  assumed  that  only  traces
of these compounds remain in the mother  liquor.

     The  average  amount  of standardized  dye  or  pigment  produced per  batch
varies between the subclasses.  The water-soluble  dyes are  produced in batches
of about  23,000 liters,  giving,  on the average, 800 kg  of  filter cake or 1700
kg of  standardized product.   The  water-insoluble compounds  are  produced  in
smaller batches of an average  12,000 liters giving  about  600 kg  of product.
These averages  were  developed from the BIOS (1945)  recipes.   The  amounts  of
each unreacted  intermediate estimated to be  in the mother liquor  (Appendix B
shows the  basis for  this  estimate) are equivalent to 2% of the standardized
water-soluble   dye  products   and  3%  of  the  standardized  water-insoluble
products.     These  amounts  represent  a  residual  concentration  for   each
intermediate in the mother  liquor of  approximately 1500  ppm for either type  of
dye.

     Because  each  coupling is  assumed to  be  only  95% complete,  the  total
amount of  by-product  formed increases with  the number of  coupling  reactions.
The  total amounts  of by-product  estimated  to be formed  when  synthesizing
monoazo, disazo, trisazo,  and  polyazo dyes  and  pigments is shown below.   (The
details of the estimation procedure are  shown in Appendix B.)


            By-Product Concentration  in  the          As  % of Final
           	Mother Liquor (ppm)	 	Standardized Product	
           Monoazo  Disazo  Trisazo   Polyazo  Monoazo  Disazo  Trisazo   Polyazo
Water-
soluble
dyes         1000     3000    5000     10,000     1.5      4      7.5      15

Pigments
or water-
insoluble
dyes         1500     4000    7500     15,000     2       6     11       22
It  is  possible that  many of  the  by-products  will  be  insoluble  or could  be
salted  out  along  with the ' product dye  or pigment  and  that  some  unreacted
intermediates  will also  salt  out  when  product dyes  are  precipitated.   This
means that substantial amounts of these materials  could  be  sold along with the
product.  However,  because no information  was  found to confirm this level  of
contamination, it was assumed that all unreacted intermediates and  by-products
remained soluble  in the mother liquor.   There  is some  justification for  this
assumption since we have  assumed  that,  on a final standardized product basis,
2% of the final dye product remains in solution in the mother liquor.   This  2%
represents a  4000-ppra  concentration of  the organic  dye  molecule,  which  is
probably  the   most  insoluble  material   present.   Each  of  the   unreacted
intermediates  is   present  at  a  level  of  1500 ppm,  and  each  by-product  is
present  at  levels  of  only  1000   ppm  to  2000  ppm.    The  concentration  of
individual by-products was derived from the  concentration  of  total  by-products
                                      68

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by dividing by the  number  of major by-products identified  in  Appendix B.   The
level of intermediates  and  by-products  in the final product vould  then be  due
only to the residual  mother liquor remaining in the filter  cake  before it  was
dried.

     Abrahart (1968)  indicates  that the  residual  water content of the filter
cake is about  10%,  which is about  80 kg  or 0.35% of the total mother  liquor.
2If  an intermediate  were  present  at  1500 ppm  in  the  mother  liquor,   the
residual water in the filter cake would contain 1500 ppm x  80  liters =  0.12  kg
of  the intermediate.  In  the  final  standardized product  dye,  this  0.12  kg
represents about 70 ppm for that intermediate.   In a  similar  manner,  the 5000
ppm  total  of by—products  in the  mother  liquor  of  a  trisazo acid dye would
result in about 230 ppm of by-product in  the final dye  product.   The final  dye
or  pigment  product could  thus  contain a total of  several hundred parts  per
million of unreacted intermediates  and by-products.

     Because the practices  used to prepare  the  metal  complexes of dyes vary,
it  is  difficult  to  quantify  the  amounts   of  metal  that  may be  present  in
process wastewaters from  product   filtration wastes.    Where  the  complex  is
prepared by adding  metal salts  to  the organic filter cake  and then drying  the
reaction mixture,  the only  significant  emissions of  metal  will  parallel  the
emissions of dye,  such  as  spillage of  product  material during transportation
to  the  product  finishing   operation.    Any excess  metal  added  to   promote
complete reaction  will  be  sold  along  with  the product.   When the complex  is
prepared in  the  mother  liquor before precipitation  and filtration, excess  or
unreacted metal salts present in the  mother  liquor would be released  to plant
wastes  along  with  metal   associated  with  dye  that  did not  precipitate.
Additional metal  releases  would occur  along with dye  releases from  residual
filter cake  in  the press and spills  during  transfer to the product finishing
operation.  The  actual  loss of  metal would be  much  higher than when only  the
precipitated dye is metallized.

     To indicate  the  magnitude  of  the  possible  losses,  we have assumed that
all  dyes are  complexed  with metal  in  the mother liquor and thereby generated
high estimates  of  metal emission  for  those dyes that  are  metallized after
precipitation and  filtration.   Based on  the recipes that were available,  for
1:1  metal  complexes,  the organic  part  of  the  molecule for all metal  complex
dyes was  assumed to  have  a  molecular  weight  of  450.   Since chromium has  a
molecular weight of 52   and  copper has  a molecular  weight of  62.5, the metal
is approximately 10%  by weight  of  the pure  dye product  even when the  chloride
anion  is  included  in the  final molecular weight.   For the more complex dyes
with higher molecular weights and  the 1:2 complexes, this  10% would represent
an overestimate.  Since unprecipitated dye  concentrations  in  the  mother liquor
have been  estimated to  be 4000  mg/liter,  the equivalent metal concentrations
would  be  400 ppm.   Under  the  acid conditions  typically  used to  precipitate
metallized dyes  before  filtration, this  level  of  metal would  be soluble  even
if it were not complexed with the  dye molecule.
                                       69

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Vapor Losses

     Vapor  losses  during  filtration would  consist  primarily  of  unreacted
intermediates  and  some   solvents  and  reagents  because  the  dye  or  pigment
product  and  most  of   the  by-products  would  not  have  signifcant   vapor
pressures.  Because all  the intermediates  are  also assumed to have  low  vapor
pressures,  total  vapor  losses  are estimated  to be minimal.  Many  facilities
have  dust  and  vapor  control  systems   that  collect  the  material  lost  from
materials  handling,  dye  synthesis,   and  the  filtration process  (DETO,  1980;
Keinath, 1976) and  process  it  through a scrubber.  Lapp (1979) estimated that
during  the manufacture  of  azo dyes  based  on benzidine, the  total  losses  of
benzidine  and  its congeners to  the  scrubber system  from  materials  handling,
dye  synthesis,  and filtration was  0.25%  of  the  amount  used.    It would  be
reasonable  to  assume  the  same  level of  losses for  each  other  intermediate
used.   Benzidine  dye manufacture should  be  typical of  the whole azo  dye
industry  because  the  same  manufacturing  steps  and  type  of  facilities  are
used.   On the average, each  intermediate  (assuming an   "average"  of  three
intermediates)  represents  approximately 17%  of  the  final  standardized  dye
product so  that the 0.25% loss of  an  ingredient  can be expressed  as  0.04% on a
final  dye  product  basis.   For pigments  and  disperse and  solvent dyes,  this
figure  is  0.08%.  If a plant did  not  have a scrubber  system, dusts  and  vapors
could severely contaminate  the work  place environment before they were washed
into the plant wastewater systems  or  released to  the outside environment.
DRYING, GRINDING, STANDARDIZATION, BLENDING, AND PACKAGING

Solid Residues

     Solid  residues  from  the   final  processing  or  finishing  of  dyes   and
pigments would consist  principally  of  dusts produced during drying,  grinding,
standardization,  blending,  and  packaging.   Most  of  these  dusts  will  be
captured by moving  air  in a vent or hood  system when they are used  and would
then be removed  from  the  air in a baghouse.  Boeniger  (1980)  details the  hood
system at  two facilities  manufacturing  dyes and  pigments  based on  benzidine
and  its  congeners.    Although the hood  systems were  not  adequate to  prevent
some exposure to workers,  they probably did collect most of  the  dust.   Some of
the collected dust  in pigment processing was returned  to the product.

     Lapp  (1979)  estimated that, during the manufacture  of azo dyes  based on
benzidine  and  its  congeners,  l%-5%  of  the  organic  dye  is  lost  during
finishing.  This  can  be expressed as  0.5%-2.5% of the final  standardized dye
product, and  it has been assumed  that  2% is typical.   All  azo  dyes  are assumed
to  have  similar  losses because  the  processing  steps are  nearly  identical.
This material will  be mostly dust collected in  the baghouse  at facilities  that
have good engineering controls.

     For dry  process  azo pigments based on benzidine and its  congeners,  Lapp
(1979) has estimated that  l%-3%  of the final product  is lost during drying and
grinding.     We   assumed   3%  is  lost  to  cover  additional  losses  during
standardization  and blending.    For  pigments   that  are flushed,   losses  were
                                       70

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estimated  by  Lapp to be  l%-3%,  mostly during transfers  between equipment and
containers.   To  be  conservative,  we  assumed  3%.   For  pigment sold  as  press
'cake,  losses  of  product  were  estimated  to  be  1%,  mostly  from  material
transfers.  Most of these  pigment  losses will  probably  become solid residues
that  are  either  collected in  the  baghosue  facilities  or  swept  up  from the
floor.   The  average  solid waste  production  is   2.1%  of  the final  pigment
product, computed as follows:

      (45%  dry processed pigment  x 3%  loss)  + (40%  flushed pigment  x
      3%  loss x 50%  inert) + (15% press cake x  1% loss) = 2.1%.

This  estimate  is  assumed  to hold for  the solvent  and  disperse  dyes since they
are handled in  a similar  manner.  Metal  losses  are estimated to be 10% of the
losses of  the dye or pigment that they are  complexed with.
Vapor Losses

     There   are  potential   vapor  emission   sources   in  dye  and   pigment
finishing.   The drying operation,  which  removes the 10% mother  liquor  in the
filter  press  cake,  could also  volatilize some of the unreacted  intermediates
and  by-products present.   With the exception  of  a  few intermediates  such  as
aniline and ethyl chloride,  these  materials  are known  or assumed  to have vapor
pressures far  less  than that of water.   Therefore,  significant volatilization
of  intermediates,  if  they  were present  on  the dye or  pigment,  would  not  be
expected during drying.  The  second opportunity for  unreacted  intermediates  to
volatilize  occurs  if  materials are carried from process  to  process  in open
tote  boxes.   However,  very little  volatilization is  expected because  of the
low  temperatures.   Some  of the organic  vapors from open  tote boxes will  be
entrained in air entering scrubbers or baghouses operated  to control emissions
at specific processing steps.
      &

     The  solvents  and  chemicals   other  than  intermediates   used  during  dye
manufacture  that are  carried to the drying  step in  the  residual  mother liquor
will  be vaporized with  the water  during the  drying step.   If processed by a
scrubber, the  vapors  will  be collected and  contribute to  contamination of the
process wastewater.   If  processed  through a  baghouse,  the  vapors  will probably
escape  to the  atmosphere.
 SUMMARY OF AQUEOUS AND  SOLID  RESIDUE  DISCHARGE ESTIMATES

     The  estimated  amounts of  intermediates,  by-products,  and dye  or  pigment
 that  are  discharged  by the  various  operations  used in azo  dye and  pigment
 manufacturing  are  summarized in Table  10 for water-soluble dyes  and  Table 11
 for  pigments  and  solvent  and  disperse dyes.    As  was  discussed  in  detail
 previously,  these estimates  are assumed to  be either  typical  or worst  case for
 the industry and have not  taken into  account site-specific  factors such as the
 absence or  presence  of  scrubbers on  process  vents  at  a  particular site.  They
 do  not  include specific  dye or pigment chemistry that might  require  more or
 less  excess  ingredients  than  assumed  or yield  more  or less  by-product;  the
                                       71

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                                                             Table 10
                                   SUMMARY OF THE ESTIMATED AQUEOUS WASTES AND SOLID RESIDUE
                                    PRODUCED BY WATER-SOLUBLE DYE MANUFACTURING OPERATIONS
                          (All losses are reported as a percentage of the weight of the final marketed
                               product that has been standardized by the addition of Inert salts)
                                              Aqueous Wastes
                                                                                                   Solid Residue
Tnter-
Process Step mediates By- Metal
or Operation Dye (each one) Product (as the element)
Raw material handling — a — —
Synthesisc 0.16 0.06 0.16 0.02
Product fiitrationj
Munoazo \ 1.5 \
Dlsazo 1 2.5 2 4 0.25
Trlsazo ( 7.5 (
Polyazo ) 1.5 '
Air pollution
control6 — 0.04 '
Product finishing
Total8 2.7 2.1 b. 0.27

Inter- By- Metal
Dye mediates Product (as the element)
0.05b — 0.05b
__

—
= :: :: ~~
__
3 — — 0.3
3 t o b
 Losses were not quantified separately but are included in air pollution control
'intermediate residue on fiber drums and shipping containers.  The estiroated loss of each intermediate is  this inumber divided by  the
 number of intermediates in the dye.
 Material in wash down of equipment and floors, laundry, and worker showers.
 Material in mother liquor and process wastewaters from washdown of the filter press.
""Scrubber treating vents and hoods associated with raw material handling,  synthesis, and product filtration.
 Dusts from drying anu grinding collected in a baghouse.
8Rounded.
Total depends  on subclass.

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                                                                  Table 11

                                          SUMMAKY OF THE ESTIMATED AQUEOUS WASTE AND SOLID RESIDUE
                                            PRODUCED BY  PIGMENT  AND SOLVENT AND DISPERSE DYE
                                                          MANUFACTURING OPERATIONS

                                  (All losses are reported as a percentage of the final marketed product that
                                              includes inert ingredients such as oil and filler)
                                              Aqueous Wastes
                                                                                                          Solid Residue
Process Step
or Operation
tc
rials handling
Insoluble
Dye or
Pigment
0.24
Inter-
mediates
(each one)
a
0.00
By-
product
0.24
Metal
(as the element)
0.024
Dye
or
Pigment
Inter-
mediates
0.075b
By-
products
—
Metal
(as the eler.\ent)
0.075b
Synthus
Product filtration
  Munonzo
  Oisazo
  Trisazo
  Polyazo
Air pollution control6

Product finishing
(including baghouse)
                            0.75
                                       0.08
                                       3.1
 2
 6
11
22
                                                                    0.075
                                                                    0.1
                                                                                     2.1
                                                                                     2.1
                                                                                                                                  0.21
u|,oM«t:s were not quantified separately, but are  included  In  air pollution control.

  Intermediate  residue on  fiber drums and  shipping containers.   The estimated loss of each  intermediate  is  this number divided by  the
  number of  intermediates  in the dye or pigment.

cMaterial from washdown of equipment and  floors, laundry, and worker showers.  Pigment
  present will probably be suspended rather than dissolved.

  Material in the mother liquor and process wastewater from washdown of the filter press.
  Pigment present will probably be suspended rather than dissolved.
£
 Scrubber treating vents and hoods associated with raw material handling, synthesis, and product filtration.

 Dusts from drying and grinding collected in a baghouse.
gRoundud.
 Total depends on subclass.

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material estimated to be  in  the  aqueous-solid stream is subject  to  wastewater
treatment, as is discussed below.
WASTEWATER TREATMENT

     The  principal  potential  source  of  dye,   by-product,   or  intermediate
release to  the  environment from  dye  manufacturing operations  is  the aqueous
process wastewater stream.  Each  dye  producer may have a different wastewater
treatment  system.    As  discussed  previously,  some  producers use  chemical
reactions  (treatment with  nitrous acid)  to oxidize  the  organic  compounds  in
process  water   generated   by  equipment   washdown,   air  pollution  control
scrubbers,  worker  showers, and  laundry preceding discharge  of material  into
the  plant  sewer  (Keinath,  1976).    Other  producers  discharge  all process
wastewaters directly to sewers and thus to publicly owned treatment works.

     Some   producers  have  on-site   wastewater  treatment  plants   involving
primary,  secondary,  and  tertiary treatment.  These  treatment  plants  will all
be site-specific designs with site-specific behavior.  Games and Hites (1977),
for  example, have  reported plant discharge after  secondary treatment of  2200
kg  of  organics  daily   from  a  South  Carolina  dye manufacturer  using  eleven
million  liters  of  process water  per  day.  The waste before  treatment  had  a
chemical  oxygen  demand  (COD) of  about  670 ppm.   Treatment plant performance
averaged about 70% and 80% reduction of COD and BOD (biological oxygen demand)
to produce  an effluent  with  a COD of 200 ppm and  a BOD  of  60 ppm.    The plant
wastewater   treatment    system   consisted   of   an   equilization    pond,   a
neutralization step, an aerated  lagoon with  a retention time  of  less  than  5
days, and two large settling ponds with a retention time of 19  days.

     Anliker and Clark  (1979) have reported  an effluent concentration before
treatment  from  a dyestuff manufacturer as  900-4000  ppm  BOD  and  600-1000 ppm
total  organic  carbon   (TOG).     Other  documents  (such  as  EPA,  1975)   give
wastewater  flows at  six different dye  manufacturing plants  as 33,   114,  175,
200, 800, and 1800 liters/kg finished product.  Sampling of these wastestreams
gave the  following  ranges: 200-5000  ppm  BOD,  1200-4000  ppm COD,  and 500-2000
ppm TOG.
                                                            /

     Keinath  (1976)  reports  that  typical wastewater  flows (including mother
liquor) are 250-750 liters/kg finished product.  Based on the aqueous emission
levels indicated in  Tables 10  and 11  these wastewater flows might have 25-100
ppm of each unreacted intermediate and 30-100 ppm of  by-products for  a monoazo
dye  and  200-900 ppm of by-products  for  a polyazo  dye.   Dye concentrations
might be 30 to 100 mg/liter,  and if metals were used  their  concentration could
be 3 to 10  mg/liter.  For  example, manufacture of  1 kg of standardized monoazo
dye  is estimated to  release  0.017 kg  of by-products  to the process sewer.   In
250  liters  of  water,   this  material  would  have  a  concentration  of  70
mg/liter.

     A complete  assessment of emissions  to all  media (air, water, and solid)
would  have  to  consider  each  manufacturer's  plant  individually  in  terms  of
plant  operation, wastewater  treatment plant  operation,  and the specific  dyes


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produced.   This  is beyond  the  scope of  the  current  study, which  necessarily
must  neglect  site-specific  factors.     Consequently,   the  behavior  of   the
organics that  might be  present in  wastewaters  is discussed  with respect  to
potential wastewater treatment operations.  We focused on biological  treatment
processes because these will  be present  either at most manufacturing  sites  or
at  the  municipal wastewater  treatment  systems receiving  the wastewater  from
the manufacturing site.

     The behavior of the materials during wastewater treatment is  discussed  in
terms of the following four classes of material thought to be present:

     (1)  Unreacted organic intermediates

     (2)  Product dye

     (3)  Reaction by-products

     (4)  Metals.
Dnreacted Intermediate
     Physical properties  data and biotreatability  information were found for
only a  few  intermediates.   These  data indicated  that  the intermediates have
moderate to high  solubility  in water  and  weak adsorption to organic material
(low K  )•   Therefore, it seems reasonable to assume that these materials will
not  partition  strongly  onto  sludge  during  wastewater  treatment.    Some
compounds,  such as phenol, are readily biodegradable in adapted systems.  Some
of  the  sulfonated  aromatics  are  resistant  to  degradation  (Meyer  et  al.,
1979).    In  this  study,  biodegradation was  assumed not  to  occur  because the
episodic  nature  of   discharges  that  result  from the  batch  nature  of  dye
manufacture   does  not  permit  an  adapted  culture  to  develop.    However,  an
adapted culture may  develop  for  intermediates common to  many different dyes
and pigments such as 8-naphthol, aniline, or phenol.
Product Dye

     The  sources  of  information  on  biodegradation  of dyes   indicated  that
biodegradation of dyes and pigments does  not occur to a significant extent in
aerobic wastewater  treatment  processes.  In particular,  biotreatment systems
were not  found to  acclimate to  dyes  (ADMI, 1973),  and some  systems  may be
inhibited by some dyes (ADMI,  1973).   Brown et al. (1981) have shown that  the
 ADMI (1973), Keinath (1976), DETO (1980), Hitz et al.  (1973), Dieckhues
(1961),  Tincher (1978),  Baird et al. (1977), Porter  (1973), Dubin and Wright
(1975),  Tabak and Barth (1978), Uroshigawa and Yonezawa  (1977), Kappeler  et
al. (1978), Flege (1970),  Idaka et al. (1978), Meyer et  al. (1979), Brown et
al. (1981).
                                      75

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majority  of  dyes tuff  types  (including many  azo dyes)  are not  likely to  be
significantly toxic to aerobic  sewage  treatment processes.  The pigments  are,
in general, not  readily biodegradable  in  aerobic systems  (Anliker and  Clarke,
1979).    Several of  these  studies  also  indicate  that,  at  sewage bacteria
concentrations  typical of wastewater  treatment  facilities,  adsorption would
not be  significant except  for  some  direct  dyes that  have an  affinity  for
bacteria.

     The removal of color from the waste stream occurs when  the soluble  dye is
absorbed on the  bacterial  sludge  or  the insoluble dyes and pigments settle to
the bottom of a nonagitated basin or lagoon.  Because the  dyes are designed to
resist oxidative degradation,  it  is  not  likely  that the aerobic biological
process would have much effect on them.


Reaction By-Products

     Only  a  few  of   the  many  by-products  possible   based  on  theoretical
chemistry may have been identified by  actual  chemical analysis.   As discussed
in Section  3,  the diazotized  amine  may decompose  (the  diazonium group being
replaced  by  a  hydroxide or  chloride).   The  by-products  of more complex  dyes
will  include  these  types  of  compounds  plus  some  coupled products.    N-
nitrosamines may be present in the process wastewater.

     Little information was  found on  the  physical or biological properties  of
these  compounds, so  it  is  difficult  to  determine  how  wastewater  treatment
would  affect  them.   Substantial  rates of biodegradation are  not  expected.
Meyer  (1979) found that, under  aerobic conditions,  the biodegradation rate  of
derivatives of  the simple  azo  compound, phenylazonaphthalene, was affected  by
the  nature  of  the   substituents present  (e.g.,  SC^H  and  COOH).     Double
substitution was found to inhibit  the degradation,  and,  whenever  a sulfonic
acid group was present, the degradation was significantly  reduced in all cases
studied.

     For  this  assessment,  we  have assumed that  by-products  are  only  slowly
biodegraded and  not strongly adsorbed  to  sediment or biological material.  The
previously cited studies have  shown  that  the  dyes themselves are not strongly
sorbed under  the conditions  of  wastewater treatment, so  related but  smaller
molecules are not likely to be either.
Metals
     The  fate  of  the  metals  used to  produce premetallized  dyes  depends  on
their chemical state when they enter the  treatment system.  Metals that  have
not  reacted  with dye molecules,  either because they  were  added in excess  or
because  the metallization  reaction  was  incomplete,  should  be  removed  by
probable   treatment  processes,   including   neutralization  using  lime   and
biological  treatment.    The  metals (Cr,  Co,  Cu,  Ni)  are  soluble  under  acid
conditions, but become insoluble under  moderately  basic conditions.  Chromium,
for example, has a solubility of 4 mg/liter  at pH  7, a higher  solubility  at pH


                                      76

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6, and  a  solubility  of  less  than  0.1  mg/liter  at pH  8 to  9.   Solubility
increases again at pH values above 9 (Patterson and Minear, 1971).  Copper has
its minimum solubility in the pH 9-10 range, whereas for nickel the solubility
minimum is at pH 10.  The insoluble species is the metal hydroxide.  Cobalt  is
assumed to behave similarly to chromium.

     Patterson and  Minear  (1971)  and Hanson  (1979) report  actual treatment
results where metal levels  as high  as  several hundred ppm were reduced  to 1-2
ppm by  lime  neutralization and  settling.   These  results  are not  as  good  as
might be  expected  based  on solubility  because  some  of  the  metal hydroxide
precipitate is colloidal and does not settle well.

     Biological processes remove  metal salts from solution.   Peck and  Gorton
(1977),   and  Vigon  et  al.  (1977)  reviewed  the  behavior  of  heavy  metals   in
activated sludge systems.  Their results indicate that from 50% to 60% removal
of Cu,  Ni, Cu,  and Co might be  expected  in wastewaters  containing ppm  levels
of metal.  The  metals are  adsorbed  on the biological  solids. Two factors are
probably  involved in  this  adsorption.    The sludge  may physically  collect
colloidal  metal  hydroxide  particles  that   are  too   small  to  settle   by
themselves.   There  could  also  be  ionic  interactions  with  constituents   in
bacterial cell walls.

     The  estimates  of waste emissions  from dye manufacture  in this  study  do
not assume that excess metal is added to the reaction mixture.  Therefore, the
3-10 ppm  of metal  estimated to  be in the  plant wastewater is assumed to be  in
the form  of the dye-metal complexes.   The majority of the metallized dyes (by
production volume) are  acid  dyes   that  are  acid  insoluble  but  soluble   in
neutral and basic solutions.  Because these dyes are designed to be colorfast,
which means that  the  dye-metal  complex is strongly bonded to the fiber, it  is
not  believed  that  the  mildly  alkaline   conditions  used for  neutralization
during  wastewater  treatment will free  the metal from the dye-metal complex.
Therefore, neutralization  is  not expected to cause much  metal precipitation
either  as an insoluble  dye-metal complex  or  the insoluble  metal hydroxide.
The  dye-metal complex  is  not  expected  to  adsorb  strongly  to  the  calcium
hydroxide and calcium carbonate sludge produced by neutralization because acid
dyes are designed to bond ionically to positively charged amine groups in wool
protein.  The neutralization sludge particles will most likely have a negative
surface charge.   Even so, the neutralization sludge will probably contain some
dye.    [This   conclusion  is based on  Keinath's  (1976)  observation  that lime
neutralization sludge did  adsorb some of  the  dye intermediate benzidine from
wastewaters and  on Tincher's  (1978) finding  of  acid  azo dyes  on river muds
downstream from carpet mills.]

     Biological treatment is not expected  to  be  effective in removing  metals
in soluble metallized dyes  from wastewater  because biological treatment  is not
effective  in  removing   the dyes  themselves.    However,  as  discussed when
considering biological treatment of dyes,   some adsorption  to  biological  solids
is expected.

     Some of   the  metal complexes  are disperse dyes and pigments.  These would
be present in plant wastewaters as suspended solids  that would be  removed by a
neutralization and settling treatment.
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Summary of Results of Wastewater Treatment

     The previous discussion has shown that the behavior of dye intermediates,
by-products,   dyes,  and  metals  is  incompletely  understood  with  respect  to
biodegradability and sorption  onto solids.  In addition,  even compounds  that
are biodegradable may not be degraded in a wastewater treatment system because
of the episodic nature of discharges due to the batch production of dyes.  The
interval between batches may be  long enough for the bacteria in the system  to
lose  the  ability to  degrade a  particular compound.   Compounds may  also  be
present that  interfere with biodegradation.   As a way of dealing  with  this
uncertainty as  to  treatability of  dye  plant aqueous wastes,  we  have assumed
that biological wastewater treatment is ineffective.  Consequently,  a majority
of the  material released to process sewers is assumed to  be  released to the
environment.   Furthermore,  although it  is  recognized that  some  components  in
the wastewater are more likely to be found on the solids produced by treatment
than  in the  aqueous phase,  all  material  emissions  are considered  to  be in a
joint aqueous-solid phase.   This  assignment actually reflects the expectation
that every chemical in process wastewater  will  be found at some concentration
in both the solid and aqueous phases produced by wastewater treatment.
                                      78

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                                  SECTION  6

                  SOLID RESIDUE AND  AQUEOUS WASTE PRODUCTION
     The amounts of  solid  residue and aqueous wastes  produced by azo dye and
pigment  manufacture  were   estimated  for   each   dye   and  pigment  using  the
methodology  developed in  Section  5.    For  this  analysis,   "solid  residue"
includes  only  the  identifiable  solid  material  associated  with  shipping
container  disposal  and  dye or  pigment fines  collected  in  baghouses.   The
"aqueous waste" is  the estimated amount  of material  in dye  or pigment plant
process  wastewater   before  the  final  wastewater  treatment.    Wastewater
treatment,  which  may  take  place at  the manuafacturing  site  or  a municipal
wastewater treatment  system,  is  assumed to involve sedimentation followed by
biological treatment and final clarification.   These treatments are assumed to
be ineffective  in reducing  the  amount of  each  compound  by  degradation,  but
will  partition the   material  between  wastewater  treatment   solids  and  the
aqueous effluent.   The wastewater treatment solids will probably be disposed
in a  landfill  and  the effluent eventually  discharged  to  surface waters after
treatment.    Because  it  was impossible  to predict what   the  partitioning of
intermediates between the wastewater treatment solids and  the aqueous effluent
would be, each aqueous emission was  considered to be in a  joint "aqueous-solid
waste" stream.

     It  is  important  to realize  that  dyes  and  by-products  may  be  on. the
wastewater" treatment  solids because  if these  solids are placed in a landfill,
they  will  be  in an  anaerobic  environment  where  reductive reactions  can take
place.   Diekhues   (1961)  found,   for  a variety  of azo dyes,  that reductive
splitting of  the azo  linkage occurred.   This  means that the dye intermediates
could be released  in a landfill even  from  dye wastes  that did not originally
contain these materials in a free state.

     Table  12  summarizes   the   estimated  emissions  of dye  or  pigment,
intermediates,  and   by-products  for   azo  dyes  and  pigments   where  the
intermediates  could  be  identified  from  information  in  Colour  ladex  (The
Society  of  Dyers  and  Colourists,  1980).    For  the dyes and  pigments without
C.I.   numbers,  the  emissions  could not be estimated because the intermediates
are not  identified.   The dyes  and  pigments  in  the table  are  listed by C.I.
number.   Table 13  lists the  chemical name  for  the  intermediates  with  the
common names  shown  in Table 12.   Letter codes  (defined in Table 14) indicate
the producers for  each dye or pigment.  Tables 15 through  19 list the dyes and
pigments that  each  producer makes.   The identity  and corporate ownership of
the producers  is  based on  1978  information.   Siace it was compiled, several
dye  production facilities  or  dye  lines  have  been  sold.   Sales  that  were
announced in trade journals  are shown as footnotes  in  Table 14.  A  systematic


                                      79

-------
search was  not  made to  verify  that all  such sales have  been listed, so  the
table may not be complete.

     The amount of  each  of  the  intermediates in the solid residue  or  aqueous-
solid waste  stream  was  obtained by multiplying  the dye or pigment  production
value from  Table  1  by  the  emission  factors  in Table  10  or Table  11.    For
example, for  Disperse  Orange 3 (which  is  the  second  dye in  Table 12),  the
solid residue due  to materials  handling  of  each intermediate was  obtained by
multiplying the production  value of 21.4 metric tons for the standardized  dye
product  by  the emission  factor 0.075%  to  obtain  the estimate  of 16 kg/yr.
This value was then divided by the number of  intermediates (2) to give  8  kg/yr
as  the  amount  of  each  of the intermediates  aniline and p-nitroanitine in  the
solid residue stream.   This procedure was  followed for each dye and  pigment.
Each organic  intermediate  and metal salt was counted,  but phosgene and  ethyl
chloride were  not  because  of their  low  molecular  weight  contribution to  the
final  dye  product.   For  dyes and  pigments  where  production  levels  were
reported in  public  sources only as  greater  than some  lower  limit, the  lower
limit  was  used because  there  was  no  way  to estimate  the  actual amount
produced.

     The  esterifying  components  and  condensation  components   used  in  the
production of several dyes  do not become part  of  the  dye  molecule via an  azo
linkage.   For  these components  it  is   assumed that  no  excess  reactant  is
required.  When these were solids,  the only significant losses were  assumed to
be  the solid residue from materials handling.

     The  estimated   discharges  of  each  intermediate   from  specific  dye  and
pigment  manufacturing  were  summed  to   indicate   the  total amount,  on   an
industry-wide basis  for  the azo dyes  and pigments  covered  in this study,  of
each intermediate  estimated to  be  in solid  residue  and in the aqueous-solid
waste   streams.     These   industry-wide   emission   estimates   (for   those
intermediates with  estimates greater  than  50  kg/yr)  are shown  in Table  20,
listed in the order of the amount estimated to be in the solid residue.   These
industry-wide estimates could overstate  the emissions of some intermediates if
industry practice  is different  from  the assumptions  developed  in Section  5.
The  estimates  also  probably understate  the emissions  for  the intermediates
used  in azo  dyes   and  pigments where   only  the  lower production  limit  was
known.   It  is possible  that  if  actual  production  values were known for  these
dyes and pigments   and  used to   estimate emissions, some  of  the intermediate
emissions now judged to be minor could become more  important.

     Based  on  the   estimates  in Table 12,  the  industry-wide  total amount  of
identified organic  intermediates in the  solid residue from the manufacture of
the  azo dyes  and  pigments  covered  in  this study  is  15.6  mt/yr.  The  total
amount of dye or pigment  in the solid residue (obtained by summing  the values
for  each dye and  pigment  in Table  12)   is  estimated to be  550 mt/yr,  which
makes the dyes  and  pigments themselves  the  more significant  synthetic  organic
component of the total solid residue stream.  The total amount,  industry-wide,
of  intermediates  estimated  to  be  in the  aqueous-solid waste  is   650 mt/yr.
This aqueous-solid  waste is also  estimated  to  contain  330  mt/yr of dyes  and
pigments  and 640  mt/yr  of  reaction  by-products.   It  is  interesting  to  note
                                       80

-------
that if  only  2.5% of  the  intermediates estimated  to  be in the  aqueous-solid
stream were actually adsorbed on wastewater treatment solids,  then the  amount
of  intermediates  estimated to  be  in the  solid residue from  dye and pigment
manufacture would double.  In a similar manner, if only  10% of the by-products
were to  be adsorbed  on wastewater  treatment  solids then  these by-products
would be a  significant  fraction of the  synthetic  organic  chemicals contained
in the solid residue stream.

     The intermediates  in  Table 20 with the largest  estimated  emissions  are
mostly associated with the  dyes and pigments that  are produced in the largest
volume.  The  ten largest volume dyes and  pigments  are produced by an average
of  ten  companies.   Thus these  intermediates should  not be site-specific  and
should   be   detectable  at  most   major   production   facilities.     Several
intermediates,  such as  2-amino-l-naphthalene  sulfonic acid  and  6-amino-m-
toluene  sulfonic  acid,  may be  used in  only one  major dye or  pigment;  thus
their release may be periodic.   However,  2-naphthol  is  used  in many dyes  and
pigments and  it  should be  detectable  in the process  wastewaters on a  nearly
continuous   basis.    2-Naphthol  and  3-hydroxy-2-naphthoic acid  account   for
nearly 50% of the combined  intermediates estimated  to be in the aqueous-solid
waste and thus should be present at levels below 100 ppm in the total combined
wastewater before wastewater treatment.
                                      81

-------
                                                   Table 12
                     ESTIMATED WASTES PRODUCED IN MANUFACTURING AZO DYES AND PIGMENTS OTHER
                                THAN THOSE BASED ON BENZIDINE AND ITS CONGENERS
        'riuliifor
     HSH
   C.I,
	No.

11000
      Dye
Solvent Yellow 1
    Annual
  Production
metric tons/yr

  >2.3
     Material Released
       to Environment
Solvent Yellow 1
Aniline
                                                                                                  Quantity Releasedc
                                                                                                        (kg/yr)
Solid
Residue
 48
  1.7
Vtaste-
water
                                                                                                                  23
                                                                 By-products
                                                                                                51
     AC
     ALT
     ATL
     TRC
11005      Disperse Orange 3
           Solvent Orange 9
                     21.4
CO
                 Disperse Orange
                 p-Nitroaniline
                 Aniline

                 By-products
                              450
                                8
                  214

                  660

                  470
     ACY
11014
Basic Red 30
  >2.3
Basic Red 30                   69
2-Amino-N-methypyridinium       0.6
Salt                            0.6
Aniline
By-products                     0
                   61

                   48

                   39
     aAn entry of — means that none of this material is estimated to be
      released to the waste water.
      An entry of 0  means that only traces of this material are estimated
      to be released to the solid waste.

-------
                                     Table 12 (Continued)
                                                                                             Quantity Released
                                               Annual
C.I.
Producer No.
ACY 11021
PSC


ACY 11043



Production Material Released
Dye metric tons/yr to Environment
Solvent Yellow 56 >4.5 Solvent Yellow 56
Aniline
N, N-Diethylaniline
By- products
Basic Violet 18 >2.3 Basic Violet 18
2-Amino-N-me thylpyr idinium
Salt
N,N-Dimethylaniline
By-products
Solid
Residue
94
1.7
1.7
0
69
0.6
0.6

0
Waste.
water
45
—
140
99
61
48

39
ACY
BAS
GAP
11052
Basic Blue 54
>6.8
hThe dye  is  sold  as  the  quatenary  ammonium methosulfate,
 sii! fate  intermediate was made.
  Basic Blue 54                 204              180
  2-Amino-6-methoxy-3-methyl-     1.7             —
    benzothiazole
  N,N-Dimethylaniline             1.7            143
  Methyl sulfateb

  By-products                      0              116

No estimation of the quantity of the methy]

-------
                                             Table 12  (Continued)
                                                Annual
                                                                                Quantity Released
                                                                                     (kg/yr)
C.I.
Producer No .
TRC 11055




HUP 11056

Production Material Released
Dye metric tons/yr to Environment
Basic Red 22 >2.3 Basic Red 22
5-Mino-l, 4-dimethyl-lH-
1,2,4-triazole
NfN-Dimethylaniline
By-products
Basic Orange 24 >2.3 Basic Orange 24
(p-Aminobenzoylmethyl)
Solid
Residue
69
0.6

0.6
0
69
0.6
Waste-
water
61
—

48
39
61
—
OO
-P-
                                                  trimethylammonium chloride
                                               3-(N-Methylanilino)
                                                  propionitrile

                                               By-products
                                                                                              0.6
                                                                                      48
                                                                                                               39
   DUP
   IIST
   VPC
11077
Disperse Blue 165    >6.8
Disperse Blue 165              143
2-Amino-5-nitro-iso-             2.6
  phthalonitrile
m-Diethylaminoacetanilide        2.6

By-products                      0
 68


211

150
   15 AS
   A 1,1'
   KKT
   MAY
           Disperse Blue 79
                                               1284
                                    Disperse Blue 79              27000
                                    2-Bromo-4,6-dinitroaniline      480
                                    m-Diethanolamino-p-methoxy-
                                      acetanilide                   480

                                    By-products                       0
                                              12840


                                              39800

                                              28200

-------
                                              Table  12  (Continued)
                                                Annual
                                                                                Quantity Released
                                                                                     (kg/yr)
C.I.
Producer No. Dye
ATL 11085 Basic Red 18
WAS
DUP
CAP
VPC
Production Material Released
metric tons/yr to Environment
147.3 Basic Red 18
2-Chloro-4-nitroaniline
[ 2- (N-ethylanilino) ethyl]
trimethyl ammonium salt
Solid
Residue
4420
37
37
Waste-
water
3980
—
3090
                                                             By-products
                                                                                              2500
   DUP
GO
Ln
11087
Basic Yellow 15
>2.3
Basic Yellow 15                 69
(p-Aminobenzoylmethyl)           0-6
  trimethylammonium chloride
3~(2-Chloroanilino)              0.6
  propionitrile

By-products                    0
61
                                                                                                              48
                                                                                                              39
              11100
           Disperse Orange 5    >4.5
                                    Disperse Orange 5             95
                                    2,6-Dichloro-4-nitroaniline    1.7
                                    2-(N-Methylanilino)ethanol     1.7

                                    By-products                    0
                                                                45

                                                               140

                                                                99

-------
   AC   EKT
   ALT  GAF
   ATL  HSH
   BAS  TRC
   DUP
  ATL
  BAS
  GAF
CO
o\
  BAS
  TRC
                                              Table 12 (Continued)
                                                Annual
                                                                                 Quantity Released
                                                                                      (kg/yr)
                 C.T
   I'riuliieer      No.
11110
11115
11116

Dye
Disperse Red 1

Disperse Red 13


Disperse Red 73

Production Material Released
metric tons/yr to Environment
174.1 Disperse Red 1
p-Nitroaniline
2- (N-Ethylanilino) ethanol
By-products
>6.8 Disperse Red 13
2-Chloro-4-nitroaniline
2- (N-Ethylanilino) ethanol
: By-products
>4.5 Disperse Red 73
2-Amino-5-Nitrobenzonitrile
3- (N-Ethylanilino)
Solid
Residue
3660
66
66
0
143
2.5
2.5
0
95
1.7
1.7
Waste-
water
1740
5400
3830
68
211
150
45
140
                                                                propionitrile
                                                              By-products
                                                                                                  99

-------
                                           Table 12  (Continued)
                                              Annual
                                                                                Quantity Released
                                                                                     (kg/yr)
ATI,
FAB
TRC
AC
11119
           11150
Production
Dye metric tons/yr
Disperse Red 90 >2.3




Disperse Orange 30 >6.8


Material Released
to Environment
Disperse Red 90
2-Amino-5-nitrobenzonitrile
3-(N-2-Cyanoethylanilino)
propionic acid methylester
By-products
Disperse Orange 30
2 , 6-Dichloro-4-nitroaniline
3-(N-2-Hydroxyethylanilino)
Solid
Residue
48
0.8
0.8

0
143
2.6
2.6
Waste-
water
23
—
71

51
68
—
211
propionitrile, acetate ester

Disperse Red 54 >4.5





Disperse Red 7 >2.3

By-products
Disperse Red 54
2-Chloro-4-nitro-aniline
3- (N-2-Hydroxyethyl-
anilino) -propionitrile ,
acetate ester
By-products
Disperse Red 7
p-Nitroaniline
2 . 2x-(m-Chlorophenylimino)
0
95
1.7
1.7


0
48
0.8
0 .8
150
45
' 	
140


99
23
71
                                                             diethanol
                                                           By-products
                                                                                                            51

-------
                                              Table 12 (Continued)
oo
00
                                                Annual
                                                                               Quantity Released
                                                                                    (kg/yr)
C.I.
Producer No.
AC 11152
ALT
ATL
BUG
IIST
ICT
SDC
TRC
HAS 11154
TRC
Production Material Released
Dye metric tons/yr to Environment
Disperse Brown 1 18.2 Disperse Brown 1
2 , 6-Dichloro-4-nitroaniline
2 , 2 '- (m-Chlorophenylimirio)
diethanol



By-products
Basic Blue 41 >4.5 Basic Blue 41
2-Amino-6-methoxy-3-methyl-
Solid
Residue
382
6.8
6.8




o.
135
1.1
Waste-
vjater
182
—
564




400
120
—
                                                 benzothiazole
                                               N-methyl-N-(2,3-dimethoxy-
                                                 propyl) aniline

                                               By-products
                                                                                              1.1
                                                                                     95
                                                                                                              77
   PSC
11160
Solvent Yellow 3
Solvent Yellow 3
o-Toluidine
290
 11
140
                                                              By-products
                                                                                              314

-------
Table 12 (Continued)
  Annual
Quantity Released
     (kg/yr)
C.T.
Producer No.
AC 11210
ALT
BAS
EKT
GAP
TRC
AC 11215
ALT
HSU

ALT 11227
DUP
EKT
TRC
VPC
Production Material Released
Dye metric tons/yr to Environment
Disperse Red 17 77.3 Disperse Red 17
P-Nitroaniline
2 , 2 '- (m-Tolylimino) diethanol


By-products
Disperse Red 5 36.4 Disperse Red 5
Solvent Red 117 2-Chloro-4-nitroaniline
2 , 2' -(m-Tolylimino)diethanol
By-products
Disperse Orange 25 325.5 Disperse Orange 25
p-Nitroaniline
3- (N-Ethylanilino)-
propionitrile

Solid
Residue
1620
29
29


0
764
14
14
0
6840
122
122


Waste-
water
77
—
2400


1700
364
—
1130
800
3260

10100


                By-products
              7160

-------
                                           Table 12 (Continued)
 'r mincer
  C.I.
  No.
io_.	Dye
AC
ALT
HKT
TRC
11228
ACY
ATL
BAS
DUP
GAP
PSC
TRC

ACY
GAF
PSC
TRC
11270
11270:1
11320
11320:1
       Disperse Red 65
       Basic Orange 2
       Solvent Orange 3
       Basic Orange 1
       Solvent Orange 4
    Annual
          p
  Production
metric tons/yr


    104.5
    283.6
    94.1
                                                                                           Quantity Released
                                                                                                 (kg/yr)
Material Released
to Environment
Disperse Red 65
2-Chloro-4- nitroaniline
3- (N-Ethyl-m-toluidino) -
propionitrile
By-products
Basic Orange 2
Aniline
m-Phenylenediamine
By-products
Basic Orange 1
Aniline
Toluene-2,4-diamlne
Solid
Residue
2190
36
36
0
8510
71
71
0
2820
24
24
Waste_
water
1050
3240
2300
7650
5960
4820
2540
1980
                                                           By-products
                                                                                             1600

-------
                           Table 12 (Continued)
                             Annual
                                  Quantity Released
                                        (kg/yr)
C.I.
Producer No.
AC 11365



BAS 11460



ACY 11480
HAS
Production Material Released
Dye metric tons/yr to Environment
Disperse Black 1 >5 Disperse Black 1
p-Nitroaniline
1-Naphthylaraine
By-products
Basic Red 29 >5 Basic Red 29
2-Amino-3-methylthiazole
l-Methyl-2-phenyl-lH-indole
1 By-products
Basic Yellow 24 >4.5 Basic Yellow 24
2-Amino-3-methylbenzo-
Solid
Residue
100
1.8
1.8
0
150
1.2
1.2
0
135
1.1
Waste-
water
50
—
150
110
130
—
100
90
120
—
                                             thiazol .
                                           l,2,3-Trimethyl-2H-
                                             benzimidazole
                                           Methyl sulfate?

                                           By-products
                                  1.1
95
                                                 190
.'is L!K' .'|ual:ernory ammonium mcthosulfate.
ui Lu waa made.
No estimation of the quantity  of  the  nethyj

-------
                                    Table 12 (Continued)
                C.I
  Producer      No.
                        Dye
UPC
KCW
       11660
HPC
       11670
AMS
DUP
CLX
HPC
use
1IRC
HSU
HST
KCW
KON
S
SDH
SNA
       11680
                       Annual
                     Production
                   metric tons/yr
Pigment Yellow 5   >0.9
Pigment Yellow 6   >0.5
Pigment Yellow 1   199.5
                                    By-products
                                                                                             Quantity  Released
                                                                                                   (kg/yr)
Material Released
to Environment
Pigment Yellow 5
o-Nitroaniline
Acetoacetanilide
By-products
Pigment Yellow 6
4-Chloro-2-nitroaniline
Acetoacetanilide
By-products
Pigment Yellow 1
2-Nitro-p-toluidine
Acetoace tanilide
Solid
Residue
19
0.4
0.4
0
10
0.2
0.2
0
4190
75
75
Waste-
water
9
28
20
5
15
11
2000
6180
4390

-------
                                    Table 12 (Continued)
  Producer
          C.I,
          No.
                 Dye
                       Annual
                     Production
                   metric tons/yr
     Material Released
       to Environment
   Quantity Released
	    (kg/yr)	
Solid            Waste-
Residue          water
BNS
UPC
1IRC
1ISC
HSU
HST
K.CW
K.ON
11710
Pigment Yellow 3   66.4
Pigment Yellow 3
4-Chloro-2-nitroaniline
o-Chloroacetoacetanilide

By-products
1390
  25
  25

   0
 664

2060

1460
HST
       11720
           Pigment Yellow 9   >0.5
                                    Pigment Yellow 9
                                    2-Nitro-p-toluidine
                                    o-Acetoacetotoluidide

                                    By-products
                                10
                                 0.2
                                 0.2

                                 0
                    5

                   15

                   11
HRC
KCW
       11725
           Pigment Orange 1   >0.9
                                    Pigment Orange 1
                                    2-Nitro-p-anisidine
                                    o-Acetoacetotoluidide

                                    By-products
                                19
                                 0-4
                                 0.4

                                 0
                     9

                    28

                    20

-------
Table 12 (Continued)
           Annual
Quantity Released
     (kg/yr)
C.T. Production Material Released
Producer No. Dye metric tons/yr to Environment
KCW 11727 Pigment Yellow 98 >0.5 Pigment Yellow 98
4-Chloro-2-nitroaniline
4-Chloro-o-acetoaceto-
toluidide
By-products
KCW 11730 Pigment Yellow 2 i>0.5 Pigment Yellow 2
4-Chloro-2-nitroaniline
2 , 4-Acetoacetoxylidide
By-products
IIPC 11738 Pigment Yellow 73 245.5 Pigment Yellow 73
HRC 4-Chloro-2-nitroaniline
HSU o-Acetoacetanisidide
HST
SNA By-products
Solid
Residue
10
2
2

0
10
0.2
0.2
0
5160
92
92

0
Waste-
water
5
15

11
5
15
11
2455
7610

5400

-------
                                     Table 12 (Continued)
                C.I
   Producer      No.
11RC
HSU
SNA
11740
                 Dye
                       Annual
                     Production
                   metric tons/yr
Pigment Yellow 65  >50
DUP  HSU
GLX  HST
HPC  SDH
HRC  SNA
HSC  VPC
11741
Pigment Yellow 74  588.2
                                               By-products
                                                                                             Quantity Released
                                                                                                  (kg/yr)
Material Released
to Environment
Pigment Yellow 65
2-Nitro-p-anisidine
o-Acetoacetanisidide
By-products
Pigment Yellow Ik
4-Nitro-o-anisidine
o-Acetoacetanisidide
Solid
Residue
1050
18
18
0
12400
220
220
Waste.
water
500
1550
1100
5880
18200
                                                                                  12900
             11765
           Pigment Yellow 49  >0.5
                                    Pigment Yellow 49               10
                                    4-Chloro-o-toluidine             0.2
                                    4'-Chloro-2',5'-dimethoxy-       0.2
                                      acetoacetanilide
 5

15
                                                            By-products
                                                                                                1]

-------
                                     Table 12 (Continued)
   Producer
HST
II PC
AC
ALT
EKT
HSU
TRC
                                                Annual
                                 Quantity Released
                                       (kg/yr)
C.I.
No.
11767


11770


11855
Production Material Released
Dye metric tons/yr to Environment
Pigment Yellow 97 >0.5 Pigment Yellow 97
4-Amino-2,5-dimethoxybenzene-
sulfonanilide
4 ' -Chloro-2 ' , 5 ' -diiuethoxy-
acetoacetanilide
By-products
Pigment Yellow 75 >0.5 Pigment Yellow 75
4-Chloro-2-nitroaniline
p-Acetoacetophenetidide
By-products
Disperse Yellow 3 >95 Disperse Yellow 3
Solvent Yellow 77 p-Aminoacetanilide
p-Cresol
Solid
Residue
10
0.2
0.2
0
10
0.2
0.2
0
2000
36
36
Waste.
water
5
15
11
5
15
11
950
2900
By-products
2100

-------
                                     Table 12 (Continued)
  Producer
ACY
A'J'L
DUP
PSC
VPC
11 PC
KCW
UI1L
CCY
HSU
SDH
KCW
Quantity Released

C.I.
No.
12055



12060



12070


Annual
Production Material Released
Dye metric tons/yr to Environment
Solvent Yellow 14 173.2 Solvent Yellow 14
Aniline
2-Naphthol
By-products
Pigment Orange 2 >5 Pigment Orange 2
o-Nitroaniline
2-Naphthol
By-products
Pigment Red 1 >2 . 7 Pigment Red I
p-Nitroaniline
2-Naphthol
(kg/yr)
Solid
Residue
3640
65
65
0
100
1.8
1.8
0
57
1
1

Waste-
Water
1730
—
5370
3810
50
—
150
110
27
—
84
                                                              By-products
59

-------
                                             Table 12  (Continued)
                                               Annual
                                                                                Quantity Released
                                                                                     (kg/yr)
C.I. Production
Producer No . Dye Metric • tons/yr
ACY 12075 Pigment Orange 5 309.1
UPC
use
HSU
HST
SDH
SNA
Material Released
to Environment
Pigment Orange 5
2 , 4-Dinitroaniline
2-Naphthol

By-products


Solid
Residue
6490
116
116

0


Waste-
water
3090
—
9580

6800


   ACY
   AMS
^  UPC
00  11SC
   RON
   MRX
   SDH
   UIIL
             12085
           Pigment Red 4
                   49.5
                 Pigment Red 4
                 2-Chloro-4-nitroaniline
                 2-Naphthol

                 By-products
1040
18
18
0
495
—
1530
1090
UUP
1IS1I
KCW
RON
12090
Pigment Red 6
10.5
                                                                Pigment Red 6                 220
                                                                4-Chloro-2-nitroaniline         4
                                                                2-Naphthol                      4

                                                                By-products                     0
                                                                                               105

                                                                                               325

                                                                                               231

-------
                                             Table 12 (Continued)
                C.I,
   1 r 1 1 1 li i ( • cr
PSC
             12100
                                                                                              Quantity  Released
Annual
Production
Dye metric tons/yr
Solvent Orange 2 >2.3




Material Released
to Environment
Solvent Orange 2
o-Toluidine
2-Naphthol
Rv-oroducts
(kg/
Solid
Residue
48
0.8
0.8
0
yr)
Waste-
water
23
—
71
5
ACY  KCW
C1K  KON
UUP  MKX
UPC  SDH
I1SC  SNA
IIS1I  UUL
             12120
Pigment Red 3
485.9
Pigment Red 3
2-Nitro-p-toluidine
2-Naphthol

By-products
10200
  182
  182

    0
 4859

15100

10700
ACY
A'I'L
PSC
             12140
Solvent Orange 7   >6.8
                 Solvent Orange
                 2,4-Xylidine
                 2-Naphthol

                 By-products
                               140-
                                 2.6
                                 2.6

                                 0
                    68

                   210

                   150

-------
                                              Table 12  (Continued)
                 C.T,

   Producer      No.
 1'SC
 BCC
o
o
12150
12156
                                                 Annual
                                                                                 Quantity Released

                                                                                      (kg/yr)
Dye
Solvent Red 1

Solvent Red 80

Production Material Released
metric tons/yr to Environment
>2.3 Solvent Red 1
o-Anisidine
2-Naphthol
By-products
>2.3 Solvent Red 80
2 , 5-Dime thoxyaniline
2-Naphthol
By-products
Solid
Residue
48
0-8
0.8
0
48
0-8
0.8
0
Waste-
water
23
71
51
23
71
51

-------
Table 12 (Continued)
  Annual
Quantity Released
     (kg/yr)
C.I.
Producer No. Dye
BNS 12300 Pigment Red 21



HPC 12310 Pigment Red 2
IIRC
HSU
KCW
S
ACY 12315 Pigment Red 22
nut'
GLX
UPC
KCW
MRX
SNA
Production Material Released
metric tons/yr to Environment
>5 Pigment Red 21
o-Chloroaniline
3-Hydroxy-2-naphthanilide
By-products
23.2 Pigment Red 2
2 , 5-Dichloroaniline
3-Hydroxy-2-naphthanilide

By-products
35.5 Pigment Red 22
5-Nitro-o-toluidine
3-Hydroxy-2-naphthanilide

By-products


Solid
Residue
100
1.8
1.8
0
487
8.5
8.5

0
745
14
14.

0


Waste-
water
50
—
150
110
232
—
719.

510
355
—
1100

781

•

-------
                                                Table 12 (Continued)
                                                   Annual
                                                                                Quantity Released
                                                                                      (kg/yr)
o
ho

I1
CLX
INI)


ACY
BUG
1)1 IP
GLX
11 PC
1ISI1
C.I.
rinliK'er No. Dye
12320 Pigment Red 32



INI) 12355 Pigment Red 23
KCW
ROM
SDH
UIIL

Production Material Released
metric tons/y'r to Environment
>0.9 Pigment Red 32
3-Amino-p-anisanilide
3-Hydroxy-2-naphthanilide
By-products
200.0 Pigment Red 23
5-Nitro-o-anisidine
3-Hydroxy-3'-nitro-2-naphth-
anilide

i By-products
Solid
Residue
19
0.4
0.4
0
4200
75
75


0
Waste-
water
9
—
28
20
2000
—
6200


4400
   ROM
   SIM!
12360
Pigment Red 31
>0.9
Pigment Red 31                  19
3-Amino-p-anisanilide            d.4
3-Hydroxy-3'-nitro-2-naphth-
  anilide                        0.4

By-products                      0
                                                                                                                 28

                                                                                                                 20

-------
                                             Table 12 (Continued)
                C. I.
                              Dye
                                  Annual
                                Production
                              metric tons/yr
HST
12367
Pigment Orange 38  >0.5
                                         Material Released
                                           to Environment
                                                  Quantity Released
                                               	(kg/yr)	
                                               Solid            Waste-
                                               Residue          water
                 Pigment Orange 38
                 3-Amino-4-chlorobenzamide
                 4"-Acetamido-3-hydroxy-2-
                   naphthanilide

                 By-products
                                10
                                 0.2
                                 0.2
                                                                                                              15
                                                                                                              11
IIIJC
HST
12370
Pigment Red 112    >0.9
                 Pigment Red 112
                 2 , 4 , 5-Trichloroaniline
                 3-Hydroxy-2-naphtho-o-
                   toluidide
                                19
                                 0.4
                                 0.4
                   9

                  28
                                                            By-products
                                                                                                20
ACY
BNS
UPC
ICC
ROM
SNA
DHL
12390
Pigment Red 17
41.4
Pigment Red 17
5-Nitro-o-toluidine
3-Hydroxy-2-naphtho-o-
  toluidide
By-products
870
 16
 16

  0
 414

1280

 911

-------
                                             Table 12 (Continued)
                                               Annual
                                                              naphtho-o-toluidide

                                                            By-products
                                                                                Quantity Released
                                                                                     (kg/yr)
C.I.
Producer No. Dye
UPC 12395 Pigment Red 13
KCW



HST 12420 Pigment Red 7
S

Production Material Released
metric tons/yr to Environment
>0.9 Pigment Red 13
2-Nitro-p-toluidine
3-Hydroxy-2-naphtho-o-
toluidide
By-products
>0.9 Pigment Red 7
4-Chloro-o-toluidine
4 ' -Chloro-3-hydroxy-2-
Solid
Residue
19
0.4
0.4

0
19
0.4
0.4
Waste-
water
9
—
28

20
9
—
28
                                                                                                20
UPC
HST
MKX
12460
Pigment Red 9
Pigment Red 9
2,5-Dichloroaniline
3-Hydroxy-2-naphth-o-
  anisidide
210
  3.8
  3.8
100

310
                                                            By-products
                                                                                               220

-------
                                              Table 12  (Continued)
                                                                                              Quantity  Released
                                                Annual
C.I.
I'roiliiocr No.
11ST 12465


1IST 12467
Production Material Released
Dye metric tons/yr to Environment
Pigment Red 15 >0.5 Pigment Red 15
4-Chloro-2-nitroaniline
3-Hydroxy-2-naphth-o-
anisidide
By-products
Pigment Red 188 >0.5 Pigment Red 188
2-Amino-4-(2,5-dichloro-
Solid
Residue
10.
0.2
0.2
0
10
0.2
Waste-
water
5
15
11
5
O
Ln
                                                 phenylcarbamoyl)  benzoic
                                                 acid, methyl ester
                                               3-Hydroxy-2-naphtho-o-
                                                 anisidide

                                               By-products
                                                                                              0.2
                                                                                     15
                                                                                                              11
HST
S
12475
Pigment Red 170    >0.9
Pigment Red 170
p-Aminobenzamide
3-Hydroxy-2-naphtho-o-
  phenetidide
19
 0.4
 0.4
 9

28
                                                            By-products
                                                                                                20

-------
                                             Table 12 (Continued)
  Producer
DUP
                                               Annual
                                                              phenetidide

                                                            By-products
                                                                                Quantity Released
                                                                                     (kg/yr)
C.I.
No.
12476

Production
Dye
Disperse Red 220

metric
>2.3

tons/yr


Material Released
to Environment
Disperse Red 220
4-Chloro-o-toluidine
3-Hydroxy-2-naphtho-o-
Solid
Residue
48
0.8
0.8
Waste-
water
23
71
                                                                                                51
             12480
           Pigment Brown 1    >0.5
                                    Pigment Brown 1
                                    2 j5-Dichloroaniline
                                    3-Hydroxy-2',5"-dimethoxy-2-
                                      naphthanilide

                                    By-products
                                10
                                 0.2
                                 0.2
  5

 15


 11
IIST
12485
Pigment Red 146    >5
Pigment Red 146                100
3-Amino-p-anisanilide            1.8
4'-Chloro-3-hydroxy-2',5'-       1.8
  dimethoxy-2-naphthanilide
 50

150
                                                            By-products
                                                                                               110

-------
                                              Table 12  (Continued)
                                                Annual
  I'nuluccr
GAP
CLX
UPC
HSU
ROM
S
                                 Quantity Released
                                      (kg/yr)
C.I.
No.
90
Dye
Pigment Red 5
Production
metric tons/yr
25.9
Material Released
to Environment
Pigment Red 5
NfN-Diethyl-4-tnethoxy-
Solid
Residue
544
9.7
Waste-
water
259
  metanilamide
5'-Chloro-3-hydroxy-2',4'-
  dimethoxy-2-naph than Hide

By-products
9.7
803
                                                                                                             570

-------
                                    Table 12  (Continued)
                                     Annual
Quantity Released
     (kg/yr)
C.I.
Producer No.
PSC 12700



1ISII 12705
RON

D
o
HAS 12715


Production Material Released
Dye metric tons/yr to Environment
Solvent Yellow 16 >2.3 Solvent Yellow 16
Aniline
3-Methyl-l-phenyl-5-pyrazolone
By-products
Pigment Yellow 60 >0.9 Pigment Yellow 60
o-Ch lor oani line
3-Me thyl-l-phenyl-5-pyrazolone
By-products
Solvent Red 8 >2.3 Solvent Red 8
2-Amino-5-nitrophenol
3-Me thyl-l-phenyl-5-pyrazolone
+3
Chromium (Cr )
Solid
Residue
48
0.8
0.8
0
19
0.4
0.4
0
48
0.6
0.6
5.4
Waste-
water
23
—
71
51
9
28
20
23
71
2.3
                                                 Formamide
                                                 By-products
                 51
dyu is heated with chromium formate in formamide solution.  No estimation of the
LiL  of this solvent was made.

-------
                                               Table 12  (Continued)
                 C.I
   Producer      No.
 VPC
 DUP
 HFC
12770
12775
                                                Annual
                                                                                 Quantity Released
                                                                                      (kg/yr)
Production
Dye metric tons/yr
Disperse Yellow 4 >2.3



Pigment Green 10 >0.9



Material Released
to Environment
Disperse Yellow 4
Aniline
2,4-Quinolinediol
By-products
Pigment Green 10
p-Chloroaniline
2,4-Quinolinediol
Nickel (Ni~K^)
Solid
Residue
48
0-8
0.8
'0
17,
0.2
0-2
1.1
Waste-
water
23
	
71
51
9
—
28
0.9
o
                                                             By-products
                                                                                                  20

-------
                                                 Table 12 (Continued)
                                                 Annual
o
Quantity Released
     (kg/yr)
C.I. Production
Producer No. Dye metric tons/yr
ATL 13025 Acid Orange 52 >2.3

HAS 13065 /cid Yellow 36 >6.8
DUP
TRC

ACY 13080 Acid Orange 5 >2.3

Material Released
to Environment
Acid Orange 52
Sulfanilic acid
N,N-Dimethylaniline
By-products
Acid Yellow 36
Metanilic acid
Diphenylamine
By-products
Acid Orange 5
Sulfanilic acid
Diphenylamine
By-products
Solid
Residue
69
0.6
0.6
0
200
1.7
1.7
0
69
0.6
0.6
0
Waste-
water
61
48
39
180
140
120
61
48
39

-------
                                              Table 12 (Continued)
  Producer
AC
                                               Annual
                                                                              Quantity  Released
                                                                                   (kg/yr)
C.T.
No.
13091

Production
Dye metric tons/yr
Acid Orange 1 >2.3

Material Released
to Environment
Acid Orange le
Sulfanilic acid
Diphenylamine
By-products
Solid
Residue
69
0.6
0.6
0
Waste-
water
61
48
39
AC
13095
Acid Yellow 63
>2.3
Acid Yellow 63

Sulfanilic acid
Diphenylamine

By-products
69

 0.6
 0.6

 0
61


48

39
AC
13150
Acid Orange 50
                                                >2.3
              Acid Orange 50
              2,5-Dichlorosulfanilic
                acid
              N-Ethyl-N-phenyl-
                benzylamine

              By-products
                              69
                               0.6

                               0.6
                                                                                              61
                                                                                                             39
        'robable main component made by nitration of C.I. 13080.

-------
                                            Table 12 (Continued)
                                             Annual
                                                                              Quantity  Released
                                                                                   (kg/yr)
C.I. Production
Producer No. Dye?. metric t'ons/yr
TCI 13190 Reactive Yellow 4 >2.3





TUG 13245 Reactive Yellow 3 >2.3

Material Released
to Environment
Reactive Yellow 4
3-Amino-l , 5-naphthalene
disulfonic acid
m-Toluidine
Cyanuric chloride
By-products
Reactive Yellow 3
3-Amino-l , 5-naphthalene
Solid
Residue
69
0.4

0.4
—
0
69
0.4
Waste-
water
61
—

—
48
39
6.1
—
PDC
TRC
13250
Mordant Brown 33
                                              >4.5
  disulfonic acid
N~.(3-Aminophenyl) acetamide    0.4
Cyanuric chloride             —
Ammonia^                      —

By-products                    0

Mordant Brown 33              95
2-Amino-4-nitrophenol          1.7
2,4-Diaminobenzene sulfonic    1.7
  acid
                                                            By-products

       Ammonia was not quantified but  is assumed  to be  in  the aqueous phase.
 39

 45

140


 99

-------
                                            Table 12  (Continued)
ProcNicer

pnc
TKC
ATL
FAN
                                             Annual
Quantity Released
     (kg/yr)
C.T. Production
No. Dye metric tons/yr
13265 Mordant Brown 70 >2.3






13361 Acid Green 35 >2.3




13390 Acid Blue 92 >9

Material Released
to Environment
Mordant Brown 70
Picramic acid
2,4-Diaminobenzene sulfonic
acid
N-(3-Amino-4-sulfophenyl)
glycine
By-products
Acid Green 35
Picramic acid
Naphthionic acid
Chromium (Cr )
By-products
Acid Blue 92
H-ArHH
Solid
Residue
48
0-9
0.4

0.4

0.
69
0.4
0.4
7.3
0
270
2.2
Waste-
water
23
—
36

36

50
61
—
48.
6.1
39
240
—
                                                             N-Phenyl Peri acid

                                                             By-products
2.2

0
190

150

-------
Table 12 (Continued)
 Annual
Quantity Released
     (kg/yr)
C.I. Production
Producer No. Dye metric tons/yr
BAS 13900 Acid Yellow 99 >9.1
CAP 13900:1 Solvent Yellow 19
TRC




AC 13906 Acid Yellow 151 1620.9
DUP
TRC
VPC


ATL 13950 Direct Yellow 27 >2.3




Material Released
to Environment
Acid yellow 99

6-Amino-4-ni tro-1-phenol-
2-sulfonic acid
Acetoacetanilide
Chromium (Cr+3)
By-products
Acid Yellow 151
2-Amino-l-phenol-4-
sulfonamide
Acetoacetanilide
Cobalt (Cr+3)
By-products
Direct Yellow 27
Dehydrothio-p-toluidine
disulfonic acid
o-Acetoacetanisidide
By-products
Solid
Residue
270


1.5
1.5
29
0
48600
270

270
5140
0
69.
0.6

0.6
0
Waste-
water
250


—
190
25
150
43800
—

34000
4380
27600
61
—

48
39

-------
                                            Table 12  (Continued)
                                             Annual
                                                                             Quantity Released
                                                                                   (kg/yr)
C.T. Production Material Released
Producer No. Dye metric tons/yr to Environment
PDC 14025 Mordant Yellow 1 >2.3 Mordant Yellow 1
m-Nitroaniline
Salicylic acid
By-products
PDC 14030 Mordant Orange 1 >4.5 Mordant Orange 1
TRC p-Nitroaniline
Salicylic acid
i Bv-Droducts
Solid
Residue
48
0.8
0.8
0
95
1.7
1.7
0
Waste-
water
23
—
71
50
45
—
140
99
PDC
14110
Mordant Yellow 20
>2.3
Mordant Yellow 20             48
7-Amino-l,3-naphthalene-
  disulfonic acid              0-8
Salicylic acid                 0.8

By-products                    0
23


71

50

-------
                                            Table 12 (Continued)
Producer
 C.I.
 No.
     Dye
    Annual
  Production
metric tons/yr
   Material Released
     to Environment
                                                                                           Quantity Released
                                                                                                (kg/yr)
Solid
Residue
Waste-
water
TRC
14155
Direct Green 28
     >2.3
Direct Green 28               69
2~Amino-5-(4-amino-3-sulfo-    0.3
  1-anthraquinpnylamino)
  benzene-sulfonic acid
5-(p-Aminophenylazo)-salicy-   0.3
   lie acid
Aniline                        0 .3
Cyanuric chloride

By-products                    0
                                                                                                           61
                                                                                                           39
ATT,
TRC
14170
Acid Yellow 65
     >4.5
Acid Yellow 65               138
2-(p-Aminoanilino)-5-          0.8
  nitrobenzenesulfonic acid
o-Cresol                       0.8
Benzenesulfonyl chloride       0.8
                                                                                                          120
                                                            By-products
                                                                                              78

-------
                                              Table  12  (Continued)
Producer^

HAS
TRC
ALT
BCC
AC
HAS
I! DO
OAF
PDC
TRC
                                              Annual
                               Quantity Released
                                    (kg/yr)
C.I. Production
No. Dye metric tons/yr
14645 Mordant Black 11 >45




14700 Food Red 1 >4.5




14710 Acid Red 4 19.5


Material Released
to Environment
Mordant Black 11
l-Amino-6— nitro-2-naphthol-
4-sulfonic acid
1-Naphthol
By-products
Food Red 1
5-Amino-2 , 4-Xylenesulf onic
acid
Nevile and Winther's acid
By-products
Acid Red 4
o-Anisidine
Nevile and Winther's acid
Solid
Residue
950
17

17
0
135
1.1

1.1
0
585
4.9
4.9
Waste.
toater
450
—

1400
990
120
—

95
77
530
—
410
By-products
330

-------
                                               Table 12  (Continued)
                                                Annual
Quantity Released

     (kg/yr)
 I1SII
i—•
M
OO
C.T. Production
No. Dye metric tons/yr
14720 Acid Red 14 >25.5
Food Red 3
Mordant Blue 79

14830:1 Pigment Red 54 >0.5
14830 Acid Red 20


14880 Acid Blue 158 >4 . 5





15050 Acid Blue 158:1 >4.5




Material Released
to Environment
Acid Red 14
Naphthionic acid
Nevile and Winther's acid
By-products
Pigment Red 54
1-Naphthylamine
l-Naphthol-5-sulfonic acid
By-products
Acid Blue 158
l-Amino-2-naphthol-4-
sulfohic acid
l-Naphthol-8-sulf onic acid
Chromium (Cr+3)
By-products i
Acid Blue 158:1
l-Amino-2-naphthol-4-
sulfonic acid
l-Naphthol-8-sulfonamide
Chromium (Cr+3)
Solid
Residue
765
6.4
6.4
0
10
0.2
0.2
0
140
0.8

0.8
14
0
140
0.8

0.8
14.
Waste-
water
690
—
536
433
5
—
15
11
120
—

95
12
76
120
—

95
12
                                                                By-products
                 76

-------
                                            Table 12 (Continued)
              C.I.
              No.
 AC
 ACY
 ATI,
 HAS
 BDO
 CAF
 1'DC
 TRC
 VPC
         15510
                                        Annual
                                      Production
                                    metric tons/yr
          Acid Orange 7
          Pigment Orange 17
          Pigment Orange 17:1
          Solvent Orange 49
206.8
                                                  Material Released
                                                    to Environmen't
Acid Orange 7
Sulfanilic acid
2-Naphthol

By-products
                                             Quantity  Released
                                         	(kg/yr)
                                          Solid             Waste-
                                          Residue          water
6200
  52
  52

   0
5580

4340

3520
AC
ACY
ATL
TRC
VPC
        15575
          Acid Orange 8
142.7
Acid Orange 8
4-Amino—m-toluene-
  sulfonic acid
2-Naphthol

By-products
4280
  36

  36

   0
3840


3000

2430
ACY
AMS
APO
150R
CTK
1ISC
11 SI I
TCC
IDC
KON
MGK
MRX
SDH
SNA
TMS
15585     Pigment Red 53
          D & C Red 8
15585:1   Pigment Red 53:1!
          D & C Red 9
                                              1800
              Pigment Red 53             37800
              2-Amino-5- chloro-p-toluene-  675
                sulfonic acid
              2-Naphthol                   675
                                               By-products
                                             0-
                                            18000


                                            55800

                                            39600
          ft
            :1 is  the barium  salt.   No  estimation of the release of this metal-was made.

-------
                                                Table 12 (Continued)
                                                 Annual
Quantity Released
     (kg/yr)
K>
O

Producer
BAS




ATL
BAS
GAP
TRC

ACY ICC
AMS IDC
BNS KON
BOR SDH
CTK SNA
HSC UI1L,
C.T. Production Material Released
No. Dye metric tons/yr to Environment
15602 Pigment Orange 46 >0.5 Pigment Orange 46
2-Amino-5-chloro-4-ethyl-
benzenesulf onic acid
2-Naphthol
By-products
15620 Acid Red 88 40 Acid Red 88
Naphthionic acid
2-Naphthol

By-products
15630 Pigment Red 49 3150 Pigment Red 49
15630:1 Pigment Red 49:1;* Tobias acid •
15630:2 Pigment Red 49 : 2h
2-Naphthol

By-products
Solid
Residue
10
0.2

0.2
0
1200
10
10

0
66150
1180

1180.

0
Waste-
water
5
—

15
11
1080
—
840

680
31500
—

97650

69300
                  :1 is the barium salt,  :2  is  the  calcium salt.   No estimation of the release of
                  these metals was' made.

-------
Table 12 (Continued)
 Annual
Quantity Released
     (kg/yr)
C.I.
Producer No.
PDC 15670




HAS 15705
TRC

M
NJ
}— i

AC 15711
SDH
ATL
BAS
FAB
TRC
Production Material Released
Dye metric tons/yr to Environment
Mordant Violet 5 >2.3 Mordant Violet 5
2-Amino-l-phenol~4-
sulfonic acid
2-Naphthol
By-products
Mordant Black 17 >4.5 Mordant Black 17
l-Amino-2-naphthol-4-
sulfonic acid
2-Naphthol

By-products
Acid Black 52 406.8 Acid Black 52
l-Amino-6-nitro-2-naphthol-
4-sulfonic acid
2-Naphthol ^
Chromium (Cr )

Solid
Residue
48
0-8

0.8
0
95
1.7

1.7

0
12200
68

68
1290

Waste.
water
23
—

71
50
45
—

140

99
1100
—

8540
110

                By-products
              6920

-------
                                                Table  12  (Continued)
                                                Annual
                                                                              Quantity Released
                                                                                   (kg/yr)
C. L. Production
Producer No. Dye metric tons/yr
GLX XL. 8
HRC 15800:2 Pigment Broxm 5
ICC
ROM

DUP 15825 Pigment Red 58 >0.9
UPC


Material Released
to Environment
Pigment Brown 5
Aniline
3-Hydroxy-2-naphthoic acid

By-products
Pigment Red 58
6-Chlorometanilic acid
3-Hydroxy-2-naphthoic acid
Bv-nroducts
Solid
Residue
38
0.7
0.7

0
19
0.4
0.4
0
Waste
water
18
—
56

40
9.
—
28
20
K3
ho
 ACY   IDC
 AMS   RON
 APO   MC.R
 BNS   SDH
 BOR   SNA
 CTK   TMS
 DUP   UUL
 UPC
 1ISI!
 ICC
15850     Pigment Red 57

15850:1   Pigment Red 57:1i
1550.0
Pigment Red 57             32550
6-Amino-m-toluene            580
  sulfonic acid
3-Hydroxy-2-naphthoic acid   580
                                               By-products
                               0.
                                                                                                           15500
                                                                                           48000
                                                          34100
                  is  the  calcium salt.   No estimation of the release of this metal was made.

-------
                                                Table 12 (Continued)
    Producer
               C.I.
               No.
     Dye
    Annual
  Production
metric tons/yr
   Material Released
     to Environment
   Quantity Released
	(kg/yr)	
Solid            Waste-
Residue          water
   ACY  MRX
   AMS  SNA
   UPC  UllL
   use
   11SH
   NCR
              15860:1   Pigment Red  52:1^
              15860:2   Pigment Red  52:2J
                       798.6
                   Pigment Red 52             16770
                   2-Amino-5~chloro-p-toluener-  300
                    sulfonic acid
                   3-Hydroxy-2-naphthoic acid   300
                                                             By-products
                                                                    0
                                             7990


                                            24700

                                            17600
to
LJ
ACY  HSH
AMS  ICC
BOR  MGR
DUP  MRX
UPC  S
HRC  SNA
HSC  UllL
                 15865
Pigment Red 48
     1135.5
                 15865:1-4 Pigment Red 48:1-4
Pigment Red 48             23800
6-Amino-4-chloro-m-toluene-  426.
  sulfonic acid
3-Hydroxy-2-naphthoic acid   426
                                                                By-products
                                                                                                          11400
                                                                                 35200
                                                                                 25000
   use
   HSU
   RON
   SNA
              15880
Pigment Red 63
     25.9
Pigment Red 63
Tobias acl-i

3-Hydroxy-2-naphthoic.
  acid
 544
   9.7

   9.7
                                                                                                               259
                                                                                                            803
                                                                By-products
                                                                                            0
                  ;l is the calcium salt,  :2 is the manganese salt.
                  ;l is the barium salt, :2 is the calcium salt,  :3 is the strontium salt,
                  :4 is the manganese salt.   No estimation of the release of these metals was made.
                                                                                   570

-------
Table 12 (Continued)
 Annual
Quantity Released
     (kg/yr)
C.I. Production
Producer No. Dye metric tons/yr
PSC 15970 Acid Orange 12 >2.3
Food Orange 1

ALT 15985 Food Yellow 3 488.2
BCC
KON
SDH
STG
WJ
ALT 16035 Food Red 17 867.3
BCC
KON
SDH
WJ
Material Released
to Environment
Acid Orange 12
Aniline
Schaeffer's acid
By-products
Food Yellow 3
Sulfanilic acid
Schaeffer's acid

By-products
Food Red 17
4-Amino-5-methoxy-o-
sulfonic acid
Schaeffer's acid

Solid
Residue
69
0-6
0.6
0
10300
183
183

0
18200
toluene 325
325

Waste-
water
61
48
39
4880
15134

10700
8670
26900

                By-products
             19100

-------
                                              Table 12  (Continued)
  "roihu'cr
snn
HSU
KON
MKX
SNA
ACY
SDH
                                               Annual
Quantity Released
     (kg/yr)
C.I. Production
No. Dye metric tons/yr
16105 Mordant Red 9 >140.
16105:1 Pigment Red 60: I1

16150 Acid Red 26 >2.3
Food Red 5

16185 Acid Red 27 >2.3
Food Red 9

Material Released
to Environment
Mordant Red 9
Anthranilic acid
R acid
By-products
Acid Red 26
2,4-Xylidine
R. acid
By-products
Acid Red 27
Naphthionic acid
R acid
By-products
Solid
Residue
2940
52
52
0
69
0.6
0.6
0
69
0.6
0.6
0
Waste-
water
1400
4340
3080
61
48
39
61
48
39
                 :1 is  the barium  salt.   No estimation of the release of this metal was made.

-------
                                             Table  12  (Continued)
                                             Annual
TRC
Quantity Released
     (kg/yr)
C.I.
Producer No.
AC 16230
ACY
ATL
BAS
GAP
TRC
ATL 16255
TRC

M
to
cr.

ACY 16580
ATL
Production Material Released
Dye metric tons/yr to Environment
Acid Orange 10 65.9 Acid Orange 10
Food Orange 4 Aniline
G-acid


By-products
Acid Red 18 >4.5 Acid Red 18
Food Red 7 Naphthionic acid
G acid


By-products
Acid Violet 3 >6.8 Acid Violet 3
p-Nitroaniline
Solid
Residue
1980.
16
16


0
130
1.1
1.1


0
204
1.7
Waste
water
1780
—
1380


1120
120
—
94


76
180
—
                                                             Chromotropic  acid
1.7
140
                                                            By-products
               115

-------
                                               Table 12 (Continued)
                                                               sulfonic acid
                                                             Gamma acid
                                                                                              Quantity Released
Producer
EDO
C.I.
No.
17025
Dye
Acid Violet 1
Annual
Production
metric tons/yr
>2.3
Material Released
to Environment
Acid Violet 1
2 -Amino-5 -nitrobenzene"
(kg/
Solid
Residue
69
0-6
yr)
Waste
water
61
                                                                                0.6
                                                                                     48
                                                             By-products
                                                                                                              39
  AC
  IRC
17045
to
-4
Acid Red 37
>4.5
Acid Red 37
5-Acetamido-2-amino-
  benzene -sulfonic acid
Gamma acid
135
  1.1

  1.1
                                                                                                              120
                                                                                                               94
                                                             By-products
                                                                                                               76
  ICI
  TRC
17053
Acid Red 57
                                            >4.5
                 Acid,Red 57
                 2-Amino-N-ethyl-benzene-
                   sulfonanilide
                 Gamma acid
                               135,
                                 1.1

                                 1.1
                                                                                                              120
                                                                                                               94
                                                             By-products
                                                                                                76

-------
Table 12 (Continued)
  Annual
Quantity Released
     (kg/yr)
C.I.
Producer No. Dye

ACY 17100 Acid Brown 90



*
BAS 17101 Acid Red 266
ALT
ICI
TRC
j
J
0
ATL — Acid Red 337
ALT
DUP
TRC
VPC
BCC 17200 Acid Red 33
KON Food Red 12
Production Material Released
metric tons/yr to Environment
\v-
>2.3 Acid Brown 90 ^)
p-Amino- a— toluene 'sulfonic
acid
Gamma acid
By-products
>9.1 Acid Red 266
4-Chloro-a,cc,a-trifluoro-
o-toluidine
Gamma acid
By-products
794 Acid Red 337
a > a , a-Trif luoro-o-
toluidine
Gamma acid
By-products
>4.5 Acid Red 33
Aniline
H-acid
Solid
Residue

69
0.6

0.6
0
270
2.3

2.3
0
23800
200

200
0
135
1 T
1. 1
1.1
Waste-
water

61
—

48
39
250
—

190
155
21400
—

16700
13500
120
94
              By-products
                                                                 76

-------
Table 12 (Continued)
 Annual
Quantity Released
     (kg/yr)
C.I.
Producer No.
PDC 17590


ATL 17755
BAS
DUP
GAP
TRC
VPC

HST 17757

Production Material Released
Dye metric tons/yr to Environment
Mordant Brown 40 >2.3 Mordant Brown 40
Anthranilic acid
N-Phenyl Gamma acid
By-products
Acid Red 137 41.8 Acid Red 137
! p-Aminoacetanilide
N-Acetyl J acid


By-products
Reactive Orange 16 >2.3 Reactive Orange 16
2-(p-Aminophenylsulf onyl)
ethanol sulfate ester
N-Acetyl Gamma acid
Solid
Residue
48
0.8
0.8
0
1250
10
10


0
69
0.6
0.6
Waste
water
2 j
71
50
1130
878


710
61
48
              By-products
                  39

-------
                                                Table 12  (Continued)
                                                 Annual
                                                                                 Quantity Released
                                                                                      (kg/yr)

Producer
ICI




C.I. Production
No. Dye Metric t'ons/yr
17907 Reactive Orange 1 >2.3




Material Released
to Environment
Reactive Orange 1
Orthanilic acid
J Acid
Cyanuric chloride
Bv-t>roducts
Solid
. Residue
69
0.4
0.4
0
0
Waste
water
61
—
—
48
39
  ICI
17908
Reactive Red 8
>2.3
U)
o
Reactive Red 8
2-Amino-5-methoxy~benzene-
  sulfonic acid
J acid
Cyanuric chloride

By-products
69

 0.4
 0.4
61



48

39
 AC
 ACY
 ATL
 EDO
 DUP
 GAP
 TRC
 VPC
18050      Acid Red 1
           Food Red 10
                   154.1
                 Acid Red 1
                 Aniline
                 N-Acetyl H acid
                                               By-products
                               4620.
                                 38
                                 38
               4160

               3240



               2620

-------
                                              Table 12 (Continued)
  Producer
ATL
BDO
                                                                                             Quantity Released
C.I.
No.
18055


Dye
Acid Violet 7
Food Red 11
Annual
Production
metric tons/yr
>4.5

(kg/yr)
Material Released
to Environment
Acid Violet
p-Aminoacetanilide
N-Acetyl H acid
Solid
Residue
135
1.1
1.1
Waste
water
120
94
                                                           By-products
                                                                                                             76
BDO
18075
Acid Violet 12     >2.3
Acid Violet 12
o-Anisidine
N-Acetyl H acid
69
 0.6
 0.6
61

48
                                                           By-products
                                                                                                              39
HST
18097
Reactive Violet 5  >2.3
Reactive Violet 5                68
2-(4-Amino-3-methoxyphenyl-       0.4
  sulfonyl) ethanol sulfate
  ester
N-Acetyl H acid                   0.4
Copper  -(Cu*2)                    7.3
                                                                                                              61
                                                                                                              48
                                                                                                               6.1
                                                           By-products
                                                                                                              38

-------
Table 12 (Continued)
 Annual
Quantity Released
     (kg/yr)
C.I.
Producer No. Dye
ICI 18158 Reactive Red 1





TRC 18165 Acid Black 60



M
LO
NJ

FAB 18200 Reactive Red 2
ICI



Production Material Released
Metric tons Ayr to Environment
>2.3 Reactive Red 1
2-Aminobenzenesulfonic
acid
H-Acid
Cyanuric chloride
" By-products
>2.3 Acid Black 60
2-Amino-N-methyl-l-phenol-
4-sulfonamide
N- ( 7-Hydr oxy-1-naphthyl)
! acetamide
Chromium (Or )
By-products
>4.5 Reactive Red 2
Aniline
H acid
Cyanuric chloride
By-products
Solid
Residue
69
0.4

0.4
—
0
69
0.4

0.4

7.3
0
135
0.7
0.7
—
0
Waste
water
61
—

—
48
39
61
—

48

6.1
39
120
—
—
94
76

-------
                                              Table 12 (Continued)
  Producer
    C.I.
    No.
       Dye
FAB
ICI
18260
Reactive Orange 4
    Annual
  Production
metric tons/yr

   >4.5
                                                                 Material Released
                                                                   to Environment
                                                                                             Quantity Released
                                                                                                  (kg/yr)
                                                                   Solid
                                                                   Residue
Reactive Orange 4
2-Amino-l,5-naphthalene
  disulfonic acid
N-Methyl J Acid
Cyanuric chloride
135
  0.7

  0.7
                                                Waste
                                                water
                                                                                                             120
                                                                                                              94
                                                           By-products
                                                                                                  76
ICI
18270
Reactive Orange 13
   >2.3
Reactive Orange 13
2-Amino-l,5-naphthalene
  disulfonic acid
N-Methyl-J acid
Cyanuric. chloride
Ammonia™
 69
  0.4

  0.4
61
                                                           By-products
                                                                                                  39
            in
             'Ammonia release was not quantified,but  is assumed  to be  in  the  aqueous  phase.

-------
                                  Table 12  (Continued)
                                   Annual
               Quantity Released
                    (kg/yr)
C.I.
Producer No.
BAS 18690





AC 18732
ALT
ATL
DUP
TRC
VPC
ACY 18740




Production Material Released
Dye metric tons/yr to Environment
Acid Yellow 121 >2.3 Acid Yellow 121
Solvent Yellow 21 Anthranilic acid
3-Methyl-l-phenyl-5-pyrazolone
Chromium (Cr+3)
Formamide
By-products
Acid Orange 60 298.6 Acid Orange 60
2-Amino-l-phenol-4-sulfonamide
3-Methyl-l-phenyl-5-pyrazolone
Chromium (Cr+3)

By-products
Acid Orange 72 >2.3 Acid Orange 72
2-Amino-6-nitro-l-phenol-4-
sulfonic acid
3-Methyl-l-phenyl-5-pyrazolone
Chromium (Cr+3)
Solid
Residue
69
0.4
0.4
7.3
— —
0
8960
50
50
950

0
69
0.4

0.4
7.3
Waste
water
61
—
48
6.1
— —
39
8060
—
6270
810

5080
61
—

48
6.1
                                               By-products
                               39
n The dye is heated with chromium formate in formamide solution.
  of  the quantity of this solvent was made.
No estimation

-------
Table 12 (Continued)
  Annual
Quantity Released
     (kg/yr)
C.I. Production Material Released
Producer No. Dye metric tons/yr to Environment
18745 Acid Orange 74 >4.5 Acid Orange 74
GAP Chromium (Cr+3)


XRC 6-Amino-4-nitro-l-phenol-2-
sulfonic acid

3-Methyl-l-phenyl-5-pyrazolone
By-products
ACY 18760 Mordant Red 7 >9.1 Mordant Red 7


ATL l-Amino-2-naphthol-4-
M BDO , sulfonic acid

^ PDC 3-Methyl-l-phenyl-5-pyrazolone
By-products
AC 18810 Acid Red 186 >2.3 Acid Red 186
l-Amino-2-naphthc


)l-4-sulf onic
Solid
Residue
130
13.8
0.8

0.8
0
190
3.4

3.4
0
69
0.4
Waste
Water
120
12
—

95
77
91
—

280
200
61
—
                acid
              3-Methyl-l-(m-sulfophenyl)
                -5-pyrazolone
              Chromium (Cr+3)

              By-products
0.4

7.3

0
48

 6.1

39

-------
                                               Table 12 (Continued)
                                               Annual
                                                                                 Quantity Released
                                                                                      (kg/yr)
C.I.
Producer No.
EDO 18820



Dye
Acid Yellow 11


Production
metric tons/yr
>2.3


Material Released
to Environment
Acid Yellow 11
Aniline
3-Methyl-l-(p-sulfophenyl)-
Solid
Residue
69
0.6
0.6
Waste
Water
61
—
48
                                                              5-pyrazolone

                                                            By-products
                                                                                                 39
PDC
18821
OJ
cr.
Mordant Yellow 8
>2.3
Mordant Yellow 8
Anthranilic acid
3-Methyl-l-(p-sulfophenyl)
  -5-pyrazolone

By-products
48
 0.8
 0.8
23

71


50
AC
18835
Acid Yellow 25
>2.3
Acid Yellow 25
5-Amino-o-t oluenesulfon-
  anilide
3-Methyl-l-(p-sulfophenyl)
  -5-pyrazolone
69
 0.6

 0.6
                                                                                                              61
                                                                                                              48
                                                            By-products
                                                                                                 39

-------
Table 12 (Continued)
                                              Quantity Released
                                                   (kg/yr)
r T
*_j • j_ •
Producer No.
HST 18852






ATL 18890
EDO



TRC 18900


n-iiiiuct j_
Production Material Released
Dye metric tons/yr to Environment
Reactive Yellow 17 >2.3 Reactive Yellow 17
2- ( 4-Amino-3 , 6-dime thoxy-
phenylsulfonyl) ethanol
sulfate ester
3-Methyl-l-(4-sulfophenyl)
-5-pyrazolone
By-products
Acid Yellow 34 >4.5 Acid Yellow 34
Aniline
l-(2-Chloro-5-sulfophenyl)-
3-methyl-5-pyrazolone
By-products
Acid Yellow 29 >2.3 Acid Yellow 29
Metanilanilide
1- (2-Chloro-5-sulf ophenyl)
Solid
Residue
69
0.6


0.6

0
135
1.1
1.1

0
69
0.6
0.6
Waste
water
61
—


48

39
120
—
94

76
61
—
48
              -3-methyl-5-pyrazolone

            By-products
39

-------
Table 12 (Continued)
 Annual
                                               Quantity Released
                                                     (ke/yr)
C.I.
Producer No. Dye
DUP 18930 Acid Yellow 200




ALT 18950 Acid Yellow 40
ATL
TRC



ATL 18965 Acid Yellow 17
EDO Food Yellow 5
SDH
TRC
Production Material Released
metric tons/yr to Environment
>2.3 Acid. Yellow 200
Tobias acid
l-(2-Chloro-5-sulfophenyl)
3-methyl-5-pyrazolone
By-products
>6.8 Acid Yellow 40
p-Aminophenol
l-(4-Chloro-2-sulfophenyl)
3-methyl-5-pyrazolone
p-Toluenesulfonyl chloride
By-products
84.1 Acid Yellow 17
Sulfanilic acid
l-(2 , 5-Dichloro-4- sulf o-
phenyl) -3-methyl-5-
Solid
Residue
69
0.6
0.6

0
204
1.1
•1.1

1.1
0
2520
21
21

Waste
Water
61
—
48

39
180
—
140

140
115
2270
—
1760

               pyrazolone
             By-products
1430

-------
                                                Table 12 (Continued)
                                                 Annual
                                                                                 Quantity Released
                                                                                       (kg/yr)

Producer
AC
ALT
ATL
ICI
C.I.
No. Dye
18967 Acid Yellow 19



Production
metric tons/yr
>9.1



Material Released
to Environment
Acid Yellow 19
Tobias acid

1-C2 . 5-Dirhl nrn-4-siil f rv
Solid
Residue
273
2.3

7. 1
Waste
Water
250


l on
                                                              " phenyl)-3-methyl-5-pyra-
                                                               zolone
                                                             By-products
                                                                                                 154
 ICI
18971
Reactive Yellow 1
                                               >2.3
u>
i-D
 TRC
18972
                        Reactive Yellow  2
                                 >2.3
                                    Reactive Yellow 1                69
                                    2,4-Diaminobenzene sulfonic       0.4
                                      acid
                                    3-Methyl-l-(2,4-dichloro-4-       0.4
                                      sulfophenyl)-5-pyrazolone
                                    Cyanuric chloride                	

                                    By-products                       Q

                                    Reactive Yellow 2                69
                                    4-Aminobenzene sulfonic acid      0.3
                                    2,4-Diaminobenzene sulfonic
                                      acid                    -0.3
                                    3-Methyl-l-(2,4-dichloro-4-       0.3
                                      sulfophenyl)-5-pyrazolone
                                    Cyanuric chloride

                                    By-products                       Q
 61


 48

 48

 39

 61
 48


48

48

39

-------
  Producer
    C.I,
    No.
       Dye
TRC
19005
Acid Yellow 127
                                              Table 12 (Continued)
                                               Annual
                                             Production
                                           metric tons/yr
>2.3
                                                                                             Quantity  Released
Material Released
to Environment
^cid Yellow 127
>-Amino-4-(3-chloro-l-oxido-
Solid
Residue
69
0.6
Waste
water
61
                                                 1 , 2 , 4-benzotriazine-7-car-
                                                 boxamido)benzene sulfonic acid
                                               l-(6-Chloro-o-tolyl)-3-methyl-
                                                 5-pyrazolone

                                               By-products
                                                                                             0.6
                                                                                      48
                                                                                                             39
AC
TRC
19010
Acid Yellow 54
>4.5
Acid Yellow 54                  140
4-Sulfoanthranilic acid           '0.8
3-Methyl-l-(4-sulfo-o-tolyl)-     0.8
  5-pyrazolone
Chromium salt                    14

By-products                       0
120

 95

 12

 77
ALT   AC
BCC   ACY
KON   BAS
SDH   GAF
STG   MRX
WJ    TRC
19140      Acid Yellow 23
           Food Yellow 4
                                           730
                                    Acid Yellow 23
                                    Sulfanilic acid
                                    3-Carboxy-l-(p-sulfophenyl)
                                      5-pyrazolone

                                    By-products
                                               21900
                                                 182
                                                 182
                                               19700

                                               15300


                                               12400

-------
                                             Table 12 (Continued)
 Producer
C.I.
No.
                 Dye
    Annual
  Production
metric tons/yr
                                                                Material Released
                                                                  to Environment
                                Quantity Released
                             	(kg/yr)	
                             Solid            Waste
                             Residue          tfater
TRC
            19351
          Acid Red
                                             Acid Red 179                   69
                                             6-Amino-4-chloro-l~phenpl-      0.4
                                               2-sulfonic acid
                                             2,4-Quinolinediol               0.4
                                             Chromium (Cr+3)                  7.3

                                             By-products                     0
                                                                  61


                                                                  48
                                                                   6.1

                                                                  39
ATL
BAS
DUP
GAF
PDC
TRC
19555
        Direct  Yellow 28
    25.9
Direct Yellow 28
Sodium dlhydrothio-p-
  toluidine sulfonate
                                               By-products
780
 13
700
                                                                                            440

-------
        Table 12 (Continued)
Annual
Quantity Released
     (kg/yr)
C.I.
Producer No.
HST 20040




ATL 20110
TRC

Production Material Released
Dye metric tons/yr to Environment
Pigment Yellow 16 >0.4 Pigment Yellow 16
2,4 - Dichloroaniline
4 ',4'"- Bi-o-acetoaceto-
toluidide
By-products
Mordant Brown 1 >4.5 Mordant Brown 1
2-Amino-4-nitrophenol
5-Amino-l-naphthalene-
Solid
Residue
9
0.2
0.1

0
90
1.1
1.1
Waste
water
4
—
14

28
45
—
—
                sulfonic acid
              m-Phenylenediamine

              By-products
1.1

0.
140

280

-------
                                                     Table 12  (Continued)
 Producer
     C.I.
     No.
       Dye
    Annual
  Production
metric tons/yr
Material Released
  to Environment
   Quantity Released
	(kg/yr)	
Solid            Waste
Residue          water
 PDC
  20150
                       Mordant Brown 18
                                   >2.3
                                                            Mordant Brown 18
                                                            Sulfanilic acid
                                                            p-Nitroaniline
                                                            Salicylic acid

                                                            By-products
                                                                     46
                                                                      0.6
                                                                      0.6
                                                                      0.6

                                                                      0
                                                                                                  23


                                                                                                  71

                                                                                                 142
ACY
ATL
BAS
ALT
FAB
TRC
  20170
Acid Orange 24
                                   >13.6
                 Acid Orange 24
                 Sulfanilic acid
                 Xylidine (crude)
                 Resorcinol

                 By-products0
                                                                                410
                                                                                  2.3
                                                                                  2.3
                                                                                  2.3

                                                                                  0
                                                                                     370


                                                                                     285,

                                                                                     570
ACY
 20177
Acid Brown 354
                                             >2.3
                                                Acid Brown 354                  69
                                                2-(p-Aminoanilino)-5-nitro-      0.4
                                                  benzenesulfonic acid
                                                Resorcinol                       0.8

                                                By-products                      0
                                                                                                            61


                                                                                                            48

                                                                                                            96
The by-product estimate assumed pure xylidine.
increase the amount of by-products.
                                                           Impurities in crude xylidine would

-------
                                           Table 12  (Continued)
                                 Annual
Quantity Released
     (kg/yr)
C.I.
Producer No. Dye
AC 20195 Acid Brown 14
ACY
ATL
BAS
ALT
TRC
VPC 20250 Acid Brown 83


M
-P~
4>

POP 20460 Acid Blue 29




Production Material Released
metric tons/yr to Environment
106.4 Acid Brown 14
Naphthionic acid
Resorcinol

By-products

>2.3 Acid Brown 83
4-Methoxytnetanilic acid
Resorcinol
4-Nitro-m-phenylenediamine
1 Copper (CvT2)
Ammonia P
By-products
>2.3 Acid Blue 29
m-Nitroaniline
Aniline
H acid
By-products
Solid
. Residue
3190.
36
18

0.

69
0.3
0.3
0.3
7.2
0
0
69
0.4
0.4
0.4
0,
Waste
water
2870
—
2230

4470

61
—
48
6.1
96
61
—
—
48
96
''Ammonia release was not quantified but is assumed to be in the aqueous phase.

-------
                                                Table 12 (Continued)
 Producer
   C.I.
   No.
       Dye
    Annual
  Production
metric tons/vr
Material Released
  to Environment
   Quantity Released
	(kg/yr)	
Solid            Waste
Residue          water
AC    ALT
ACY   FAB
ATL   PDC
BAS   TRC
EDO
20470
Acid Black  \
    169.1
                                               Acid Black 1
                                               p-Nitroaniline
                                               Aniline
                                               H acid

                                               By-products
                                                                   5070
                                                                     28,
                                                                     28,
                                                                     28.

                                                                      0
                                                                 4560


                                                                 3550

                                                                 7100
PDC
20480
Acid Black 41
                                             >2.3
                                               Acid Black 41
                                               p-Nitroaniline
                                               Sulfanilic acid
                                               H acid

                                               By-products
                                                                                           69
                                                                                           -•0.4
                                                                                            0.
                                                                                            0.

                                                                                            0
                                                                        .4
                                                                        .4
                                                                  61


                                                                  48

                                                                  96
ATL
EDO
PDC
TRC
20495
Acid Green 20
                                               Acid Green 20
                                               p-Nitroaniline
                                               Aniline
                                               H -acid
                                                                    180
                                                                      2.3
                                                                      2.3
                                                                      2.3
                                                                  91
                                                                                                           280
                                                           By-products
                                                                                               560

-------
                                         Table 12 (Continued)
                                 Annual
Quantity Released
     (kg/yr)

Producer
HST


ACY
DUP
M PSC
£ TRC

ACY
HAS
PSC
TRC
I5AS
C.I. Production Material Released
No. Dye metric tons/yr to Environment
20505 Reactive Black 5 >2.3 Reactive Black 5
2- (p-Aminophenylsulf onyl)
ethanol sulfate ester
H acid
By-products
21000 Basic Brown 1 41.8 Basic Brown 1
m-Pheny 1 ened iamine

By-products
21010 Basic Brown 4 >HQ Basic Brown 4
21010:1 Solvent Brown 12 Toluene-2,4-diamine
21010:2 Pigment Brown 3 ~~~" \ ^
By-products
21030 Basic Brown 2 >2.3 Basic Brown 2
4-Methoxy-m-phenyl ened iamine
m-Phenylened iamine
Solid
Residue
69
0.4
0.8
0
1250
21

0
3300
55
0
69
0.4
0.8
Waste
water
61
48
96
1130

1760
2970
6890
61
48
                                              By-products
                                                                                               96
:2 is the phosphotungstomolybdic acid complex.

-------
       Table 12 (Continued)
Annual
Quantity Released
     (kR/yr)
C.I.
Producer No.
BAS 21230
GAP



PSC 21240


P^
~-4
BAS 21250




TRC 24810

Production Material Released
Dye metric tons/yr to Environment
Solvent Yellow 29 >4.5 Solvent Yellow 29
4,4* -Cyclohexylidenedl-o-
toluidine
p-Cyclohexylphenol
By-products
Solvent Yellow 30 >2.3 Solvent Yellow 30
4,4' -Benzylidenedi-2 , 5-
xylidine
p-Cresol
By-products
Solvent Red 22 >2.3 Solvent Red 22
4,4 '-(o-Chlorobenzylidene)-
di-2,5-xylidine
2-Naphthol
By-products
Acid Red 134 >2.3 Acid Red 134
4,4' -Cyclohexylidenedi-
Solid
Residue
90.
1.1

2.2
0
48

•0.6
•1.2
0
48

0.6
1.2
0
69
0.4
Waste
witer
45
—

140
280
23

—
71
142
23

—
71
142
61
—
                o-anisidine
              4,6-Dihydroxy-2-naphthalene-
                sulfonic  acid
0.8
48
             By-products
                 96

-------
                                                Table 12 (Continued)
                                                                                              Quantity Released
C.I.
Producer No. Dye
ACY 24890 Direct Yellow 4
ATL
BAS
DUP
LVR
SDH
TRC
^11 1 1 1 UC-i J_
Production
metric tons/yr
300.4






Material Released
to Environment
Direct Yellow 4
4,4'-Diamino-2,2' stilbene-
disulfonic acid
Phenol


By-products
Solid
Residue
9010
50

100


0
Waste
water
8110
—

6310,


12600
-p-
CO
   ACY
   ATL
   TRC
24895
Direct Yellow 12
>6.8
Direct Yellow 12               200
4,4'-Diamino-2,2' stilbene-
  disulfonic acid                1.1
Phenol                           2.2
Ethyl chloride                   0

By-products                      0
                                                                                                              180
                                                                                                              285
   ATL
25100
Mordant Yellow 16
>2.3
Mordant Yellow 16               46
4,4'(and 2 ,4')-Thiodianiline     0.6
Salicylic acid '                  1.2

By-products                      0
 23

 71

140

-------
                                                     Table 12 (Continued)
 Producer
ATL
                                                                                            Quantity  Released

C.I.
No. Dye
25135 Acid Yellow 38



Annual
Production
metric tons/yr
>2.3




Material Released
to Environment
Acid Yellow 38
6,6* Thiodimetanilic acid
Phenol (2 mol)
Ethyl chloride
Ug/
Solid
Residue
69
-0.4
0.8
0
yrj
Waste
water
61
—
— •
—
                                                           By-products
                                                                                                95
TRC
25200
Direct Orange 73
>2.3
Direct Orange 73
3,3'-Diaminobenzanilide
3-Carboxy-l-(m-nitrophenyl)-
  5-pyrazolone (2 mol)

By-products
69.
 0.4
 0.8
                                                                                                             61
                                                                                                             95
ATL
25380
Direct Red 75
>2.3
Direct Red 75
5,5'-Ureylenebis(2-araino-
  benzene)sulfonic acid
Gamma acid
60
 0.4

 0.8
                                                                                                            61
                                                                                                            47
                                                           Phosgene

                                                           By-products
                                                                                                95.
                  rPhosgene is assumed to be unstable.

-------
  Table 12 (Continued)
Annual
Quantity Released
     (kg/yr)
C.I.
Producer No.
MRT 26050



ATL 26070
ALT
EKT
TRC
M
l_n
AC 26077
ALT
BAS
SDC
VPC

Production Material Released
Dye metric tons/yr to Environment
Solvent Red 19 >2.3 Solvent Red 19
p-Phenylazoaniline
N-E thy 1- 2-naphthylamine
By-products
Disperse Yellow 23 217.7 Disperse Yellow 23
p- Phenylazoaniline
Phenol

By-products
Disperse Orange 29 196.8 Disperse Orange 29
p-Nitroaniline
o-Anisidine
Phenol

By-products
Solid
Residue
48
-0.8
0.8
0
4350
82.
82.

0
3940
49
49
49

0
Waste
water
23
—
71.
1 142
2180
—
6750

142
1970
—
—
6100

12200

-------
       Table 12 (Continued)
Annual
Quantity Released
     (kg/yr)
C.l, Production Material Released
Producer No. Dye metric tons/yr to Environment
PSC 26100 Solvent Red 23 >2.3 Solvent Red 23
p-Phenylazoaniline
2-Naphthol
By-products
AC 26105 Solvent Red 24 >9.1 Solvent Red 24
ACY " 4-o-Tolylazo-o-toluidine
ATL 2-Naphthol
PSC
M i By-products
Ln
M
ACY 26120 Solvent Red 26 >4.5 Solvent Red 26
PSC o-Toluidine
2,5-Xylidine
2-Naphthol
By-products
Solid
Residue
48
0.8
0.8
0
182
3.4
3.4

•o

90
1.1
1.1
1.1
0
Waste
water
23
—
71
140
91
—
280

560

45
—
—
140
280

-------
   Table 12 (Continued)
Annual
Quantity Released
     (kg/yr)
C.i. Production Material Released
Producer No. Dye metric tons/yr to Environment
PSC 26125 Solvent Red 27 >2.3 Solvent Red 27
Xylylazoxylidine
2-Naphthol
By-products
AC 26360 Acid Blue 113 >9 Acid Blue 113
ALT Metanilic acid
1-Naphthylamine
N-Phenyl Peri acid
i— «
>-n By-products
AC 26370 Acid Black 24 >2.3 Acid Black 24,
5-Amino-l-naphthalene-
sulfonic acid
1-Naphthylamine
N-Phenyl Peri acid
By-products
Solid
Residue
48
-Q. 8
0.8
0
270
1.5
1.5
1.5
0
69
0.4

0.4
0.4
0
Waste
water
23
—
71
14
240
—
—
190
380
61
—

—
48
96

-------
                                                Table 12  (Continued)
                                              Annual
                                Quantity Released
                                      (kg/yr)
C.I. Production Material Released Solid
Producer No Dye metric tons/yr to Environment Residue
AC 26410 Acid Blue 118 >2.3 Acid Blue 118
Aniline
1,7-Cleve's Acid
N-p-Tolyl Peri acid
By-products
ICI 26440 Reactive Brown 1 >2.3 Reactive Brown 1
Sulfanilic acid
o-Aminobenzenesulfonic acid
K :. l,6(and l,7)-Cleve's acid
co
Cyanuric chloride
By-products
ATL 26520 Mordant Orange 6 >9.1 Mordant Orange 6
BAS p-(p-Aminophenylazo)benzene-
69
0.4
0.4
0.4
0
69
0.2
0.2
0.2

0
0
180
3.4
Waste
water
61
—
48
96
61
—
—
—

—
96
91
PDC
TRC
  sulfonic acid
Salicylic acid

By-products
3.4

0
280

560

-------
                                                         Table 12 (Continued)
                                                   Annual
Quantity Released
     (kg/yr)
Ul
-P-
C.I.
Producer No. Dye
TRC 26550 Acid Orange 51






AC 26900 Acid Red 151
ACY
ATL
ALT
DUP
TRC
VPC
AC 26905 Acid Red 66

Production Material Released
metric tons/yr to Environment
>2.3 Acid Orange 51
2-(p-Aminoanilino)-5-
nitrobenzenesulfonic acid
1,6 (and l,7)-Cleve's acid
o-Cresol
p-Toluenesulfonyl chloride
By-products
>15.9 Acid Red 151
1 p-(p-Aminophenylazo)benzene-
sulfonic acid
2-Naphthol


By-products
>2.3 Acid Red 66
6-Amino-3,4'-azodibenzene-
Solid
Residue
69
0.3

0.3
0.3
0.3
0
477
4

4


0
69
0.6
Waste
water
61
—

—
—
—
96
430
—

330


660
61
—
                                                                  sulfonic acid

                                                                2-Naphthol


                                                                By-products
0.6


0
48


96

-------
                                                         Table 12 (Continued)
                                                 Annual
                                                                               Quantity Released
                                                                                     (kg/yr)
Ln
Ln
C.I.
Producer No. Dye
ATL 27200 Acid Red 115

ACY 27290 Acid Red 73
ATL
BAS
ALT
PSC
TRC
Production Material Released
metric tons/yr to Environment
>4.5 Acid Red 115
4-o-Tolylazo-o-toluidine
R acid
By-products
74.5 Acid Red 73
p-Phenylazoaniline
G acid


! By-products
Solid
Residue
135
1.1
1.1
0
2240
18
18-


0
Waste
Water
120
94
190
2010
1560


3130
    PSC
27291
Solvent Red 30
>2.3
   ATL
   TRC
27680
Direct Red 16
>4.5
Solvent Red 30
p-Phenylazoaniline
0 Acid
Dicyclohexylamine

By-products
Direct Red 16
Aniline
J acid
                                                               By-products

               sConvert C.I. 27290 to the dicyclohexylamine salt.
48
0.6
0.6
0.6
0
135
0.7
1.4
0
23
—
71
71
97
120
—
94
190

-------
       Table 12  (Continued)
Annual
Quantity Released
     (kg/yr)
C.I.
Producer No. Dye
ATL 27855 Direct Violet 7





ATL 27885 Direct Violet 9
TRC

^
°"
ATL 27925 Direct Blue 67



Production Material Released
metric tons/vr to Environment
>2.3 Direct Violet 7
2-Amino-3 , 5-xylenesulf onic
acid
2,5-Xylidine
N-Phenyl J acid
By-products
>4.5 Direct Violet 9
Sulfanilic acid
Cresidine
N-Phenyl J acid
By-products
>2.3 Direct Blue 67
Cresidine
N-Phenyl J acid
H acid
Solid
Residue
69
•0.4

0.4
0.4
0
135
0.7
0.7
•0.7
0
69
0.4
0.4
0.4
Waste
•water
61
—

—
48
96
120
—
—
94
190
61
—
48
—
              By-products
                 96

-------
                                                       Table 12 (Continued)
                                                Annual
                                                                               Quantity Released
                                                                                    (kg/yr)
C.T.
Producer No. Dye
AC 28160 Direct Red 81
ACY
ATL
BAS
ALT
DUP
LVR
TRC
Production Material Released
metric tons/yr to Environment
1066.4 Direct Red 81
p-(p'-Aminobenzylazo)
benzene •sulfonic acid
N-Benzoyl J acid



By-products
Solid
Residue
32000
266

266



0
Waste
water
28800
—

22400



44800
  DUP
28255
Direct Orange 74
Ln
—I
>4.5
Direct Orange 74
7-Amino-3-naphthalene-
  disulfonic acid
m-Toluidine
p-Nitrobenzoyl chloride
N-p-Aminobenzoyl J acid

By-products
135
 •0.8

  0.8
  0.8
  0.8

  0
                                                                                                             120
                                                                                                             140

                                                                                                             285
  AC
  ALT
  TRC
29000
Direct Yellow 44
>6.8
Direct Yellow 44
Metanillc acid
o-AnJ sidine
200
  0.8
  0.8
180.

140
                                                             'p-Nitroaniline
                                                             Salicylic acid
                                                             Phosgene*1

                                                             By-products
                                                                                0.8
                                                                                0.8
                                                                                     140
                                                                                               285
              "Phosgene is assumed to be unstable.

-------
                                                 Table 12  (Continued)
                                                Annual
   Producer
  AC
  ALT
  FAB
  TRC
  FAB
Ln
CO
  TRC
                                                                sulfonic  acid
                                                              7-Amino-l,3-naphthalene
                                                                disulfonic  acid
                                                              m-Toluidine
                                                              Phosgene

                                                              By-products
Quantity Released
     (kg/yr)
C.I.
No.
29025





29030





29042


Production Material Released
Dye metric tons/yr to Environment
4
Direct Yellow 50 102.3 Direct Yellow 50
3-Amino-l , 5-naphthalene *
disulfonic acid
m-Toluidine
Phos genet
By-products
Direct Yellow 51 >2.3 Direct Yellow 51
3-Amino-l , 5-naphthalene
disulfonic acid
2,5-Xylidine
Phosgene.
„ By-products
Direct Yellow 118 >2.3 Direct Yellow 118
Metanilic acid
o-Anis id inome thane
Solid
Residue
3070
26

26
—
0
69
0.6

0.6
—
0
69
0.3
0.3
Waste
water
2760
—

2150
—
4300
61
—

48
	
96
61
—
48
0.3

0.3


0
48
96
              Phosgene  is assumed  to be  unstable.

-------
                              Table 12  (Continued)
                                  Annual
Quantity Released
     (kg/yr)
C.I.
Producer No. Dye
AC 29058 Direct Orange 72
FAB
TRC



AC 29060 Direct Yellow 34
ALT
TRC



ALT 29065 Direct Red 79
TRC

Production Material Released
metric tons/yr to Environment
>6.8 Direct Orange 72
7-Amino-l , 3-naphthalene-
disulfonic acid
Cresidine
Phosgene
By-products
>6.8 Direct Yellow 34
3-Amino-l, 5-naphthalenei-
disulfonic acid
Cresidine
Phosgene
By-products
>4.5 Direct Red 79
p-p-Tolylsulf onyl H acid
Cresidine
Solid
Residue
204
1.7

1.7

0
204
1.7

1.7
—
0
135
1.1
1.1
Waste
water
180
—

140

285
180
—

140
—
285
121
—
94
                                               Phosgene
                                               By-products
                190
tPhosgene is assumed to be unstable.

-------
                                                     Table 12  (Continued)
 Producer
ATL
TRC
                                                                                             Quantity  Released

C.I.
No. Dye
29100 Direct Red 31



Annual
Production
metric tons/yr
>4.5



(kg/yr)
Material Released
to Environment
Direct Red 31
Aniline (2 mol)
6,6t-^Iminobis^-l-naphthol-3-
sulfonic acid
Solid
Residue
135
1.4
0.7

Waste
water
120
—
94

                                                           By-products
                                                                                               190
ATL
29105
Direct Violet 14
                                              >2.3
Direct Violet 14
2,4-Xylidine (.2 mol)
6,6' -Iminobis-l-naphthol-3^-
  sulfonic acid

By-products
69
 0.8
 0.4
61

48


96
ATL
29110
Direct Red 149
                                              >2.3
Direct Red 149                  69
m-Aminoformanilide (2--mol)       0.8
6,6'-Iminobis-l- naphthol-3-     0.4
  sulfonic acid
                 61

                 48
                                                           By-products
                                                                                                96

-------
   Table 12 (Continued)
Annual
Quantity Released
     (kg/yr)
C.I.
Producer No.
ATL 29120
TRC





TRC 29155


i — •
o\
h- '

AC 29156
ACY
ATL
BAS
DVP
Production Material Released
Dye metric tons/yr to Environment
Direct Violet 66 >4.5 Direct Violet 66
2-Amino -1 -pheno 1-4 -
sulfonamide
6,6' -Iminobis-l-naphthol-3-
sulfonic acid
Copper (Cu+2)
By-products
Direct Orange 29 >2.3 Direct Orange 29
Aniline
6 ,6 '-Ureylenebis-1-naphthol-
3-sulfonic acid
m-Aminobenzoic acid
By-products
Direct Orange 102 192.3 Direct Orange 102
Aniline.
6, 6'-Ureylenebis-l-naphthol-.
3-sulfonic acid
p-Aminobenzoic acid
Solid
Residue
135
0.7

0.7

14
0
69
0.4
0.4

0.4
0
5770
32.

32
32
Waste
Water
120
—

94

12
190
61
—
48

—
96
5190
—

4040
—
             By-products
               8070

-------
                                        Table 12  (Continued)
                                   Annual
Quantity Released
     (kg/yr)
C.I.
Producer No. Dye
AC 29160 Direct Red 23
ACY
ATL
ALT
DUP
FAB
TRC
TRC 29165 Direct Red 4

j— j
M


ATL 29175 Direct Red 62
TRC

Production Material Released
metric t'ons/yr to Environment
65.4 Direct Red 23
Aniline
6,6' Ureylenebis-1-naphthol-
3-sulfonic acid
p-Aminoacetanilide

By-products
>2.3 Direct Red 4
Aniline
6,6" -Ureylenebis-1-naphthol-.
3-sulfonic acid
Broenner's acid
By-products
>4.5 Direct Red 62
o-Toluidine.
6,6' -Urey'ienebis-1- naphthol-
Solid
Residue
1960
10.9
10.9
10.9

0
69
0.4
0.4
0.4
0
135.
0.7
0.7
Waste
water
1770
—
1370.
—

2750
61
—
48
—
96
120
—
94
                                                  3-sulfonic acid
                                                4-Amino-m-toluenesulfonic
                                                  acid (buffered with
                                                  acetic acid)
                                                By-products
 0.7
UAcetic acid release was not quantified but is assumed to be in the aqueous phase.
               190

-------
                                                      Table 12 (Continued)
                                                   Annual
Quantity Released
     (kg/yr)
CTi
U)
C.I.
Producer No. Dye
AC 29180 Direct Red 73





AC 29185 Direct Red 24
ATL
ALT
FAB
TRC


ATL 29190 Direct Red 26





Production Material Released
metric tons/yr to Environment
>2.3 Direct Red 73
o-Toluidine
6,6' -Ureylenebis-1- naph thol-
3-sulfonic acid
Broenner's acid
By-products
94.1 Direct Red 24
4-Amino-m- toluenesulf onic
acid
6,6' -Ureylenebis-1-naphthol-
3-sulfonic acid
o-Anisidine
By-products
>2.3 Direct Red 26
o-Anisidine
6,6' -Ureylenebis-1-naphthol-
3-sulfbnic acid
Naphthionic acid
By-products
Solid
Residue
69
0.4
0.4

0.4
0
2820
16

16.

16
0
69
0.4

0.4
0.4
0
Waste
water
61
—
48

—
96
'2540
—

1980

	
3950
61
—

48
—
96

-------
                                      Table 12 (Continued)
                                  Annual
Quantity Released
     (kg/yr)
C.I.
Producer No. Dye
ATL 29200 Direct Red 72
BAS
ALT
DUP
TRC


TRC 29210 Direct Red 122

j
r>


AC 29225 Direct Red 83
ATL
ALT
FAB
TRC


Production Material Released
metric tons/yr to Environment
266,4 Direct Red 72
o-Anisidine (0.6 mol) ,
o-Toluidine (0.4 mol)
6,6' -r-Ur eylenebis-1-naphthol"-
3-sulfonic acid
Broenner's acid
By-products
>2.3 Direct Red 122
m-Aminoformanilide (2 mol)
6,6' -Ur eylenebis-1-naphthol-
3-sulfonic acid
By-products
67.3 Direct Red 83
4-Methoxymetanilic acid
(2 mol)
6,6' -Ureylenebis-1-naphthol-
3-sulfonic acid
Copper (Cu"1"2)
Ammoniav
Solid
Residue
7990
27
17
44

44
0
69
0.8
0.4

0
2000
16

8

210
0.
Waste
water
7190
—
—
5590

—
11200
61
—
48

96
1800
. —

1400

180
—
                                                By-products
7Ammonia release was not quantified but is assumed to be in the aqueous phase.
              2800

-------
                                                      Table 12 (Continued)
  Producer
AC
   C.I,
   No.

30015
Dye
                        Direct Black  78
    Annual
  Production
metric tons/yr

>2.3
AC
ATL
ALT
FAB
31600
                        Direct Black 80
             >9.5
ATL
34010
                        Direct Blue  126
             >2.3
                                                                 Material Released
                                                                   to Environment
                                                                                             Quantity Released
                                                                                                   (kg/yr)
                              Direct Black 78
                              1,6(and l,7)-Cleve's acid
                              p-Nitroaniline
                              S acid

                              By-products
                 Direct Black 80
                 Gamma Acid
                 l,6(and l,7)-Cleves acid
                 p-Aminoacetanilide

                 By-products
                 Direct Blue 126
                 3-Aminorl,5-naphthalene
                   disulfonic acid
                 1-Naphthylamine
                 l,6(and l,7)-Cleve's acid
                 Cresidine
Solid
Residue
69
0.3
0.6
Q.3
0
285
2.4
1.2
1.2
0
69
0.3
0.3
0.3
0.3
Waste
water
61
48
—
48
180
255
200
200
—
730
61
—
	
. —
48
                                                             By-products
                                                                                                180

-------
                                              Table 12  (Continued)
   Producer
                 C.I.
                 No.
                 Dye
 TRC
34045
                        Direct  Green 26
                        Annual
                      Production
                    metric tons/yr

                    >2.3
                                                    Material Released
                                                       to Environment
                 Direct Green 26
                 Cyanuric Chloride
                 H acid
                 p—Nitroaniline
                 Salicylic acid
                 Aniline
                 Cresidine

                 By-products
                                                  Quantity Released
                                               	(kg/yr)	
                                               Solid            Waste
                                               Residue          water
                                                                                 69
                                                                                                ,2
                                                                                                .2
                                                                                  0.
                                                                                  0.
                                                                                  0.2
                                                                                  0.2
                                                                                  0.2

                                                                                  0
                                                  61
                                                                                                              180
AC
TRC
34085
Direct Blue 120
>4.5
Direct Blue 120                 135
p-Aminooxanilic acid              0. 6
1,6-Cleve's acid                   1.2
Nevile and Winther's ac;Ld         0.6

By-products                       0
                 120


                  94

                 340
AC
TRC
34090
Direct Blue 120A
>4.5
Direct Blue 120A
p-Aminooxanilic acid
1,6-Cleve's acid
Schaeffer's; acid

By-products
135
  0.6
  1.2
 '0.6

  0
120


 94

340

-------
                                                  Table 12 (Continued)
  Producer
                C.I.
                No.
                 Dye
AC
34200
                       Direct Blue  78
                        Annual
                      Production
                    Metric tons/yr

                    >2.3
                                                    Material Released
                                                      to Environment
                                                  Quantity Released
                                               	(kg/yr)	
                                               Solid            Waste
                                               Residue          water
                 Direct Blue 78
                 2-Amino-p-benzene-
                   disulf onic. aClid
                 1,7-Cleve's acid
                 1-Naphthylamine
                 N-Phenyl J acid

                 By-products
                                 69

                                  0.3
                                  0.3
                                  0.3
                                  0.3

                                  0
                 61
                                                                                                               48

                                                                                                              180
TRC
34220
Direct Blue 75
>2.3
Direct Blue 75
Metanilic acid
1,6-Cleve's acid
N-Phenyl J acid

By-products
69
 0.3
 0.6
 0.3

 0
 61


 48

180
TRC
34260
Direct Green 51
>2.3
Direct Green 51
Metanilic acid
1,7-Cleve's acid
5-Amino-6-ethoxy-2-naph-
 j thalene sulfonic acid
N-m-Aminobenzoyl J acid
Pyridine"

By-products
69
 0.3
 0.3
 0.3

 0.3
 61
                                                                                                               48
                                                                                                              180
             wPyridine is used as a  solvent.   No  estimation  of  the  quantity  of  this  solvent was made.

-------
                 C.I
   Producer      No.
  FAB
 TRC
ON
00
               35005
                                                Table 12 (Continued)
                                                Annual
35255
                                                              By-products
                                                                                Quantity Released
                                                                                     (kg/yr)
Production Material Released
Dye metric tons/yr to Environment
Direct Brown 44 >4.5 Direct Brown 44
Sulfanilic acid
tn-Phenylenediamine
By-products
Direct Black 19 >2.3 Direct Black 19
p-Nitroan±line
m-Pheny lene d iamine
H acid
Solid
Residue
136
0.9
1.4
0
69
0.5
0.5
0.2
Waste
water
123
—
96
690
61
—
48
—
                                                                                                350
 AC
 ATL
 ALT
 TRC
 VPC
35435
Direct Black 22
Direct Black 22                 342
5-Amino-2-(p-aminoanilino)-        1.2
  benzenesulfonic acid
Gamma Acid                        2.4
m-Phenylenediamine                2.4

By-products                       0
 308



 239

1740

-------
                                     Table 12  (Concluded)
                                 Annual
Quantity Released
     (kg/yr)
Producer
AC
ATL
ALT
FAB
TRC
C.I.
No. Dye
35780 Direct Red 80



Production
metric tons/yr
200.9



Material Released
to Environment
Direct Red 80
6-Amino-3 , 4 ' -azod ibenzene-
sulfonic acid-
N-Acetyl J acid
Phosgene*
Solid
Residue
6030
50

50
Waste
w'a t c r
5420
—

	
                                              By-products
              30500
Phosgene is assumed to be unstable.

-------
                               Table 13

        INTERMEDIATES USED IN TABLE 12 THAT HAVE COMMON NAMES
l-Amino-4-naphthalene sulfonic acid

l-Amino-6-naphthalene sulfonic acid

l-Amino-7-naphthalene sulfonic acid

2-Amino-6-naphthalene sulfonic acid

l-Amino-8-hydroxy-4-naphthalene sulfonic acid

6-Amino-4-hydroxy-2-naphthalene sulfonic acid

7-Amino-4-hydroxy-2-naphthalene sulfonic acid

l-Amino-8-hydroxy-3,6-naphthalene disulfonic
  acid

4-Amino-5-hydroxy-l,3-naphthalene disulfonic
  acid

1,S-Dihydroxy-3,6-naphthalene disulfonic
  acid

2-Hydroxy-3,6-naphthalene disulfonic acid

2-Hydroxy-6,8-naphthalene disulfonic acid

N-Acetyl-l-amino-8-hydroxy-3,6-naphthalene
  disulfonic acid

N-Acetyl-2-amino-5-hydroxy-7-naphthalene
  sulfonic acid

N-Acetyl-7-amino-l-hydroxy-3-naphthalene
  sulfonic acid

N-Benzoyl-7-amino-4-hydroxy-2-naphthalene
  sulfonic acid

N-Phenyl-l-amino-8-naphthalene
  sulfonic acid

N-Phenyl-2-amino-8-hydroxy-6-naphthalene
  sulfonic acid

N-Phenyl-7-amino-4-hydroxy-2-naphthalene
  sulfonic acid
(Naphthionic acid)

(1,6-Cleve's acid)

(1,7-Cleve's acid)

(Broenner's  acid)

(S acid)

(Gamma acid)

(J acid)

(H acid)


(Chicago  acid)


(Chromotrophic  acid)


(R acid)

(G acid)

(N-Acetyl H  acid)


(N-Acetyl J  acid)


(N-Acetyl Gamma acid)


(N-Benzoyl J acid)


(N-Phenyl Peri  acid)


(N-Phenyl Gamma acid)


(N-Phenyl J  acid)
                                  170

-------
                          Table 13  (Concluded)
N-m-Aminobenzoyl-7-amino-4-hydroxy-2-
  naphthalene. sulfonic acid

N-p—Aminobenzoyl-7- amino--4-hydroxy-2-
  naphthalene sulfonic acid

N-p-Tolyl-1-amino—8-napb.thalene sulfonic
  acid

o-Phenylsulfonyl-l-amino-8-hydroxy-3,6-
  naphthalene disulfonic acid

o-Phenylsulfonyl-2-amino-8-hydroxy-3,6-
  naphthalene disulfonic acid

o-Tolysulfonyl-l-amino-8-hydroxy-3,6-
  naphthalane disulfonic acid

2-Aminobenzene sulfonic acid

4-Aminobenzene sulfonic acid

3-Methyl-2-hydroxy-benzoic acid
(N-m-Aminobenzoyl J acid)


(N-p-Aminobenzoyl J acid)


(N-p-Tolyl Peri acid)


(o-Phenylsulfonyl H acid)


(o-Phenylsulfonyl 2 R acid)


(o-Tolylsulfonyl H acid)


(Orthanilic acid)

(Sulfanilic acid)

(2 ,3-Cresotic acid)
                                 171

-------
                                Table 14
     DIRECTORY OF AZO DYE AND ORGANIC PIGMENT MANUFACTURERS, 1978
  Names of manufacturers that- reported production and/or sales of azo
  dyes and pigments (other than those based on benzidine and its
  congeners)  to the U.S. International Trade Commission for 1978 are
  listed below in order of their identification codes as used in Table 12.
Code
            Name of Company
AC   American Color c Chemical Corp.
ACY  American Cyanamid Co.
ALL  Alliance Chemical Corp.
ALT  Crompton & Knowles Corp.,
       Dyes and Chemical Div.
AMS  Ridgway Color & Chemicals
APO  Apollo Colors, Inc.
ATL  Atlantic Chemical Corp.
     BASF Wyandotte Corp.
     Buffalo Color Corp.
     Benzenoid Organics Inc.
     Binney and Smith, Inc.
BAS
BCC
EDO
BNS
BOR
BUG
Borden, Inc., Printing
  Ink Div., Pigments Div.
Synalloy Corp., Blackman-
  Uhler Chemical Div.
CGY  Ciba-Geigy Corp.
CIK  Flint Ink Corp.
DUPaE.I. du Font de Nemours
       & Co., Inc.
EKT  Eastman Kodak Co.
FAB  Fabricolor Incorporated
GAF  GAF Corp.
GLX  Galaxie Chemical  Corp.
HPC  Hercules, Inc.
HRC  Harmon Colors Corp.
   c
HSC  Chemetron Corp.,  Pigments
       Div., Subsid. of  Allegheny
       Ludlum Industries,  Inc.
Code
HST
ICC
ICI
IDC
IND
KWC
KON
LVR
MAY

MGR
MRT
MRX
PCW
PDC
PSC
ROM
                                      SDC
                                      SDH

                                      SNA

                                      STG
                                      TMS
                                           Name of Company
American Hoechst Corp.
Inmont Corp.
ICI Americas  Inc.
Industrial Color, Inc.
Indol Chemical Co., Inc.
Keystone Color Works Inc.
H. Kohnstamm & Co., Inc.
C. Lever Co.  Inc.
Otto B. May Co.
  Div. of  Cone Mills Corp.
Magruder Color Co.
Morton Norwich Products Inc.
Max Marx Color & Chem.  Co.
Pfister Chemical VIorks
Berncolors-Poughkeepsie Co.
Passaic Color &  Chem. Co.
                                        United Merchants & Manufac-
                                          turers, Inc. Roma Chemical
                                          Div.
                                        Sandoz, Inc., Colors &
                                          Chemicals Div.
                                        Martin-Marietta Corp.
                                        Sterling Drug, Inc. Hilton
                                          Davis Chemical Co. Div.
                                        Sun  Chemical  Corp., Pigments
                                          Div.
                                        Stange  Co.
                                        Sterling Drug, Inc., Thomasset
                                          Colors Div.
                                    172

-------
                          Table 14  (Concluded)
IISH  Harshaw Chemical Co.
TRC    Tons River Chemical Corp,

UHL    Paul Uhlich & Co. Inc.

VPC
                                      WJ
llobay Chemical Corp.
  Verona Dyestuff Div.

Warner-Jenkinson Co.
   In 1979 duPont sold its paper dye operations to Mobay Chemical Corp.,
   and its textile dye operations to Ciba-Geigy Corp. and Crompton and
   Knowles Corp.  In 1979 duPont sold its dyes for ink operations to
   Morton Norwich Products Inc., Morton Chemical Co. Division.

  3In 1978 GAF Corp. sold its dye operations to BASF Wyandotte Corp.

  "In 1978 Chemetron Corp. sold its dye operations to BASF Wyandotte Corp
                                    173

-------
                                     Table 15
                    PRODUCERS OF MONOAZO DYES AND PIGMENTS
CM.  No.    	C.I.  Name
American  Color  & Chemical Corp.
18967      Acid Yellow 19
18835      Acid Yellow 25
19010      Acid Yellow 54
13906      Acid Yellow 151
15510      Acid Orange 7
15510:1    Pigment Orange 17
15510:2    Pigment Orange 17:1
15510:3    Solvent Orange 49
15575      Acid Orange 8
16230      Acid Orange 10
13150      Acid Orange 50
18732      Acid Orange 60
18050      Acid Red 1
14710      Acid Red 4
17045      Acid Red 37
18810      Acid Red 186
14880      Acid Blue 158
15711      Acid Black  52
19140      Food Yellow 4
19140:1    Pigment Yellow 100
11855      Disperse Yellow 3
11005      Disperse Orange 3
11110      Disperse Red 1
11215      Disperse Red 5
11150      Disperse Red 7
11210      Disperse Red 17
11228      Disperse Red 65
11152      Disperse Brown 1
11365      Disperse Black 1
15050      Acid Blue 158:1
C.I. No.
13095
13091
       C.I. Name
Acid Yellow 63
Acid Orange 1
American Cyanamid Co.

13080       Acid Orange 5
15510       Acid Orange 7
15510:1     Pigment Orange 17
15510:2     Pigment Orange 17:1
15510:3     Solvent Orange 49
15575       Acid Orange 8
16230       Acid Orange 10
18740       Acid Orange 72
18050       Acid Red 1
16150       Acid Red 26
16580       Acid Violet 3
19140       Food Yellow 4
19140:1     Pigment Yellow 100
12055       Solvent Yellow 14
11021       Solvent Yellow 56
12140       Solvent Orange 7
11320       Basic Orange 1
11320:1     Solvent Orange 4
11270       Basic Orange 2
11270:1     Solvent Orange 3
11052       Basic Blue 54
18760       Mordant Red 7
12075       Pigment Orange 5
12120       Pigment Red 3
12085       Pigment Red 4
12390       Pigment Red 17
12315       Pigment Red  22
                                        174

-------
C.I. No.
12355
15865
15630
15860
15585
15850
17100
11043
11014
11480
C.I. Name
Pigment Red
Pigment Red
Pigment Red
Pigment Red
Pigment Red
Pigment Red

23
48
49
52
53
57
Acid Brown 90
Basic Violet
Basic Red 30
18

Basic Yellow 24
Crompton & Rnowles Corp.
Dyes- and Chemical Div.
17101
18967
18732
15985
19140
19140:1
11855
11005
11227
11110
11215
11210
11228
11152
14700
16035
18950
_
Acid Red 266
Acid Yellow
Acid Orange
Food Yellow
Food Yellow
>
19
60
3
4
Pigment Yellow 100
Disperse Yellow 3
Disperse Orange 3
Disperse Orange 25
Disperse Red
Disperse Red
Disperse Red
Disperse Red
1
5
17
65
Disperse Brown 1
Food Red 1
Food Red 17
Acid Yellow
Acid Red 337


40

— Disperse Blue 79
Ridgxtfay Color & Chemicals-
11680
12085
15865
15630
Pigment Yellow 1
Pigment Red
Pigment Red
Pigment Red
4
48
49
Table 15 (Continued)
              C.I. No.
              1586Q
              15585
              15850
  C.I. Name
Pigment Red 52
Pigment Red 53
Pigment Red 57
              Apollo Colors,  Inc.
              15585       Pigment  Red 53
              15850       Pigment  Red 57

              Atlantic Chemical Corp.
              18965       Acid Yellow 17

              18967       Acid Yellow 19
              18890.       Acid Yellow 34
              14170       Acid Yellow 65
              15510       Acid Orange 7
              15510:1     Pigment  Orange  17
              15510:2     Pigment  Orange  17:1
              15510:3     Solvent  Orange  49
              15575       Acid Orange 8
              16230       Acid Orange 10
              13025       Acid Orange 52
              18732       Acid Orange 6Q
              18050       Acid Red 1
              147 20.       Acid Red 14
              16255       Acid Red 18
              15620       Acid Red 88
              17755       Acid Red 137
              16580       Acid Violet 3
              18055       Acid Violet 7
              13390       Acid Blue  92
              15711       Acid Black 52
              12055       Solvent Yellow 14
              12140       Solvent Orange 7
              11270       Basic Orange 2
              11270:1     Solvent Orange 3
          175

-------
C.I.  No.          C.I.  Name
11085       Basic Red  18
13950       Direct Yellow 27
18760       Mordant Red 7
19555       Direct Yellow 28
11005       Disperse Orange 3
11100       Disperse Orange 5
11119       Disperse Orange 30
11110       Disperse Red 1
11115       Disperse Red 13
11152       Disperse Brown 1
18950       Acid Yellow 40

BASF Wyandotte Corp.
Table 15 (Continued)
             C.I. No.
             11085
             11460
             11154
             11052
             15602
             19555
             14645
             15705
             11110
   ;          11115
             11210
             11116
             11480
     C.I. Name
13065       Acid Yellow 36
13900       Acid Yellow 99
13900:1     Solvent Yellow 19
18690       Acid Yellow 121
15510       Acid Orange 7
15510:1     Pigment Orange 17
15510:2     Pigment Orange 17:1
15510:3     Solvent Orange 49
16230       Acid Orange 10
14710       Acid Red 4
14720       Acid Red 14
15620       Acid Red 88
17101       Acid Red 266
17755       Acid Red 137
15711       Acid Black 52
19140       Food Yellow 4
19140:1     Pigment Yellow 100
12715       Solvent Red 8
11270       Basic Orange 2
11270:1     Solvent Orange 3
   -        Acid Red 337
    —       Disperse Blue 79
Basic Red 18
Basic Red 29
Basic Blue 41
Basic Blue 54
Pigment Orange 46
Direct Yellow 28
Mordant Black 11
Mordant Black 17
Disperse Red 1
Disperse Red 13
Disperse Red 17
Disperse Red 73
Basic Yellow 24
             Buffalo  Color Corporation
             17200       Acid Red 33
             15985       Food Yellow 3
             19140       Food Yellow 4
             19140:1      Pigment Yellow 100
             12156       Solvent Red 80
             14700       Food Red 1
             16035       Food Red 17

             Benzenoid Organics  Inc.
             18820       Acid Yellow 11
             18965       Acid Yellow 17
             18890       Acid Yellow 34
             15510.       Acid Orange 7
             15510:1      Pigment Orange 17
             15510:2      Pigment Orange 17:1
             15510:3      Solvent Orange 49
             18050       Acid Red 1
             14710       Acid Red 4
             17025       Acid Violet 1
                                       176

-------
                               Table
C.I. No.
18055
18075
18760
    C.I. Name
Acid Violet 7
Acid Violet 12
Mordant Red 7
15 (Continued)
       C.I. No.
C.I. Name
Binney and Smith,  Inc.
11710       Pigment Yellow 3
12390       Pigment Red 17
12300       Pigment Red 21
15630       Pigment Red 49
15850       Pigment Red 57

Borden, Inc.,  Printing  Ink Div.,
  Pigments Div.	
15865       Pigment Red 48
15630       Pigment Red 49
15585       Pigment Red 53
15850       Pigment Red 57

Synalloy Corp.,  Blackman-Uhler
  Chemical Div.	
12355       Pigment Red 23
11152       Disperse Brown 1

Ciba-Geigy Corp.
12070       Pigment Red 1

Flint Ink Corp.
12120       Pigment Red 3
15630       Pigment Red 49
15585       Pigment Red 53
15850       Pigment Red 57

E. I. du Pont  de Nemours & Co., Inc.
13065       Acid Yellow 36
13906       Acid Yellow 151
18930       Acid Yellow 200
       18732        Acid  Orange 60
       18050        Acid  Red  1
       17755        Acid  Red  137
       12055        Solvent Yellow  14
       11270        Basic Orange  2
       11270:1     Solvent Orange  3
       11056        Basic Orange  24
       11085        Basic Red 18
       11680        Pigment Yellow  1
       11741        Pigment Yellow  74
       12120        Pigment Red 3
       12090        Pigment Red 6
       12315        Pigment Red 22
       12355        Pigment Red 23
       15865        Pigment Red 48
       15850        Pigment Red 57
       15825        Pigment Red 58
       12775        Pigment Green 10
       19555        Direct Yellow 28
       11227        Disperse  Orange 25
       11110        Disperse  Red 1
       12476        Disperse  Red 220
       11077        Disperse  Blue 165
       11087        Basic Yellow 15
                   Acid  Red 337
       Eastman Kodak Co.
       11855        Disperse  Yellow 3
       11100        Disperse  Orange 5
       11227        Disperse  Orange 25
       11110        Disperse Red 1
       11210       Disperse Red 17
       11228        Disperse Red 65
                   Disperse Blue  79
       Fabricolor Incorporated
                                 13390
                   Acid Blue 92
                                        177

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                              Table 15
C.I. No.    _   C.I. Name
15711       Acid Black 52
11119       Disperse Orange 30
18200       Reactive Red 2
18260       Reative Orange 4
 —         Disperse Red 54
GAP Corp.
13900       Acid Yellow 99
13900:1     Solvent Yellow 19
15510       Acid Orange 7
15510:1     Pigment Orange 17
15510:2    -Pigment Orange 17:1
15510:3     Solvent Orange 49
16230       Acid Orange 10
18745       Acid Orange 74
18050       Acid Red 1
14710       Acid Red 4
14720       Acid Red 14
15620       Acid Red 88
17755       Acid Red 137'
19140       Food Yellow 4
19140:1     Pigment Yellow 100
11320       Basic Orange 1
11320:1     Solvent Orange 4
11270       Basic Orange 2
11270:1     Solvent Orange 3
11085       Basic Red 18
11052       Basic Blue 54
12490       Pigment Red 5
19555       Direct Yellow 28
11110       Disperse Red 1
11115       Disperse Red 13
11210       Disperse Red 17
(Continued)
C.I. No.
Galaxie
11680
11741
12490
12315
12355
12320
15800:2
15800
Hercules
11680
11710
11660
11670
11738
11741
11770
120.60
12075-
12310
12120
12085
12490
12460
12395
12390
12315
12355
15865
15860
15850
15825
12370
12775
C.I. Name
Chemical Corp.
Pigment Yellow 1
Pigment Yellow 74
Pigment Red 5
Pigment Red 22
Pigment Red 23
Pigment Red 32
Pigment Brown 5
Pigment Red 64
, Inc .
Pigment Yellow 1
Pigment Yellow 3
Pigment Yellow 5
Pigment Yellow 6
Pigment Yellow 73
Pigment Yellow 74
Pigment Yellow 75
Pigment Orange 2
Pigment Orange 5
Pigment Red 2
Pigment Red 3
Pigment Red 4
Pigment Red 5
Pigment Red 9
Pigment Red 13
Pigment Red 17
Pigment Red 22
Pigment Red 23
Pigment Red 48
Pigment Red 52
Pigment Red 57
Pigment Red 58
Pigment Red 112
Pigment Green 10
                                        178

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C.I. No.
Table 15
C.I. Name
Harmon Colors Corp .
11680
11710
11740
11738
11741
11725
12310
15865
15800:2
15800

Pigment Yellow 1
Pigment Yellow 3
Pigment Yellow 65
Pigment Yellow 73
Pigment Yellow 74
Pigment Orange 1
Pigment Red 2
Pigment Red 48
Pigment Brown 5
Pigment Red 64

Chemetron Corp . , Pigments Div . ,
Subsid

11680

11710

11741

12075
12120

12085
15865
15630
15860
15585
15880

Harshaw

11000
11680
11710
12705
11740
11738
11741
12075
. of Allegheny Ludlum Ind . Inc .

Pigment Yellow 1

Pigment Yellow 3

Pigment Yellow 74

Pigment Orange 5
Pigment Red 3

Pigment Red 4
Pigment Red 48
Pigment Red 49
Pigment Red 52
Pigment Red 53
Pigment Red 63

Chemical Co .

Solvent Yellow 1
Pigment Yellow 1
Pigment Yellow 3
Pigment Yellow 60
Pigment Yellow 65
Pigment Yellow 73
Pigment Yellow 74
Pigment Orange 5
(Continued)
C.I. No.
12070
12310
12120
1249-0
12090
12355
15865
15860
15585
14830:1
14830
15850
15880

11855

11110

11215

16105:1


American

C.I. Name
Pigment Red 1
Pigment Red 2
Pigment Red 3
Pigment Red 5
Pigment Red 6
Pigment Red 23
Pigment Red 48
Pigment Red 52
Pigment Red 53
Pigment Red 54
Acid Red 20
Pigment Red 57
Pigment Red 63

Disperse Yellow 3

Disperse Red 1

Disperse Red 5

Pigment Red 60:1


Hoechst Corn.
Industrial Chemicals Div.
18852
17757
11680
11710
11720
11738
11741
11767
12075
12367
12420
12460
12465
12370
12485
Reactive Yellow 17
Reactive Orange 16
Pigment Yellow 1
Pigment Yellow 3
Pigment Yellow 9
Pigment Yellow 73
Pigment Yellow 74
Pigment Yellow 97
Pigment Orange 5
Pigment Orange 38
Pigment Red 7
Pigment Red 9
Pigment Red 15
Pigment Red 112
Pigment Red 146
179

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                              Table 15
C.I. No.
12475
12467
11077
11152
18097
Inmont Corp.
C.I. Name
Pigment Red 170
Pigment Red 188
Disperse Blue 165
Disperse Brown 1
Reactive Violet 5
12390 Pigment Red 17
15865 Pigment Red 48
15630 Pigment Red 49
15585 Pigment Red 53
15850 Pigment Red 57
15800:2 Pigment Brown 5
15800 Pigment Red 64
ICI Americas Inc.
18967
17101
17053
Acid Yellow 19
Acid Red 266
Acid Red 57
(Continued)
    C.I.  No.
                                                            C.I. Name
           Reactive Yellow 1
13190      Reactive Yellow 4
—         Reactive Orange 1
18158      Reactive Red  1
17908      Reactive Red  8
11152      Disperse Brown  1
18200      Reactive Red  2
18260      Reactive Orange 4
18270      Reactive Orange 13

Industrial Color,  Inc.
15630      Pigment Red 49
15585      Pigment Red 53
15850      Pigment Red 57

Indol Chemical Co., Inc.
12355      Pigment Red 23
12320       Pigment Red 32
    Keystone Color Works Inc.
    11680  '     Pigment Yellow 1
    11730       Pigment Yellow 2
    11710       Pigment Yellow 3
    11660       Pigment Yellow 5
    11727       Pigment Yellow 98
    11725       Pigment Orange 1
    12060       Pigment Orange 2
    12070       Pigment Red 1
    12310       Pigment Red 2
    12120       Pigment Red 3
    12090       Pigment Red 6
    12395       Pigment Red 13
    12315       Pigment Red 22
    12355       Pigment Red 23

    H. Konnstamm & Co., Inc.
    17200       Acid Red 33
    15985       Pigment Yellow 1Q4
    19140       Food Yellow 4
    19140:1     Pigment Yellow 100
    11680       Pigment Yellow 1
    11710       Pigment Yellow 3
    12705       Pigment Yellow 60
    12120       Pigment Red 3
    12085       Pigment Red 4
    12090       Pigment Red 6
    15630       Pigment Red 49
    15585       Pigment Red 53
    15850       Pigment Red 57
    15880       Pigment Red  63
    16105:1     Pigment Red  60:1
    16035       Food  Red  17
                                        180

-------
                                Table 15
C.I. No.
C.I. Name
(Continued)
    C.I.  No.
                    C.I.  Name
Magruder Color Co.
15865         Pigment Red 48
15860         Pigment Red 52
15585         Pigment Red 53
15850         Pigment Red 57

Max Marx Color & Chem. Co.
19140         Food Yellow 4
19140:1      Pigment Yellow 100
12120         Pigment Red 3
12085         Pigment Red 4
12460         Pigment Red 9
12315         Pigment Red 22
15865         Pigment Red 48
15860         Pigment Red 52
15585         Pigment Red 53
16105:1      Pigment Red 60:1

 Berncolors-Poughkeepsie  Co.
15510        Acid Orange 7
15510:1      Pigment Orange 17
15510:2      Pigment Orange 17:1
15510:3      Solvent Orange 49
14710        Acid Red 4
14720        Acid Red 14
14025        Mordant Yellow 1
18821        Mordant Yellow 8
14110        Mordant Yellow 20
14030        Mordant Orange 1
18760        Mordant Red  7
15670        Mordant Violet 5
 19555        Direct Yellow 28
 13250        Mordant Brown 33
 17590        Mordant Brown 40
 13265        Mordant Brown 70
                            Passaic Color & Chem. Co.
                            15970       Acid Orange  12
                            11160       Solvent Yellow 3
                            12055       Solvent Yellow 14
                            12700       Solvent Yellow 16
                            11021       Solvent Yellow 56
                            12100       Solvent Orange 2
                            12140       Solvent Orange 7
                            12150       Solvent Red  1
                            11320       Basic Orange 1
                            11320:1     Solvent Orange 4
                            11270       Basic Orange 2
                            11270:1     Solvent Orange 3
                             United Merchants  & Manufacturers,  Inc.
                               Roma Chemical Div.
                             12490
                             12390
                             12355
                             12360
                             15800:2
                             15800
                Pigment Red 5
                Pigment Red 17
                Pigment Red 23
                Pigment Red 31
                Pigment Brown 5
                Pigment Red 64
                             Sandoz,  Inc.,  Colors & Chemicals Div.
                             11680       Pigment Yellow 1
                             11765       Pigment Yellow 49
                             12310       Pigment Red 2
                             12490       Pigment Red 5
                             12420       Pigment Red 7
                             15865       Pigment Red 48
                             12475       Pigment Red 170
                             12480       Pigment Brown 1

                             Martin-Marietta Coro.
                             11152
                Disperse  Brown 1
                                         181

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                             Table 15
 C.I.  No.         C.I. Name
 Sterling  Drug,  Inc.
  Hilton Davis Chemical Co0  Dlv.
18965         Acid  Yellow 17
15711         Acid  Black 52
15985         Food  Yellow 3
19140         Food  Yellow 4
19140:1       Pigment  Yellow 100
16105:1       Mordant  Red 9
11680         Pigment  Yellow  1
11741         Pigment  Yellow 74
12075         Pigment  Orange  5
12070         Pigment  Red 1
12120         Pigment  Red 3
12085         Pigment  Red 4
12355         Pigment  Red 23
12360         Pigment  Red 31
15630         Pigment  Red 49
15585         Pigment  Red 53
15850         Pigment  Red 57
16035         Food  Red 17
16185         Acid  Red 27

Sun Chemical Corp., Pigments Div.
11680         Pigment  Yellow 1
11740         Pigment  Yellow 65
11738         Pigment  Yellow 73
11741         Pigment  Yellow 74
12075         Pigment  Orange 5
12120         Pigment  Red 3
12390         Pigment  Red 17
12315         Pigment  Red 22
15865         Pigment  Red 48
15630         Pigment  Red 49
15860         Pigment  Red 52
15585         Pigment  Red 53
15850         Pigment  Red 57
15880         Pigment  Red 63
16105:1       Pigment  Red 60:1
(Continued)
       C.I.  No.
       Stange Co.
       15935
       19140
       19140:1
    C.I. Name
Food Yellow 3
Food Yellow 4
Pigment Yellow 100
       Sterling Drug,  Inc.,
         Thomas-set Colors: Div.
       15585       Pigment Red  53
       15850       Pigment Red  57

       Toms. River Chemical Corp.
       189.65       Acid Yellow  17
       18900       Acid Yellow 29
       13065       Acid Yellow  36
       19010       Acid Yellow  54
       14170       Acid Yellow 65
       13900       Acid Yellow  99
       139.0.0:1     Solvent Yellow  19
       19005       Acid Yellow  127
       13906       Acid Yellow  151
       15510  v     Acid Orange  7
       15510:1     Pigment Orange  17
       15510:2     Pigment Orange  17:1
       15510:3     Solvent Orange  49
       15575       Acid Orange  8
       16230       Acid Orange  1Q
       18732       Acid Orange  60
       18745       Acid Orange  74
       18050       Acid Red 1
       14710       Acid Red 4
       16255       Acid Red 18
       17045       Acid Red 37
       17053       Acid Red 57
       17101       Acid Red 266
       15620       Acid Red 88
       17755       Acid Red 137
       19351       Acid Red 179
       16580       Acid Violet 3
       14880       Acid Blue 158
                                         182

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                              Table 15
C.I. No.        C.I. Name
13361       Acid Green 35
15711       Acid ELack  52
18165       Acid Black 60
19140       Food Yellow 4
19140:1     Pigment Yellow 100
11320       Basic Orange 1
11320:1     Solvent Orange 4
11270       Basic Orange 2
11270:1     Solvent Orange 3
11055       Basic Red 22
11154       Basic Blue 41
—          Reactive Yellow 2
13245       Reactive Yellow 3
14030       Mordant Orange 1
19555       Direct Yellow 28
13250       Mordant Brown 33
14645       Mordant Black 11
15705       Mordant Black 17
11855       Disperse Yellow 3
11005       Disperse Orange 3
11227       Disperse Orange 25
11119       Disperse Orange 30
11110       Disperse Red 1
11210       Disperse Red 17
11228       Disperse Red 65
11116       Disperse Red 73
11152       Disperse Brown 1
14155       Direct Green 28
15050       Acid Blue  158:1
18950       Acid Yellow 40
17101       Acid Red 266
  -         Acid Red 337
  —        Disperse Blue 79
Paul Uhlrich &  Co.  Inc.
12060       Pigment  Orange  2
12120       Pigment  Red  3
12085       Pigment  Red  4
(Concluded)
     C.I.  No.
     12390
     12355
     15865
     15630
     15860
     15850
    C.I. Name
Pigment Red 17
Pigment Red 23
Pigment Red 48
Pigment Red 49
Pigment Red 52
Pigment Red 57
    Mob.ay Chemical  Corp.
       Verona Dyestuff  Div.
    13906       Acid Yellow 151
    15510       Acid Orange 7
    15510:1      Pigment Orange 17
    15510:2      Pigment Orange 17:1
    15510:3      Solvent Orange 49
    15575       Acid Orange 8
    18732       Acid Orange 60
    18050       Acid Red  1
    17755       Acid Red  137
    12055       Solvent Yellow 14
    11085       Basic  Red 18
    11741       Pigment Yellow 74
    12770       Disperse  Yellow  4
    11227       Disperse  Orange  25
    11117       Disperse  Red 90
    11077       Disperse  Blue 165
       -         Acid Red  337
    Warner-Jenkinson Co.
    15985       Food Yellow 3
    19140       Food Yellow 4
    19140:1      Pigment Yellow 100
    16035       Food Red  17
       —         Disperse  Blue 79
    Cone Mills Corp.
       Otto B. May Co.  Div.
       —        Disperse  Blue 79
                                        183

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                                    Table 16



                    PRODUCERS  OF DISAZO  DYES  AND PIGMENTS
C.I.  No.
C.I. Name
C.I. No.
                                           C.I.  Name
American
20195
20470
22240
26077
26105
26360
26370
26410
26900
26905
28160
29000
29025
29058
29060
29156
29160
29180
29185
29225

American
20170
20177
20195
20470
21000
21010
24890
24895
26105
Color & Chem. Co.
Acid Brown 14
Acid Black 1
Direct Blue 22
Disperse Orange 29
Solvent Red 24
Acid Blue 113
Acid Black 24
Acid Blue 118
Acid Red 151
Acid Red 66
Direct Red 81
Direct Yellow 44
Direct Yellow 50
Direct Orange 72
Direct Yellow 34
Direct Orange 102
Direct Red 23
Direct Red 73
Direct Red 24
Direct Red 83

Cyanamid Co.
Acid Orange 24
Acid Brown 354
Acid Brown 14
Acid Black 1
Basic Brown 1
Basic Brown 4
Direct Yellow 4
Direct Yellow 12
Solvent Red 24
26120
26900
27290
28160
29156
29160

Crompton &
Dyes and

20170
20195
20470
26070
26077
26360
26900
27290
28160
29000
29025
29060
29065
29160
29185
29200
29.225






Solvent Red 26
Acid Red 151
Acid Red 73
Direct Red 81
Direct Orange 102
Direct Red 23

Knowles Corp. ,
Chemical Div.

Acid Orange 24
Acid Brown 14
Acid Black 1
Disperse Yellow 23
Disperse Orange 29
Acid Blue 113
Acid Red 151
Acid Red 73
Direct Red 81
Direct Yellow 44
Direct Yellow 50
Direct Yellow 34
Direct Red 79
Direct Red 23
Direct Red 24
Direct Red 72
Direct Red 83






                                        184

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                              Table 16
C.I. No.
C.I. Name
                       (Continued)
                            C.I. No.
     C.I.  Name
Atlantic Chemical Corp.
20110       Mordant Brown 1
20170       Acid Orange 24
20195       Acid Brown 14
20470       Acid Black 1
20495       Acid Green 20
24890       Direct Yellow 4
24895       Direct Yellow 12
25100       Mordant Yellow 16
25135       Acid Yellow 38
25380       Direct Red 75
26070       Disperse Yellow 23
26105       Solvent Red 24
26520       Mordant Orange 6
26900       Acid Red 151
27200/27201 Acid Red 115
27290       Acid Red 73
27680       Direct Red 16
27855       Direct Violet 7
27885       Direct Violet 9
27925       Direct Blue 67
28160       Direct Red 81
29100       Direct Red 31
29105       Direct Violet 14
29110       Direct Red 149
29120       Direct Violet 66
29156       Direct Orange 102
29160       Direct Red 23
29175       Direct Red 62
29185       Direct Red 24
29190       Direct Red 26
29200       Direct Red 72
29225       Direct Red 83

BASF Wyandotte Corp.
20170       Acid Orange 24
20195       Acid Brown 14
                            20470
                            21010
                            21030
                            21230
                            21250
                            24890
                            26077
                            26520
                            27290
                            28160
                            29156
                            29200
Acid Black 1
Basic Brown 4
Basic Brown 2
Solvent Yellow 29
Solvent Red 22
Direct Yellow 4
Disperse Orange 29
Mordant Orange 6
Acid Red 73
Direct Red 81
Direct Orange 102
Direct Red 72
                            Benzenoid Organics Inc.
                            20470       Acid Black 1
                            20495       Acid Green 20
                            'E. I. du Pont de Nemours & Co., Inc.
                            21000       Basic Brown 1
                            24890       Direct Yellow 4
                            269.00       Acid Red 151
                            28160       Direct Red 81
                            28255       Direct Orange 74
                            29156       Direct Orange 102
                            29160       Direct Red 23
                            29200       Direct Red 72

                            Eastman Kodak Co.
                            260.70
 Disperse Yellow 23
                                         185

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                              Table 16
C_.I.  No.
Fabricolor
      C.I. Name
Incorporated
20170        Acid Orange 24
20470        Acid Black 1
29025        Direct Yellow 50
29030        Direct Yellow 51
29058        Direct Orange 72
29160        Direct Red 23
29185        Direct Red 24
29225        Direct Red 83

GAF Corp.
21230        Solvent Yellow 29
American Hoechst Corp.
  Industrial Chemicals Div.
 20040
 20505
  Pigment Yellow  16
  Reactive Black  5
 Id Americas Inc.
 26440        Reactive Brown 1


 Keystone Color Works Inc.
 21010:2      Pigment Brown 3
(Continued)
      C.I. No.
                                                   C.I. Name
      C.  Lever Co. Inc.
      24890       Direct Yellow 4
      28160       Direct Red 81

      Morton Norwich Products Inc.
                                   26050
                  Solvent Red 19
                                   Berncolors-Poughkeepsie Co.
20150
20460
20470
20480
20495
26520
Passaic
21000
21010
21010:1
21240
26100
26105
26120
26125
27290
27291
Mordant Brown 18
Acid Blue 29
Acid Black 1
Acid Black 41
Acid Green 20
Mordant Orange 6
Color & Chem. Co.
Basic Brown 1
Basic Brown 4
Solvent Brown 12
Solvent Yellow 30
Solvent Red 23
Solvent Red 24
Solvent Red 26
Solvent Red 27
Acid Red 73
Solvent Red 30
  H. Kohnstamm & Co., Inc.
  21010:2      Pigment Brown  3
                                    Martin-Marietta Corp.
                                               26077
                                                Disperse Orange 29
                                          186

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                             Table 16
C.I. No.
    C.I. Name
Sterling  Drug,  Inc.
  Hilton  Davis  Chemical Co.  Div.
24890
Direct Yellow 4
Toms River Chemical Corp.
20110       Mordant Brown 1
20170       Acid Orange 24
20195       Acid Brown 14
20470       Acid Black 1
20495       Acid Green 20
21000       Basic Brown 1
21010       Basic Brown 4
24810       Acid Red 134
24890       Direct Yellow 4
24895       Direct Yellow 12
25200       Direct Orange 73
26070       Disperse Yellow 23
26520       Mordant Orange 6
26550       Acid Orange 51
26900       Acid Red 151
27290       Acid Red 73
27680       Direct Red 16
27885       Direct Violet 9
28160       Direct Red 81
29000       Direct Yellow 44
29025       Direct Yellow 50
29042       Direct Yellow 118
29058       Direct Orange 72
29060       Direct Yellow 34
29065       Direct Red 79
29100       Direct Red 31
29120       Direct Violet 66
(Concluded)
        C.I.  No.
     C.I.  Name
       29155
       29160
       29165
       29175
       29185
       29200
       29210
       29225
Direct Orange 29
Direct Red 23
Direct Red 4
Direct Red 62
Direct Red 24
Direct Red 72
Direct Red 122
Direct Red 83
                                  Mobay Chemical Corp.
                                    Verona Dyestuff Div.
                                  20250       Acid Brown 83
                                  26077       Disperse Orange 29
                                  26900       Acid Red 151
                                        187

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                                   Table  17
          PRODUCERS OF TRISAZO, TETRAKIS, AND POLYAZO DYES AND PIGMENTS
C.I.  No.
C.I.  Name
C.I.  No.
C.I.  Name
American
30015
31600
34085
34090
34200
35435
35780
Color & Chemical Corp .
Direct Black 78
Direct Black 80
Direct Blue 120
Direct Blue 120A
Direct Blue 78
Direct Black 22
Direct Red 80
Crompton & Knowles Corp.,
Dyes and Chemical Div.
31600
35435
35780
Atlantic
31600
34010
35435
35780
Direct Black 80
Direct Black 22
Direct Red 80
Chemical Corporation
Direct Black 80
Direct Blue 126
Direct Black 22
Direct Red 80
                                           Fabricolor Incorporated
                                           31600       Direct Black 80
                                           35005       Direct Brown 44
                                           35780       Direct Red 80
                                           Toms River Chemical Corp.
                                           34045       Direct Green 26
                                           34085       Direct Blue 120
                                           34090       Direct Blue 120A
                                           34260       Direct Green 51
                                           35255       Direct Black 19
                                           35435       Direct Black 22
                                           35780       Direct Red 80
                                           Mobay Chemical Corp.
                                             Verona Dyestuff -Div.
                                           35435
                                         Direct Black 22
                                       188

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            Table 18





PRODUCERS OF AZOIC DIAZO COMPONENTS

C.I.
No.
Synalloy
Azoic
Diazo
Component
Corp., Blackman-
Uhler Chemical Div.
37010
37040
37050
37105
37110
37120
37125
37130
37135
Atlantic

370QO
37120
37175

E.I. du
& Co. ,
37040
37125
37135
3
9
49
12
8
10
5
13
1
Chemical Corp .

44
10
20

Pont de Nemours
Inc .
9
5
1

C.I.
No.

Alliance
37000
37010
37025
37040
37050
37085
37090
37100
37110
37120
37125
37130
37135
37150
37151





Azoic
Diaz.o
Component

Chemical Corp.
44
3
6
9
49
11
32
34
8
10
5
13
1
42
14





                 189

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               Table 19
PRODUCERS OF AZOIC COUPLING COMPONENTS
C.I.
No.
Azoic
Coupling
Component
Pfister Chemical Works
37505
37510
37515
37525
37526
37527
37530
37531
37545
37550
37558
37565
37615
2
10
17
8
21
29
20
34
19
12
14
7
35
Azoic
C.I. Coupling
No . Component
Synalloy Corp., Blackman-
Uhler Chemical Div.
37520
37526
37527
37530
37531
37558
37565
37600
—
Alliance Chemical
—

18
21
29
20
34
14
7
15
43
Corp .
43

                190

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                               Table 20

    ESTIMATED TOTAL QUANTITY OF ORGANIC INTERMEDIATES IN SOLID AND
  AQUEOUS-SOLID WASTES FROM THE MANUFACTURE OF AZO DYES AND PIGMENTS
        OTHER THAN THOSE BASED ON BENZIDINE AND ITS CONGENERS
           Intermediate
2-Naphthol

3-Hydroxy-2-naphthoic acid

2-Amino-l-naphthalene sulfonic acid

2-Amino-5-chloro-p-toluene sulfonic
  acid

6-Amino-m-toluene sulfonic acid

2-Hydroxy-6-naphthalene sulfonic
  acid

2-Bromo-4,6-dinitroaniline

m-Diethanolamino-p-methoxy-
  acetanilide

4-Aiainobenzene sulfonic acid

6-Amino-4-chloro-m-toluene
  sulfonic acid

Acetoacetanilide

o-Acetoacetanisidide

4-Amino-5-methoxy-o-toluene sulfonic
  acid

2-Amino-l-phenol-4-sulfonamide

Aniline

p-(p-Aminophenylazo)benzene sulfonic
  acid

p-Nitroaniline
Solid Residues
   (kg/yr)

    2430

    1320

    1190

     975


     580

     510


     480

     480


     450


     430

     350

     330

     325


     320

     310

     270


     270
Aqueous Solid
    Wastes
   (kg/yr)

  204000

  109000
   42200
   39800
      96
   40400

   27400
      710
                                  191

-------
                          Table 20 (Continued)
            Intermediate
N-Benzoyl-7-amino-4-hydroxy-2—
  naphthalene sulfonic acid

2-Nitro-p-toluidine

Phenol

4-Nitro-o-anisidine

6-Amino-4-hydroxy-2-naphthalene
  sulfonic acid

a,a,a-Trifluoro-o-toluidine

3-Carboxy-l-(p-sulfophenyl) -5-
  pyrazolone

3-(N-Ethylanilino) propionitrile

4-Chloro-2-nitroaniline

2,4-Dinitroaniline

6,6'-Ureylenebis-l-naphthol-3-
  sulfqnic acid

2-Chloro-4-nitroaniline

p-Phenylazoaniline

o-Anisidine

m-Phenylenediamine

2,4-Diaminotoluene

5-Nitro-o-anisidine

3-Hydroxy-3'-nitro-2-naphthanilide

2-(N-Ethylanilino) ethanol

l-Amino-2-hydroxy-6-nitro-4-naph-
  thalene sulfonic acid
                Aqueous Solid
Solid Residues     Wastes
   (kg/yr)          (kg/yr)
     270


     260

     235

     220

     203


     200

     180


     120

     120

     120

     115


     110

     100

     100

      98

      80

      75

      75

      70

      70
22400
19200
17400
15300
10200
14700
  140

 6500

 1980



 6230

 5600
                                 192

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                        Table 20 (Concluded)
            Intermediate
                                                        Aqueous Solid
                                        Solid Residues       Wastes
(kg/yr)
N-Acetyl-2-amino-5-hydroxy-7-                  60
  naphthalene sulfonic acid

l-Amino-4-naphthalene sulfonic acid            60

3-Methyl-l-phenyl-5-pyrazolone                 60

p-Aminoacetanilide                             60

2-Hydroxy-3,6-naphthalene                      55
  disulfonic acid

2-Aminobenzene carboxylic acid                 55

4,4'-Diamino-2,2'-stilbene disulfonic acid     50

6-Amino-3,4'-azodibenzene sulfonic acid        50
                                                           (kg/yr)
                 880


                  50

                6900



                4530
                                193

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ADMI  (American Dye  Manufacturers  Institute,  Inc.).    1973.    Dyes  and  the
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Anliker,  R.,   and  E.  A.  Clarke,    1979.    The  Ecology  and  Toxicology  of
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Baird, R., L.  Carmona, and R. L.  Jenkins.   1977.  Behavior  of Benzidine  and
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BIOS (British Intelligence Objectives Subcommittee).  1945.   German Dyestuffs
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Boeniger, M.   1980.    Carcinogenicity and Metabolism  of  Azo  Dyes,  Especially
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    Department   of   Health   and   Human   Services,   National   Institute   of
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Brown, D., H. R.  Hitz, and L. Schafer.  1981.   Chemosphere 10(5):245-261.

The  Society  of  Dyers  and Colourists.    1980.    Colour  Index  Lund Humphries
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Crossley, Kienle, and Benbrook.  1940.  JACS 62:1400.

DETO  (Dyes  Environmental  and  Toxicology  Organization,  Inc.),  New  York.
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Dieckhues, B.   1961.  Experiments  on the Reductive Splitting of Azo Dyes by
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Dubin,  P.,  and K.  L.  Wright.   1975.  Reduction of Azo Dyes  in Cultures  of
    Proteus Vulgaris, Zenobiotica 5:563-571.

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EPA  (U.  S.  Environmental  Protection Agency).   1975.   Development  Document,
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Flege, R. K. 1970.   Determination  of Degraded Dyes and Auxiliary Chemicals in
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Games, L. M., and R. A. Hites.  1977.  Analytical Chemistry 49:1433-1440.

Hansch,  C.  1978.   Pomona  College  Data  System,  Seaver  Chemistry Laboratory,
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Hanson,  J.  B.  1979.   Development  Document for Existing  Source  Pretreatment
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    Washington, D.C.

Hitz,  H.  R., W.  Huber,  and  R.  H.  Reed.   1978.   The Adsorption of  Dyes on
    Activated Sludge.   Journal of  the Society of  Dyers  and Colourists 94:71-
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Hughes, E.  C.,  C.  K. Ingold, and J. H.  Ridd.   1958.   Journal of the Chemical
    Society (London)  1958:58, 65,  70, 77,  82, 86.

Idaka,  E.,  et  al.    1978.    Degradation  of  Azo  Compounds  by  Aeromonas
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    March 1978.  pp. 91-94.

Kappeler, T.,  et al.   1978.   Are  Azo Dyes Degradable?   Textile Chemist and
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Kenaga,  E.   E.,  and  C.  A.  I.  Goring.    1978.    Relationship  Between Water
    Solubility,     Soil-Sorption,      Octanol-Water     Partitioning,     and
    Bioconcentration of  Chemicals  in Biota.  Preprint  of  paper given at ASTM
    3rd Aquatic Toxicol.  Symp., October 17-18, 1978, New Orleans, Louisiana.

Keinath,  T. M.   1976.   Benzidine:   Wastewater  Treatment Technology.   EPA-
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Kent,  J.  A.,  Editor.   1974.   Riegel's  Handbook  of  Industrial Chemistry, 2nd
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Kirk-Othmer Encyclopedia  of  Chemical Technology, 3rd  edition.   1978.   3:772-
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Lapp,  T.  W.,  et al.   1979.   A Preliminary Materials  Balance  for Dyes and
    Pigments from Benzidine and Three Benzidine Derivatives.  Midwest Research
    Institute Draft  Report.   U.  S.  Environmental Protection Agency, Office  of
    Toxic Substances, Washington, D.C.
                                      195

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Lubs, H.  A.   1955.   The  Chemistry of Synthetic Dyes  and  Pigments.   American
    Chemical  Society  Monograph No. 127-   Van Nostrand  Reinhold  Company,  New
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Mabey,  W.  R. et  al.,  1981.   Aquatic  Fate Process Data for  Organic Priority
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Melnikov,  B.  N.,  and  M.  N. Kirillova.    1969.   Thermal  Stability  of Direct
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Meyer,  U.,  et  al.   1979.     The  Biologic  Degradation  of  1920  Azo  Dyes.
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Mill, T.,  et  al. 1980.    Laboratory Protocols  for  Evaluating  the  Fate  of
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Peck, K.,  and J.  C.  Gorton, Jr.   1977.   Industrial Waste  Pretreatment in the
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Porter,  J.  J. 1973.   Stability  and  Removal  of Commercial Dyes  from Process
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Roberts,  J.   D.,  and  M.  C.  Caserio.   1964.   Basic  Principles of  Organic
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Rys,  P.,  and  H. Zollinger.     1972.    Fundamentals  of   the  Chemistry  and
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Saunders and Waters.   J. C. S.  1154 (1946).

Shreve;, R.  N.,   and  J.  A.  Brink.    1977.   Chemical  Process  Industries,  4th
    ed. McGraw-Hill Book Company, New York.

Smith, J. H., W. R. Mabey, N. Bohonos, B. R. Holt, S. S. Lee, T. W. Chou,
    D.  C.  Bomberger,  and  T. Mill.   1977.   Environmental Pathways of Selected
    Chemicals  in  Freshwater Systems.   Part  I:   Background  and  experimental
    Procedures,  U.S. Environmental Protection Agency.  EPA-600-7-77-113.

Smith, J. H., W. R. Mabey, N. Bohonos, B. R. Holt, S. S. Lee, T. W. Chou,
    D.  C.  Bomberger,  and  T. Mill.   1978.   Environmental Pathways of Selected
    Chemicals  in  Freshwater Systems.   Part  II:   Laboratory  Studies.   U.S.
    Environmental Protection Agency, Off. Res. Dev., EPA-600/7-78-074.
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Snow.  1932, Ind. Eng. Chem. 24:1420.

Steadman, T. R., et  al.   1977.   Industrial Process Profiles for Environmental
     Use;   Chapter  7,  Organic  Dyes  and  Pigments  Industry.    EPA  600/2-77-
     023g.  U.  S. Environmental Protection Agency; Washington, B.C.

Swett,  L., A.  Twhigg, and K. E. McCaleb.  1983.  The Organic Dyes and Pigments
     Data   Base.     U.S.    Environmental   Protection   Agency,   Industrial
     Environmental Research Laboratory, Cincinnati, Ohio.  Contract No. 68-03-
     2944.
                                      197

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                                  APPENDIX A

             EXAMPLE  OF MULTISTAGE  PROCESS  FOR A COMPLEX AZO  DYE
     For many azo dyes,  two  or  three stages of diazotization and coupling are
required.  Other  types  of reactions may  also  be  required for these dyes, and
they  are performed  in  either  the  coupling or  diazotization  reactors.   An
intricate piping  system  is  provided to interconnect the various diazotization
and  coupling  reactors,  and  the filter  presses.    Some recipes call  for the
clarification of  certain solutions  or  reaction intermediates,  and clarifying
filters are provided for this.

     As  an  example of  the processes used  for manufacturing most  of  the azo
dyes  and pigments, Figure A-l  shows  the  steps  necessary  for  producing one
complex  azo dye—Direct  Green 1 (Colour  Index  No.  30280) based on benzidine.
This benzidine example  is used because  the  description was  already available
from  a  previous   report  that considered  azo dyes  and  pigments  produced from
benzidine and its  congeners separately because  they were  perceived  to  be
especially hazardous.

     The synthesis consists of two  diazotizations and three coupling reactions
involving four  organics: a  diamine(benzidine), H  acid,  aniline,  and phenol.
The  ingredients   are  added   at  each  stage  in  the  clockwise  order of the
arrows.  The  diamine  is converted  to  the tetrazonium salt,  H acid is coupled
to  one  diazonium group  on  the  diamine,  aniline  is diazotized  and coupled to
the  H  acid,  and  finally  phenol   is  coupled  to  the  other diazonium   group
remaining  on  the diamine.   Figure A-2 shows  the  representative  chemical
reactions at  each step, assuming  that the  reactions are  complete and no by-
products are formed.

     The detailed recipe  for  producing Direct  Green 1, which was  adapted from
the BIOS (1945)  reports, is as follows:

    Stir  400  kg  benzidine  hydrochloride  in  3,200  liters   water   in   a
    diazotization  reactor,  add  500  liters  30%  hydrochloric acid,  and stir
    overnight.  Cool to  0°C  with 1,500 kg ice; add 250 kg sodium  nitrite as  a
    30%  solution  (temp 0°-4°C,  volume  5,000 liters).   Diazotization should be
    complete in two hours.

    For  the  first  coupling   (on  the acid  side),  transfer  to  a  12,000-liter
    vessel  containing  1,500-2,000  kg  ice.   Stir  555 kg  H acid  into  1,800
    liters water  at  40°C and dissolve  (by  dusting  in) 80 kg soda  ash  (volume
    2,500-3,000  liters).   Run  the  H acid into  the tetrazonium salt over  two
    hours with rapid stirring (temp  0°C,  volume 9,000  liters).  Stir  slowly
                                      198

-------
                                              1800 kg H20
                                 555 kg H Acid
                      80 kg Soda Ash
                250 kg NaN02
                580 kg H20
     1500 kg Ice
  178 kg HCI
  476 kg H20~*

400 kg Benzidine
   Hydrochloride
2000 kg Ice
                                          1800 kg H20
                3200 kg H20
          D =  Diazotization Reactor
          C =  Coupling Reactor
          F =  Filter Press
          D =  Tunnel Dryer
          G =  Grinder
          B =  Blender
/ 50 kg Chalk
    2000 kg Ice
                          650 kg Soda Ash
 149 kg HCI
 330 kg H20

i— 162 kg Aniline


 1500 kg Ice
                                         120 kg NaN02
                                         400 kg H20
                                                                            185 kg Phenol

                                                                          1000 kg H20
                                                        1000 kg Salt
                                                      To Standardize
                                                3150 kg

                                            DIRECT GREEN 1


                      FIGURE A-1  STEPS REQUIRED FOR PRODUCTION OF DIRECT GREEN 1

                                 (Components added in clockwise order.)
                                                             JA-1706-2

-------
N>
O
O
              H2N
                                   NH-,
                      Benzidine
          NaN0
\
            H20	^ Diazotization
            HCI •
             Ice •
                         Reactor
                Benzidine Tetrazonium Chloride
                     HO
                          Phenol
                                                                          NH2  OH
                                                                  H03S
                                                             S03H
                                                                            H Acid
                                                                  Soda Ash
                                                                                    H20
                                                                                     NH2 OH
                                                    cr+N
HO3S
                                                                       1st Coupling Product
                                                                  Soda AsrT\  I   /"Ice
                                                                     S03H
CI-*N = N-/   V/   VN = N
                                                                               NH2  OH
                                                                                         N = N
                                                                       HO3S
                                                                      2nd Coupling Product
                                                                                   NaCI
                                                   \r
                                                                                     NH2 OH
                                             HO
                                                                                          H2N
                                                                                                                         Aniline
                                                                                              Diazotization
                                                                                            •H20
                                                                                             HCI
                                                                                             H2S04
                                                                                             Ice
                                                                                             NaNO,
                                                                                   -CP +N = N

                                                                                         Aniline Oiazonium Chloride
                                                                                               S03Na
                                                                       DIRECT GREEN 1

                                        FIGURE A-2  REPRESENTATIVE CHEMICAL REACTIONS IN THE MANUFACTURE OF DIRECT GREEN 1

-------
for three hours, then add slowly 25 kg powdered chalk and later that night
25  kg  more.   The  next  day  the batch  should have  a  slight  excess  of H
acid.  Add more chalk if the coupling is not  complete.  Run  into a 30,000-
liter coupling vessel.

In a diazotization reactor,  dissolve  162 kg aniline in 1,800  liters water
with 420  liters  30%  hydrochloric acid or  310 liters 40°Be  sulfuric acid;
add 1,500 kg  ice.   Diazotize at 0°C  by  adding 120 kg  sodium nitrite as a
30% solution (volume 3,500 liters).  In a separate reactor dissolve 185 kg
phenol in 1,000 liters water at 70°C by adding 100 liters 50%  caustic soda
solution.

Add  2,000 kg  ice  to  the  first  coupling  product,  then add  the  aniline
diazonium salt,  then,  immediately  and as rapidly  as possible, add 650 kg
solid soda  ash,  keeping the batch at 0°C.   After  two  hours,  the aniline
diazonium  salt  should  be  gone,  or  almost  so.    Then  add   the  phenol
solution.   The  batch gets  very thick  and  the  stirring  may  have  to be
stopped.   Allow to  stand  overnight  to  complete the reaction and permit
Crystal growth.  Next morning heat to 65°C with direct steam,  add 3,500 kg
salt, stir  two  hours  while cooling  to  50°C,  and  filter.   The  filtrate
should  be a pale blue-black color.   Dry at  95°C,  grind,  and  standardize
with salt in a blender.

Yield  is about  2,000  kg,   before standardization.    After  blending,  a
typical final product yield is 3150 kg.
                                  201

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                                  APPENDIX B

            ESTIMATION  OF  BY-PRODUCTS  AND UNREACTED INTERMEDIATES
                    PRODUCED BY DYE  AND PIGMENT MANUFACTURE
     It Is not possible  to  calculate the amounts of by-products and unreacted
Intermediates that are produced  for  each dye and pigment.  Recipes reflecting
current practice  are  not available,  and  rates  for  conversion to the numerous
possible by—products  have not been  determined. A procedure  was  developed to
obtain order of magnitude estimates of the amounts of unreacted intermediates
and by-products that might be present in  the reaction mixture after all of the
coupling reactions  were  completed.   The final result  was a set  of emission
factors for  these dyes  and pigments  that  expressed the  amount  of unreacted
intermediate and  by-product  in the final reaction mixture (the  mother liquor)
as a percentage of the final standardized product.  These  emission factors can
be  used to  estimate  the amounts  of unreacted  intermediate  and  by-product
produced without  working out in  detail  the stoichlometry of all  of the dyes
and pigments included  in this study.  Several  assumptions were required.  It
was assumed  that  each coupling  component was  added  to the  reaction  at  a 5%
molar excess with respect  to the diazo  component.    It  was  also assumed that
during  each coupling  reaction 5% of  the  dlazonium  salt present in the vessel
decomposes  and   terminates.     Production  of  other   by-products  such  as
miscouplings, was estimated and  included in an  overall by—product estimate.
It was assumed that the diazotization reactions are complete.

     The consequences  of these assumptions  are worked  out  in  Table B-l, for
Acid  Black  1.     It  is  made  by  first  coupling  diazotized  p-nitroaniline
(component A) to  H acid  (component  C) under acid conditions  and then coupling
diazotized  aniline  (component  A')   to   the  monoazo  product  under alkaline
conditions.

     The  three  starting  materials  are  added   on  a  1  molar basis  with  a 5%
excess  for the coupling component H  acid.   After  the  first  coupling,  only
traces  of  the diazotized p—nitroaniline  are  expected.  The monoazo  product is
assumed to account for  95% of the  Initial  p-nitroaniline  charge  of  L  mole,
which leaves 5% as the  terminated p-nitroaniline by-product  (assumed to  be p-
chloronitrobenzene).    The coupling  component,  which  was  added  in 0.05  molar
excess, is estimated  to  be  0.1  molar excess after the  first  coupling  reaction
because 0.05 mole of the diazo  compound did not react  (1.05 moles of H acid
was added  but  only 0.95  was estimated to be in the  monoazo product,  leaving
0.1 mole of unreacted  intermediate).   The second coupling reaction  is  assumed
to  yield  0.9 mole of the disazo  product  (95%  or 0.90 mole).  This  means  that
0.1 mole of diazotized  aniline must  either terminate or  react with  the free  H
acid remaining after the  first coupling  reaction.  For  consistency;  0.05  mole

                                      202

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                       Table B-l
    EXAMPLE ESTIMATION OF BY-PRODUCTS AND UNREACTED
     INTERMEDIATES FROM PRODUCTION OF ACID BLACK 1
                                           Weight
           Material
Starting materials
  p-Nitroaniline (A)
  H acid (C)
  Aniline (A1)
Compounds after first coupling
  p-Nitroaniline (A)
  H acid (C)
  Monoazo product (A-C)
  By-products (terminated A)
Compounds after second coupling
  p-Nitroaniline (A)
  H acid (C)
  Aniline (A1)
  Disazo product (A-C-A1)
  By-products
(kg-mole)
 1.0
 1.05
 1.0

Trace
 0.1
 0.95
 0.05
(kg)
138
335
 93
 36
488
Trace
0.05
Trace
0.90
0.20
—
18
—
554
61
     Organic dye yield
     Total unreacted intermediates
     Total by-products
             554
              18
              61
                          203

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of diazotized aniline was  assumed  to  terminate (to phenol), and 0.05 mole was
assumed to  couple  to free H acid  giving  a monoazo by-product.   The remaining
by-product  could be  0.05 mole of  the  monoazo  product from the first coupling
reaction.    This  gives the  total estimated by-product  formation  as 0.2 mole.
The net results are  18 kg of unreacted intermediates (3.2% of the organic dye
yield) and 61 kg of by-products  (11% of the organic dye yield).

     In a similar  manner,  the by—product  formation was estimated for several
dyes and pigments from each azo  subclass  (monoazo, Disazo I, Disazo II, and so
forth).   The compounds  chosen  were among the  large  volume dyes  and pigments
included in this study, namely:

       Monoazo

          Pigment Red  49

          Pigment Red  53

          Pigment Red  57

          Acid Yellow 151

       Disazo
          Acid Black  1

          Direct Yellow  4

          Direct Red 81

          Direct Yellow 50

       Trisazo
          Direct Black 78

          Direct Black 80
          Direct Blue 126

       Tetrakisazo
          Direct Black 22

          Direct Black 19

     Although some  variation in by-product formation may occur between these
subgroupings, it  was assumed  that the  estimates could  be  averaged for each
major subclass.  The results of this  analysis is  shown in Table B-2.  The by-
product production  is estimated to  double with  each added  azo bond.   The
tetrakis  and polyazo  compounds  could be  expected  to  have high  amounts of
impurities,  whereas  the  monoazo compounds  should be  relatively pure.   The
unreacted  intermediates   remaining after completed  dye  synthesis  represent
about 4 wt% of the pure dye product for all azo dye and pigment subclasses.
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                                   Table B-2

           RESULTS  OF  BY-PRODUCT  ESTIMATION  FROM AZO  DYE  SYNTHESIS
                         (%  dye  product  as pure color)
                                                             Average
                                       Average              wt% Unreacted
    Azo Dye Subclass              wt% By-Product        Intermediates

      Monoazo                           3                        5

      Disazo                            8                        4

      Trisazo                          15                        4

      Tetrakisazo                      30                        4
     The  condensation,  esterification,  and  premetallization  reactions  are
discussed  in  Section  3.    The  completeness  of  these  reactions  and  the  by-
products formed are discussed below.


Condensation Reactions with Cyanuric Chloride

     The conditions for  reaction of an amine  with  cyanuric chloride together
with the  high reactivity of  cyanuric chloride are assumed  to  lead to nearly
complete reaction with few degradation by-products.  The major source of
by-products will  be from the  condensation of cyanuric  chloride  with the by-
products and excess intermediates remaining from previous coupling reactions.
     A  100%  yield was  assumed for  each  condensation  reaction  with cyanuric
chloride,  and,   because   of  the  high  reactivity  of  cyanuric   chloride,  no
unreacted material was assumed  to  remain.  The unreacted intermediate release
estimate, due to previous reactions, was  reassigned to  the by-product category
since  any unreacted  amine  intermediates  would be  condensed  with cyanuric
chloride to produce by-products.
Premetallized Dyes

     The conditions used to premetallize a dye are  such  that  the metallization
reaction is essentially  complete.   The unreacted intermediates will not  react
to form  a  metal complex but  certain  monoazo by-products (in the poly azo  dye
categories) may metallize along with  the dye.  A majority of  the premetallized
dyes  included  in  this study  belong to the monoazo class;  thus it was assumed
that no by-products are  formed from the metallization  reaction.

                                      205

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Esterification Reactions

     Esterification  reactions  are  specific  and under the  conditions -used in
azo  dye  manufacture  should not  produce significant amounts  of by-products;
therefore  it  was assumed  that no  excess esterifying compound  was required.
Since the  esterifying  compound is added  on  a molar basis with respect to the
diazonium  starting   material,  it  will  be  in  excess  because  of  incomplete
coupling  reactions.    The  by-products  that  will  occur  are  the condensation
products of the esterifying compound with any excess coupling component or by-
product  from  previous reaction  steps  that  carry  free hydroxyl  groups.   The
unreacted  intermediate  release   estimate  from  the  previous  coupling  is
reassigned  to  the   by-product category  to  account for  this  effect.    The
esterifying reactions were assumed to be  complete giving 100% yield.
Phosgenation Reactions

     Because the degradation  product  of  an isocyanate is the parent amine, no
by-products are expected  to occur  from this reaction step.  The procedure for
the  reaction  calls for  the addition  of  phosgene until no  residual amine is
detected.  From the above considerations, it was assumed that the phosgenation
reaction was  complete and  led  to  no  by-products.   The by-products that will
arise,  however,  are  from  the  phosgenated unreacted  intermediates  and by-
products from previous coupling reactions.
                                       206

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