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
-------
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
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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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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.
-------
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
-------
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
-------
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.
-------
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
-------
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
-------
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.
-------
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
-------
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
-------
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
-------
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
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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
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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
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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
-------
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.
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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.
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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.
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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.
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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.
-------
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.
-------
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
74
-------
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.
77
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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
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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
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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
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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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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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Hitz, H. R., W. Huber, and R. H. Reed. 1978. The Adsorption of Dyes on
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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
-------
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
-------
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.
204
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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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