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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- Table 1 (Continued) C.I. Subgroup C.I. No. C.I. Name Production (mt/yr) 21230-21280 21230 21240 21250 Solvent Yellow 29 Solvent Yellow 30 Solvent Red 22 > 4.5 > 2.3 > 2.3 24750-24840 24810 Acid Red 134 > 2.3 24850-24920 24890 Direct Yellow 4 24895 Direct Yellow 12 300.4 > 6.8 25080-25135 25100 Mordant Yellow 16 25135 Acid Yellow 38 > 2.3 > 2.3 25200-25450 25200 25380 Direct Orange 73 Direct Red 75 > 2.3 > 2.3 Disazo Dyes III 26006-26150 26050 Solvent Red 19 26070 Disperse Yellow 23 26077 Disperse Orange 29 26100 Solvent Red 23 26105 Solvent Red 24 26120 Solvent Red 26 26125 Solvent Red 27 > 2.3 217.7 196.8 > 2.3 > 9.1 > 4.5 > 2.3 26200-26440 26360 Acid Blue 113 26370 Acid Black 24 10 ------- Table 1 (Continued) C.I. Subgroup C.I. No. C.I. Dye Name Production (mt/yr) 26200-26440 (Continued) 26410 Acid Blue 118 26440 Reactive Brown 1 > 2.3 > 2.3 26500-26580 26520 26550 Mordant Orange 6 Acid Orange 51 > 9.1 > 2.3 26900-27311 26900 Acid Red 151 26905 Acid Red 66 27200 Acid Red 115 27290 Acid Red 73 27291 Solvent Red 30 > 15.9 > 2.3 > 4.5'a 74.5 > 2.3 27600-27790 27680 Direct Red 16 > 4.5 27850-27990 27855 27885 27925 Direct Violet 7 Direct Violet 9 Direct Blue 67 > 2.3 > 4.5 > 2.3 28100-28500 28160 Direct Red 81 28255 Direct Oranse 74 1066.4 a > 4.5 Disazo Dyes IV 29000-29090 29000 29025 29030 Direct Yellow 44 Direct Yellow 50 Direct Yellow 51 > 6.8 102.3 > 2.3 11 ------- Table 1 (Continued) I. Subgroup 29000-29090 (Continued) 29100-29130 29150-29232 C.I. No. 29042 29058 29060 29065 29100 29105 29110 29120 29155 29156 29160 29165 29175 29180 29185 29190 29200 29210 29225 C.I. Dye Name Direct Yellow 118 Direct Orange 72 Direct Yellow 34 Direct Red 79 Direct Red 31 Direct Violet 14 Direct Red 149 Direct Violet 66 Direct Orange 29 Direct Orange 102 Direct Red 23 Direct Red 4 Direct Red 62 Direct Red 73 Direct Red 24 Direct Red 26 Direct Red 72 Direct Red 122 Direct Red 83 Production (mt/yr) > 2.3 > 6.8 > 6.8 > 4.5 > 4.5 > 2.3 > 2.3 > 4.5 > 2.3 192.3 65.4 > 2.3 > 4.5 > 2.3 94.1 > 2.3 266.4 > 2.3 67.3 12 ------- C.I. Subgroup C.I. Trisazo Dyes and Pigments Trisazo I Table 1 (Continued) C.I. Dye Name Production (mt/yr) 30000-30030 30015 Direct Black 78 > 2.3 Trisazo II 31500-32055 31600 Direct Black 80 > 9.5 Trisazo IV 34005-34025 34010 Direct Blue 126 > 2.3 34040-34060 34045 Direct Green 26 > 2.3 34080-34100 34085 34090 Direct Blue 120 Direct Blue 120A > 4.5 > 4.5 34200-34230 34200 34220 Direct Blue 78 Direct Blue 75 > 2.3 > 2.3 34260 34260 Direct Green 51 > 2.3 13 ------- C.I. Subgroup Tetrakisazo Dyes and Pigments 35000-35900 Table 1 (Concluded) C.I. No. 35005 35255 35435 35780 C.I. Dye Name Production (mt/yr) . Direct Brown 44 Direct Black 19 Direct Black 22 Direct Red 80 > 4.5' > 2.3 > 11.4 200.9 1977 production range minimum from CICIS. 14 ------- the marketed product (including inert salts and other material used to produce a standardized product) are also shown in this table. The data in this table were taken from the Organic Dyes and Pigments Data Base, which was prepared by SRI International (Swett, et al., 1983). For some dyes and pigments, production is shown only as greater than a minimum number. These are dyes and pigments produced by three or fewer manufacturers so that public sources do not list specific production amounts. The CICIS data base lists production ranges for some of these dyes and pigments in its nonconfidential files. The production ranges cover an order of magnitude that does not always overlap the 1978 values derived from the U.S. International Trade Commission (1979) which was the basis of the production amounts in the Organic Dyes and Pigments Data Base. The CICIS values are shown in Table 1 when they exceeded the minimum U.S. International Trade Commission values. It is important to note that the CICIS production values are for the unstandardized material and do not include the inert ingredients used to standardize the product. In addition, production claimed confidential is not included. This means that, since Table 1 is based primarily on standardized products, the minimums for the CICIS production range values are definitely only a lower bound on production. The azo dyes and pigments that have proprietary structures and that have not been assigned C.I. numbers by the Society of Dyers and Colourists (1980) are listed in Table 2. Because no information is available on the intermediates used to produce these dyes, no waste production estimates can be made; therefore, these dyes and pigments are not discussed in this report. In 1972, the azoic compounds, shown in Table 3, accounted for about 4650 metric tons (mt) of product (U.S. Tariff Commission, 1975). The 1972 production of each subclass was as follows: Azoic Compound mt Azoic diazo components 2180 Azoic coupling components 1320 Azoic compositions 1146 Because the compounds involved in producing these azoics are identical to intermediates that are used for dye synthesis, no waste production estimates were made for azoics. In the following sections of this report the process chemistry of the azo dyes and pigments and the sources of waste during azo dye and pigment manufacture are discussed in detail. The final section gives the estimated amounts of solid and aqueous wastes produced during azo dye and pigment manufacture developed from the engineering analysis of Section 5. Chemicals in Commerce Information System (CICIS) (Nonconfidential files of the TSCA Inventory). U.S. Environmental Protection Agency; Office of Pesticides and Toxic Substances, Washington, D.C. 15 ------- Table 2 AZO DYES AND PIGMENTS FOR WHICH NO STRUCTURE INFORMATION WAS AVAILABLE Monoazo Dyes C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid C.I. Acid o C.I. Acid C.I. Acid C.I. Acid and Pigments Black 107 Black 172 Brown 31 Brown 223 Green 70 Orange 64 Orange 119 Red 132 Red 194 Red 211 Red 257 Red 278 Red 309 Red 324 Red 361 Red 384 Yellow 128 Yellow 129 Yellow 169 Yellow 174 Yellow 221 C.I. Basic Orange 26 C.I. Basic Orange 28 C.I. Basic Orange 31 C.I. Basic Orange 39 C.I. Basic Red 17 C.I. Basic Red 23 C.I. Basic Red 73 C.I. Basic Red 101 C.I. Direct Yellow 127 C.I. Direct Yellow 137 C.I. Direct Yellow 147 C.I. Disperse Blue 94 C.I. Disperse Blue 102 C.I. Disperse Blue 122 C.I. Disperse Blue 125 C.I. Disperse Blue 148 C.I. Disperse Blue 174 C.I. Disperse Blue 200 C.I. Disperse Blue 283 C.I. Disperse Blue 322 C.I. Disperse Brown 2 C.I. Disperse Brown 5 C.I. Disperse Orange 17 C.I. Disperse Orange 31 C.I. Disperse Orange 37 C.I. Disperse Orange 41 C.I. Disperse Orange 44 C.I. Disperse Orange 53 C.I. Disperse Orange 56 C.I. Disperse Orange 62 C.I. Disperse Orange 77 C.I. Disperse Orange 78 C.I. Disperse Orange 79 C.I. Disperse Orange 89 C.I. Disperse Orange 90 C.I. Disperse Orange 98 C.I. Disperse Orange 125 C.I. Disperse Red 30 C.I. Disperse Red 35 16 ------- Table 2 (Continued) Disazo Dyes and Pigments c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Red Red Red Red Red Red Red Red Red Red Red Red Red Red Red Red 50 76 32 88 105 106 108 109 117 135 137 140 193 271 273 316 Violet 33 C. C. C. C. C. C. C. C. C. C. C. C. C. C. C. C. C. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Orange Red 5 Red 21 Red 29 Red 40 Red 41 Red 43 Red 49 Red 123 Yellow Yellow Yellow Yellow Yellow Yellow Yellow Yellow 78 6 15 18 22 24 25 27 42 Violet 40 Violet 43 C. I. Solvent Red 210 Yellow 74 Yellow 136 Yellow 138 Yellow 143 Yellow 198 C.I. Mordant Brown 50 C.I. Mordant Orange 8 C.I. Reactive Blue 13 C.I. Reactive Brown 10 C.I. Reactive Orange 12 C.I. Reactive Qror.^e 14 17 ------- Table 2 (Continued) Disazo Dyes and Pigments (Continued) C.I. Acid Yellow 159 C.I. Acid Yellow 219 C.I. Acid Orange 116 C.I. Acid Orange 128 C.I. Acid Orange 132 C.I. Acid Orange 152 C.I. Acid Orange 156 C.I. Acid Red 119 C.I. Acid Red 299 C.I. Acid Brown 158 C.I. Basic Yellow 83 C.I. Direct Yellow 84 C.I. Direct Yellow 107 C.I. Direct Yellow 132 C.I. Direct Yellow 139 C.I. Direct Orange 80 C.I. Direct Orange 118 C.I. Direct Red 236 C.I. Direct Red 238 C.I. Direct Red 239 C.I. Direct Blue 191 C.I. Direct Blue 260 C.I. Direct Blue 263 C.I. Direct Blue 279 C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I, C.I. C.I. C.I. C.T. Disperse Orange 66 Disperse Orange 75 Disperse Red 161 Disperse Red 219 Disperse Blue 194 Pigment Pigment Pigment Pigment Pigment Pigment Pigment Pigment Pigment Pigment Yellow 93 Yellow 95 Yellow 126 Yellow 128 Orange 31 Red 144 Red 166 Red 220 Red 221 Brown 23 Reactive Blue 173 Reactive Brown 18 Reactive Black 9 Solvent Yellow 87 Solvent Red 33 Solvent Red 74 Solvent Red 164 Solvent Red 165 C.I. Disperse Yellow 56 C.I. Disperse Orange 38 18 ------- Table 2 (Continued) and Higher Azo Dyes and Pigments Trisazo C.I. Acid Yellow 59 C.I. Acid Yellow 114 C.I. Acid Yellow 135 C.I. Acid Yellow 199 C.I. Acid Yellow 216 C.I. Acid Orange 161 C.I. Acid Brown 97 C.I. Acid Brown 98 C.I. Acid Brown 239 C.I. Acid Black 29 C.I. Acid Black 92 C.I. Acid Black 194 C.I. Basic Yellow 41 C.I. Basic Orange 40 C.I. Basic Red 51 C.I. Basic Blue 76 C.I. Basic Blue 78 C.I. Direct Red 209 C.I. Direct Red 212 C.I. Direct Red 251 C.I. Direct Green 27 C.I. Direct Green 47 C.I. Direct Green 69 C.I. Disperse Yellow 96 C.I. Disperse Yellow 114 C.I. Disperse Yellow 126 C.I. Disperse Yellow 219 C.I. Disperse Orange 21 C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. C.I. Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Orange 55 Orange 57 Orange 58 Orange 73 Orange 88 Orange 94 Orange 129 Orange 136 Red 118 Red 128 Red 136 Red 153 Red 163 Red 167 Red 177 Red 179 Red 195 Red 214 Red 274 Red 275 Red 278 Red 305 Red 309 Red 313 Red 319 Red 333 Violet 42 Violet 60 Blue 121 Blue 138 Blue 139 19 ------- Table 2 (Concluded) Trisazo and Higher Azo Dyes and Pigments c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. c. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. I. Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Disperse Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Reactive Blue 175 C.I Blue 177 C.I Blue 281 C.I Blue 284 C.I Blue 291 C.I Blue 317 C.I Green Brown Brown Black Black Yellow Yellow Yellow Yellow Yellow Orange Orange Orange Orange Red 11 Red 31 Red 33 Red 58 9 C.I 10 C.I 18 9 33. 7 86 132 133 135 64 70 84 86 Red 120 Violet 1 Blue 89 Blue 109 Brown 17 (continued) Solvent Yellow 13 Solvent Yellow 71 Solvent Yellow 72 Solvent Orange 20 Solvent Orange 73 Solvent Orange 74 Solvent Red 105 Solvent Red 173 20 ------- 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 ------- Table 9 (Continued) Ethyl acetoacetate p-Phenylazoaniline 2,5-Xylidine 2,4-Dichloroaniline o-Toluidide m-Aminoformanilide p-Aminooxanilic acid 3-Methyl-2-hydroxybenzoic acid (2,3-Cresotic acid) 4-Sulfoanthranilic acid 2,4-Quinolinediol 2-Amino-N-methylpyridinium salt l-Naphthol-8-sulfonamide N,N-Diethyl-4-methoxymetanilamide 2-5-Dichlorosulfanilic acid 3-Amino-4-chlorobenzamide 5-(p-Aminophenylazo)-salicylic acid N-(3-Amino-4-sulfophenyl)glycine Xylylazoxylidine p-Toluenesulfonyl chloride 4,4'-Benzylidenedi-2,5-xylidine 4,4'-(o-Chlorobenzylidene)di-2,5-xylidine 4 ,4 '-Cyclohexylidenedi-o-anisidine 4,4'-Diamino-2,2'-stilbene disulfonic acid 6, 6'-Thiodenet'aanilic acid 3,3'-Diaminobenzanilide 4-o-Tolyazo-o-toluidine 4-Nitro-m-phenylenediamine.1Diazotized Toluene-2,4-diamine hydrochloride 4-L-iethoxy-m-phenylenediamine 57 ------- Table 9 (Concluded) m-Phenylenediamine p-Nonylphenol 4,4'-Cyclohexylidenedi-o-toluidine 2-Amino-5-tiitrobenzonitrile [2-(N-Ethylanilino)ethyl]trimethylammonium salt 2-Amino-4-(2,5-dichlorophenylcarbamoyl)benzoic acid methyl ester (p-Aminobenzoylmethyl)trimethylanmionium chloride 2-Amino-5-nitroisophthalonitrile 6-Chlorometanilic acid 2-Bromo-4,6-dinitroaniline 4-Chloro-a,a,a-trifluoro-o-toluidine a,a,a-trifluoro-o-toluidine m-Dieth anolamino-p-methoxyacetanilide 3-(N-2-Hydroxyethylanilino)-propionitrile, acetate ester 58 ------- SECTION 5 SOURCES OF WASTE DISCHARGES DURING AZO DYE AND PIGMENT MANUFACTURE The wide range of azo dye and pigment production processes and the specific plant characteristics and process control capabilities make estimation of material losses during dye manufacture a difficult task. In general, though, the most significant material losses will be intermediates that do not react and by-products, such as incomplete dye or pigment molecules. The intermediates and by-products from dye manufacture are present either in the product or in the solid waste streams regulated under RCRA— wastewater, solid residues, or the vapor and dust emissions. The material in the wastewater may be discharged in the plant effluent (although some will be destroyed by treatment as described below), and some will be discharged on wastewater treatment solids. Published information and industry contacts concerning the presence of organic materials in the wastewaters of several unit operations of dye production (e.g., Steadman et al., 1977; Lapp et al., 1979; Abrahart, 1968; Boeniger, 1980) were used to develop materials release estimates for intermediates, by-products, and dyes and pigments in the azo dye and pigment manufacturing processes. This section first gives a general overview of azo dye and pigment production processes and then describes the bases used for developing estimates of the amounts of material lost (expressed as a percentage of the finished and standardized dye or pigment). The losses from both dye and pigment manufacture are discussed below according to the stages of production in which they would occur (i.e., raw material receiving, synthesis, drying, grinding, standardization, blending, and packaging). The solid residues are assumed to be placed in a landfill, either on the manufacturing property or at a commercial facility. The process wastewaters are processed through a wastewater treatment system that may include physical, chemical and/or biological treatment of all or just some of the effluent. In some cases, the wastewater treatment system may discharge partially treated wastewater to municipal treatment systems. Concentrated aqueous waste streams may also be concentrated further and landfilled. The actual environmental releases that occur after wastewater treatment are discussed at the end of the section. 59 ------- 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 ------- 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 ------- of this material. One industry contact stated that his company which manufactures azo dyes and pigments, sends about one truckload of fiber drums and paper waste to a dump every day. Thus any chemicals in the drums or on the paper would be transferred to the dump site. Manufacturing operations that receive material in temporary storage and transportation containers from their own chemical manfuacturing operation may wash the containers and return them to duty so that any chemicals remaining in the containers would then go into the process wastewater treatment system. To indicate the order of magnitude of the potential solid residue disposal required by azo dye and pigment manfuacturing, it has been assumed that all intermediates arrive in fiber drums or bags, which are later disposed of in a landfill. We have estimated that 0.1% of the material in a bag or drum is retained in cracks or as a coating on wall surfaces when the container is emptied. This would represent only 0.05 Ib of material in a 50—Ib bag and less than 0.25 Ib in a 30-gallon drum. Because the water-soluble dyes have been assumed to be 50% inert salts, a 0.1% loss of the delivered intermediates is equivalent to a total intermediate loss of 0.05% on a final marketed product basis. Thus the manufacture of 100 pounds of a standardized monoazo dye would result in a total of 0.05 pound of intermediates in discarded drums and bags. However, because monoazo dyes require two intermediates, there would be only 0.025 pound of each intermediate if we assume that all the intermediates all have approximately the same molecular weight. (Because of the assumptions used to obtain the 0.05% estimate for material loss from material handling, it was not considered reasonable to correct for molecular weight differences when estimating the residue production for each dye). Disazo dyes require three intermediates so that the loss of each intermediate would be only 0.017 pound. In general, the solid residue associated with each intermediate is determined by dividing 0.05% by the number of intermediates used to build the dye molecule. For dyes that are premetallized, the metal is considered as an additional intermediate. The assumption of similar molecular weights for all intermediates is not unreasonable even when metals are included in the dye. A common source of chrome for dyes is chromium formate, which has a molecular weight of 187, or chrome oxide, which has a molecular weight of 152, compared to a molecular weight of 93 for aniline or 144 for 8-naphthol, which are both common organic intermediates in azo dye production. The chromium in the dye might have an equivalent molecular weight of 87.5 or 123 because of the chlorides necessary to make a neutral salt when the dye precipitates. Metals may actually be lost in their oxide form because the metal formate is often made in situ from the oxide. * Personal communication M. B. Bochner, Atlantic Chemical Corporation, Sept, 10, 1980. 63 ------- The same general procedure was followed for pigments and disperse and solvent dyes, which are assumed to be 75% active ingredients. For these dyes the total amount of intermediate in the solid residue stream would be 0.075% of the final marketed product. This amount was divided by the number of intermediates to determine the loss for each intermediate. In this procedure for calculating intermediate solid residue losses, several special cases need to be treated. Some dyes use phosgene to couple two aromatic amines together. Phosgene is not counted as an intermediate because its total weight contribution to the final product is very small (equivalent to urea). Phosgene is generated on-site from gaseous ingredients (such as carbon monoxide and chlorine), and its use would not result in a solid residue. Cyanuric chloride, which is used for various dyes, is counted as an intermediate but is not included in the solid residue stream from materials handling. It is made, on-site from gaseous and volatile liquid components (such as HCN, chloroform and chlorine). Process Wastewater The material from spills during transfer operations and residual material in temporary storage and transfer containers may be washed away. The amount of water required and the frequency of cleaning is difficult to quantify, and no quantitative estimates have been made. Vapor and Dust Losses Vapor losses during chemical intermediate transferring and weighing operations are expected to be small because most of the chemicals are estimated to have low vapor pressures and to be solids atQroom temperature. The loss of solid material from dusts may occur during handling. The vapors and dusts at the weighing and tranfer operations at some facilities will be vented to a scrubber unit (DETO, 1980; Keinath, 1976). In this study, the vapor and dust losses of intermediates are not estimated separately, but are included in the estimates of the vapor losses that occur during dye synthesis and product filtering. Most of the chemicals with high vapor pressures at room temperature (see Section 3) are chemicals used as solvents or reaction aids. These materials are not incorporated into the dye molecule and are not truly dye intermediates. In general, these chemicals have low melting points and will be transferred as liquids. The scrubber blowdown from the material receiving and handling area could contain these materials and may be a logical sampling point for chemicals of interest (such as formaldehyde). No estimate of losses of these compounds was made because it was difficult to quantify the amounts of material used. 64 ------- 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 ------- every synthesis, because the dyes are sometimes produced in a light-to-dark sequence, which would disguise any carryover from uncleaned or incompletely cleaned equipment. Also, for a major dye or pigment, a train of equipment may be exclusively used for that dye. Thus cleaning frequency may be decreased. Because there was no information on cleanup frequency and no data on the chemical content of cleanup waters, the loss of materials from equipment cleanup was not quantified separately, but instead was included in an overall loss estimate. Other sources of wastewater from dye synthesis include floor washdown, laundry, worker showers (Keinath, 1976), and blowdown from scrubbers. The amount of material in the combined process wastewater has not been well determined. Lapp's (1979) estimate of a 1% loss based on the raw materials added to the process was used to estimate the loss of intermediates to the process wastewater. These losses would be in the form of unreacted intermediates, by-products, and dye. Because the final product is assumed to be 50% inert salt for a water-soluble dye and 25% inert ingredients for pigments, disperse dyes, and solvent dyes, these losses are equivalent to 0.5% and 0.75%, respectively, based on final product. Because the losses could occur before significant reaction had occurred or after completion of the synthesis or anywhere in between, it is assumed that one-third of the intermediates were lost as intermediates, that one-third were lost in the form of by-products, which include incomplete couplings, and that one-third were lost in the form of the final dye or pigment product. The one-third share of these losses assigned to intermediates was divided by three to obtain an estimate for individual intermediates because three is a typical number of intermediates. A more rigorous approach would be to choose the number of intermediates for each class or dye (i.e., two for monoazo, three for disazo, and so forth) instead of using the "average"' of three. However, the emission factor is small compared with other sources of emission, and it was assumed that the above method was satisfactory. If nitrous acid treatment of the process wastewater, such as was practiced by the Allied Chemical Co. when it was producing benzidine dyes (Keinath, 1976), is used, the estimated loss of intermediates in the process wastewater is probably an overestimate of the amount of the actual intermediates, by-products, and dye released to the process sewer, because chemical changes will occur during treatment. Nitrous oxide treatment will convert amines to diazonium salts, which will then decay to the by-products discussed in Section 3, including replacement of the amine with hydroxide or chloride. Nitrosamines may also be formed. The value may be a reasonable estimate of the total amount of organic material, however, because nitrous acid treatment was not reported to completely oxidize organics to C0~ and water. Because the extent to which all manufacturers chemically treat process wastewaters was not known, chemical treatment was not assumed for the industry. The overall waste emission estimate for the entire dye or pigment manufacturing process is not sensitive to these assumptions because much larger losses occur later in the process. 66 ------- 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 ------- 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 ------- by dividing by the number of major by-products identified in Appendix B. The level of intermediates and by-products in the final product vould then be due only to the residual mother liquor remaining in the filter cake before it was dried. Abrahart (1968) indicates that the residual water content of the filter cake is about 10%, which is about 80 kg or 0.35% of the total mother liquor. 2If an intermediate were present at 1500 ppm in the mother liquor, the residual water in the filter cake would contain 1500 ppm x 80 liters = 0.12 kg of the intermediate. In the final standardized product dye, this 0.12 kg represents about 70 ppm for that intermediate. In a similar manner, the 5000 ppm total of by—products in the mother liquor of a trisazo acid dye would result in about 230 ppm of by-product in the final dye product. The final dye or pigment product could thus contain a total of several hundred parts per million of unreacted intermediates and by-products. Because the practices used to prepare the metal complexes of dyes vary, it is difficult to quantify the amounts of metal that may be present in process wastewaters from product filtration wastes. Where the complex is prepared by adding metal salts to the organic filter cake and then drying the reaction mixture, the only significant emissions of metal will parallel the emissions of dye, such as spillage of product material during transportation to the product finishing operation. Any excess metal added to promote complete reaction will be sold along with the product. When the complex is prepared in the mother liquor before precipitation and filtration, excess or unreacted metal salts present in the mother liquor would be released to plant wastes along with metal associated with dye that did not precipitate. Additional metal releases would occur along with dye releases from residual filter cake in the press and spills during transfer to the product finishing operation. The actual loss of metal would be much higher than when only the precipitated dye is metallized. To indicate the magnitude of the possible losses, we have assumed that all dyes are complexed with metal in the mother liquor and thereby generated high estimates of metal emission for those dyes that are metallized after precipitation and filtration. Based on the recipes that were available, for 1:1 metal complexes, the organic part of the molecule for all metal complex dyes was assumed to have a molecular weight of 450. Since chromium has a molecular weight of 52 and copper has a molecular weight of 62.5, the metal is approximately 10% by weight of the pure dye product even when the chloride anion is included in the final molecular weight. For the more complex dyes with higher molecular weights and the 1:2 complexes, this 10% would represent an overestimate. Since unprecipitated dye concentrations in the mother liquor have been estimated to be 4000 mg/liter, the equivalent metal concentrations would be 400 ppm. Under the acid conditions typically used to precipitate metallized dyes before filtration, this level of metal would be soluble even if it were not complexed with the dye molecule. 69 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- SECTION 6 SOLID RESIDUE AND AQUEOUS WASTE PRODUCTION The amounts of solid residue and aqueous wastes produced by azo dye and pigment manufacture were estimated for each dye and pigment using the methodology developed in Section 5. For this analysis, "solid residue" includes only the identifiable solid material associated with shipping container disposal and dye or pigment fines collected in baghouses. The "aqueous waste" is the estimated amount of material in dye or pigment plant process wastewater before the final wastewater treatment. Wastewater treatment, which may take place at the manuafacturing site or a municipal wastewater treatment system, is assumed to involve sedimentation followed by biological treatment and final clarification. These treatments are assumed to be ineffective in reducing the amount of each compound by degradation, but will partition the material between wastewater treatment solids and the aqueous effluent. The wastewater treatment solids will probably be disposed in a landfill and the effluent eventually discharged to surface waters after treatment. Because it was impossible to predict what the partitioning of intermediates between the wastewater treatment solids and the aqueous effluent would be, each aqueous emission was considered to be in a joint "aqueous-solid waste" stream. It is important to realize that dyes and by-products may be on. the wastewater" treatment solids because if these solids are placed in a landfill, they will be in an anaerobic environment where reductive reactions can take place. Diekhues (1961) found, for a variety of azo dyes, that reductive splitting of the azo linkage occurred. This means that the dye intermediates could be released in a landfill even from dye wastes that did not originally contain these materials in a free state. Table 12 summarizes the estimated emissions of dye or pigment, intermediates, and by-products for azo dyes and pigments where the intermediates could be identified from information in Colour ladex (The Society of Dyers and Colourists, 1980). For the dyes and pigments without C.I. numbers, the emissions could not be estimated because the intermediates are not identified. The dyes and pigments in the table are listed by C.I. number. Table 13 lists the chemical name for the intermediates with the common names shown in Table 12. Letter codes (defined in Table 14) indicate the producers for each dye or pigment. Tables 15 through 19 list the dyes and pigments that each producer makes. The identity and corporate ownership of the producers is based on 1978 information. Siace it was compiled, several dye production facilities or dye lines have been sold. Sales that were announced in trade journals are shown as footnotes in Table 14. A systematic 79 ------- search was not made to verify that all such sales have been listed, so the table may not be complete. The amount of each of the intermediates in the solid residue or aqueous- solid waste stream was obtained by multiplying the dye or pigment production value from Table 1 by the emission factors in Table 10 or Table 11. For example, for Disperse Orange 3 (which is the second dye in Table 12), the solid residue due to materials handling of each intermediate was obtained by multiplying the production value of 21.4 metric tons for the standardized dye product by the emission factor 0.075% to obtain the estimate of 16 kg/yr. This value was then divided by the number of intermediates (2) to give 8 kg/yr as the amount of each of the intermediates aniline and p-nitroanitine in the solid residue stream. This procedure was followed for each dye and pigment. Each organic intermediate and metal salt was counted, but phosgene and ethyl chloride were not because of their low molecular weight contribution to the final dye product. For dyes and pigments where production levels were reported in public sources only as greater than some lower limit, the lower limit was used because there was no way to estimate the actual amount produced. The esterifying components and condensation components used in the production of several dyes do not become part of the dye molecule via an azo linkage. For these components it is assumed that no excess reactant is required. When these were solids, the only significant losses were assumed to be the solid residue from materials handling. The estimated discharges of each intermediate from specific dye and pigment manufacturing were summed to indicate the total amount, on an industry-wide basis for the azo dyes and pigments covered in this study, of each intermediate estimated to be in solid residue and in the aqueous-solid waste streams. These industry-wide emission estimates (for those intermediates with estimates greater than 50 kg/yr) are shown in Table 20, listed in the order of the amount estimated to be in the solid residue. These industry-wide estimates could overstate the emissions of some intermediates if industry practice is different from the assumptions developed in Section 5. The estimates also probably understate the emissions for the intermediates used in azo dyes and pigments where only the lower production limit was known. It is possible that if actual production values were known for these dyes and pigments and used to estimate emissions, some of the intermediate emissions now judged to be minor could become more important. Based on the estimates in Table 12, the industry-wide total amount of identified organic intermediates in the solid residue from the manufacture of the azo dyes and pigments covered in this study is 15.6 mt/yr. The total amount of dye or pigment in the solid residue (obtained by summing the values for each dye and pigment in Table 12) is estimated to be 550 mt/yr, which makes the dyes and pigments themselves the more significant synthetic organic component of the total solid residue stream. The total amount, industry-wide, of intermediates estimated to be in the aqueous-solid waste is 650 mt/yr. This aqueous-solid waste is also estimated to contain 330 mt/yr of dyes and pigments and 640 mt/yr of reaction by-products. It is interesting to note 80 ------- that if only 2.5% of the intermediates estimated to be in the aqueous-solid stream were actually adsorbed on wastewater treatment solids, then the amount of intermediates estimated to be in the solid residue from dye and pigment manufacture would double. In a similar manner, if only 10% of the by-products were to be adsorbed on wastewater treatment solids then these by-products would be a significant fraction of the synthetic organic chemicals contained in the solid residue stream. The intermediates in Table 20 with the largest estimated emissions are mostly associated with the dyes and pigments that are produced in the largest volume. The ten largest volume dyes and pigments are produced by an average of ten companies. Thus these intermediates should not be site-specific and should be detectable at most major production facilities. Several intermediates, such as 2-amino-l-naphthalene sulfonic acid and 6-amino-m- toluene sulfonic acid, may be used in only one major dye or pigment; thus their release may be periodic. However, 2-naphthol is used in many dyes and pigments and it should be detectable in the process wastewaters on a nearly continuous basis. 2-Naphthol and 3-hydroxy-2-naphthoic acid account for nearly 50% of the combined intermediates estimated to be in the aqueous-solid waste and thus should be present at levels below 100 ppm in the total combined wastewater before wastewater treatment. 81 ------- Table 12 ESTIMATED WASTES PRODUCED IN MANUFACTURING AZO DYES AND PIGMENTS OTHER THAN THOSE BASED ON BENZIDINE AND ITS CONGENERS 'riuliifor HSH C.I, No. 11000 Dye Solvent Yellow 1 Annual Production metric tons/yr >2.3 Material Released to Environment Solvent Yellow 1 Aniline Quantity Releasedc (kg/yr) Solid Residue 48 1.7 Vtaste- water 23 By-products 51 AC ALT ATL TRC 11005 Disperse Orange 3 Solvent Orange 9 21.4 CO Disperse Orange p-Nitroaniline Aniline By-products 450 8 214 660 470 ACY 11014 Basic Red 30 >2.3 Basic Red 30 69 2-Amino-N-methypyridinium 0.6 Salt 0.6 Aniline By-products 0 61 48 39 aAn entry of — means that none of this material is estimated to be released to the waste water. An entry of 0 means that only traces of this material are estimated to be released to the solid waste. ------- Table 12 (Continued) Quantity Released Annual C.I. Producer No. ACY 11021 PSC ACY 11043 Production Material Released Dye metric tons/yr to Environment Solvent Yellow 56 >4.5 Solvent Yellow 56 Aniline N, N-Diethylaniline By- products Basic Violet 18 >2.3 Basic Violet 18 2-Amino-N-me thylpyr idinium Salt N,N-Dimethylaniline By-products Solid Residue 94 1.7 1.7 0 69 0.6 0.6 0 Waste. water 45 — 140 99 61 48 39 ACY BAS GAP 11052 Basic Blue 54 >6.8 hThe dye is sold as the quatenary ammonium methosulfate, sii! fate intermediate was made. Basic Blue 54 204 180 2-Amino-6-methoxy-3-methyl- 1.7 — benzothiazole N,N-Dimethylaniline 1.7 143 Methyl sulfateb By-products 0 116 No estimation of the quantity of the methy] ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No . TRC 11055 HUP 11056 Production Material Released Dye metric tons/yr to Environment Basic Red 22 >2.3 Basic Red 22 5-Mino-l, 4-dimethyl-lH- 1,2,4-triazole NfN-Dimethylaniline By-products Basic Orange 24 >2.3 Basic Orange 24 (p-Aminobenzoylmethyl) Solid Residue 69 0.6 0.6 0 69 0.6 Waste- water 61 — 48 39 61 — OO -P- trimethylammonium chloride 3-(N-Methylanilino) propionitrile By-products 0.6 48 39 DUP IIST VPC 11077 Disperse Blue 165 >6.8 Disperse Blue 165 143 2-Amino-5-nitro-iso- 2.6 phthalonitrile m-Diethylaminoacetanilide 2.6 By-products 0 68 211 150 15 AS A 1,1' KKT MAY Disperse Blue 79 1284 Disperse Blue 79 27000 2-Bromo-4,6-dinitroaniline 480 m-Diethanolamino-p-methoxy- acetanilide 480 By-products 0 12840 39800 28200 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. Dye ATL 11085 Basic Red 18 WAS DUP CAP VPC Production Material Released metric tons/yr to Environment 147.3 Basic Red 18 2-Chloro-4-nitroaniline [ 2- (N-ethylanilino) ethyl] trimethyl ammonium salt Solid Residue 4420 37 37 Waste- water 3980 — 3090 By-products 2500 DUP GO Ln 11087 Basic Yellow 15 >2.3 Basic Yellow 15 69 (p-Aminobenzoylmethyl) 0-6 trimethylammonium chloride 3~(2-Chloroanilino) 0.6 propionitrile By-products 0 61 48 39 11100 Disperse Orange 5 >4.5 Disperse Orange 5 95 2,6-Dichloro-4-nitroaniline 1.7 2-(N-Methylanilino)ethanol 1.7 By-products 0 45 140 99 ------- AC EKT ALT GAF ATL HSH BAS TRC DUP ATL BAS GAF CO o\ BAS TRC Table 12 (Continued) Annual Quantity Released (kg/yr) C.T I'riuliieer No. 11110 11115 11116 Dye Disperse Red 1 Disperse Red 13 Disperse Red 73 Production Material Released metric tons/yr to Environment 174.1 Disperse Red 1 p-Nitroaniline 2- (N-Ethylanilino) ethanol By-products >6.8 Disperse Red 13 2-Chloro-4-nitroaniline 2- (N-Ethylanilino) ethanol : By-products >4.5 Disperse Red 73 2-Amino-5-Nitrobenzonitrile 3- (N-Ethylanilino) Solid Residue 3660 66 66 0 143 2.5 2.5 0 95 1.7 1.7 Waste- water 1740 5400 3830 68 211 150 45 140 propionitrile By-products 99 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) ATI, FAB TRC AC 11119 11150 Production Dye metric tons/yr Disperse Red 90 >2.3 Disperse Orange 30 >6.8 Material Released to Environment Disperse Red 90 2-Amino-5-nitrobenzonitrile 3-(N-2-Cyanoethylanilino) propionic acid methylester By-products Disperse Orange 30 2 , 6-Dichloro-4-nitroaniline 3-(N-2-Hydroxyethylanilino) Solid Residue 48 0.8 0.8 0 143 2.6 2.6 Waste- water 23 — 71 51 68 — 211 propionitrile, acetate ester Disperse Red 54 >4.5 Disperse Red 7 >2.3 By-products Disperse Red 54 2-Chloro-4-nitro-aniline 3- (N-2-Hydroxyethyl- anilino) -propionitrile , acetate ester By-products Disperse Red 7 p-Nitroaniline 2 . 2x-(m-Chlorophenylimino) 0 95 1.7 1.7 0 48 0.8 0 .8 150 45 ' 140 99 23 71 diethanol By-products 51 ------- Table 12 (Continued) oo 00 Annual Quantity Released (kg/yr) C.I. Producer No. AC 11152 ALT ATL BUG IIST ICT SDC TRC HAS 11154 TRC Production Material Released Dye metric tons/yr to Environment Disperse Brown 1 18.2 Disperse Brown 1 2 , 6-Dichloro-4-nitroaniline 2 , 2 '- (m-Chlorophenylimirio) diethanol By-products Basic Blue 41 >4.5 Basic Blue 41 2-Amino-6-methoxy-3-methyl- Solid Residue 382 6.8 6.8 o. 135 1.1 Waste- vjater 182 — 564 400 120 — benzothiazole N-methyl-N-(2,3-dimethoxy- propyl) aniline By-products 1.1 95 77 PSC 11160 Solvent Yellow 3 Solvent Yellow 3 o-Toluidine 290 11 140 By-products 314 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.T. Producer No. AC 11210 ALT BAS EKT GAP TRC AC 11215 ALT HSU ALT 11227 DUP EKT TRC VPC Production Material Released Dye metric tons/yr to Environment Disperse Red 17 77.3 Disperse Red 17 P-Nitroaniline 2 , 2 '- (m-Tolylimino) diethanol By-products Disperse Red 5 36.4 Disperse Red 5 Solvent Red 117 2-Chloro-4-nitroaniline 2 , 2' -(m-Tolylimino)diethanol By-products Disperse Orange 25 325.5 Disperse Orange 25 p-Nitroaniline 3- (N-Ethylanilino)- propionitrile Solid Residue 1620 29 29 0 764 14 14 0 6840 122 122 Waste- water 77 — 2400 1700 364 — 1130 800 3260 10100 By-products 7160 ------- Table 12 (Continued) 'r mincer C.I. No. io_. Dye AC ALT HKT TRC 11228 ACY ATL BAS DUP GAP PSC TRC ACY GAF PSC TRC 11270 11270:1 11320 11320:1 Disperse Red 65 Basic Orange 2 Solvent Orange 3 Basic Orange 1 Solvent Orange 4 Annual p Production metric tons/yr 104.5 283.6 94.1 Quantity Released (kg/yr) Material Released to Environment Disperse Red 65 2-Chloro-4- nitroaniline 3- (N-Ethyl-m-toluidino) - propionitrile By-products Basic Orange 2 Aniline m-Phenylenediamine By-products Basic Orange 1 Aniline Toluene-2,4-diamlne Solid Residue 2190 36 36 0 8510 71 71 0 2820 24 24 Waste_ water 1050 3240 2300 7650 5960 4820 2540 1980 By-products 1600 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. AC 11365 BAS 11460 ACY 11480 HAS Production Material Released Dye metric tons/yr to Environment Disperse Black 1 >5 Disperse Black 1 p-Nitroaniline 1-Naphthylaraine By-products Basic Red 29 >5 Basic Red 29 2-Amino-3-methylthiazole l-Methyl-2-phenyl-lH-indole 1 By-products Basic Yellow 24 >4.5 Basic Yellow 24 2-Amino-3-methylbenzo- Solid Residue 100 1.8 1.8 0 150 1.2 1.2 0 135 1.1 Waste- water 50 — 150 110 130 — 100 90 120 — thiazol . l,2,3-Trimethyl-2H- benzimidazole Methyl sulfate? By-products 1.1 95 190 .'is L!K' .'|ual:ernory ammonium mcthosulfate. ui Lu waa made. No estimation of the quantity of the nethyj ------- Table 12 (Continued) C.I Producer No. Dye UPC KCW 11660 HPC 11670 AMS DUP CLX HPC use 1IRC HSU HST KCW KON S SDH SNA 11680 Annual Production metric tons/yr Pigment Yellow 5 >0.9 Pigment Yellow 6 >0.5 Pigment Yellow 1 199.5 By-products Quantity Released (kg/yr) Material Released to Environment Pigment Yellow 5 o-Nitroaniline Acetoacetanilide By-products Pigment Yellow 6 4-Chloro-2-nitroaniline Acetoacetanilide By-products Pigment Yellow 1 2-Nitro-p-toluidine Acetoace tanilide Solid Residue 19 0.4 0.4 0 10 0.2 0.2 0 4190 75 75 Waste- water 9 28 20 5 15 11 2000 6180 4390 ------- Table 12 (Continued) Producer C.I, No. Dye Annual Production metric tons/yr Material Released to Environment Quantity Released (kg/yr) Solid Waste- Residue water BNS UPC 1IRC 1ISC HSU HST K.CW K.ON 11710 Pigment Yellow 3 66.4 Pigment Yellow 3 4-Chloro-2-nitroaniline o-Chloroacetoacetanilide By-products 1390 25 25 0 664 2060 1460 HST 11720 Pigment Yellow 9 >0.5 Pigment Yellow 9 2-Nitro-p-toluidine o-Acetoacetotoluidide By-products 10 0.2 0.2 0 5 15 11 HRC KCW 11725 Pigment Orange 1 >0.9 Pigment Orange 1 2-Nitro-p-anisidine o-Acetoacetotoluidide By-products 19 0-4 0.4 0 9 28 20 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.T. Production Material Released Producer No. Dye metric tons/yr to Environment KCW 11727 Pigment Yellow 98 >0.5 Pigment Yellow 98 4-Chloro-2-nitroaniline 4-Chloro-o-acetoaceto- toluidide By-products KCW 11730 Pigment Yellow 2 i>0.5 Pigment Yellow 2 4-Chloro-2-nitroaniline 2 , 4-Acetoacetoxylidide By-products IIPC 11738 Pigment Yellow 73 245.5 Pigment Yellow 73 HRC 4-Chloro-2-nitroaniline HSU o-Acetoacetanisidide HST SNA By-products Solid Residue 10 2 2 0 10 0.2 0.2 0 5160 92 92 0 Waste- water 5 15 11 5 15 11 2455 7610 5400 ------- Table 12 (Continued) C.I Producer No. 11RC HSU SNA 11740 Dye Annual Production metric tons/yr Pigment Yellow 65 >50 DUP HSU GLX HST HPC SDH HRC SNA HSC VPC 11741 Pigment Yellow 74 588.2 By-products Quantity Released (kg/yr) Material Released to Environment Pigment Yellow 65 2-Nitro-p-anisidine o-Acetoacetanisidide By-products Pigment Yellow Ik 4-Nitro-o-anisidine o-Acetoacetanisidide Solid Residue 1050 18 18 0 12400 220 220 Waste. water 500 1550 1100 5880 18200 12900 11765 Pigment Yellow 49 >0.5 Pigment Yellow 49 10 4-Chloro-o-toluidine 0.2 4'-Chloro-2',5'-dimethoxy- 0.2 acetoacetanilide 5 15 By-products 1] ------- Table 12 (Continued) Producer HST II PC AC ALT EKT HSU TRC Annual Quantity Released (kg/yr) C.I. No. 11767 11770 11855 Production Material Released Dye metric tons/yr to Environment Pigment Yellow 97 >0.5 Pigment Yellow 97 4-Amino-2,5-dimethoxybenzene- sulfonanilide 4 ' -Chloro-2 ' , 5 ' -diiuethoxy- acetoacetanilide By-products Pigment Yellow 75 >0.5 Pigment Yellow 75 4-Chloro-2-nitroaniline p-Acetoacetophenetidide By-products Disperse Yellow 3 >95 Disperse Yellow 3 Solvent Yellow 77 p-Aminoacetanilide p-Cresol Solid Residue 10 0.2 0.2 0 10 0.2 0.2 0 2000 36 36 Waste. water 5 15 11 5 15 11 950 2900 By-products 2100 ------- Table 12 (Continued) Producer ACY A'J'L DUP PSC VPC 11 PC KCW UI1L CCY HSU SDH KCW Quantity Released C.I. No. 12055 12060 12070 Annual Production Material Released Dye metric tons/yr to Environment Solvent Yellow 14 173.2 Solvent Yellow 14 Aniline 2-Naphthol By-products Pigment Orange 2 >5 Pigment Orange 2 o-Nitroaniline 2-Naphthol By-products Pigment Red 1 >2 . 7 Pigment Red I p-Nitroaniline 2-Naphthol (kg/yr) Solid Residue 3640 65 65 0 100 1.8 1.8 0 57 1 1 Waste- Water 1730 — 5370 3810 50 — 150 110 27 — 84 By-products 59 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Production Producer No . Dye Metric • tons/yr ACY 12075 Pigment Orange 5 309.1 UPC use HSU HST SDH SNA Material Released to Environment Pigment Orange 5 2 , 4-Dinitroaniline 2-Naphthol By-products Solid Residue 6490 116 116 0 Waste- water 3090 — 9580 6800 ACY AMS ^ UPC 00 11SC RON MRX SDH UIIL 12085 Pigment Red 4 49.5 Pigment Red 4 2-Chloro-4-nitroaniline 2-Naphthol By-products 1040 18 18 0 495 — 1530 1090 UUP 1IS1I KCW RON 12090 Pigment Red 6 10.5 Pigment Red 6 220 4-Chloro-2-nitroaniline 4 2-Naphthol 4 By-products 0 105 325 231 ------- Table 12 (Continued) C.I, 1 r 1 1 1 li i ( • cr PSC 12100 Quantity Released Annual Production Dye metric tons/yr Solvent Orange 2 >2.3 Material Released to Environment Solvent Orange 2 o-Toluidine 2-Naphthol Rv-oroducts (kg/ Solid Residue 48 0.8 0.8 0 yr) Waste- water 23 — 71 5 ACY KCW C1K KON UUP MKX UPC SDH I1SC SNA IIS1I UUL 12120 Pigment Red 3 485.9 Pigment Red 3 2-Nitro-p-toluidine 2-Naphthol By-products 10200 182 182 0 4859 15100 10700 ACY A'I'L PSC 12140 Solvent Orange 7 >6.8 Solvent Orange 2,4-Xylidine 2-Naphthol By-products 140- 2.6 2.6 0 68 210 150 ------- Table 12 (Continued) C.T, Producer No. 1'SC BCC o o 12150 12156 Annual Quantity Released (kg/yr) Dye Solvent Red 1 Solvent Red 80 Production Material Released metric tons/yr to Environment >2.3 Solvent Red 1 o-Anisidine 2-Naphthol By-products >2.3 Solvent Red 80 2 , 5-Dime thoxyaniline 2-Naphthol By-products Solid Residue 48 0-8 0.8 0 48 0-8 0.8 0 Waste- water 23 71 51 23 71 51 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. Dye BNS 12300 Pigment Red 21 HPC 12310 Pigment Red 2 IIRC HSU KCW S ACY 12315 Pigment Red 22 nut' GLX UPC KCW MRX SNA Production Material Released metric tons/yr to Environment >5 Pigment Red 21 o-Chloroaniline 3-Hydroxy-2-naphthanilide By-products 23.2 Pigment Red 2 2 , 5-Dichloroaniline 3-Hydroxy-2-naphthanilide By-products 35.5 Pigment Red 22 5-Nitro-o-toluidine 3-Hydroxy-2-naphthanilide By-products Solid Residue 100 1.8 1.8 0 487 8.5 8.5 0 745 14 14. 0 Waste- water 50 — 150 110 232 — 719. 510 355 — 1100 781 • ------- Table 12 (Continued) Annual Quantity Released (kg/yr) o ho I1 CLX INI) ACY BUG 1)1 IP GLX 11 PC 1ISI1 C.I. rinliK'er No. Dye 12320 Pigment Red 32 INI) 12355 Pigment Red 23 KCW ROM SDH UIIL Production Material Released metric tons/y'r to Environment >0.9 Pigment Red 32 3-Amino-p-anisanilide 3-Hydroxy-2-naphthanilide By-products 200.0 Pigment Red 23 5-Nitro-o-anisidine 3-Hydroxy-3'-nitro-2-naphth- anilide i By-products Solid Residue 19 0.4 0.4 0 4200 75 75 0 Waste- water 9 — 28 20 2000 — 6200 4400 ROM SIM! 12360 Pigment Red 31 >0.9 Pigment Red 31 19 3-Amino-p-anisanilide d.4 3-Hydroxy-3'-nitro-2-naphth- anilide 0.4 By-products 0 28 20 ------- Table 12 (Continued) C. I. Dye Annual Production metric tons/yr HST 12367 Pigment Orange 38 >0.5 Material Released to Environment Quantity Released (kg/yr) Solid Waste- Residue water Pigment Orange 38 3-Amino-4-chlorobenzamide 4"-Acetamido-3-hydroxy-2- naphthanilide By-products 10 0.2 0.2 15 11 IIIJC HST 12370 Pigment Red 112 >0.9 Pigment Red 112 2 , 4 , 5-Trichloroaniline 3-Hydroxy-2-naphtho-o- toluidide 19 0.4 0.4 9 28 By-products 20 ACY BNS UPC ICC ROM SNA DHL 12390 Pigment Red 17 41.4 Pigment Red 17 5-Nitro-o-toluidine 3-Hydroxy-2-naphtho-o- toluidide By-products 870 16 16 0 414 1280 911 ------- Table 12 (Continued) Annual naphtho-o-toluidide By-products Quantity Released (kg/yr) C.I. Producer No. Dye UPC 12395 Pigment Red 13 KCW HST 12420 Pigment Red 7 S Production Material Released metric tons/yr to Environment >0.9 Pigment Red 13 2-Nitro-p-toluidine 3-Hydroxy-2-naphtho-o- toluidide By-products >0.9 Pigment Red 7 4-Chloro-o-toluidine 4 ' -Chloro-3-hydroxy-2- Solid Residue 19 0.4 0.4 0 19 0.4 0.4 Waste- water 9 — 28 20 9 — 28 20 UPC HST MKX 12460 Pigment Red 9 Pigment Red 9 2,5-Dichloroaniline 3-Hydroxy-2-naphth-o- anisidide 210 3.8 3.8 100 310 By-products 220 ------- Table 12 (Continued) Quantity Released Annual C.I. I'roiliiocr No. 11ST 12465 1IST 12467 Production Material Released Dye metric tons/yr to Environment Pigment Red 15 >0.5 Pigment Red 15 4-Chloro-2-nitroaniline 3-Hydroxy-2-naphth-o- anisidide By-products Pigment Red 188 >0.5 Pigment Red 188 2-Amino-4-(2,5-dichloro- Solid Residue 10. 0.2 0.2 0 10 0.2 Waste- water 5 15 11 5 O Ln phenylcarbamoyl) benzoic acid, methyl ester 3-Hydroxy-2-naphtho-o- anisidide By-products 0.2 15 11 HST S 12475 Pigment Red 170 >0.9 Pigment Red 170 p-Aminobenzamide 3-Hydroxy-2-naphtho-o- phenetidide 19 0.4 0.4 9 28 By-products 20 ------- Table 12 (Continued) Producer DUP Annual phenetidide By-products Quantity Released (kg/yr) C.I. No. 12476 Production Dye Disperse Red 220 metric >2.3 tons/yr Material Released to Environment Disperse Red 220 4-Chloro-o-toluidine 3-Hydroxy-2-naphtho-o- Solid Residue 48 0.8 0.8 Waste- water 23 71 51 12480 Pigment Brown 1 >0.5 Pigment Brown 1 2 j5-Dichloroaniline 3-Hydroxy-2',5"-dimethoxy-2- naphthanilide By-products 10 0.2 0.2 5 15 11 IIST 12485 Pigment Red 146 >5 Pigment Red 146 100 3-Amino-p-anisanilide 1.8 4'-Chloro-3-hydroxy-2',5'- 1.8 dimethoxy-2-naphthanilide 50 150 By-products 110 ------- Table 12 (Continued) Annual I'nuluccr GAP CLX UPC HSU ROM S Quantity Released (kg/yr) C.I. No. 90 Dye Pigment Red 5 Production metric tons/yr 25.9 Material Released to Environment Pigment Red 5 NfN-Diethyl-4-tnethoxy- Solid Residue 544 9.7 Waste- water 259 metanilamide 5'-Chloro-3-hydroxy-2',4'- dimethoxy-2-naph than Hide By-products 9.7 803 570 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. PSC 12700 1ISII 12705 RON D o HAS 12715 Production Material Released Dye metric tons/yr to Environment Solvent Yellow 16 >2.3 Solvent Yellow 16 Aniline 3-Methyl-l-phenyl-5-pyrazolone By-products Pigment Yellow 60 >0.9 Pigment Yellow 60 o-Ch lor oani line 3-Me thyl-l-phenyl-5-pyrazolone By-products Solvent Red 8 >2.3 Solvent Red 8 2-Amino-5-nitrophenol 3-Me thyl-l-phenyl-5-pyrazolone +3 Chromium (Cr ) Solid Residue 48 0.8 0.8 0 19 0.4 0.4 0 48 0.6 0.6 5.4 Waste- water 23 — 71 51 9 28 20 23 71 2.3 Formamide By-products 51 dyu is heated with chromium formate in formamide solution. No estimation of the LiL of this solvent was made. ------- Table 12 (Continued) C.I Producer No. VPC DUP HFC 12770 12775 Annual Quantity Released (kg/yr) Production Dye metric tons/yr Disperse Yellow 4 >2.3 Pigment Green 10 >0.9 Material Released to Environment Disperse Yellow 4 Aniline 2,4-Quinolinediol By-products Pigment Green 10 p-Chloroaniline 2,4-Quinolinediol Nickel (Ni~K^) Solid Residue 48 0-8 0.8 '0 17, 0.2 0-2 1.1 Waste- water 23 71 51 9 — 28 0.9 o By-products 20 ------- Table 12 (Continued) Annual o Quantity Released (kg/yr) C.I. Production Producer No. Dye metric tons/yr ATL 13025 Acid Orange 52 >2.3 HAS 13065 /cid Yellow 36 >6.8 DUP TRC ACY 13080 Acid Orange 5 >2.3 Material Released to Environment Acid Orange 52 Sulfanilic acid N,N-Dimethylaniline By-products Acid Yellow 36 Metanilic acid Diphenylamine By-products Acid Orange 5 Sulfanilic acid Diphenylamine By-products Solid Residue 69 0.6 0.6 0 200 1.7 1.7 0 69 0.6 0.6 0 Waste- water 61 48 39 180 140 120 61 48 39 ------- Table 12 (Continued) Producer AC Annual Quantity Released (kg/yr) C.T. No. 13091 Production Dye metric tons/yr Acid Orange 1 >2.3 Material Released to Environment Acid Orange le Sulfanilic acid Diphenylamine By-products Solid Residue 69 0.6 0.6 0 Waste- water 61 48 39 AC 13095 Acid Yellow 63 >2.3 Acid Yellow 63 Sulfanilic acid Diphenylamine By-products 69 0.6 0.6 0 61 48 39 AC 13150 Acid Orange 50 >2.3 Acid Orange 50 2,5-Dichlorosulfanilic acid N-Ethyl-N-phenyl- benzylamine By-products 69 0.6 0.6 61 39 'robable main component made by nitration of C.I. 13080. ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Production Producer No. Dye?. metric t'ons/yr TCI 13190 Reactive Yellow 4 >2.3 TUG 13245 Reactive Yellow 3 >2.3 Material Released to Environment Reactive Yellow 4 3-Amino-l , 5-naphthalene disulfonic acid m-Toluidine Cyanuric chloride By-products Reactive Yellow 3 3-Amino-l , 5-naphthalene Solid Residue 69 0.4 0.4 — 0 69 0.4 Waste- water 61 — — 48 39 6.1 — PDC TRC 13250 Mordant Brown 33 >4.5 disulfonic acid N~.(3-Aminophenyl) acetamide 0.4 Cyanuric chloride — Ammonia^ — By-products 0 Mordant Brown 33 95 2-Amino-4-nitrophenol 1.7 2,4-Diaminobenzene sulfonic 1.7 acid By-products Ammonia was not quantified but is assumed to be in the aqueous phase. 39 45 140 99 ------- Table 12 (Continued) ProcNicer pnc TKC ATL FAN Annual Quantity Released (kg/yr) C.T. Production No. Dye metric tons/yr 13265 Mordant Brown 70 >2.3 13361 Acid Green 35 >2.3 13390 Acid Blue 92 >9 Material Released to Environment Mordant Brown 70 Picramic acid 2,4-Diaminobenzene sulfonic acid N-(3-Amino-4-sulfophenyl) glycine By-products Acid Green 35 Picramic acid Naphthionic acid Chromium (Cr ) By-products Acid Blue 92 H-ArHH Solid Residue 48 0-9 0.4 0.4 0. 69 0.4 0.4 7.3 0 270 2.2 Waste- water 23 — 36 36 50 61 — 48. 6.1 39 240 — N-Phenyl Peri acid By-products 2.2 0 190 150 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Production Producer No. Dye metric tons/yr BAS 13900 Acid Yellow 99 >9.1 CAP 13900:1 Solvent Yellow 19 TRC AC 13906 Acid Yellow 151 1620.9 DUP TRC VPC ATL 13950 Direct Yellow 27 >2.3 Material Released to Environment Acid yellow 99 6-Amino-4-ni tro-1-phenol- 2-sulfonic acid Acetoacetanilide Chromium (Cr+3) By-products Acid Yellow 151 2-Amino-l-phenol-4- sulfonamide Acetoacetanilide Cobalt (Cr+3) By-products Direct Yellow 27 Dehydrothio-p-toluidine disulfonic acid o-Acetoacetanisidide By-products Solid Residue 270 1.5 1.5 29 0 48600 270 270 5140 0 69. 0.6 0.6 0 Waste- water 250 — 190 25 150 43800 — 34000 4380 27600 61 — 48 39 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.T. Production Material Released Producer No. Dye metric tons/yr to Environment PDC 14025 Mordant Yellow 1 >2.3 Mordant Yellow 1 m-Nitroaniline Salicylic acid By-products PDC 14030 Mordant Orange 1 >4.5 Mordant Orange 1 TRC p-Nitroaniline Salicylic acid i Bv-Droducts Solid Residue 48 0.8 0.8 0 95 1.7 1.7 0 Waste- water 23 — 71 50 45 — 140 99 PDC 14110 Mordant Yellow 20 >2.3 Mordant Yellow 20 48 7-Amino-l,3-naphthalene- disulfonic acid 0-8 Salicylic acid 0.8 By-products 0 23 71 50 ------- Table 12 (Continued) Producer C.I. No. Dye Annual Production metric tons/yr Material Released to Environment Quantity Released (kg/yr) Solid Residue Waste- water TRC 14155 Direct Green 28 >2.3 Direct Green 28 69 2~Amino-5-(4-amino-3-sulfo- 0.3 1-anthraquinpnylamino) benzene-sulfonic acid 5-(p-Aminophenylazo)-salicy- 0.3 lie acid Aniline 0 .3 Cyanuric chloride By-products 0 61 39 ATT, TRC 14170 Acid Yellow 65 >4.5 Acid Yellow 65 138 2-(p-Aminoanilino)-5- 0.8 nitrobenzenesulfonic acid o-Cresol 0.8 Benzenesulfonyl chloride 0.8 120 By-products 78 ------- Table 12 (Continued) Producer^ HAS TRC ALT BCC AC HAS I! DO OAF PDC TRC Annual Quantity Released (kg/yr) C.I. Production No. Dye metric tons/yr 14645 Mordant Black 11 >45 14700 Food Red 1 >4.5 14710 Acid Red 4 19.5 Material Released to Environment Mordant Black 11 l-Amino-6— nitro-2-naphthol- 4-sulfonic acid 1-Naphthol By-products Food Red 1 5-Amino-2 , 4-Xylenesulf onic acid Nevile and Winther's acid By-products Acid Red 4 o-Anisidine Nevile and Winther's acid Solid Residue 950 17 17 0 135 1.1 1.1 0 585 4.9 4.9 Waste. toater 450 — 1400 990 120 — 95 77 530 — 410 By-products 330 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) I1SII i—• M OO C.T. Production No. Dye metric tons/yr 14720 Acid Red 14 >25.5 Food Red 3 Mordant Blue 79 14830:1 Pigment Red 54 >0.5 14830 Acid Red 20 14880 Acid Blue 158 >4 . 5 15050 Acid Blue 158:1 >4.5 Material Released to Environment Acid Red 14 Naphthionic acid Nevile and Winther's acid By-products Pigment Red 54 1-Naphthylamine l-Naphthol-5-sulfonic acid By-products Acid Blue 158 l-Amino-2-naphthol-4- sulfohic acid l-Naphthol-8-sulf onic acid Chromium (Cr+3) By-products i Acid Blue 158:1 l-Amino-2-naphthol-4- sulfonic acid l-Naphthol-8-sulfonamide Chromium (Cr+3) Solid Residue 765 6.4 6.4 0 10 0.2 0.2 0 140 0.8 0.8 14 0 140 0.8 0.8 14. Waste- water 690 — 536 433 5 — 15 11 120 — 95 12 76 120 — 95 12 By-products 76 ------- Table 12 (Continued) C.I. No. AC ACY ATI, HAS BDO CAF 1'DC TRC VPC 15510 Annual Production metric tons/yr Acid Orange 7 Pigment Orange 17 Pigment Orange 17:1 Solvent Orange 49 206.8 Material Released to Environmen't Acid Orange 7 Sulfanilic acid 2-Naphthol By-products Quantity Released (kg/yr) Solid Waste- Residue water 6200 52 52 0 5580 4340 3520 AC ACY ATL TRC VPC 15575 Acid Orange 8 142.7 Acid Orange 8 4-Amino—m-toluene- sulfonic acid 2-Naphthol By-products 4280 36 36 0 3840 3000 2430 ACY AMS APO 150R CTK 1ISC 11 SI I TCC IDC KON MGK MRX SDH SNA TMS 15585 Pigment Red 53 D & C Red 8 15585:1 Pigment Red 53:1! D & C Red 9 1800 Pigment Red 53 37800 2-Amino-5- chloro-p-toluene- 675 sulfonic acid 2-Naphthol 675 By-products 0- 18000 55800 39600 ft :1 is the barium salt. No estimation of the release of this metal-was made. ------- Table 12 (Continued) Annual Quantity Released (kg/yr) K> O Producer BAS ATL BAS GAP TRC ACY ICC AMS IDC BNS KON BOR SDH CTK SNA HSC UI1L, C.T. Production Material Released No. Dye metric tons/yr to Environment 15602 Pigment Orange 46 >0.5 Pigment Orange 46 2-Amino-5-chloro-4-ethyl- benzenesulf onic acid 2-Naphthol By-products 15620 Acid Red 88 40 Acid Red 88 Naphthionic acid 2-Naphthol By-products 15630 Pigment Red 49 3150 Pigment Red 49 15630:1 Pigment Red 49:1;* Tobias acid • 15630:2 Pigment Red 49 : 2h 2-Naphthol By-products Solid Residue 10 0.2 0.2 0 1200 10 10 0 66150 1180 1180. 0 Waste- water 5 — 15 11 1080 — 840 680 31500 — 97650 69300 :1 is the barium salt, :2 is the calcium salt. No estimation of the release of these metals was' made. ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. PDC 15670 HAS 15705 TRC M NJ }— i AC 15711 SDH ATL BAS FAB TRC Production Material Released Dye metric tons/yr to Environment Mordant Violet 5 >2.3 Mordant Violet 5 2-Amino-l-phenol~4- sulfonic acid 2-Naphthol By-products Mordant Black 17 >4.5 Mordant Black 17 l-Amino-2-naphthol-4- sulfonic acid 2-Naphthol By-products Acid Black 52 406.8 Acid Black 52 l-Amino-6-nitro-2-naphthol- 4-sulfonic acid 2-Naphthol ^ Chromium (Cr ) Solid Residue 48 0-8 0.8 0 95 1.7 1.7 0 12200 68 68 1290 Waste. water 23 — 71 50 45 — 140 99 1100 — 8540 110 By-products 6920 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C. L. Production Producer No. Dye metric tons/yr GLX XL. 8 HRC 15800:2 Pigment Broxm 5 ICC ROM DUP 15825 Pigment Red 58 >0.9 UPC Material Released to Environment Pigment Brown 5 Aniline 3-Hydroxy-2-naphthoic acid By-products Pigment Red 58 6-Chlorometanilic acid 3-Hydroxy-2-naphthoic acid Bv-nroducts Solid Residue 38 0.7 0.7 0 19 0.4 0.4 0 Waste water 18 — 56 40 9. — 28 20 K3 ho ACY IDC AMS RON APO MC.R BNS SDH BOR SNA CTK TMS DUP UUL UPC 1ISI! ICC 15850 Pigment Red 57 15850:1 Pigment Red 57:1i 1550.0 Pigment Red 57 32550 6-Amino-m-toluene 580 sulfonic acid 3-Hydroxy-2-naphthoic acid 580 By-products 0. 15500 48000 34100 is the calcium salt. No estimation of the release of this metal was made. ------- Table 12 (Continued) Producer C.I. No. Dye Annual Production metric tons/yr Material Released to Environment Quantity Released (kg/yr) Solid Waste- Residue water ACY MRX AMS SNA UPC UllL use 11SH NCR 15860:1 Pigment Red 52:1^ 15860:2 Pigment Red 52:2J 798.6 Pigment Red 52 16770 2-Amino-5~chloro-p-toluener- 300 sulfonic acid 3-Hydroxy-2-naphthoic acid 300 By-products 0 7990 24700 17600 to LJ ACY HSH AMS ICC BOR MGR DUP MRX UPC S HRC SNA HSC UllL 15865 Pigment Red 48 1135.5 15865:1-4 Pigment Red 48:1-4 Pigment Red 48 23800 6-Amino-4-chloro-m-toluene- 426. sulfonic acid 3-Hydroxy-2-naphthoic acid 426 By-products 11400 35200 25000 use HSU RON SNA 15880 Pigment Red 63 25.9 Pigment Red 63 Tobias acl-i 3-Hydroxy-2-naphthoic. acid 544 9.7 9.7 259 803 By-products 0 ;l is the calcium salt, :2 is the manganese salt. ;l is the barium salt, :2 is the calcium salt, :3 is the strontium salt, :4 is the manganese salt. No estimation of the release of these metals was made. 570 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Production Producer No. Dye metric tons/yr PSC 15970 Acid Orange 12 >2.3 Food Orange 1 ALT 15985 Food Yellow 3 488.2 BCC KON SDH STG WJ ALT 16035 Food Red 17 867.3 BCC KON SDH WJ Material Released to Environment Acid Orange 12 Aniline Schaeffer's acid By-products Food Yellow 3 Sulfanilic acid Schaeffer's acid By-products Food Red 17 4-Amino-5-methoxy-o- sulfonic acid Schaeffer's acid Solid Residue 69 0-6 0.6 0 10300 183 183 0 18200 toluene 325 325 Waste- water 61 48 39 4880 15134 10700 8670 26900 By-products 19100 ------- Table 12 (Continued) "roihu'cr snn HSU KON MKX SNA ACY SDH Annual Quantity Released (kg/yr) C.I. Production No. Dye metric tons/yr 16105 Mordant Red 9 >140. 16105:1 Pigment Red 60: I1 16150 Acid Red 26 >2.3 Food Red 5 16185 Acid Red 27 >2.3 Food Red 9 Material Released to Environment Mordant Red 9 Anthranilic acid R acid By-products Acid Red 26 2,4-Xylidine R. acid By-products Acid Red 27 Naphthionic acid R acid By-products Solid Residue 2940 52 52 0 69 0.6 0.6 0 69 0.6 0.6 0 Waste- water 1400 4340 3080 61 48 39 61 48 39 :1 is the barium salt. No estimation of the release of this metal was made. ------- Table 12 (Continued) Annual TRC Quantity Released (kg/yr) C.I. Producer No. AC 16230 ACY ATL BAS GAP TRC ATL 16255 TRC M to cr. ACY 16580 ATL Production Material Released Dye metric tons/yr to Environment Acid Orange 10 65.9 Acid Orange 10 Food Orange 4 Aniline G-acid By-products Acid Red 18 >4.5 Acid Red 18 Food Red 7 Naphthionic acid G acid By-products Acid Violet 3 >6.8 Acid Violet 3 p-Nitroaniline Solid Residue 1980. 16 16 0 130 1.1 1.1 0 204 1.7 Waste water 1780 — 1380 1120 120 — 94 76 180 — Chromotropic acid 1.7 140 By-products 115 ------- Table 12 (Continued) sulfonic acid Gamma acid Quantity Released Producer EDO C.I. No. 17025 Dye Acid Violet 1 Annual Production metric tons/yr >2.3 Material Released to Environment Acid Violet 1 2 -Amino-5 -nitrobenzene" (kg/ Solid Residue 69 0-6 yr) Waste water 61 0.6 48 By-products 39 AC IRC 17045 to -4 Acid Red 37 >4.5 Acid Red 37 5-Acetamido-2-amino- benzene -sulfonic acid Gamma acid 135 1.1 1.1 120 94 By-products 76 ICI TRC 17053 Acid Red 57 >4.5 Acid,Red 57 2-Amino-N-ethyl-benzene- sulfonanilide Gamma acid 135, 1.1 1.1 120 94 By-products 76 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. Dye ACY 17100 Acid Brown 90 * BAS 17101 Acid Red 266 ALT ICI TRC j J 0 ATL — Acid Red 337 ALT DUP TRC VPC BCC 17200 Acid Red 33 KON Food Red 12 Production Material Released metric tons/yr to Environment \v- >2.3 Acid Brown 90 ^) p-Amino- a— toluene 'sulfonic acid Gamma acid By-products >9.1 Acid Red 266 4-Chloro-a,cc,a-trifluoro- o-toluidine Gamma acid By-products 794 Acid Red 337 a > a , a-Trif luoro-o- toluidine Gamma acid By-products >4.5 Acid Red 33 Aniline H-acid Solid Residue 69 0.6 0.6 0 270 2.3 2.3 0 23800 200 200 0 135 1 T 1. 1 1.1 Waste- water 61 — 48 39 250 — 190 155 21400 — 16700 13500 120 94 By-products 76 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. PDC 17590 ATL 17755 BAS DUP GAP TRC VPC HST 17757 Production Material Released Dye metric tons/yr to Environment Mordant Brown 40 >2.3 Mordant Brown 40 Anthranilic acid N-Phenyl Gamma acid By-products Acid Red 137 41.8 Acid Red 137 ! p-Aminoacetanilide N-Acetyl J acid By-products Reactive Orange 16 >2.3 Reactive Orange 16 2-(p-Aminophenylsulf onyl) ethanol sulfate ester N-Acetyl Gamma acid Solid Residue 48 0.8 0.8 0 1250 10 10 0 69 0.6 0.6 Waste water 2 j 71 50 1130 878 710 61 48 By-products 39 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) Producer ICI C.I. Production No. Dye Metric t'ons/yr 17907 Reactive Orange 1 >2.3 Material Released to Environment Reactive Orange 1 Orthanilic acid J Acid Cyanuric chloride Bv-t>roducts Solid . Residue 69 0.4 0.4 0 0 Waste water 61 — — 48 39 ICI 17908 Reactive Red 8 >2.3 U) o Reactive Red 8 2-Amino-5-methoxy~benzene- sulfonic acid J acid Cyanuric chloride By-products 69 0.4 0.4 61 48 39 AC ACY ATL EDO DUP GAP TRC VPC 18050 Acid Red 1 Food Red 10 154.1 Acid Red 1 Aniline N-Acetyl H acid By-products 4620. 38 38 4160 3240 2620 ------- Table 12 (Continued) Producer ATL BDO Quantity Released C.I. No. 18055 Dye Acid Violet 7 Food Red 11 Annual Production metric tons/yr >4.5 (kg/yr) Material Released to Environment Acid Violet p-Aminoacetanilide N-Acetyl H acid Solid Residue 135 1.1 1.1 Waste water 120 94 By-products 76 BDO 18075 Acid Violet 12 >2.3 Acid Violet 12 o-Anisidine N-Acetyl H acid 69 0.6 0.6 61 48 By-products 39 HST 18097 Reactive Violet 5 >2.3 Reactive Violet 5 68 2-(4-Amino-3-methoxyphenyl- 0.4 sulfonyl) ethanol sulfate ester N-Acetyl H acid 0.4 Copper -(Cu*2) 7.3 61 48 6.1 By-products 38 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. Dye ICI 18158 Reactive Red 1 TRC 18165 Acid Black 60 M LO NJ FAB 18200 Reactive Red 2 ICI Production Material Released Metric tons Ayr to Environment >2.3 Reactive Red 1 2-Aminobenzenesulfonic acid H-Acid Cyanuric chloride " By-products >2.3 Acid Black 60 2-Amino-N-methyl-l-phenol- 4-sulfonamide N- ( 7-Hydr oxy-1-naphthyl) ! acetamide Chromium (Or ) By-products >4.5 Reactive Red 2 Aniline H acid Cyanuric chloride By-products Solid Residue 69 0.4 0.4 — 0 69 0.4 0.4 7.3 0 135 0.7 0.7 — 0 Waste water 61 — — 48 39 61 — 48 6.1 39 120 — — 94 76 ------- Table 12 (Continued) Producer C.I. No. Dye FAB ICI 18260 Reactive Orange 4 Annual Production metric tons/yr >4.5 Material Released to Environment Quantity Released (kg/yr) Solid Residue Reactive Orange 4 2-Amino-l,5-naphthalene disulfonic acid N-Methyl J Acid Cyanuric chloride 135 0.7 0.7 Waste water 120 94 By-products 76 ICI 18270 Reactive Orange 13 >2.3 Reactive Orange 13 2-Amino-l,5-naphthalene disulfonic acid N-Methyl-J acid Cyanuric. chloride Ammonia™ 69 0.4 0.4 61 By-products 39 in 'Ammonia release was not quantified,but is assumed to be in the aqueous phase. ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. BAS 18690 AC 18732 ALT ATL DUP TRC VPC ACY 18740 Production Material Released Dye metric tons/yr to Environment Acid Yellow 121 >2.3 Acid Yellow 121 Solvent Yellow 21 Anthranilic acid 3-Methyl-l-phenyl-5-pyrazolone Chromium (Cr+3) Formamide By-products Acid Orange 60 298.6 Acid Orange 60 2-Amino-l-phenol-4-sulfonamide 3-Methyl-l-phenyl-5-pyrazolone Chromium (Cr+3) By-products Acid Orange 72 >2.3 Acid Orange 72 2-Amino-6-nitro-l-phenol-4- sulfonic acid 3-Methyl-l-phenyl-5-pyrazolone Chromium (Cr+3) Solid Residue 69 0.4 0.4 7.3 — — 0 8960 50 50 950 0 69 0.4 0.4 7.3 Waste water 61 — 48 6.1 — — 39 8060 — 6270 810 5080 61 — 48 6.1 By-products 39 n The dye is heated with chromium formate in formamide solution. of the quantity of this solvent was made. No estimation ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Production Material Released Producer No. Dye metric tons/yr to Environment 18745 Acid Orange 74 >4.5 Acid Orange 74 GAP Chromium (Cr+3) XRC 6-Amino-4-nitro-l-phenol-2- sulfonic acid 3-Methyl-l-phenyl-5-pyrazolone By-products ACY 18760 Mordant Red 7 >9.1 Mordant Red 7 ATL l-Amino-2-naphthol-4- M BDO , sulfonic acid ^ PDC 3-Methyl-l-phenyl-5-pyrazolone By-products AC 18810 Acid Red 186 >2.3 Acid Red 186 l-Amino-2-naphthc )l-4-sulf onic Solid Residue 130 13.8 0.8 0.8 0 190 3.4 3.4 0 69 0.4 Waste Water 120 12 — 95 77 91 — 280 200 61 — acid 3-Methyl-l-(m-sulfophenyl) -5-pyrazolone Chromium (Cr+3) By-products 0.4 7.3 0 48 6.1 39 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. EDO 18820 Dye Acid Yellow 11 Production metric tons/yr >2.3 Material Released to Environment Acid Yellow 11 Aniline 3-Methyl-l-(p-sulfophenyl)- Solid Residue 69 0.6 0.6 Waste Water 61 — 48 5-pyrazolone By-products 39 PDC 18821 OJ cr. Mordant Yellow 8 >2.3 Mordant Yellow 8 Anthranilic acid 3-Methyl-l-(p-sulfophenyl) -5-pyrazolone By-products 48 0.8 0.8 23 71 50 AC 18835 Acid Yellow 25 >2.3 Acid Yellow 25 5-Amino-o-t oluenesulfon- anilide 3-Methyl-l-(p-sulfophenyl) -5-pyrazolone 69 0.6 0.6 61 48 By-products 39 ------- Table 12 (Continued) Quantity Released (kg/yr) r T *_j • j_ • Producer No. HST 18852 ATL 18890 EDO TRC 18900 n-iiiiuct j_ Production Material Released Dye metric tons/yr to Environment Reactive Yellow 17 >2.3 Reactive Yellow 17 2- ( 4-Amino-3 , 6-dime thoxy- phenylsulfonyl) ethanol sulfate ester 3-Methyl-l-(4-sulfophenyl) -5-pyrazolone By-products Acid Yellow 34 >4.5 Acid Yellow 34 Aniline l-(2-Chloro-5-sulfophenyl)- 3-methyl-5-pyrazolone By-products Acid Yellow 29 >2.3 Acid Yellow 29 Metanilanilide 1- (2-Chloro-5-sulf ophenyl) Solid Residue 69 0.6 0.6 0 135 1.1 1.1 0 69 0.6 0.6 Waste water 61 — 48 39 120 — 94 76 61 — 48 -3-methyl-5-pyrazolone By-products 39 ------- Table 12 (Continued) Annual Quantity Released (ke/yr) C.I. Producer No. Dye DUP 18930 Acid Yellow 200 ALT 18950 Acid Yellow 40 ATL TRC ATL 18965 Acid Yellow 17 EDO Food Yellow 5 SDH TRC Production Material Released metric tons/yr to Environment >2.3 Acid. Yellow 200 Tobias acid l-(2-Chloro-5-sulfophenyl) 3-methyl-5-pyrazolone By-products >6.8 Acid Yellow 40 p-Aminophenol l-(4-Chloro-2-sulfophenyl) 3-methyl-5-pyrazolone p-Toluenesulfonyl chloride By-products 84.1 Acid Yellow 17 Sulfanilic acid l-(2 , 5-Dichloro-4- sulf o- phenyl) -3-methyl-5- Solid Residue 69 0.6 0.6 0 204 1.1 •1.1 1.1 0 2520 21 21 Waste Water 61 — 48 39 180 — 140 140 115 2270 — 1760 pyrazolone By-products 1430 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) Producer AC ALT ATL ICI C.I. No. Dye 18967 Acid Yellow 19 Production metric tons/yr >9.1 Material Released to Environment Acid Yellow 19 Tobias acid 1-C2 . 5-Dirhl nrn-4-siil f rv Solid Residue 273 2.3 7. 1 Waste Water 250 l on " phenyl)-3-methyl-5-pyra- zolone By-products 154 ICI 18971 Reactive Yellow 1 >2.3 u> i-D TRC 18972 Reactive Yellow 2 >2.3 Reactive Yellow 1 69 2,4-Diaminobenzene sulfonic 0.4 acid 3-Methyl-l-(2,4-dichloro-4- 0.4 sulfophenyl)-5-pyrazolone Cyanuric chloride By-products Q Reactive Yellow 2 69 4-Aminobenzene sulfonic acid 0.3 2,4-Diaminobenzene sulfonic acid -0.3 3-Methyl-l-(2,4-dichloro-4- 0.3 sulfophenyl)-5-pyrazolone Cyanuric chloride By-products Q 61 48 48 39 61 48 48 48 39 ------- Producer C.I, No. Dye TRC 19005 Acid Yellow 127 Table 12 (Continued) Annual Production metric tons/yr >2.3 Quantity Released Material Released to Environment ^cid Yellow 127 >-Amino-4-(3-chloro-l-oxido- Solid Residue 69 0.6 Waste water 61 1 , 2 , 4-benzotriazine-7-car- boxamido)benzene sulfonic acid l-(6-Chloro-o-tolyl)-3-methyl- 5-pyrazolone By-products 0.6 48 39 AC TRC 19010 Acid Yellow 54 >4.5 Acid Yellow 54 140 4-Sulfoanthranilic acid '0.8 3-Methyl-l-(4-sulfo-o-tolyl)- 0.8 5-pyrazolone Chromium salt 14 By-products 0 120 95 12 77 ALT AC BCC ACY KON BAS SDH GAF STG MRX WJ TRC 19140 Acid Yellow 23 Food Yellow 4 730 Acid Yellow 23 Sulfanilic acid 3-Carboxy-l-(p-sulfophenyl) 5-pyrazolone By-products 21900 182 182 19700 15300 12400 ------- Table 12 (Continued) Producer C.I. No. Dye Annual Production metric tons/yr Material Released to Environment Quantity Released (kg/yr) Solid Waste Residue tfater TRC 19351 Acid Red Acid Red 179 69 6-Amino-4-chloro-l~phenpl- 0.4 2-sulfonic acid 2,4-Quinolinediol 0.4 Chromium (Cr+3) 7.3 By-products 0 61 48 6.1 39 ATL BAS DUP GAF PDC TRC 19555 Direct Yellow 28 25.9 Direct Yellow 28 Sodium dlhydrothio-p- toluidine sulfonate By-products 780 13 700 440 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. HST 20040 ATL 20110 TRC Production Material Released Dye metric tons/yr to Environment Pigment Yellow 16 >0.4 Pigment Yellow 16 2,4 - Dichloroaniline 4 ',4'"- Bi-o-acetoaceto- toluidide By-products Mordant Brown 1 >4.5 Mordant Brown 1 2-Amino-4-nitrophenol 5-Amino-l-naphthalene- Solid Residue 9 0.2 0.1 0 90 1.1 1.1 Waste water 4 — 14 28 45 — — sulfonic acid m-Phenylenediamine By-products 1.1 0. 140 280 ------- Table 12 (Continued) Producer C.I. No. Dye Annual Production metric tons/yr Material Released to Environment Quantity Released (kg/yr) Solid Waste Residue water PDC 20150 Mordant Brown 18 >2.3 Mordant Brown 18 Sulfanilic acid p-Nitroaniline Salicylic acid By-products 46 0.6 0.6 0.6 0 23 71 142 ACY ATL BAS ALT FAB TRC 20170 Acid Orange 24 >13.6 Acid Orange 24 Sulfanilic acid Xylidine (crude) Resorcinol By-products0 410 2.3 2.3 2.3 0 370 285, 570 ACY 20177 Acid Brown 354 >2.3 Acid Brown 354 69 2-(p-Aminoanilino)-5-nitro- 0.4 benzenesulfonic acid Resorcinol 0.8 By-products 0 61 48 96 The by-product estimate assumed pure xylidine. increase the amount of by-products. Impurities in crude xylidine would ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. Dye AC 20195 Acid Brown 14 ACY ATL BAS ALT TRC VPC 20250 Acid Brown 83 M -P~ 4> POP 20460 Acid Blue 29 Production Material Released metric tons/yr to Environment 106.4 Acid Brown 14 Naphthionic acid Resorcinol By-products >2.3 Acid Brown 83 4-Methoxytnetanilic acid Resorcinol 4-Nitro-m-phenylenediamine 1 Copper (CvT2) Ammonia P By-products >2.3 Acid Blue 29 m-Nitroaniline Aniline H acid By-products Solid . Residue 3190. 36 18 0. 69 0.3 0.3 0.3 7.2 0 0 69 0.4 0.4 0.4 0, Waste water 2870 — 2230 4470 61 — 48 6.1 96 61 — — 48 96 ''Ammonia release was not quantified but is assumed to be in the aqueous phase. ------- Table 12 (Continued) Producer C.I. No. Dye Annual Production metric tons/vr Material Released to Environment Quantity Released (kg/yr) Solid Waste Residue water AC ALT ACY FAB ATL PDC BAS TRC EDO 20470 Acid Black \ 169.1 Acid Black 1 p-Nitroaniline Aniline H acid By-products 5070 28, 28, 28. 0 4560 3550 7100 PDC 20480 Acid Black 41 >2.3 Acid Black 41 p-Nitroaniline Sulfanilic acid H acid By-products 69 -•0.4 0. 0. 0 .4 .4 61 48 96 ATL EDO PDC TRC 20495 Acid Green 20 Acid Green 20 p-Nitroaniline Aniline H -acid 180 2.3 2.3 2.3 91 280 By-products 560 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) Producer HST ACY DUP M PSC £ TRC ACY HAS PSC TRC I5AS C.I. Production Material Released No. Dye metric tons/yr to Environment 20505 Reactive Black 5 >2.3 Reactive Black 5 2- (p-Aminophenylsulf onyl) ethanol sulfate ester H acid By-products 21000 Basic Brown 1 41.8 Basic Brown 1 m-Pheny 1 ened iamine By-products 21010 Basic Brown 4 >HQ Basic Brown 4 21010:1 Solvent Brown 12 Toluene-2,4-diamine 21010:2 Pigment Brown 3 ~~~" \ ^ By-products 21030 Basic Brown 2 >2.3 Basic Brown 2 4-Methoxy-m-phenyl ened iamine m-Phenylened iamine Solid Residue 69 0.4 0.8 0 1250 21 0 3300 55 0 69 0.4 0.8 Waste water 61 48 96 1130 1760 2970 6890 61 48 By-products 96 :2 is the phosphotungstomolybdic acid complex. ------- Table 12 (Continued) Annual Quantity Released (kR/yr) C.I. Producer No. BAS 21230 GAP PSC 21240 P^ ~-4 BAS 21250 TRC 24810 Production Material Released Dye metric tons/yr to Environment Solvent Yellow 29 >4.5 Solvent Yellow 29 4,4* -Cyclohexylidenedl-o- toluidine p-Cyclohexylphenol By-products Solvent Yellow 30 >2.3 Solvent Yellow 30 4,4' -Benzylidenedi-2 , 5- xylidine p-Cresol By-products Solvent Red 22 >2.3 Solvent Red 22 4,4 '-(o-Chlorobenzylidene)- di-2,5-xylidine 2-Naphthol By-products Acid Red 134 >2.3 Acid Red 134 4,4' -Cyclohexylidenedi- Solid Residue 90. 1.1 2.2 0 48 •0.6 •1.2 0 48 0.6 1.2 0 69 0.4 Waste witer 45 — 140 280 23 — 71 142 23 — 71 142 61 — o-anisidine 4,6-Dihydroxy-2-naphthalene- sulfonic acid 0.8 48 By-products 96 ------- Table 12 (Continued) Quantity Released C.I. Producer No. Dye ACY 24890 Direct Yellow 4 ATL BAS DUP LVR SDH TRC ^11 1 1 1 UC-i J_ Production metric tons/yr 300.4 Material Released to Environment Direct Yellow 4 4,4'-Diamino-2,2' stilbene- disulfonic acid Phenol By-products Solid Residue 9010 50 100 0 Waste water 8110 — 6310, 12600 -p- CO ACY ATL TRC 24895 Direct Yellow 12 >6.8 Direct Yellow 12 200 4,4'-Diamino-2,2' stilbene- disulfonic acid 1.1 Phenol 2.2 Ethyl chloride 0 By-products 0 180 285 ATL 25100 Mordant Yellow 16 >2.3 Mordant Yellow 16 46 4,4'(and 2 ,4')-Thiodianiline 0.6 Salicylic acid ' 1.2 By-products 0 23 71 140 ------- Table 12 (Continued) Producer ATL Quantity Released C.I. No. Dye 25135 Acid Yellow 38 Annual Production metric tons/yr >2.3 Material Released to Environment Acid Yellow 38 6,6* Thiodimetanilic acid Phenol (2 mol) Ethyl chloride Ug/ Solid Residue 69 -0.4 0.8 0 yrj Waste water 61 — — • — By-products 95 TRC 25200 Direct Orange 73 >2.3 Direct Orange 73 3,3'-Diaminobenzanilide 3-Carboxy-l-(m-nitrophenyl)- 5-pyrazolone (2 mol) By-products 69. 0.4 0.8 61 95 ATL 25380 Direct Red 75 >2.3 Direct Red 75 5,5'-Ureylenebis(2-araino- benzene)sulfonic acid Gamma acid 60 0.4 0.8 61 47 Phosgene By-products 95. rPhosgene is assumed to be unstable. ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. MRT 26050 ATL 26070 ALT EKT TRC M l_n AC 26077 ALT BAS SDC VPC Production Material Released Dye metric tons/yr to Environment Solvent Red 19 >2.3 Solvent Red 19 p-Phenylazoaniline N-E thy 1- 2-naphthylamine By-products Disperse Yellow 23 217.7 Disperse Yellow 23 p- Phenylazoaniline Phenol By-products Disperse Orange 29 196.8 Disperse Orange 29 p-Nitroaniline o-Anisidine Phenol By-products Solid Residue 48 -0.8 0.8 0 4350 82. 82. 0 3940 49 49 49 0 Waste water 23 — 71. 1 142 2180 — 6750 142 1970 — — 6100 12200 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.l, Production Material Released Producer No. Dye metric tons/yr to Environment PSC 26100 Solvent Red 23 >2.3 Solvent Red 23 p-Phenylazoaniline 2-Naphthol By-products AC 26105 Solvent Red 24 >9.1 Solvent Red 24 ACY " 4-o-Tolylazo-o-toluidine ATL 2-Naphthol PSC M i By-products Ln M ACY 26120 Solvent Red 26 >4.5 Solvent Red 26 PSC o-Toluidine 2,5-Xylidine 2-Naphthol By-products Solid Residue 48 0.8 0.8 0 182 3.4 3.4 •o 90 1.1 1.1 1.1 0 Waste water 23 — 71 140 91 — 280 560 45 — — 140 280 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.i. Production Material Released Producer No. Dye metric tons/yr to Environment PSC 26125 Solvent Red 27 >2.3 Solvent Red 27 Xylylazoxylidine 2-Naphthol By-products AC 26360 Acid Blue 113 >9 Acid Blue 113 ALT Metanilic acid 1-Naphthylamine N-Phenyl Peri acid i— « >-n By-products AC 26370 Acid Black 24 >2.3 Acid Black 24, 5-Amino-l-naphthalene- sulfonic acid 1-Naphthylamine N-Phenyl Peri acid By-products Solid Residue 48 -Q. 8 0.8 0 270 1.5 1.5 1.5 0 69 0.4 0.4 0.4 0 Waste water 23 — 71 14 240 — — 190 380 61 — — 48 96 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Production Material Released Solid Producer No Dye metric tons/yr to Environment Residue AC 26410 Acid Blue 118 >2.3 Acid Blue 118 Aniline 1,7-Cleve's Acid N-p-Tolyl Peri acid By-products ICI 26440 Reactive Brown 1 >2.3 Reactive Brown 1 Sulfanilic acid o-Aminobenzenesulfonic acid K :. l,6(and l,7)-Cleve's acid co Cyanuric chloride By-products ATL 26520 Mordant Orange 6 >9.1 Mordant Orange 6 BAS p-(p-Aminophenylazo)benzene- 69 0.4 0.4 0.4 0 69 0.2 0.2 0.2 0 0 180 3.4 Waste water 61 — 48 96 61 — — — — 96 91 PDC TRC sulfonic acid Salicylic acid By-products 3.4 0 280 560 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) Ul -P- C.I. Producer No. Dye TRC 26550 Acid Orange 51 AC 26900 Acid Red 151 ACY ATL ALT DUP TRC VPC AC 26905 Acid Red 66 Production Material Released metric tons/yr to Environment >2.3 Acid Orange 51 2-(p-Aminoanilino)-5- nitrobenzenesulfonic acid 1,6 (and l,7)-Cleve's acid o-Cresol p-Toluenesulfonyl chloride By-products >15.9 Acid Red 151 1 p-(p-Aminophenylazo)benzene- sulfonic acid 2-Naphthol By-products >2.3 Acid Red 66 6-Amino-3,4'-azodibenzene- Solid Residue 69 0.3 0.3 0.3 0.3 0 477 4 4 0 69 0.6 Waste water 61 — — — — 96 430 — 330 660 61 — sulfonic acid 2-Naphthol By-products 0.6 0 48 96 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) Ln Ln C.I. Producer No. Dye ATL 27200 Acid Red 115 ACY 27290 Acid Red 73 ATL BAS ALT PSC TRC Production Material Released metric tons/yr to Environment >4.5 Acid Red 115 4-o-Tolylazo-o-toluidine R acid By-products 74.5 Acid Red 73 p-Phenylazoaniline G acid ! By-products Solid Residue 135 1.1 1.1 0 2240 18 18- 0 Waste Water 120 94 190 2010 1560 3130 PSC 27291 Solvent Red 30 >2.3 ATL TRC 27680 Direct Red 16 >4.5 Solvent Red 30 p-Phenylazoaniline 0 Acid Dicyclohexylamine By-products Direct Red 16 Aniline J acid By-products sConvert C.I. 27290 to the dicyclohexylamine salt. 48 0.6 0.6 0.6 0 135 0.7 1.4 0 23 — 71 71 97 120 — 94 190 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. Dye ATL 27855 Direct Violet 7 ATL 27885 Direct Violet 9 TRC ^ °" ATL 27925 Direct Blue 67 Production Material Released metric tons/vr to Environment >2.3 Direct Violet 7 2-Amino-3 , 5-xylenesulf onic acid 2,5-Xylidine N-Phenyl J acid By-products >4.5 Direct Violet 9 Sulfanilic acid Cresidine N-Phenyl J acid By-products >2.3 Direct Blue 67 Cresidine N-Phenyl J acid H acid Solid Residue 69 •0.4 0.4 0.4 0 135 0.7 0.7 •0.7 0 69 0.4 0.4 0.4 Waste •water 61 — — 48 96 120 — — 94 190 61 — 48 — By-products 96 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.T. Producer No. Dye AC 28160 Direct Red 81 ACY ATL BAS ALT DUP LVR TRC Production Material Released metric tons/yr to Environment 1066.4 Direct Red 81 p-(p'-Aminobenzylazo) benzene •sulfonic acid N-Benzoyl J acid By-products Solid Residue 32000 266 266 0 Waste water 28800 — 22400 44800 DUP 28255 Direct Orange 74 Ln —I >4.5 Direct Orange 74 7-Amino-3-naphthalene- disulfonic acid m-Toluidine p-Nitrobenzoyl chloride N-p-Aminobenzoyl J acid By-products 135 •0.8 0.8 0.8 0.8 0 120 140 285 AC ALT TRC 29000 Direct Yellow 44 >6.8 Direct Yellow 44 Metanillc acid o-AnJ sidine 200 0.8 0.8 180. 140 'p-Nitroaniline Salicylic acid Phosgene*1 By-products 0.8 0.8 140 285 "Phosgene is assumed to be unstable. ------- Table 12 (Continued) Annual Producer AC ALT FAB TRC FAB Ln CO TRC sulfonic acid 7-Amino-l,3-naphthalene disulfonic acid m-Toluidine Phosgene By-products Quantity Released (kg/yr) C.I. No. 29025 29030 29042 Production Material Released Dye metric tons/yr to Environment 4 Direct Yellow 50 102.3 Direct Yellow 50 3-Amino-l , 5-naphthalene * disulfonic acid m-Toluidine Phos genet By-products Direct Yellow 51 >2.3 Direct Yellow 51 3-Amino-l , 5-naphthalene disulfonic acid 2,5-Xylidine Phosgene. „ By-products Direct Yellow 118 >2.3 Direct Yellow 118 Metanilic acid o-Anis id inome thane Solid Residue 3070 26 26 — 0 69 0.6 0.6 — 0 69 0.3 0.3 Waste water 2760 — 2150 — 4300 61 — 48 96 61 — 48 0.3 0.3 0 48 96 Phosgene is assumed to be unstable. ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. Dye AC 29058 Direct Orange 72 FAB TRC AC 29060 Direct Yellow 34 ALT TRC ALT 29065 Direct Red 79 TRC Production Material Released metric tons/yr to Environment >6.8 Direct Orange 72 7-Amino-l , 3-naphthalene- disulfonic acid Cresidine Phosgene By-products >6.8 Direct Yellow 34 3-Amino-l, 5-naphthalenei- disulfonic acid Cresidine Phosgene By-products >4.5 Direct Red 79 p-p-Tolylsulf onyl H acid Cresidine Solid Residue 204 1.7 1.7 0 204 1.7 1.7 — 0 135 1.1 1.1 Waste water 180 — 140 285 180 — 140 — 285 121 — 94 Phosgene By-products 190 tPhosgene is assumed to be unstable. ------- Table 12 (Continued) Producer ATL TRC Quantity Released C.I. No. Dye 29100 Direct Red 31 Annual Production metric tons/yr >4.5 (kg/yr) Material Released to Environment Direct Red 31 Aniline (2 mol) 6,6t-^Iminobis^-l-naphthol-3- sulfonic acid Solid Residue 135 1.4 0.7 Waste water 120 — 94 By-products 190 ATL 29105 Direct Violet 14 >2.3 Direct Violet 14 2,4-Xylidine (.2 mol) 6,6' -Iminobis-l-naphthol-3^- sulfonic acid By-products 69 0.8 0.4 61 48 96 ATL 29110 Direct Red 149 >2.3 Direct Red 149 69 m-Aminoformanilide (2--mol) 0.8 6,6'-Iminobis-l- naphthol-3- 0.4 sulfonic acid 61 48 By-products 96 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. ATL 29120 TRC TRC 29155 i — • o\ h- ' AC 29156 ACY ATL BAS DVP Production Material Released Dye metric tons/yr to Environment Direct Violet 66 >4.5 Direct Violet 66 2-Amino -1 -pheno 1-4 - sulfonamide 6,6' -Iminobis-l-naphthol-3- sulfonic acid Copper (Cu+2) By-products Direct Orange 29 >2.3 Direct Orange 29 Aniline 6 ,6 '-Ureylenebis-1-naphthol- 3-sulfonic acid m-Aminobenzoic acid By-products Direct Orange 102 192.3 Direct Orange 102 Aniline. 6, 6'-Ureylenebis-l-naphthol-. 3-sulfonic acid p-Aminobenzoic acid Solid Residue 135 0.7 0.7 14 0 69 0.4 0.4 0.4 0 5770 32. 32 32 Waste Water 120 — 94 12 190 61 — 48 — 96 5190 — 4040 — By-products 8070 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. Dye AC 29160 Direct Red 23 ACY ATL ALT DUP FAB TRC TRC 29165 Direct Red 4 j— j M ATL 29175 Direct Red 62 TRC Production Material Released metric t'ons/yr to Environment 65.4 Direct Red 23 Aniline 6,6' Ureylenebis-1-naphthol- 3-sulfonic acid p-Aminoacetanilide By-products >2.3 Direct Red 4 Aniline 6,6" -Ureylenebis-1-naphthol-. 3-sulfonic acid Broenner's acid By-products >4.5 Direct Red 62 o-Toluidine. 6,6' -Urey'ienebis-1- naphthol- Solid Residue 1960 10.9 10.9 10.9 0 69 0.4 0.4 0.4 0 135. 0.7 0.7 Waste water 1770 — 1370. — 2750 61 — 48 — 96 120 — 94 3-sulfonic acid 4-Amino-m-toluenesulfonic acid (buffered with acetic acid) By-products 0.7 UAcetic acid release was not quantified but is assumed to be in the aqueous phase. 190 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) CTi U) C.I. Producer No. Dye AC 29180 Direct Red 73 AC 29185 Direct Red 24 ATL ALT FAB TRC ATL 29190 Direct Red 26 Production Material Released metric tons/yr to Environment >2.3 Direct Red 73 o-Toluidine 6,6' -Ureylenebis-1- naph thol- 3-sulfonic acid Broenner's acid By-products 94.1 Direct Red 24 4-Amino-m- toluenesulf onic acid 6,6' -Ureylenebis-1-naphthol- 3-sulfonic acid o-Anisidine By-products >2.3 Direct Red 26 o-Anisidine 6,6' -Ureylenebis-1-naphthol- 3-sulfbnic acid Naphthionic acid By-products Solid Residue 69 0.4 0.4 0.4 0 2820 16 16. 16 0 69 0.4 0.4 0.4 0 Waste water 61 — 48 — 96 '2540 — 1980 3950 61 — 48 — 96 ------- Table 12 (Continued) Annual Quantity Released (kg/yr) C.I. Producer No. Dye ATL 29200 Direct Red 72 BAS ALT DUP TRC TRC 29210 Direct Red 122 j r> AC 29225 Direct Red 83 ATL ALT FAB TRC Production Material Released metric tons/yr to Environment 266,4 Direct Red 72 o-Anisidine (0.6 mol) , o-Toluidine (0.4 mol) 6,6' -r-Ur eylenebis-1-naphthol"- 3-sulfonic acid Broenner's acid By-products >2.3 Direct Red 122 m-Aminoformanilide (2 mol) 6,6' -Ur eylenebis-1-naphthol- 3-sulfonic acid By-products 67.3 Direct Red 83 4-Methoxymetanilic acid (2 mol) 6,6' -Ureylenebis-1-naphthol- 3-sulfonic acid Copper (Cu"1"2) Ammoniav Solid Residue 7990 27 17 44 44 0 69 0.8 0.4 0 2000 16 8 210 0. Waste water 7190 — — 5590 — 11200 61 — 48 96 1800 . — 1400 180 — By-products 7Ammonia release was not quantified but is assumed to be in the aqueous phase. 2800 ------- Table 12 (Continued) Producer AC C.I, No. 30015 Dye Direct Black 78 Annual Production metric tons/yr >2.3 AC ATL ALT FAB 31600 Direct Black 80 >9.5 ATL 34010 Direct Blue 126 >2.3 Material Released to Environment Quantity Released (kg/yr) Direct Black 78 1,6(and l,7)-Cleve's acid p-Nitroaniline S acid By-products Direct Black 80 Gamma Acid l,6(and l,7)-Cleves acid p-Aminoacetanilide By-products Direct Blue 126 3-Aminorl,5-naphthalene disulfonic acid 1-Naphthylamine l,6(and l,7)-Cleve's acid Cresidine Solid Residue 69 0.3 0.6 Q.3 0 285 2.4 1.2 1.2 0 69 0.3 0.3 0.3 0.3 Waste water 61 48 — 48 180 255 200 200 — 730 61 — . — 48 By-products 180 ------- Table 12 (Continued) Producer C.I. No. Dye TRC 34045 Direct Green 26 Annual Production metric tons/yr >2.3 Material Released to Environment Direct Green 26 Cyanuric Chloride H acid p—Nitroaniline Salicylic acid Aniline Cresidine By-products Quantity Released (kg/yr) Solid Waste Residue water 69 ,2 .2 0. 0. 0.2 0.2 0.2 0 61 180 AC TRC 34085 Direct Blue 120 >4.5 Direct Blue 120 135 p-Aminooxanilic acid 0. 6 1,6-Cleve's acid 1.2 Nevile and Winther's ac;Ld 0.6 By-products 0 120 94 340 AC TRC 34090 Direct Blue 120A >4.5 Direct Blue 120A p-Aminooxanilic acid 1,6-Cleve's acid Schaeffer's; acid By-products 135 0.6 1.2 '0.6 0 120 94 340 ------- Table 12 (Continued) Producer C.I. No. Dye AC 34200 Direct Blue 78 Annual Production Metric tons/yr >2.3 Material Released to Environment Quantity Released (kg/yr) Solid Waste Residue water Direct Blue 78 2-Amino-p-benzene- disulf onic. aClid 1,7-Cleve's acid 1-Naphthylamine N-Phenyl J acid By-products 69 0.3 0.3 0.3 0.3 0 61 48 180 TRC 34220 Direct Blue 75 >2.3 Direct Blue 75 Metanilic acid 1,6-Cleve's acid N-Phenyl J acid By-products 69 0.3 0.6 0.3 0 61 48 180 TRC 34260 Direct Green 51 >2.3 Direct Green 51 Metanilic acid 1,7-Cleve's acid 5-Amino-6-ethoxy-2-naph- j thalene sulfonic acid N-m-Aminobenzoyl J acid Pyridine" By-products 69 0.3 0.3 0.3 0.3 61 48 180 wPyridine is used as a solvent. No estimation of the quantity of this solvent was made. ------- C.I Producer No. FAB TRC ON 00 35005 Table 12 (Continued) Annual 35255 By-products Quantity Released (kg/yr) Production Material Released Dye metric tons/yr to Environment Direct Brown 44 >4.5 Direct Brown 44 Sulfanilic acid tn-Phenylenediamine By-products Direct Black 19 >2.3 Direct Black 19 p-Nitroan±line m-Pheny lene d iamine H acid Solid Residue 136 0.9 1.4 0 69 0.5 0.5 0.2 Waste water 123 — 96 690 61 — 48 — 350 AC ATL ALT TRC VPC 35435 Direct Black 22 Direct Black 22 342 5-Amino-2-(p-aminoanilino)- 1.2 benzenesulfonic acid Gamma Acid 2.4 m-Phenylenediamine 2.4 By-products 0 308 239 1740 ------- Table 12 (Concluded) Annual Quantity Released (kg/yr) Producer AC ATL ALT FAB TRC C.I. No. Dye 35780 Direct Red 80 Production metric tons/yr 200.9 Material Released to Environment Direct Red 80 6-Amino-3 , 4 ' -azod ibenzene- sulfonic acid- N-Acetyl J acid Phosgene* Solid Residue 6030 50 50 Waste w'a t c r 5420 — By-products 30500 Phosgene is assumed to be unstable. ------- Table 13 INTERMEDIATES USED IN TABLE 12 THAT HAVE COMMON NAMES l-Amino-4-naphthalene sulfonic acid l-Amino-6-naphthalene sulfonic acid l-Amino-7-naphthalene sulfonic acid 2-Amino-6-naphthalene sulfonic acid l-Amino-8-hydroxy-4-naphthalene sulfonic acid 6-Amino-4-hydroxy-2-naphthalene sulfonic acid 7-Amino-4-hydroxy-2-naphthalene sulfonic acid l-Amino-8-hydroxy-3,6-naphthalene disulfonic acid 4-Amino-5-hydroxy-l,3-naphthalene disulfonic acid 1,S-Dihydroxy-3,6-naphthalene disulfonic acid 2-Hydroxy-3,6-naphthalene disulfonic acid 2-Hydroxy-6,8-naphthalene disulfonic acid N-Acetyl-l-amino-8-hydroxy-3,6-naphthalene disulfonic acid N-Acetyl-2-amino-5-hydroxy-7-naphthalene sulfonic acid N-Acetyl-7-amino-l-hydroxy-3-naphthalene sulfonic acid N-Benzoyl-7-amino-4-hydroxy-2-naphthalene sulfonic acid N-Phenyl-l-amino-8-naphthalene sulfonic acid N-Phenyl-2-amino-8-hydroxy-6-naphthalene sulfonic acid N-Phenyl-7-amino-4-hydroxy-2-naphthalene sulfonic acid (Naphthionic acid) (1,6-Cleve's acid) (1,7-Cleve's acid) (Broenner's acid) (S acid) (Gamma acid) (J acid) (H acid) (Chicago acid) (Chromotrophic acid) (R acid) (G acid) (N-Acetyl H acid) (N-Acetyl J acid) (N-Acetyl Gamma acid) (N-Benzoyl J acid) (N-Phenyl Peri acid) (N-Phenyl Gamma acid) (N-Phenyl J acid) 170 ------- Table 13 (Concluded) N-m-Aminobenzoyl-7-amino-4-hydroxy-2- naphthalene. sulfonic acid N-p—Aminobenzoyl-7- amino--4-hydroxy-2- naphthalene sulfonic acid N-p-Tolyl-1-amino—8-napb.thalene sulfonic acid o-Phenylsulfonyl-l-amino-8-hydroxy-3,6- naphthalene disulfonic acid o-Phenylsulfonyl-2-amino-8-hydroxy-3,6- naphthalene disulfonic acid o-Tolysulfonyl-l-amino-8-hydroxy-3,6- naphthalane disulfonic acid 2-Aminobenzene sulfonic acid 4-Aminobenzene sulfonic acid 3-Methyl-2-hydroxy-benzoic acid (N-m-Aminobenzoyl J acid) (N-p-Aminobenzoyl J acid) (N-p-Tolyl Peri acid) (o-Phenylsulfonyl H acid) (o-Phenylsulfonyl 2 R acid) (o-Tolylsulfonyl H acid) (Orthanilic acid) (Sulfanilic acid) (2 ,3-Cresotic acid) 171 ------- Table 14 DIRECTORY OF AZO DYE AND ORGANIC PIGMENT MANUFACTURERS, 1978 Names of manufacturers that- reported production and/or sales of azo dyes and pigments (other than those based on benzidine and its congeners) to the U.S. International Trade Commission for 1978 are listed below in order of their identification codes as used in Table 12. Code Name of Company AC American Color c Chemical Corp. ACY American Cyanamid Co. ALL Alliance Chemical Corp. ALT Crompton & Knowles Corp., Dyes and Chemical Div. AMS Ridgway Color & Chemicals APO Apollo Colors, Inc. ATL Atlantic Chemical Corp. BASF Wyandotte Corp. Buffalo Color Corp. Benzenoid Organics Inc. Binney and Smith, Inc. BAS BCC EDO BNS BOR BUG Borden, Inc., Printing Ink Div., Pigments Div. Synalloy Corp., Blackman- Uhler Chemical Div. CGY Ciba-Geigy Corp. CIK Flint Ink Corp. DUPaE.I. du Font de Nemours & Co., Inc. EKT Eastman Kodak Co. FAB Fabricolor Incorporated GAF GAF Corp. GLX Galaxie Chemical Corp. HPC Hercules, Inc. HRC Harmon Colors Corp. c HSC Chemetron Corp., Pigments Div., Subsid. of Allegheny Ludlum Industries, Inc. Code HST ICC ICI IDC IND KWC KON LVR MAY MGR MRT MRX PCW PDC PSC ROM SDC SDH SNA STG TMS Name of Company American Hoechst Corp. Inmont Corp. ICI Americas Inc. Industrial Color, Inc. Indol Chemical Co., Inc. Keystone Color Works Inc. H. Kohnstamm & Co., Inc. C. Lever Co. Inc. Otto B. May Co. Div. of Cone Mills Corp. Magruder Color Co. Morton Norwich Products Inc. Max Marx Color & Chem. Co. Pfister Chemical VIorks Berncolors-Poughkeepsie Co. Passaic Color & Chem. Co. United Merchants & Manufac- turers, Inc. Roma Chemical Div. Sandoz, Inc., Colors & Chemicals Div. Martin-Marietta Corp. Sterling Drug, Inc. Hilton Davis Chemical Co. Div. Sun Chemical Corp., Pigments Div. Stange Co. Sterling Drug, Inc., Thomasset Colors Div. 172 ------- Table 14 (Concluded) IISH Harshaw Chemical Co. TRC Tons River Chemical Corp, UHL Paul Uhlich & Co. Inc. VPC WJ llobay Chemical Corp. Verona Dyestuff Div. Warner-Jenkinson Co. In 1979 duPont sold its paper dye operations to Mobay Chemical Corp., and its textile dye operations to Ciba-Geigy Corp. and Crompton and Knowles Corp. In 1979 duPont sold its dyes for ink operations to Morton Norwich Products Inc., Morton Chemical Co. Division. 3In 1978 GAF Corp. sold its dye operations to BASF Wyandotte Corp. "In 1978 Chemetron Corp. sold its dye operations to BASF Wyandotte Corp 173 ------- Table 15 PRODUCERS OF MONOAZO DYES AND PIGMENTS CM. No. C.I. Name American Color & Chemical Corp. 18967 Acid Yellow 19 18835 Acid Yellow 25 19010 Acid Yellow 54 13906 Acid Yellow 151 15510 Acid Orange 7 15510:1 Pigment Orange 17 15510:2 Pigment Orange 17:1 15510:3 Solvent Orange 49 15575 Acid Orange 8 16230 Acid Orange 10 13150 Acid Orange 50 18732 Acid Orange 60 18050 Acid Red 1 14710 Acid Red 4 17045 Acid Red 37 18810 Acid Red 186 14880 Acid Blue 158 15711 Acid Black 52 19140 Food Yellow 4 19140:1 Pigment Yellow 100 11855 Disperse Yellow 3 11005 Disperse Orange 3 11110 Disperse Red 1 11215 Disperse Red 5 11150 Disperse Red 7 11210 Disperse Red 17 11228 Disperse Red 65 11152 Disperse Brown 1 11365 Disperse Black 1 15050 Acid Blue 158:1 C.I. No. 13095 13091 C.I. Name Acid Yellow 63 Acid Orange 1 American Cyanamid Co. 13080 Acid Orange 5 15510 Acid Orange 7 15510:1 Pigment Orange 17 15510:2 Pigment Orange 17:1 15510:3 Solvent Orange 49 15575 Acid Orange 8 16230 Acid Orange 10 18740 Acid Orange 72 18050 Acid Red 1 16150 Acid Red 26 16580 Acid Violet 3 19140 Food Yellow 4 19140:1 Pigment Yellow 100 12055 Solvent Yellow 14 11021 Solvent Yellow 56 12140 Solvent Orange 7 11320 Basic Orange 1 11320:1 Solvent Orange 4 11270 Basic Orange 2 11270:1 Solvent Orange 3 11052 Basic Blue 54 18760 Mordant Red 7 12075 Pigment Orange 5 12120 Pigment Red 3 12085 Pigment Red 4 12390 Pigment Red 17 12315 Pigment Red 22 174 ------- C.I. No. 12355 15865 15630 15860 15585 15850 17100 11043 11014 11480 C.I. Name Pigment Red Pigment Red Pigment Red Pigment Red Pigment Red Pigment Red 23 48 49 52 53 57 Acid Brown 90 Basic Violet Basic Red 30 18 Basic Yellow 24 Crompton & Rnowles Corp. Dyes- and Chemical Div. 17101 18967 18732 15985 19140 19140:1 11855 11005 11227 11110 11215 11210 11228 11152 14700 16035 18950 _ Acid Red 266 Acid Yellow Acid Orange Food Yellow Food Yellow > 19 60 3 4 Pigment Yellow 100 Disperse Yellow 3 Disperse Orange 3 Disperse Orange 25 Disperse Red Disperse Red Disperse Red Disperse Red 1 5 17 65 Disperse Brown 1 Food Red 1 Food Red 17 Acid Yellow Acid Red 337 40 — Disperse Blue 79 Ridgxtfay Color & Chemicals- 11680 12085 15865 15630 Pigment Yellow 1 Pigment Red Pigment Red Pigment Red 4 48 49 Table 15 (Continued) C.I. No. 1586Q 15585 15850 C.I. Name Pigment Red 52 Pigment Red 53 Pigment Red 57 Apollo Colors, Inc. 15585 Pigment Red 53 15850 Pigment Red 57 Atlantic Chemical Corp. 18965 Acid Yellow 17 18967 Acid Yellow 19 18890. Acid Yellow 34 14170 Acid Yellow 65 15510 Acid Orange 7 15510:1 Pigment Orange 17 15510:2 Pigment Orange 17:1 15510:3 Solvent Orange 49 15575 Acid Orange 8 16230 Acid Orange 10 13025 Acid Orange 52 18732 Acid Orange 6Q 18050 Acid Red 1 147 20. Acid Red 14 16255 Acid Red 18 15620 Acid Red 88 17755 Acid Red 137 16580 Acid Violet 3 18055 Acid Violet 7 13390 Acid Blue 92 15711 Acid Black 52 12055 Solvent Yellow 14 12140 Solvent Orange 7 11270 Basic Orange 2 11270:1 Solvent Orange 3 175 ------- C.I. No. C.I. Name 11085 Basic Red 18 13950 Direct Yellow 27 18760 Mordant Red 7 19555 Direct Yellow 28 11005 Disperse Orange 3 11100 Disperse Orange 5 11119 Disperse Orange 30 11110 Disperse Red 1 11115 Disperse Red 13 11152 Disperse Brown 1 18950 Acid Yellow 40 BASF Wyandotte Corp. Table 15 (Continued) C.I. No. 11085 11460 11154 11052 15602 19555 14645 15705 11110 ; 11115 11210 11116 11480 C.I. Name 13065 Acid Yellow 36 13900 Acid Yellow 99 13900:1 Solvent Yellow 19 18690 Acid Yellow 121 15510 Acid Orange 7 15510:1 Pigment Orange 17 15510:2 Pigment Orange 17:1 15510:3 Solvent Orange 49 16230 Acid Orange 10 14710 Acid Red 4 14720 Acid Red 14 15620 Acid Red 88 17101 Acid Red 266 17755 Acid Red 137 15711 Acid Black 52 19140 Food Yellow 4 19140:1 Pigment Yellow 100 12715 Solvent Red 8 11270 Basic Orange 2 11270:1 Solvent Orange 3 - Acid Red 337 — Disperse Blue 79 Basic Red 18 Basic Red 29 Basic Blue 41 Basic Blue 54 Pigment Orange 46 Direct Yellow 28 Mordant Black 11 Mordant Black 17 Disperse Red 1 Disperse Red 13 Disperse Red 17 Disperse Red 73 Basic Yellow 24 Buffalo Color Corporation 17200 Acid Red 33 15985 Food Yellow 3 19140 Food Yellow 4 19140:1 Pigment Yellow 100 12156 Solvent Red 80 14700 Food Red 1 16035 Food Red 17 Benzenoid Organics Inc. 18820 Acid Yellow 11 18965 Acid Yellow 17 18890 Acid Yellow 34 15510. Acid Orange 7 15510:1 Pigment Orange 17 15510:2 Pigment Orange 17:1 15510:3 Solvent Orange 49 18050 Acid Red 1 14710 Acid Red 4 17025 Acid Violet 1 176 ------- Table C.I. No. 18055 18075 18760 C.I. Name Acid Violet 7 Acid Violet 12 Mordant Red 7 15 (Continued) C.I. No. C.I. Name Binney and Smith, Inc. 11710 Pigment Yellow 3 12390 Pigment Red 17 12300 Pigment Red 21 15630 Pigment Red 49 15850 Pigment Red 57 Borden, Inc., Printing Ink Div., Pigments Div. 15865 Pigment Red 48 15630 Pigment Red 49 15585 Pigment Red 53 15850 Pigment Red 57 Synalloy Corp., Blackman-Uhler Chemical Div. 12355 Pigment Red 23 11152 Disperse Brown 1 Ciba-Geigy Corp. 12070 Pigment Red 1 Flint Ink Corp. 12120 Pigment Red 3 15630 Pigment Red 49 15585 Pigment Red 53 15850 Pigment Red 57 E. I. du Pont de Nemours & Co., Inc. 13065 Acid Yellow 36 13906 Acid Yellow 151 18930 Acid Yellow 200 18732 Acid Orange 60 18050 Acid Red 1 17755 Acid Red 137 12055 Solvent Yellow 14 11270 Basic Orange 2 11270:1 Solvent Orange 3 11056 Basic Orange 24 11085 Basic Red 18 11680 Pigment Yellow 1 11741 Pigment Yellow 74 12120 Pigment Red 3 12090 Pigment Red 6 12315 Pigment Red 22 12355 Pigment Red 23 15865 Pigment Red 48 15850 Pigment Red 57 15825 Pigment Red 58 12775 Pigment Green 10 19555 Direct Yellow 28 11227 Disperse Orange 25 11110 Disperse Red 1 12476 Disperse Red 220 11077 Disperse Blue 165 11087 Basic Yellow 15 Acid Red 337 Eastman Kodak Co. 11855 Disperse Yellow 3 11100 Disperse Orange 5 11227 Disperse Orange 25 11110 Disperse Red 1 11210 Disperse Red 17 11228 Disperse Red 65 Disperse Blue 79 Fabricolor Incorporated 13390 Acid Blue 92 177 ------- 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 ------- REFERENCES Abrahart, E. N. 1968. Dyes and Their Intermediates. Pergamon Press, New York. ADMI (American Dye Manufacturers Institute, Inc.). 1973. Dyes and the Environment, Vol 1. Anliker, R., and E. A. Clarke, 1979. The Ecology and Toxicology of Synthetic Organic Pigments. Ecological and Toxicological Association of the Dyestuffs Manufacturing Industry, Clara Strasse 4/6, P.O. Box CH-4005, Basel, Switzerland. Baird, R., L. Carmona, and R. L. Jenkins. 1977. Behavior of Benzidine and Other Aromatic Amines in Aerobic Wastewater Treatment. Journal of the Water Pollution Control Federation 49:1609-1615. BIOS (British Intelligence Objectives Subcommittee). 1945. German Dyestuffs and Dyestuffs Intermediates, Azo and Lake Dyestuffs. BIOS Final Report No. 961, Item No. 22. H. M. Stationery Office, London. Boeniger, M. 1980. Carcinogenicity and Metabolism of Azo Dyes, Especially Those Derived from Benzidine. Technical Report DHHS 80-119. US Department of Health and Human Services, National Institute of Occupational Safety and Health, Cincinnati, Ohio. Brown, D., H. R. Hitz, and L. Schafer. 1981. Chemosphere 10(5):245-261. The Society of Dyers and Colourists. 1980. Colour Index Lund Humphries Printers, London, England, Volumes 1-3, third edition, 1971 Volume 6, revised third edition, 1975; additions and amendments numbers 13-16, October 1974-July 1980. Crossley, Kienle, and Benbrook. 1940. JACS 62:1400. DETO (Dyes Environmental and Toxicology Organization, Inc.), New York. 1980. Comments on the Testing Recommendations of the TOSCA Interagency Testing Committee for Benzidine-based Dyes. Dieckhues, B. 1961. Experiments on the Reductive Splitting of Azo Dyes by Bacteria. Zentbl. Bakt. Parasitkde 180:244-249. Dubin, P., and K. L. Wright. 1975. Reduction of Azo Dyes in Cultures of Proteus Vulgaris, Zenobiotica 5:563-571. 194 ------- EPA (U. S. Environmental Protection Agency). 1975. Development Document, Significant Organic Products of Organic Chemical Manufacturing. EPA- 440/1-75-045. U.S. Environmental Protection Agency, Washington, D.C. Flege, R. K. 1970. Determination of Degraded Dyes and Auxiliary Chemicals in Effluents from Textile Dyeing Processes. Georgia Institute of Technology, Atlanta, Georgia. Games, L. M., and R. A. Hites. 1977. Analytical Chemistry 49:1433-1440. Hansch, C. 1978. Pomona College Data System, Seaver Chemistry Laboratory, Pomona College. Hanson, J. B. 1979. Development Document for Existing Source Pretreatment Standards for the Electroplating Point Source Category, EPA 440/1-79/003, U. S. Environmental Protection Agency, Effluent Guidelines Division, Washington, D.C. Hitz, H. R., W. Huber, and R. H. Reed. 1978. The Adsorption of Dyes on Activated Sludge. Journal of the Society of Dyers and Colourists 94:71- 76. Hughes, E. C., C. K. Ingold, and J. H. Ridd. 1958. Journal of the Chemical Society (London) 1958:58, 65, 70, 77, 82, 86. Idaka, E., et al. 1978. Degradation of Azo Compounds by Aeromonas hydrophila var. 24B. Journal of the Society of Dyers and Colourists. March 1978. pp. 91-94. Kappeler, T., et al. 1978. Are Azo Dyes Degradable? Textile Chemist and Colourist 10:10. Kenaga, E. E., and C. A. I. Goring. 1978. Relationship Between Water Solubility, Soil-Sorption, Octanol-Water Partitioning, and Bioconcentration of Chemicals in Biota. Preprint of paper given at ASTM 3rd Aquatic Toxicol. Symp., October 17-18, 1978, New Orleans, Louisiana. Keinath, T. M. 1976. Benzidine: Wastewater Treatment Technology. EPA- 440/9-76-018. U.S. Environmental Protection Agency, Washington, D.C. Kent, J. A., Editor. 1974. Riegel's Handbook of Industrial Chemistry, 2nd Edition. Van Nostrand Reinhold Company, New York. Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition. 1978. 3:772- 777- John Wiley and Sons, Inc., New York. Lapp, T. W., et al. 1979. A Preliminary Materials Balance for Dyes and Pigments from Benzidine and Three Benzidine Derivatives. Midwest Research Institute Draft Report. U. S. Environmental Protection Agency, Office of Toxic Substances, Washington, D.C. 195 ------- Lubs, H. A. 1955. The Chemistry of Synthetic Dyes and Pigments. American Chemical Society Monograph No. 127- Van Nostrand Reinhold Company, New York. p. 101. Mabey, W. R. et al., 1981. Aquatic Fate Process Data for Organic Priority Pollutants EPA 68-0003-2981. U.S. Environmental Protection Agency, Office of Water Regulations and Standards, Washington, D.C. Melnikov, B. N., and M. N. Kirillova. 1969. Thermal Stability of Direct Dyes in Solution. Zhurnal Prikladnoi Khimii 42. Meyer, U., et al. 1979. The Biologic Degradation of 1920 Azo Dyes. Textilveredlung 14:15-20. Mill, T., et al. 1980. Laboratory Protocols for Evaluating the Fate of Organic Chemicals in Air and Water, U.S. Environmental Protection Agency, Office of Research and Development, Environmental Research Laboratory, Athens, Georgia. Patterson, J. W., and R. A. Minear. 1971. Wastewater Treatment Technology, Illinois Institute for Environmental Quality, Chicago, Illinois. Peck, K., and J. C. Gorton, Jr. 1977. Industrial Waste Pretreatment in the Buffalo Minicipal System EPA 600/2-77-018. U. S. Environmental Protection Agency, Office of Research and Development, Robert S. Kerr Environmental Research Laboratory, Ada, Oklahoma. Porter, J. J. 1973. Stability and Removal of Commercial Dyes from Process Wastewater. Pollution Engineering. October 1973. pp. 27-30. Roberts, J. D., and M. C. Caserio. 1964. Basic Principles of Organic Chemistry. W. A. Benjamin, Inc., New York. Rys, P., and H. Zollinger. 1972. Fundamentals of the Chemistry and Application of Dyes. John Wiley and Sons, Inc., New York. Saunders and Waters. J. C. S. 1154 (1946). Shreve;, R. N., and J. A. Brink. 1977. Chemical Process Industries, 4th ed. McGraw-Hill Book Company, New York. Smith, J. H., W. R. Mabey, N. Bohonos, B. R. Holt, S. S. Lee, T. W. Chou, D. C. Bomberger, and T. Mill. 1977. Environmental Pathways of Selected Chemicals in Freshwater Systems. Part I: Background and experimental Procedures, U.S. Environmental Protection Agency. EPA-600-7-77-113. Smith, J. H., W. R. Mabey, N. Bohonos, B. R. Holt, S. S. Lee, T. W. Chou, D. C. Bomberger, and T. Mill. 1978. Environmental Pathways of Selected Chemicals in Freshwater Systems. Part II: Laboratory Studies. U.S. Environmental Protection Agency, Off. Res. Dev., EPA-600/7-78-074. 196 ------- Snow. 1932, Ind. Eng. Chem. 24:1420. Steadman, T. R., et al. 1977. Industrial Process Profiles for Environmental Use; Chapter 7, Organic Dyes and Pigments Industry. EPA 600/2-77- 023g. U. S. Environmental Protection Agency; Washington, B.C. Swett, L., A. Twhigg, and K. E. McCaleb. 1983. The Organic Dyes and Pigments Data Base. U.S. Environmental Protection Agency, Industrial Environmental Research Laboratory, Cincinnati, Ohio. Contract No. 68-03- 2944. 197 ------- 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 ------- 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 ------- 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 ------- 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 ------- |