United States
Environmental Protection
Agency
Office of
Toxic Substances
Washington DC 20460
EPA-560/2-81-001
May 1961
Toxic Substances
c/EFA
Materials Balance for Dyes and
Pigments from Benzidine and
Three Benzidine Derivatives
m
-------
This document is available through the National
Technical Information Service (NTIS), Springfield,
Virginia 22161, Telephone No. (703) 557-4650.
-
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CHEMICAL TECHNOLOGY AND ECONOMICS IN
ENVIRONMENTAL PERSPECTIVE
Task V - Materials Balance for Dyes and
Pigments from Benzidine and Three
Benzidine Derivatives
FINAL REPORT
May 1981
EPA Contract No. 68-01-3896
en
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.:!2
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c:i.
For
Environmental Protection Agency
Office of Toxic Substances
401 M Street, S.W.
Washington, D.C. 20460
Attn:
Mr. Roman Kuchkuda
Project Officer
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-------
DISCLAIMER
This report has been reviewed by the Office of Toxic Substances, U.S.
Environmental Protection Agency, and approved for publication. Approval
. does not signify that the contents necessarily reflect the views and poli-
cies of the U.S. Environmental Protection Agency, nor does mention of trade
names or commercial products constitute endorsement or recommendation for
use.
-------
PREFACE
This report presents results of a materials balance for dyes and/or
pigments produced from benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxy-
benzidine, and 3,3'-dichlorobenzidine during the period 1975 through 1978.
This study was performed by Midwest Research Institute as Task V under
Contract No. 68-01-3896 for the Office of Toxic Substances of the U.S. Envi-
ronmental Protection Agency. Project officer for this study was Mr. Roman
Kuchkuda. Principal Midwest Research Institute contributors to this study
included: Dr. Thomas W. Lapp (Task Leader), Mr. Thomas 1. Ferguson,
Mr. Howard Gadberry, Mr. Fritz Hoffmeister, Mr. Fred Hopkins, and Mr. Brian
Thompson. This contract is being performed under the supervision of
Dr. Edward W. Lawless, Head, Technology Assessment Section.
MRI would like to express a special note of appreciation to the tech-
nical advisor for this task, Ms. Elizabeth Bryan, Office of Pesticides and
Toxic Substances, for the assistance and encouragement provided during the
course of this study.
Midwest Research Institute would also like to express sincere apprecia-
tion to the many industry sources who provided technical input to this study.
Approved for:
MIDWEST RESEARCH INSTITUTE
~
Bruce W. Macy Direc~
Center for Technoeconomic
Analysis
iii
-------
Preface.
CONTENTS
. . . . . . . . . . .
. . . . .
. . . . . . . .
. . . .
1-
2.
Introduction. . . . . . . . . . . . . . . . . . . . .
Summary. . . . . . . . . . . . . . . . . . . . . . . .
Dye production and use. . . . . . . . . . . . . . . . .
Pigment production and use. . . . . . . . . . . . . . .
Miscellaneous uses. . . . . . . . . . . . . . . .
Preliminary materials balance. . . . . . . . . . . . .
Dye Production. . . . . . . . . . . . . . . . . . . . . . .
Production processes. . . . . . .. . . . .
Sources of losses during dye production. . . . .
Production of BAB dyes. . . . . . . . . . . . . . . . .
Imports and total benzenoid dye consumption. . . . . .
Materials balance for dye production. . . . . . . . . .
Dye usage. . . . . . . . . . . . . . . . .
Textile Dyeing. . . . . . . . . . . . . . . . .
Industry characterization. . . . . . . . . . . . . . .
Textile dyeing and dyestuff printing. . . . . . . . . .
Estimated consumption . . . . . . . . . . .
Estimated losses. . . . . . . . . . . . . . . . .
Leather Tanning Industry. . . . . . . . . . . .
Industry overview. . . . . . . . . . . . . . . . . . .
Leather tanning and dyeing processes. . . . . . . . . .
Dye consumption. . . . . . . . . . . . . .
Estimated losses. . . . . . . . . . . . . . . . .
Paper Industry. . .' . . . . . . . . . . . . . . . . . . . .
Industry overview. . . . . . . . . . . . . . . . . . .
Paper processing and dyeing. . . . . . . .
Dye consumption. . . . . . . . . . . . . . . . . . . .
Estimated losses. . . . . . . . . . . . . . . . .
Pigment Production. . . . . . . . . . . .
Manufacturing process. . . . . . . . . . . . . .
Production history. . . . . . . . . . . . .
Estimated losses. . . . . . . . . . . . . . . . .
Pigment usage. . . . . . . . . . . . . . . . . .
Plastics and Rubber Industry. . . . . . . . . . . . . . . .
Industry overview - plastics. . . . . . . . . . . . . .
Pigment consumption - plastics. . . . . . . . . .
Estimated losses - plastics. . . . . . . .
Industry overview - rubber industry.
Rubber production process. . . . . . . . . . . .
Pigment consumption - rubber. . . . . . . . . . . . . .
Estimated losses - rubber. . . . . . . . . . . .
3.
4.
5.
6.
7.
8.
. . . . . .
v
Hi
1-1
2-1
2-1
2-9
2-16
2-18
3-1
3-1
3-3
3-6
3-7
3-23
3-30
4-1
4-1
4-4
4-6
4-8
5-1
5-1
5-3
5-5
5-7
6-1
6-1
6-5
6-9
6-10
7-1
7-1
7-7
7-14
7-19
8-1
8-1
8-6
8-8
8-14
8-16
8-18
8-18
-------
'-
10.
11.
12.
13.
References
Appendix
A.
B.
CONTENTS (continued)
9.
Printing Inks. . . . . . . . . . . . . . . . . . . . . . .. 9-1
Industry characteristics. . . . . . . . . . . . . 9-1
Ink production by types. . . . . . . . . . . . . 9-3
Manufacture of printing inks. . . . . . . . . . . . .. 9-5
Source of production loss. . . . . . . . . . . . . .. 9-7
Waste handling and treatment. . . . . . . . . . . . . . 9-11
Estimated losses. . . . . . . . . . . . . . . . . 9-14
Ink losses in printing. . . . . . . . . . . . . . 9-14
Postprinting disposition. . . . . . . . . . . . . . . . 9-18
Paint and Coatings Industry. . . . . . . . . . . . . . 10-1
Industry characteristics. . . . . . . . . . . . . 10-1
Paint manufacturing . . . . . . . .. 10-1
Pigment usage. . . . . . . . . . . . . . . 10-5
Estimated losses in paint manufacture. . . . . . . .. 10-9
Losses in paint application. . . . . . . . . . . . . . 10-15
Textile Printing. . . . . . . . . . . . . . . . 11-1
Industry characterization. . . . . . . . . . . . . .. 11-1
Printing processes. . . . . . . . . . . . . . . . 11-1
Estimated pigment consumption. . . . . . . . . . . . . 11-5
Pigment losses. . . . . . . . . . . . . . . . . . . . . 11-6
Miscellaneous Uses. . . . . . . . . . . . . . . . . . 12-1
Laboratory and test applications. . . . . . . . . 12-1
Home use dyes. . . . . . . . . . . . . . . . . . . .. 12-2
Arts and craft dyes . . . . . . . . . 12-4
Marking instruments. . . . . . . . . . . . . . . 12-4
Other BAB dye uses. . . . . . . . . . . . . . . . . .. 12-6
Preliminary Materials Balance. . . . . . . . . . . . . 13-1
BAB dyes. . . . . . . . . . . . . . . . .. 13-1
Pigments. . . . . . . . . . . . . . . . . . . . . . .. 13-4
Overall perspective. . . . . . . . . . . . . . . . .. 13-4
. . . . . . . . . . . .
R-l
. . . . .
. . . . . . .
Report Reviewers. . . . . . . . . . . . . . .
Sample Calculations. . . . . . . . . . . . . .
. . . . . . .
A-I
B-1
. . . . . . .
vi
-------
Number
3-1
3-2
3-3
3-4
4-1
5-1
6-1
6-2
6-3
7-1
9-1
10-1
10-2
11-1
FIGURES.
Example of BAB dye manufacturing process. . . .
.. .. .. .. ..
Characteristics of BAB dye production industry. .
.. .. .. ..
Trends in BAB dye production.
.. .. .. .. ..
.. .. .. .. ..
.. .. .. ..
Materials balance for BAMB raw materials in dye manu-
facturing. . . . . . . . . . . . . . . . . . . . . . . .
Typical textile dyeing process
.. .. .. .. ..
.. .. .. .. ..
.. .. .. ..
A general process flow diagram illustrating tannery
inputs and wastestreams. . . . . . . . . . . . .
.. .. .. ..
Page
3-4
3-13
3-22
3-25
4-5
5-11
Simplified representation of a beater. . . . . 6-6
Simplified representation of a conical continuous
refiner. . . , . . . . . . . . 6-7
A general process flow diagram illustrating papermaking
inputs and wastestreams. . . . . . . . . . . . . . . . .
General flow diagram for pigment manufacture.
Sample materials balance for diarylide pigments in
printing inks in 1978. . . . . . . . . . . . . .
.. .. .. ..
Flow diagram of solvent base paint manufacturing process.
Flow diagram of water base paint manufacturing process. .
Typical printing process.
.. .. .. .. .. .. ..
.. .. .. .. .. ..
vii
6-13
7-3
9-15
10-4
10-6
11-3
-------
Number
2-1
2-2
2-3
2-4
2-5
3-1
3-2
3-3
3-4
3-5
3-6
3-7
3-8
3-9
4-1
4-2
4-3
TABLES
Estimated Quantities of BAB Dye Consumed in the
United States. . . . . . . . . . . . . . . . .
. . . . .
BAB Dye Losses from Production Processes.
. . . .
. . . .
Approximate Percent BAB Dye Consumption by Area. . . . . .
Estimated Materials Balance for BAB Dyes by Use Area
Estimated Materials Balance for 3,3'-Dichlorobenzidine,
3,3'-Dimethylbenzidine, and 3,3'-Dimethoxybenzidine
Based Pigments in Use Areas. . . . . . . . . . . . . . .
BAB Dyes on the U.S. Market in 1979.
. . . . .
Code Letters of Manufacturers, Importers, and
Distributors. . . . . . . . . . . . . . . .
. . . . . .
U.S. Production, Import, and Sales Data for Commercial
BAB Dyes (in lb), 1975 to 1978 . . . . . . . . . .
Estimated Quantities of BAB Dye Consumed in the
United States. . . . . . . . . . . . . . . . . . .
BAB Dye Losses from Production Processes
Basis for Materials Balance Calculations
. . . . .
. . . .
Unreacted BAMB Raw Material in Dye Manufacture.
. . . . .
Estimated Active Dye Consumption in the U.S. During
1975-1978. . . . . . . . . . . . . . . . . . . . . . . .
Approximate Percent BAB Dye Consumption by Area.
. . . . .
Estimated U.S. Dyed Fabric Production (106 lb) of Fabric.
Apparatus Used in Textile Dyeing. . . .
. . . . . .
Estimated Bisazobiphenyl Dye Consumption in the Textile
Industry. . . . . . . . . . . . . . . . . . . . . . . .
viii
Page
2-3
2-4
2-5
2-19
2-20
3-8
3-12
3-14
3-24
3-26
3-27
3-29
3-30
3-31
4-3
4-7
4-8
-------
Number
4-4
4-5
4-6
5-1
5-2
5-3
5-4
5-5
5-6
6-1
6-2
6-3
6-4
6-5
7-1
7-2
7-3
7-4
TABLES (continued)
Estimated Bisazobiphenyl Dye Losses in Textiles. .
. . . .
Fiber Losses During Finishing and Other Processing Steps.
Estimated Bisazobiphenyl Dye Loss in the Textile Industry.
A Partial Listing of the Categories and Types of Leather
Produced by U.S. Tanners. . . . . . . . . . . . . . . .
BAB Dyes Used in Leather Tanning, 1975-1978. . . .
. . . .
Estimated Consumption of BAB Dyes in the Leather Industry.
Overall Dye Consumption in the Leather Industry
(1975-1978). . . . . . . . . . . . . . . . . .
. . . . .
Approximate Consumption of BAB Dye by the Leather
Industry (1975-1978) . . . . . . . . . . . . . .
. . . .
Estimated Losses of Bisazobiphenyl Dyes in the Leather
Industry. . . . . . . . . . . . . . .
Origin and Use of Various Wood Pulp. .
. . . . . .
. . . .
Paper Production by End Use, 1975-1978
. . . . .
. . . . .
Commercial Dye Usage in Paper and Paperboard. . .
. . . .
Estimated Consumption of BAB Dyes by the Paper Industry. .
Summary of Estimated Bisazobiphenyl Dye Losses from
the Paper Industry. . . . . . . . . . . . . . . .
Structures of Selected Diarylide Pigments.
. . . ." .
Pigment Manufacturers, 1975-1978
. . . . .
. . . . .
U.S. Production and Imports of Selected Pigments
. . . . .
Estimated Losses of 3,3'-Dichlorobenzidine, 3,3'-Dimethyl-
benzidine, and 3,3'-Dimethoxybenzidine During their
Manufacture. . . . . . . . . . . . . . . . . . . . . . .
ix
Page
4-9
4-11
4-12
5-2
5-6
5-7
5-8
5-9
5-12
6-2
6-3
6-9
6-11
6-12
7-5
7-8
7-12
7-15
-------
Number
7-5
7-6
7-7
8-1
8-2
8-3
8-4
8-5
8-6
8-7
8-8
8-9
8-10
8-11
8-12
9-1
9-2
TABLES (continued)
Estimated Losses of 3,3'-Dichlorobenzidine, 3,3'-Dimethyl-
benzidine, and 3,3'-Dimethoxybenzidine During Pigment
Production. . . . . . . . . . . . . . . . . . . . . . .
Estimated Pigment Losses Due to Transfer and Handling at
Production Facilities, Quantity (1,000 lb) . . . .
Consumption of Pigment by Use Area. . .
Production of Selected Resins, 1975-1978 .
. . . . . . . .
Estimated Consumption of Pigments in the Plastics
Industry. . . . . . . . . . . . . . . . . . . . .
Estimated Amount of Pigments Consumed by Resin (1975)
(Quantity in 1,000 lb) . . . . . . . . . . . . . . . . .
Estimated Amount of Pigment Consumed by Resin (1976)
(Quantity in 1,000 lb) . . . . . . . . . . .
Estimated Amount of Pigments Consumed by Resin (1977)
(Quantity in 1,000 lb) . . . . . . . . . . . . . .
Estimated Amount of Pigments Consumed by Resin (1978)
(Quantity in 1,000 lb) . . . . . . . . . . . . . .
Estimated Pigment Loss in Resin Compounding Stage. .
Estimated Pigment Losses Vis Resin Processing.
. . . . . .
Standard Industrial Classification (SIC) Codes for Rubber
and Miscellaneous Plastic Products. . . . . . . .
U.s. Rubber Production by Type, 1975-1978. . .
Consumption of Pigments - Rubber Industry. . .
. . . . . .
Estimated Pigment Loss in the Rubber Industry.
1976 Production Volume in Pounds. .
. . . . .
1977 Ink Shipments by Type of Ink.
x
Page
7-16
7-18
7-19
8-2
8-7
8-9
8-10
8-11
8-12
8-13
8-14
8-15
8-17
8-18
8-19
9-2
9-2
-------
!.--
Number
9-3
9-4
9-5
9-6
9-7
9-8
10-1
10-2
10-3
10-4
10-5
10-6
10-7
10-8
10-9
11-1
11-2
11-3
11-4
TABLES (continued)
Distribution by Printing Process. . . . .
. . . . . . . .
Estimated Diarylide Pigment Consumption in Printing Inks.
Wastewater Pretreatment Prior to Discharge
. . . . . . . .
Analytical Data from Individual Plant Sites (Selected
Compounds Only). . . . . . . . . . . . . . . . . . . . .
Estimated Losses from the Printing Ink Industry. .
. . . .
Estimated Fate of Diarylide Pigments in Printed Material.
Distribution of Large Paint Plants, by State. .
. . . . .
Dairylide Pigments in Paint Production. .
. . . . .
Estimated Dairylide Pigment Consumption in Paints.
. . . .
Relative Usage of Color Pigments by Paint Plants.
. . . .
Methods of Tank Cleaning. . .
. . . . . . . . . .
. . . .
Volume of Wastewater Generated by Paint Plants
Page
9-3
9-6
9-11
9-13
9-16
9-19
10-2
10-7
10-8
10-10
10-12
10-13
Estimated Pigment Loss from Paint Manufacturing - 1978 10-14
Estimated Pigment Loss from Paint Manufacture. . . . . 10-15
Estimated Pigment Loss from Paint Application. 10-17
Estimated Quantity of Fabric Printed by Process
(1975-1978). . . . . . . . . . . . . . . .
. . . .
Estimated Dairylide Pigment Consumption in Textile
Printing. . . . . . . . . . . . . . . . . . . .
. . . .
Estimated Dye and Pigment Losses in the Textile Printing
Process. . . . . . . . . . . . . . . . . . . . . . . . .
Estimated Dairylide Pigment Loss in Textile Printing. . .
xi
11-2
11-5
11-7
11-8
-------
Number
12-1
12-2
13-1
13-2
13-3
13-4
13-5
TABLES (concluded)
Estimated Losses from Home Dyes. . . . . .
. . . . .
Estimated Losses from Crayon Production. . . . .
. . . . .
BAB Dye Losses From Production Processes. . .
Estimated Materials Balance for BAB Dyes by Use Area
Estimated Losses of Raw Material During Manufacture
and Pigment Production. . . . . . . . . . . . .
. . . .
Estimated Pigment Loss in Production Process.
. . . . . .
Estimated Materials Balance for 3,3'-Dichlorobenzidine,
3,3'-Dimethylbenzidine and 3,3'-Dimethoxybenzidine
Based Pigments in Use Areas. . . . . . . . . . . . . . .
xii
Page
12-3
12-5
13-2
13-3
13-5
13-6
13-7
-------
SECTION I
INTRODUCTION
Benzidine and three of its congeners,* 3,3'-dichlorobenzidine (DCB),
3,3'-dimethoxybenzidine (Q-dianisidine, DMOB), and 3,3'-dimethylbenzidine
(Q-tolidine, DMB), are important starting materials for the production of a
variety of dyes or pigments. Benzidine is used solely for the production
of dyes and DCB is currently used solely for the manufacture of pigments.
The other two congeners, DMB and DMOB, are used in the production of dyes
and pigments. These dyes and pigments are widely used and thus these may
have potential for widespread environmental exposure. Benzidine has been
recognized for some time as a human carcinogen. Laboratory experiments sug-
gest that the other three starting materials may also be carcinogenic to
laboratory animals. In addition, the National Cancer Institute (NCI) re-
cently recommended that three dyes based on benzidine be handled in the work-
place as if they were human carcinogens.
This study was undertaken as the first step in the evaluation of the
potential for environmental exposure due to these compounds. The overall
objective was to develop a preliminary materials balance for the production
and use of pigments or dyes based on benzidine, 3,3'-dimethylbenzidine,
3,3'-dichlorobenzidine, and 3,3'-dimethoxybenzidine.
The specific dyes and pigments considered in this report were selected
by the Environmental Protection Agency (EPA). The specific objective was
to compile, to the extent possible, a complete materials balance utilizing
available data from trade publications, government reports, and industry
sources. In those instances where data were unavailable, Midwest Research
Institute (MRI) was to estimate quantities.
~
"
In commercial practice, these three congeners are not produced from
benzidine per se, but are synthesized from other chemical precursors.
1-1
-------
Considerable information was obtained from industry sources who wished
to remain anonymous; MRI has attempted to abide by these wishes whenever
possible. As a result, industry sources are cited throughout the report,
but no specific references are provided.
During the course of this study, numerous areas were found for which
data were unavailable, and estimates were made based on the best available
information. Because a large portion of the data presented in this report
is based on estimated quantities, the results of this materials balance
should be considered preliminary until more definitive data are available.
Throughout this report, reference will be made to "benzidine based"
dyes. This terminology refers specifically to those dyes based on benzi-
dine. Similarly, dyes based specifically on 3,3'-dimethylbenzidine and
3,3'-dimethoxybenzidine will be referred to as 3,3'-dimethylbenzidine based
and 3,3'-dimethoxybenzidine based, respectively. The term "bisazobiphenyl"
(BAB)-dyes is employed where a more general term is required to include all
dyes based on benzidine, 3,3'-dimethylbenzidine, and 3,3'-dimethoxybenzi-
dine. The term "bisaminobiphenyl" (BAMB) starting material is used when
referring to benzidine, 3,3'-dimethylbenzidine, and 3,3'-dimethoxybenzidine
collectively as the starting material for dyes.
This report has been reviewed by numerous organizations and companies
directly related to dyes and pigments. A listing of those who received copies
of the draft final report (dated August 31, 1979) for review is presented
in Appendix A. This report reflects those review comments which were deemed
to have merit.
1-2
-------
SECTION 2
SUMMARY
A summary of the results of this preliminary materials balance study
is presented in this section. The processes for and losses resulting from
the manufacture of dyes and pigments are included. Consumption profiles
and estimated losses are summarized for bisazobiphenyl (BAB) dyes in the
textile, leather, and paper industries and for pigments in the rubber and
plastics, printing ink, textile printing, and paint and coatings industries.
A summation of the materials balance for the period 1975 through 1978 is
presented.
DYE PRODUCTION AND USE
Information is presented for the production of BAB dyes and usage of
these dyes by various industries. Losses occurring during the manufacture
and use have been derived from known or estimated data.
Dye Production
A number of commercial dyes are being produced in the United States
from three bisaminobiphenyl (BAMB) precursors: benzidine, 3,3'-dimethylben-
zidine, and 3,3'-dimethoxybenzidine. The production processes for these
BAB dyes involve a complex series of batch processes carried out over a range
of pHs, temperatures, and reaction times. Actual yield of saleable dye at
the end of the manufacturing process ranges from ~ 76 to ~ 93% based on the
starting BAMB raw material and depending on the particular dye and production
process involved. However, because of the complexity of the production pro-
cesses, even small operating problems or the lack of operator attention can
result in a reduction in product yield of 10% or more.
The losses of BAMB based materials during dye production processes,
i.e., conversion to unwanted by-products or removal from the process stream
had not previously been well quantified. However, the following sources of
losses have been identified, and losses have been estimated.
* By-Products - Loss of BAMB raw material from the production of unwanted
by-products or degradation products during the production process. By-product
losses typically range from 5 to 15%.
* Process Vent - Loss of material to the process vent system, estimated
to be ~ 0.1% of the original BAMB raw material, in the form of original BAMB
raw material, active dyes, and by-products.
2-1
-------
* Process
losses, spills,
process. These
1%.
Losses
leaks,
losses
- Loss of BAMB based material resulting from pumping
and intermediate purification steps in the production
are estimated to be from practically zero (0.25%) to
* Product Filtration Losses of dye during the filtration of the crude
dye product (suspension) estimated to be 1 to 3%.
* Drying, Grinding, Standardizing, and Packaging - Losses in these
final steps are estimated to be 1 to 5% as active dye.
* Raw Materials Carryover - Traces of unreacted BAMB raw materials in
the finished dye product. Dyes are usually stated to contain ~ 10 ppm of
the benzidine. It was assumed that this level applies to all three BAMB
raw materials.
Data on U.S. production, imports, and sales of standardized commercial
BAB based dyes for 1975 through 1978 have been tabulated. These data are
based on data published by the U.S. International Trade Commission and infor-
mation obtained from confidential industrial sources. The data from these
sources have been supplemented and modified where needed by Midwest Research
Institute (MRI) estimates. These data are presented in Table 2-1.
Estimates were then made of the overall materials balance for the three
BAB dyes during their production processes. These estimates were based on
the sources and levels of loss identified, the production rates given, and
other specific assumptions. Table 2-2 presents a summary of this balance.
Estimates of dye consumption data were developed for the various use
areas based on information obtained from industry sources. Most of these
sources agreed that the percentage consumption of dyes based on 3,3'-
dimethoxybenzidine and 3,3'-dimethylbenzidine had remained relatively con-
stant from 1975 through 1978. Large changes, however, had occurred for the
benzidine based dyes. A summary of BAB dye consumption by major use area
is given in Table 2-3.
Textile Dyeing
The principal BAB dye consumption occurs in textile mill products where
fibers are received and prepared for transformation into yarn, thread, or
webbing. Other processes include converting the yarn or web into fabric or
similar products and finishing of the material. Except for losses of mate-
rial as scrap when patterns are cut, no dye loss occurs in the apparel in-
dustry. Dyes of interest to this study are used primarily with cellulosic
or cotton materials; minor use areas include polyester/cotton and nylon/cotton
blends.
The same general dyeing process is employed for all the dyes of interest
with minor variations due to differences in the particular dye used, the
form of the fiber, and the type of fiber. A typical dyeing process would
include the following steps:
2-2
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TABLE 2-1.
ESTIMATED QUANTITIES OF BAB DYE CONSUMED IN THE UNITED STATES
.Quantity (106 1b)a/
Type of Dye Source 1975 1976 1977 1978
Benzidine O.S. productiorJ!-/ 3.8-4.6 5.8-7.0 4.1-4.5S/ 1.5-1.7
Import 0.8-1.0 0.5-0.7 1.4-1. 8 2.0-2.4
Consumption 4.6-5.6 6 . 0-8 . ~/ 5.3-6.5 3 . 4 -4 . 2~j
2.2-2.6 1.4-1.B£/ c/
3,3'-Dimethoxybenzidine U.S. production 1.6-2.0 2.5-3.1~/
Import 0.1-0.2 0.1-0.2 0.1-0.2c/ 0.2-0.4-
Consumption 2.0-2.4 2.1-2.5 2.5-3.1- 3.5-4. 3.U
3,3'-Dimethy1benzidine c/ 0.62-0.76 0.66-0.80 0.63-0.77 0.74-0.90
U.S. p~?duction-
Import- 0.01-0.03 0.03-0.05 0.03-0.05 0.13-0.17
ConsumptionB-/ 0.75-0.91 0.75-0.91 0.63-0.77 0.74-0.90
N
I
W
a/
All quantities are in terms of standardized commercial dyes; they do not represent 100% dye. To
convert to active dye content, see footnote (b)~ Table 3-6. Estimated error limits used to de-
rive the consumption. ranges were generally + 10%.
Data from Table 3-7.
Data supplied by DETO (1980).
Estimated by DETO (1980) to be 5.9; estimated by MRI to be 7.0 ~ 1.0.
Estimated by DETO (1980) to be 3.8.
Stated by the U.S. International Trade Commission (letter from J. O. Parker to S. D. Je11inek,
November 19~ 1979) to be 3.925 million pounds for the U.S. production quantity in 1978; estimated
by DETO to be 3.9 million pounds for the 1978 U.S. consumption 1eve1s~ including imports.
Includes approximately 340~000 lb of dye used in numerous areas exclusive of texti1es~ leather~
or paper. Examples of these use areas are lubricant and gasoline dyes (DETO, 1980).
~I
sJ
E.I
~I
il
~/
-------
TABLE 2-2.
BAB DYE LOSSES FROM PRODUCTION PROCESSE~/
Ac~ive Dye Loss (1,000 Ib)
1975 1976 1977 1978
Distribution BEJ!/ DMFI DMO#/ BEN DMB DMOB BEN DMB DMOB BEN DMB DMOB
Processing losses (0.2l-0.95%)~/ 5-26 < 1-4 1-8 7-40 < 1-4 2-10 5-26 < 1-4 1-7 2-10 < 1-5 2-12
N Filtration losses (1-3%) 23-84 4-13 6-24 35-130 4-14 9-32 25-82 4-14 6-22 9-31 4-16 10-38
I
.j:'-.
Drying, grinding, standardization,
and packaging losses (1-5%) 23-140 4-22 6-40 35-210 4-23 9-53 25-140 4-23 6-36 9-52 4-26 10-63
al
- Active dye basis; an overall product yield of 84% (BAMB raw material base) was assumed.
bl
- BEN = benzidine-based dyes.
S/
DMB = dimethylbenzidine-based.dyes.
M
DMOB = dimethoxybenzidine-based dyes.
~I
For methods of calculation used in this table, see Appendix B, I.
-------
it\
Weighing and mixing of dy~ solution
i'\
Addition of dye solution to fiber
'i'\
Water rinse of dyed fiber
"'k
Water extraction
~k
Fiber drying
TABLE 2-3.
APPROXIMATE PERCENT BAB DYE CONSUMPTION BY AREA
1975 1976 1977 1978
Benzidine based dyes:
Textile 50 - 60 45 - 55 45 - 55 40 - 50
Leather 20 - 25 20 - 25 25 - 30 45 - 55
Paper 20 - 25 2S - 30 20 - 25 5
3,3'-Dimethoxybenzidine based dyes:
Textile 38 - 42 38 - 42 33 - 37 33 - 37
Lellther 7 - 13 7 - 13 7 - 13 7 - 13
Pllper 44 - 46 44 - 46 49 - 51 45 -5S
Other "'S "'5 "'S '\.S
3,3'-Dimethylbenzidine based dyes:
'i'extile 44 - 50 44 - 50 36 - 41 45 - 50
Lellther 6 -9 6 - 9 5 - 8 4 - 9
Paper 3 - 6 3 - 6 5 - 8 "'5
Other "'41 "'41 "'41 "'41
The complexity of the textile industry and the variability in annual
consumption of specific dyes due to style changes in apparel design make
estimation of the consumption of specific BAB dyes very difficult. As a
result, dye consumption could be estimated by dye type (i. e., benzidine
based, 3,3' -dimethyl benzidine based, or 3,3' -dimethoxybenzidine based).
Estimated BAB dye consumption levels for 1975 through 1978 are as follows
(quantities of 100% dye in million pounds):
Base 1975 1976 1977 1978
Benzidine 1.2-1.7 1.4-2.3 1.2-1.8. 0.7-1.1
3,3'-Dimethylbenzidine 0.4-0.5 0.4-0.5 0.4-0.6 0.7-0.8
3,3'-Dimethoxybenzidine ~ 0.11-0.16 ~ 0.11-0.16 ~ 0.08-0.11 ~ 0.11-0.16
Total 1. 7-2.4 1.9-3.0 1.7-2.5 1.5-2.1
2-5
-------
The losses of dye during textile processing are in the dust from mixing
operations, residual dyes in shipping containers and mixing and holding con-
tainers, and liquid waste from the dyeing, rinsing, and water extraction
procedures. Sources of BAB dye losses and the estimated magnitude of each
source is as follows:
Dust from mixing
0.05-0.1%
Residual dye in containers
0.02-0.05%
Process wastewater
Direct dyes
5-30%
Acid dyes
2-5%
Unrecycled dye from
continuous units
2-10%
Solid waste from
processing (sub-
sequent to dyeing)
1.0-1.5%
A summary of the estimated BAB dye losses resulting from these sources is
shown in the following compilation (quantities of 100% active dye are in
1,000 pounds):
1975 1976 1977 1978
Dust 1-2 1-3 1-2 1-2
Residual dye ~ 1 ~ 1 ~ 1 ~ 1
Unrecycled dye 32-230 36-290 32-240 26-190
Process wastewater 80-690 90-870 80-720 65-570
Solid waste processing 16-35 18-44 16-36 13-29
Total 130-958 146-1,208 130-999 106-792
Leather Industry
In the leather tanning industry, shoe leather is the largest single
product, but a wide variety of other leather goods is also marketed. The
specific types and quantities of dyes used for leather products varies widely
from year to year due to trends in fashion and the multiplicity of current
manufacturers. The primary raw material for leather is cattle hide; all
other hides contribute less than 10% of the total hides processed.
Leather is typically dyed in a batch mode process. During the dyeing
operation, the hides and dye solution are mixed, commonly by the rotation
of the drum. Approximately 85% of all tanned hides are dyed.
The predominant colors used by leather tanners are black, brown, and
other colors used with brown to produce various shades of brown. Specific
2-6
-------
BAB dyes used in leather tanning are difficult to ascertain for any given
year due to changes in demand for different colors in different products.
Because of the difficulty in identifying specific dyes, estimates of the
total annual consumption were made for the three types of BAB dyes (i.e.,
benzidine based, 3,3'-dimethylbenzidine based, and 3,3'-dimethoxybenzidine
based). A summary of the estimated consumption is as follows (quantities
of 100% dye in 1,000 Ib): .
Base 1975 1976 1977 1978
Benzidine 460-725 620-1,025 675-990 765-1,155
3,3'-Dimethyl- 22-41 22-41 16-30 14-40
benzidine
3,3'-Dimethoxy- 49-104 49-117 63-143 84-195
benzidine
Total 531-870 691-1,183 754-1,163 863-1,390
Approximately 85 to 90% of the dye utilized in leather dyeing is success-
fully joined to the leather. If allowances are made for trimmings, buffing
losses, and other miscellaneous losses, the lower end of this range is reduced
to 80%. No definitive information was found to provide a quantitative break-
down for the fate of waste dyestuff from leather tanneries. However, from
the information that is available it is estimated that - 99.8% of the losses
occur as solid waste, - 0.1% liquid waste, and - 0.1% aerosolized waste.
The solid waste is estimated to be comprised of 60% from wastewater screen-
ings and sludge; 35% from trimmings and shavings; 3% from floor sweepings;
and 2% finishing wastes. A summary of the estimated solid, liquid, and aero-
solized wastes in terms of 100% dye is presented below (quantities in 1,000
pounds):
1975 1976 1977 1978
Solid waste (99.8%) 53-174 69-236 75-232 86-277
Liquid waste (--- 0.1%) - 0.1-0.2 "':'-0.1-0.2 - 0.1-0.2 --- 0.1-0.3
Aerosol waste (- 0.1%) - 0.1-0.2 - 0.1-0.2 - 0.1-0.2 - 0.1-0.3
Total 53-174 69-236 75-232 86-278
Paper Industry
The paper industry (including the paperboard industry) is a very large
diversified industry producing 10 general types or classifications of paper:
newsprint, printing and writing, packaging, special industrial, tissue, con-
tainerboard, box board, building paper, insulating and hard pressed board,
and wet machine board. In 1978, approximately 64 million tons of paper of
these 10 types were produced.
Though the equipment may vary, over 90% of all colored paper is dyed
in the same manner--prior to its aggregation into sheets and while in an
aqueous bath. In one very common method, dyeing occurs in a beater used to
2-7
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fragment fiber bundles and shorten individual fibers in the pulp. The prin-
cipal alternative method consists of two or three separate machines--a pulper,
a continuous refiner, and occasionally a deflaker. In each of these systems,
the dye may be added as a liquid solution or a dry powder.
. Dye consumption in the paper and paperboard industry ranges from 0 to
5 Ibfton of paper for unbleached kraft products, white paper and tissue,
and white paperboard to 60 to 80 Ibfton for full shade tissue paper and
brightly colored glassine. No data were available concerning quantities of
specific BAB dyes consumed in the paper industry; some industry estimates
were available for consumption by dye type (i.e., benzidine-based, 3,3'-
dimethylbenzidine-based, and 3,3'-dimethoxybenzidine-based). These esti-
mated consumption quantities are summarized below in thousands of pounds of
100% dye:
1975 1976 1977 1978
Benzidine 460-725 775-1,230 540-825 85-105
3,3'-Dimethoxy-
benzidine 308-368 300-414 441-550 540-825
3,3'-Dimethyl-
benzidine 11-27 11-27 16-30 18-22
Total 779.-1,120 1,094-1,671 997-1,405 643-952
Industry sources stated that 90 to 98% of the dye utilization in the
coloration of paper is successfully joined to the papermaking materials.
In order to allow for losses of dyed furnish and size, trimmings, and other
miscellanous losses during production, the range is lowered to 80 to 95%.
The remaining 5 to 15% of the dye consumed in processing is discarded as
waste; it is thought that the majority of the waste ultimately becomes solid
waste either as wastewater sludge, trimmings, plant dust, or other miscel-
laneous residues. It is estimated that ~ 99.8% of the losses are incorpo-
rated into solid waste, ~ 0.1% in liquid waste, and ~ 0.1% as aerosolized
(volatilized) waste. A summary of these estimated BAB dye losses (in
1,000 Ib of 100% dye) for the paper industry is presented below for the pe-
riod 1975 to 1978:
1975 1976 1977 1978
Solid waste 39-168 55-250 50-210 32-142
Liquid waste ~ 0.1-0.2 0.1-0.3 0.1-0.2 ~ 0.1-0.2
Volatile waste ~ 0.1-0.2 0.1-0.3 0.1-0.2 ~ 0.1-0.2
Total 39-168 55-251 50-210 32-142
2-8
-------
PIGMENT PRODUCTION AND USE
Information is presented for the production of pigments and usage of
these pigments by various ~ndustries. Losses occurring during the manufac-
ture and use have been derived from known or estimated data. For purposes
of this study, the EPA selected the following pigments: Reds 38 and 41;
Oranges 13, 15, 16, and 34; Yellows 12, 13, 14, 17, 55, and 83; and Blue 25.
Production Process
The production of pigments from 3,3'-dichlorobenzidine, 3,3'-dimethoxy-
benzidine, and 3,3'-dimethylbenzidine proceeds by a batch process using the
acid salt (usually the dihydrochloride salt) as the starting material. Prep-
aration of the dichlorobenzidine compound occurs by the reduction of
o-nitrochlorobenzene to the corresponding hydrazo compound, followed by acid
rearrangement to the 3,3'-dichlorobenzidine dihydrochloride. Estimated losses
of the dichlorobenzidine during production were 0.5 to 1. 0% in the II acid
stream" from the purification process and 0.5 to 1.5% in the waste stream
from filtration of the final product. .
Pigment production occurs by treatment of the appropriate compound with
nitrous acid (generated in situ) to form the corresponding tetrazonium chloride
which is reacted with a coupler to yield the desired pigment. On occasion
the tetrazonium solution may be filtered prior to addition of the coupler
solution; however, as a rule, this filtration step is omitted. Following
addition of the coupler solution and after pigment formation is complete,
the insoluble pigment is filtered from solution to form the presscake. The
three processing alternatives for the presscake are: (a) shipped as the
presscake, (b) transfer to a flusher and mixing with an oleoresinous material
to form a flushed color paste, and (c) drying, pulverizing, and shipment as
a dry toner.
The estimated total domestic production and published imports of the
pigments for the 4-year period were as follows:
Estimated production
Imports
1975
1976
1977
1978
10,293,000-10,443,000
14,034,000-14,179,000
15,446,000-15,701,000
19,281,000-19,536,000
124,820
275,930
64,100
35,080
In addition to losses during production of the starting material (i.e.,
3,3'-dichlorobenzidine dihydrochloride, etc.), losses of the starting material
(also includes soluble by-products) during pigment manufacture are as follows:
Filtration of tetrazonium solution
(optional)
Unreacted tetrazonium chloride
or soluble by-product
0.1-0.3%
o . 5 -1. 0%
2-9
-------
Losses of pigment during subsequent handling and processing are esti.-
mated to be:
Flushed color: handling and transfer
Dry toner: handling and transfer.
Dry toner: pulverizer cleaning
(optional)
Dry toner: blender cleaning
(optional)
Presscake: handling and transfer
1-3%
1-3%
0.5-1%
~ 1%
0.5-1%
The estimated overall pigment losses for flushed color or dry toner production
are 1 to 3%. If the optional pigment losses are employed for dry toner pro-
duction, the overall estimated loss is increased by ~ 1.5 to 2%. For presscake
production, the estimated losses are 0.5 to 1%. Estimated total loss of
3,3t-dichlorobenzidine, 3,3'-dimethylbenzidine, and 3,3t-dimethoxybenzidine
in the raw material manufacturing process and pigment production process
are as follows (quantities in 1,000 pounds):
1975 1976 1977 1978
3,3t-dichlorobenzidine 60-142 83-194 92-216 116-273
3,3t-dimethoxybenzidine 3-8 3-10 3-10 3-10
3,3'-dimethylbenzidine 0.3-0.7 0.3-0.7 0.3-0.6 0
Estimated total losses due to handling and transfer of finished pigments
derived from each of the compounds are (quantities in 1,000 pounds):
1975 1976 1977 1978
3,3t-dichlorobenzidine 91-274 126-380 137-410 177-537
3,3t-dimethoxybenzidine 6-19 7-21 6-20 6-20
3,3'-dimethylbenzidine 0.5-1 0.5-1 0.4-1 0
Pigment usage within various product areas was estimated based on infor-
mation from industry sources and published reports. Five industries were
identified as major consumers of these pigments: printing ink, plastics,
coatings, textile printing, and rubber. Pigment usage in marking instruments
was included in the miscellaneous category. In terms of total quantity of
pigment consumed, the printing ink industry consumes the majority of the
total production.
Plastics and Rubber
In 1978, total plastics sales were approximately 34 billion lb, and
the vast majority of these plastics were tinted or colored. For the pig-
ments of interest to this study, nine resins were identified as employing
one or more of these pigments. These resins were ABS, nylon, polyester/alkyd,
low density polyethylene (LDPE), high density polyethylene (HDPE), polypro-
pylene, polystyrene, polyurethane, and polyvinyl chloride. The nine resins
comprised 80% of the total plastics production in 1978; of this total produc-
tion for the nine resins, ~ 80% was tinted or colored.
2-10
-------
The pigments employed in plastics were Reds 38 and 41, Oranges 13 and
16, and Yellows 13, 14, 17, 55, and 83. Yellows 14, 17, and 83 were consumed
in quantities greater than 200,000 Ib in 1978. Red 38 and Orange 16 were
used at levels of approximately 140,000 to 160,000 lb. For all other pig-
ments, estimated consumption was less than 100,000 Ib in 1978. Estimated
consumption figures for each pigment are also presented for 1975 through
1977.
Mixing and compounding are the principal stages in plastic production
during which additives, such as pigments, plasticizers, or heat stabilizers,
are incorporated into the resin. The pigments may be added to the resin in
basically two forms: dry pigment or color concentrate. Dry pigment is added
directly to a resin during the additive blending process. In a color concen-
trate, the pigment is predispersed in a medium such as the resin itself at
levels of 35 to 50% pigment.
The majority of pigment losses are associated with the ultimate disposal
of the consumer product. Few data were available from the plastics industry
concerning losses of colorants in the resin compounding stage, but estimates
were obtained of losses during fabrication of the final product. Sources
of losses and the estimated magnitude of each loss are summarized as follows:
Handling and transfer of colorants
and concentrates during compounding
1-2%
Waste plastic during processing -
- thermoplastics
- thermosets
5-15%
10-30%
For each resin type, estimated losses were derived for thermoplastics and
thermosets. Of the nine resins, seven were thermoplastics and two were thermo-
sets. For all nine resins, the estimated total pigment losses during compound-
ing and processing are as follows: 1975, 50,000-153,000 Ib; 1976, 70,000-
207,000 Ib; 1977, 75,000-227,100 Ib; and 1978, 82,000-247,000 lb.
In the rubber industry, potential use areas for these pigments are rubber
and plastic footwear, rubber and plastic hoses and belts, and other fabricated
rubber products. Very little information was obtained from industry concerning
the percent of rubber colored by the diarylide pigments. Pigment manufacturers
estimate that only two pigments, Yellow 14 and Orange 13, are used by the
rubber industry and that these were used only to the extent of approximately
63,000 Ib of Yellow 14 and 12,000 of Orange 13 in 1978.
Coloration of the rubber occurs during the compounding stage. Pigments
are added by two processes: dry pigment or masterbatch. The composition
of a masterbatch is very similar to the color concentrate described earlier
for the addition of colorants to plastics. Sources of losses and the esti-
mated percentage loss are ~ 0.1 to 0.3% as dust during handling and mixing
of the pigment, 0.1 to 0.5% in the preparation of the masterbatch, and 2.2
to 4.2% for excess rubber produced from shaping, molding, and finishing.
All of these losses represent solid waste which is normally landfilled.
Estimated total pigment loss from the rubber industry is summarized as fol-
lows (quantities in 1,000 Ib):
2-11
-------
1975 1976 1977 1978
Compounding 0.05-0.1 0.07-0.2 0.08-0.2 0.08-0.2
Masterbatch 0.05-0.2 0.07-0.4 0.08-0.4 0.08-0.4
Shaping, molding, 1.1-2.0 1.6-3.1 1.7-3.2 1.7-3.2
finishing
Total 1.2-2.3 1.7-3.7 1.9-3.8 1.9-3.8
Printing Ink
Printing inks, particularly the process inks used in color printing,
represent the major industrial use of the pigments based on benzidine deriva-
tives. The wide variety of printing inks range from newsprint inks to spe-
cialized electrostatic jet printing inks. However, most of the inks pro-
duced for printing can be classified into two main classes and four main
types: paste inks (letterpress and lithographic) and fluid inks (flexo-
graphic and gravure).
Virtually all printing inks are produced by the batch process with some
production batches exceeding 10,000 Ib; more often the batches range from
100 to 500 lb. Essential steps in the production generally include:
*
*
Weighing ingredients into mixing tub
Dispersion of pigments into vehicle
Adjustment of properties to product
Packaging for shipment
Equipment cleanup (optional)
specifications
*
*
*
Of the pigments under study in this report, the yellows and oranges
are used extensively in printing inks. The dominant pigments in terms of
1978 estimated consumption quantities were Yellow 12 (- 11,506,000 lb), Yel-
low 14 (- 1,881,000 Ib), and Yellow 17 (- 685,000 Ib). Other pigments con-
sumed by this industry include: Oranges 13 and 16 and Yellows 13, 55, and
83. Total consumption of these pigments was an estimated 15.2 million Ib
in 1978 or approximately 78% of the total production of all pigments under
consideration in this study. Estimated consumption levels are also pre-
sented for 1975 through 1977.
The extent of production losses is markedly affected by such factors
as batch size, type of ink produced (paste or liquid), the form of pigment
(dry toner or flushed color), solvent or water-base vehicle, type of pro-
duction equipment, and the frequency and type of cleaning system employed.
For dry toner, shipping container and handling losses were estimated to be
0.05 to 0.125% whereas for flushed colors these same losses were estimated
to be 0.075 to 0.1%. Losses resulting from the processing and packaging of
inks depends upon the type being produced; paste inks and liquid inks are
estimated to have different magnitudes of loss. Within these two main
classes, differences in loss percentages will occur depending upon whether
the product is solvent- or water-based. The losses associated with the
various processing and packaging steps were estimated as follows:
2-12
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Paste Ink
- Oil base or solvent base, ink residue
- Oil base or solvent base, water or
caustic wash
- Water base, ink residue
- Water base, water or caustic wash
% Loss
1.5
1.0
1.0
3.0
Liquid Inks
- Oil base or solvent base, ink residue
- Oil or solvent base, water or caustic
wash
- Water base, ink residue
- Water base, water or caustic wash
1.2
1.0
0.8
2.5
A summary of the estimated losses of pigments resulting from printing
ink manufacture for the period 1975 to 1978 is as follows (quantities in
1,000 Ib):
Solid waste Wastewater Total
1975 135-136 83-84 218-220
1976 183-184 113-114 296-298
1977 202-203 124-125 326-328
1978 262-264 162-163 424-427
Estimated losses of pigment for the period 1975 to 1978 arising from the
subsequent use of the ink in various printing processes are summarized as
follows (quantities in 1,000 Ib): .
Solid Waste
Wastewater
Total
1975
1976
1977
1978
950-1,536
1,289-2,082
1,417-2,296
1,842-2,979
~ 34
~ 46
,..., 51
~ 66
984-1,570
1,335-2,128
1,468-2,347
1,908-3,045
Paint and Coatings
Paints can be classed as either solvent base or water base (also called
latex base), but the major production difference lies in the carrying agent.
Solvent base paints are dispersed in an oil mixture, and water base are dis-
persed in water with added surfactant.
Practically all paints are produced using a batch process. A small
paint plant may produce batches from 100 to 500 gal., while a large plant
will manufacture batches up to 6,000 gal. Paint production processes con-
sist of basically three main steps: (a) mixing and grinding of raw mate-
rials; (b) tinting and thinning; and (c) filling operations. For water base
paints, the grinding step is not required.
Pigments derived from 3,3'-dichlorobenzidine and 3,3'-dimethoxybenzidine
represent a small portion of all pigments used in the paint and coatings
2-13
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industry. While the usage of diarylide pigments is fairly widespread, it
is estimated that the paint industry accounts for less than 6% of the total
consumption of these pigments. The dominant pigments in terms of 1978 esti-
mated consumption quantities were Yellow 12 (~ 356,000 Ib), Yellow 17 (~
343,000 Ib), and Yellow 83 (~ 111-131,000 Ib). Other pigments consumed in
lesser quantities were: Yellows 13 and 14, Oranges 13 and 16, Reds 38 and
41, and Blue 25. These pigments tend to be more widely used in solvent
base coatings than in water base paints and more extensively in industrial
coatings than in over-the-counter sales products.
The manufacture of paint presents several principal sources at which
pigments or pigment-containing paint losses can occur. The magnitude of
losses throughout production and cleanup are directly affected by factors
which include size and scale of operations, paint type specialization (e.g.,
solvent based, water based, etc.), use of dedicated equipment, equipment
cleaning practices, and availability of suitable waste disposal systems.
No satisfactory data were found from which industry norms for loss rates
could be derived; estimated losses were derived from information provided
by industry sources. Overall industry loss factors for the principal
sources were estimated as follows:
Shipping container residue plus handling
and weighing (100% solid waste)
Processing and packaging waste - solvent
base coatings (80% solid waste; 20%
wastewater)
Processing and packaging waste - water
base paint (75% wastewater; 25% solid
waste)
Equipment cleaning - solvent washing
(100% solid waste)
Equipment cleaning ~ water or caustic wash
(30% of water reused; 70% to wastewater)
Miscellaneous losses (50% wastewater; 50%
solid waste)
0.2%
0.8-1.4%
0.6%
1.0-1.5%
1.6%
0.1%
A summary of the estimated losses of pigments during paint production
for the period 1975 to 1978 is as follows (quantities in 1,000 Ib):
Solid waste Wastewater Total
1975 7-11 2-3 9-14
1976 10-16 3-4 13-20
1977 12-18 ~ 4 16-22
1978 14-21 4-5 18-26
The application of protective coatings is accompanied by significant
losses due to unused paint, overspray, drop and spillage, and equipment clean-
up. The fraction of paint usefully applied to the intended surface may range
from less than 75% for unskilled brush painting to more than 90% for electro-
coating and industrial fused powder coatings methods. Specific sources of
loss were estimated; a summary of the estimated pigment losses resulting
from paint application is as follows (quantities in 1,000 Ib):
2-14
-------
r
I
Solid waste Wastewater Total
1975 40-71 35-55 75-126
1976 58-104 50-78 108~182
1977 67-117 56-88 123-205
1978 80-139 76-126 156-265
Textile Printing
The principal pigment consumption occurs in textile mill products where
fibers have been received and transformed into some form of fabric. Except
for losses of material as scrap when patterns are cut, no pigment loss occurs
in the apparel industry.
There are three basic textile printing processes: roller printing,
screen printing, and transfer printing. Screen printing is divided into
rotary screen or flat bed screen. Typical printing processes would include
the following procedures:
*
Weighing ingredients into mixing tub
*
Dispersion of the pigments into a paste
*
Application of pigment to fabric
*
Recycling excess pigment paste
~
ft
Heat curing of printed fabric
*
Steaming, washing, and drying of wet printed fabric
Of the pigments under study, the following are used in varying quanti-
ties in textile printing: Oranges 16 and 34, Yellows 12, 13, 14, and 83,
and Blue 25. In terms of total quantity consumed, Yellow 14 is the dominant
pigment (~ 950,000 Ib in 1978); other pigments with estimated consumption
. quantities greater than 100,000 Ib in 1978 were Yellow 83 and Blue 25. Esti-
mated consumption figures are also presented for 1975 to 1977.
Losses of pigment during textile printing operations are from the resid-
ual paste in dye containers, mixing and handling losses, excess pigment paste
from printing machines, and cleanup procedures. Sources of these losses
and the estimated magnitudes of each are summarized as follows:
Dust from mixing
0.05-0.10%
Residual pigment in containers
0.5-2%
Excess pigment paste - not recycled
5-20%
Cleaning waste
1-2%
Pigment in waste cloth from other finishing
steps
0.7-1.0%
2-15
-------
Based on these sources of loss, estimations of total pigment loss during
textile printing operations are as follows (quantities in 1,000 Ib):
1975 1976 1977 1978
Mixing 1 1-2 1-2 1-2
Residual dye 6-23 8-34 8-34 9-35
Excess pigment loss 56-232 82-337 81-338 83-347
Cleaning waste 11-23 16-34 16-34 17-35
Waste cloth from 8-12 12-17 11-17 12-17
finishing
Total 82-291 119-424 117-425 121-436
MISCELLANEOUS USES
Areas of pigment and dye consumption which were outside the scope of
the major areas (i.e., home use dyes, arts and crafts dyes, marking instru-
ments, and coloration of lubricants and fuels) and uses of the bases in labo-
ratory and test applications are discussed.
Laboratory and Test Applications
Little information was available concerning the use of benzidine and
3,3'-dimethylbenzidine in laboratory and test applications. Information
from industry indicates that the use of benzidine for occult blood tests
and other laboratory procedures gradually stopped approximately 3 to 4 years
ago. 3,3'-Dimethylbenzidine is used in at least one over-the-counter occult
blood test kit. Consumption figures for the 3,3'-dimethylbenzidine used in
these kits were unavailable.
In terms of material loss for the formulation of the pellets of 3,3'-
dimethylbenzidine for the kits, it is estimated that 5% or less would be
lost in formulation, probably as solid waste. The remaining 95% would be
dispersed in liquid by the consumer and discarded as liquid waste to the
sewer.
Home Use Dyes
These dyes are sold primarily in powder form in supermarkets, variety
stores, drugstores, fabric shops, and other consumer outlets. The powdered
dyes are sold in packets ranging in weight from 0.5 to 2.125 oz with com-
mercial dye content ranging from 1% (light colors) to 45% (dark colors).
Liquid dyes are sold in 8-oz containers.
Benzidine based dyes are no longer used in these formulations; however,
some of these dyes may still be found on store shelves due to warehouse sup-
plies of certain colors. The manufacturers formulate with dyes based on
dimethyl- and dimethoxybenzidine (other dyes are also employed). Dyes based
on 3,3'-dimethylbenzidine of interest to this study which are currently em-
ployed in home use products are Direct Blue 14, Direct Orange 6, Direct Red
2, and Direct Red 39; those based on 3,3'-dimethoxybenzidine are Direct Blue 1
2-16
-------
,--
and Direct Blue 218. No information was obtained from current manufacturers
concerning quantities of specific dyes or general dye consumption figures
for 1975 to 1978. Estimated total 3,3'-dimethylbenzidine and 3,3'-dimethoxy-
benzidine dye consumption levels are as follows: 1975, 230 to 255,000 Ib;
1976, 190 to 215,000 Ib; 1977, 140 to 195,000 Ib; and 1978, 120 to 130,000 lb.
These levels are for commercial dye, not active dye.
For purposes of estimating formulation losses, it was assumed that all
dyes were formulated into dry packets. Using this assumption, mixing and
handling losses in the formulation process were estimated to be 2 to 3%.
In the home dyeing process, an exhaustion (uptake of dye on fabric) was esti-
. mated to be 25 to 40% with the remaining 60 to 75% of the dye discharged to
the sewer. Estimated total losses of active dye (in 1,000 Ib) are summarized
as follows:
1975 1976 1977 1978
Formulation losses 5-8 4-6 4-6 3-4
Home use wastewater 150-188 126-158 114-143 78-98
Total 155-196 130-164 118-149 81-102
Arts and Crafts Dyes
The market for arts and crafts dyes is very fragmented and little infor-
mation was obtained concerning specific dyes or general types of dyes used
in this area. Annual consumption ~f commercial dyes based on dimethyl- or
dimethoxybenzidine are estimated to be ,very small (~ 10,000 to 20,000 Ib)
and has remained within that range since 1975.
It is estimated that 2,000 to 4,000 Ib of commercial dye would be lost
during formulation and consumer use, primarily as solid waste. The remainder
is contained in or on the finished product.
Marking Instruments
Pigments derived from 3,3' -dimethylbenzidine (Orange 15) and 3,3'-
dimethoxybenzidine (Orange 16) were used from 1975 to 1977 in the production
of childrens crayons, lumber marking crayons, china marking pencils, paint
sticks, carpenter markers, and other similar products. Orange 15 is no longer
produced in the United States and the stated 1978 import quantities were
very low. The estimated total consumption quantities of the two pigments
are as follows: 1975 (93-98,000 Ib), 1976 (107-112,000 Ib), 1977 (96-101,000 Ib),
and 1978 (66,000 Ib).
Most of these products are formulated in basically the same manner. A
mixture of waxes or gums and pigment is combined to form either a liquid
wax mixture, which is poured into molds, or a dough-like mass that is extruded.
Estimated losses during manufacture were estimated to be 0.5% due to weighing
and handling losses and 2.5 to 3.5% from trimmings or other miscel~aneous
2-17
-------
losses from the cast or extruded crayons. All losses from the production
process would likely be treated as solid waste. Total estimated losses from
the crayon production process were estimated to be 3,000 to 4,000 Ib annually
from 1975 to 1977 and approximately 3,000 Ib in 1978.
PRELIMINARY MATERIALS BALANCE
Preliminary materials balances were derived for BAB dyes and pigments
based on 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, and 3,3'-dimethyl-
benzidine produced in the United States from 1975 to 1978.
BAB Dyes
A materials balance for the production process of BAB dyes was presented
earlier in this section (see Dye Production, Table 2-2). An estimated materials
balance for BAB dyes in the use areas considered in this study is shown in
Table 2-4.
Pigments
Losses of 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, and 3,3'-
dimethylbenzidine during their manufacturing process and subsequent usage
to produce the pigments of interest to this study were presented earlier in
the pigment production subsection. Also presented in that subsection were
estimated data for pigment loss due to transfer and handling at the manu-
facturing site. An estimated m~terials balance for the pigments in the
various use areas is shown in Table 2-5.
2-18
-------
TABLE 2-4.
ESTIMATED MATERIALS BALANCE FOR BAB DYES BY USE AREA
Final Product
1975
1976
1977
1978
Losses
Solid waste:
1975
1976
1977
1978
Liquid waste:
1975
1976
1977
1978
Air losses:
1975
1976
1977
1978
Total dye in final
products
Losses
So lid
Liquid
Air
Total Losses
Textile
642-2,170
592-2,754
601-2,270
508-1,794
18-38
20-48
18-39
15-32
112-920
126-1,160
112-960
91-760
neg . £./
neg.
neg.
neg.
1975
1,629-4,133
113-386
181-1,016
neg.
294-1,402
Quantities (1.000 1b)!/
Leather Paper
357-817
455-1,114
522-1,088
585-1,304
53-174
69-236
75-232
86 - 277
0.1-0.2
0.1-0.2
0.1-0.2
0.1-0.3
0.1-0.2
0.1-0.2
0.1-0.2
0.1-0.3
Summary
1976
1,905-5,538
147-539
183-1,241
neg.
330-1,780
611-1,081
843-1,616
787-1,355
501-920
39-168
55-250
50-210
32-142
0.1-0.2
0.1.;.0.3
0.1-0.2
0.1
0.1-0.2
o . 1-0 .3
0.1-0.2
0.1
~977
1,924-4,776
145-486
154-1,034
neg.
299-1,520
Home dyes£/
19-65
15 - 54
14-63
13-36
3-6
3-5
2-5
2-4
69-96
57-81
42-74
36-49
neg.
neg.
neg.
neg.
1978
1,607-4,054
135-455
127-809
neg.
262-1,264
!/ Quantities are in terms of 100% dye, not standardized commercial dye.
£/ Includes arts and crafts uses.
£./ Negligible losses.
2-19
-------
TABLE 2-5.
ESTTIMATED MATERIALS BALANCE FOR 3,3'-DICHLOROBENZIDINE, 3,3'-DIMETHYLBENZIDINE.
AND 3,3'-DIMETHOXYBENZIDlNE BASED PIGMENTS IN USE AREAS
Ouantities (1,000 1b)
Textile Misc.;/
Printing ink printing Plastics Coatings Rubber Uses-
Final product
1975 6,033-6,662 827-1,076 689-843 481-498 46-47 89-95
1976 8,189-9,026 1,221-1,567 954-1,139 690-709 69-71 103-109
1977 8,997-9,063 1,196-1,574 1,023-1,251 784-811 73-75 92-98
1973 11,698-12,921 1,229-1,613 1,122-1,366 949-980 71-73 63
Losses
Solid waste:
1975 1,085-1,672 71-268 42-135 7-11 '" 1-2 3-4
1976 1,472-2,266 103-390 58-1R1 10-16 '" 2-4 3-4
1977 1,619-2,499 186-391 62-200 12-18 "-'2-4 3-4
1978 2,104-3,243 104-401 68-218 14-21 "'2-4 ~3
Liquid waste: Ne~ ."EJ
1975 117-118 11-23 2-3 Neg. Neg.
N 1976 159-160 16-34 Neg. 3-4 Neg. Neg.
I 1977 175-176 16-34 Neg. Neg.
N Neg.
0 1978 228-229 17-35 Neg. 4-5 Neg. Neg.
SUMMARY
1975 1976 1977 1978
Total production range
including imports 10,418-10,568 14,310-14,455 15,510-15,765 19,316-19,571
Total oigment in
final products 8,165-9,221 11,226-12,621 12,165-13,772 15,132-17,016
Losses
Solid 1,209-2,092 1,648~2,8j3 1,799-3,116 2,295-3,890
Liquid 130-144 178-198 195-214 .249-269
Air Neg. Neg. Neg. Neg.
Total 1,339-2,236 1,826-3,061 1,994-3,330 2,544-4,159
~/ Crayons and other marking instruments.
'E./ Negligible.
-------
SECTION 3
DYE PRODUCTION
A number of commercial bisazobiphenyl (BAB) dyes are being produced
from three bisaminobiphenyl (BAMB) precursors: benzidine, 3,3'-dimethyl-
benzidine, and 3,3' -dimethoxybenzidine. ~': . Colour Index (1971) lists over
500 BAMB-based dyes that have been produced commercially. The following
subsections briefly describe BAB dye production processes; the source of
materials loss during dye production; production import sales, and use data
for these dyes; and the estimated materials balance for dye production pro-
cesses.
PRODUCTION PROCESSES
The manufacture of BAB dyes from benz1dine, 3,3'-dimethylbenzidine, or
3,3'-dimethoxybenzidine involves several steps. The active dye is synthesized
using a series of batch processes carried out over a range of pHs, temper-
atures, and reaction times. These series of operations effect the tetrazoti-
zation of the BAMB raw material, followed by the coupling of the respective
tetrazo intermediate with the appropriate chemical moieties to yield the
desired structure and precipitation of the crude dye product (suspension).
The suspension is then filtered. The filter cake from the filtration step
is further processed and diluted to yield the commercial dye. Typically,
commercial dyes of this type contain from ~ 30 to 50% actual active dye.
The overall reaction
duction of a BAB dye for
page (Kent, 1974).
for the tetrazotization and coupling steps in pro-
example, Direct Blue 6 is shown on the following
The 3,3'-dimethoxybenzidine and 3,3'-dimethylbenzidine based dyes are
not synthesized from precursors actually produced from benzidine. Rather,
these dimethoxy and dimethyl precursors are produced from o-nitrochlorobenzene
and o-nitrotoluene, respectively.
'-k
Benzidine based dyes are apparently being produced from hydrazobenzene
rather than directly from benzidine as shown in Equation (3-1)
(Keinath, 1976). The hydrazobenzene, purchased from a supplier, is
charged into a closed reactor and re.arranged to benzidine hydro-
chloride upon the addition of water and muriatic acid:
@-t~-@
H20
) . H2N~H2 . 2HCl
HCl
Hydrazobenzene
Benzidine hydrochloride
3-1
-------
H2N~2
Benzidine (BAMB)
! Tetrazotization
N"~=N
Benzidine (BAMB) tetrazo
1 Coupling
H2N OH HO NHZ
Na03}~&:::~0 >-<0 ~:::~S03N'
Direct Blue 6
(3.-1)
Direct Blue 6, with a molecular weight of 936, is in the midrange of
size for BAMB based dyes. These dyes generally range in molecular weight
from ~ 600 to ~ 1,100, with the lower molecular weight dyes having relatively
simple moieties coupled to the appropriate tetrazo compound.
The specific process used for the production of a given dye is gener-
ally quite complex. Kent (1974), for example, gives the following descrip-
tion of the manufacturing process for an azo dye.
"p-Aminoacetanilide is suspended in water in a wooden or brick-
lined tub (tub 2) equipped with an agitator. Two moles of hydro-
chloric acid per mole of amine are added, and the whole is brought
to a boil by passing in live steam. As soon as the p-aminoacetanilide
has dissolved, ice is added. One mole of sodium nitrite, in solution
in tank 1, is run in slowly for about 2 hr. In the meantime, two
moles of p-cresol are dissolved in an excess of soda ash in water
(tub 3), and to this the contents of tub 2 are added with stirring.
Enough ice is added to keep the temperature at about 5°C. The
dye separates in part as the coupling proceeds. When coupling is
complete, the contents of tub 3 are warmed with steam."
DETO (1980) provided the following description of a process for the
commercial synthesis of Direct Blue 15.
3-2
-------
Step 1 - Tetrazotization: Charge 3,000 Ibs water at 15-200C to tetrazo
tank. Charge 244 Ibs 100% 3,3'-dimethoxybenzidine as the dihydrochloride.
Stir for 1 to 2 hr to give uniform slurry. Charge 350 Ibs 20° BAUME hydro-
chloric acid to tetrazo tank. Stir for 1 h. Ice tank to 4 to 6°C. Diazo-
tize with 138 Ib real sodium nitrite by addition of a solution over 15 to
30 min maintaining 5 to 10°C with ice as needed. Stir for 1 h at 5 to 10°C
maintaining positive test for excess nitrite throughout. Destroy any excess
nitrite with sulfamic acid.
If tetrazo is not clear solution, it can be clarified into coupler using
activated carbon and diatomaceous earth.
Step 2 - Preparation of Coupler Solution: Charge 6,500 Ib of water at
15 to 20°C to coupler tank. Charge 730 Ib H acid (4-amino-5-hydroxy-2,
7-naphthalene disulfonic acid) to tank. Bring into solution by adjusting
pH to 7 to 8 with sodium hydroxide solution. Charge 550 Ib sodium carbonate
to coupler tank, and ice tank to 10 to 12°C.
Step 3 Coupling:
maintaining 6 to 12°C.
to 75 to 80°C. Charge
dye (suspension).
Clarify or pump tetrazo solution to coupler tank
Stir at 6 to 12°C to complete coupling. Heat tank
15% salt on volume to complete precipitation of crude
The crude dye suspension is then filtered at 75 to 80°C to yield dye
presscake which is washed with 15% salt solution at 70 to 75°C until the
filtrate becomes pale colored.
The presscake is then dryed at 95-1000C. The dried presscake is then
ground and blended to form a standardized dye, as shown in Figure 3-1.
The yield of saleable dye in commercial production can
to ~ 93% based on the starting BAMB raw material, depending
dye and production process involved.
range from ~ 76
on the particular
Even small operating problems or the lack of operator attention to
can result in a 10% reduction of yield. Quality and yield problems can
be caused by high levels of impurities in .the raw materials.
detail
also
SOURCES OF LOSSES DURING DYE PRODUCTION
Losses of BAMB based materials from dye production processes have not
been well quantified. This is due in part to the wide range of losses ex-
perienced because of differences in the various dye production processes,
specific plant characteristics, and process control (e.g., operator error).
Keinath (1976) provided valuable information regarding the presence of benzi-
dine in dye production wastewaters. These data have been supplemented by
information obtained from industry sources, project consultants, and MRI
estimates in order to develop a materials balance for BAMB raw materials in
the dye production processes.
3-3
-------
BAMB Raw
Material 91
T etrazo Production
Tank
Dryer
Gri nder
Blender
Water, Ice,
Acid, Etc.
Filter
Packaging.
Coupl i ng
Tank
5!/ Benzidine, 3,31-Dimethylbenzidine, or 3,31-Dimethoxybenzidine
Figure 3-1.
Water, H-Acid,
Caustic, Etc.
Example of BAB dye manufacturing process.
3-4
-------
The following section presents a summary of the dye production losses.
identified during this study. Loss data are expressed in terms of the percent
of the original BAMB raw material, i.e., benzidine,* 3,3'-dimethylbenzidine,
and 3,3'-dimethoxybenzidine, lost during the production processes.
These loss estimates, however, should not be interpreted as estimates
of emissions to the environment. Rather, they indicate estimates of start-
ing raw material loss with respect to product yield.
Process Vent System
Current dye production processes are generally closed systems with all
transfers between reactor vessels made through enclosed piping systems
(Keinath, 1976). There is a potential, however, for material to be drawn
into the production equipment vent system. The maximum amount of BAMB-based
material going to the process vent system is estimated to be 0.1%, either
in the form of unreacted starting material or as decomposition products.
By-Product
The largest loss of BAMB raw material results from the production of
unwanted by-products or degradation products during the production processes.
Some of these by-products remain in the finished product, while most are
removed during the production and product filtration process. The range of
raw materials loss to by-product is typically 5 to 15%. As previously pointed
out, lack of close control of process conditions can significantly increase
the rate of by-product generation.
Process Losses
Losses of material during the synthesis process result from pumping
losses, spills, leaks, and intermediate purification (Fabricolor, Inc., for
example, reportedly filters the hydrazobenzene before it is used to form
the final product (Keinath, 1976)). These process losses are estimated to
account for practically zero (~ 0.25%) to 1% of the BAMB raw material. The
composition of the BAMB-based material lost during processing is assumed to
be 5 to 15% by-products, 85 to 95% dye.
Production Filtration
The crude dye product (suspension) is generally filtered with a plate
and frame or other type of filter press. The filtrate from this operation
removes most of the by-product impurities, but also contains some of the
product dye as well as some unreacted BAMB raw material. It is estimated
that 1 to 3% of the starting BAMB raw material (now in the form of the BAB
dye product), is lost in the filtrate. The concentration .of unreacted BAMB
raw material in the filtrate is estimated to be < 0.5 ppm.
Drying, Grinding, Standardization; and Packaging
The wet filter cake from the product filtration step is normally washed
and then blown with compressed air to remove adhering mother liquor (Kent, 1974).
*
See footnote on page 3-1.
3-5
-------
The filter cake is then dried using spray driers, circulating air, vacuum,
or drum driers. The dried filter cake (presscake) is ground and diluted
(standardized) to yield a product of predetermined, standard strength (dye-
ing intensity). Typically, these standard strength dyes contain ~ 30 to
50% actual active dye. The finished product is then packaged for sale. An
estimated additional 1 to 5% of the active dye is lost during the drying-
grinding-standardization-packaging process. The undiluted crude dye (i.e.,
the dried presscake before standardization) is estimated to contain < 20
ppm unreacted BAMB raw material and 10 to 15% salt.
Raw Material Carryover
Traces of unreacted BAMB raw material can be found in the finished dye
product. Commercial benzidine based dyes are usually certified to contain
< 10 ppm of benzidine.
Boeniger (1979) reported results of the analysis of 26 randomly collected
domestic benzidine-based dye samples. Seventy-three percent of these samples
contained ~ 10 ppm of benzidine and its salts (range = 4 to 270 ppm).
For purposes of the analysis, it has been assumed that the average con-
tent of the respective BAMB raw material is < 10 ppm for all BAB dyes.
Process Wastewater
Most of the unreacted BAMB material from the dye production processes
eventually ends up in the process wastewater. Sources of wastewater from
dye production include (a) cleaning water from slurry and salt tanks, (b)
mother liquor from product filtration, and (c) water from air pollution con-
trol devices, worker showers, and floor washdown. Sufficient data on the
BAMB raw material content of these wastewaters were not available to estimate
environmental emissions. However, effluent standards have been established
for the content of benzidine in the effluent from benzidine manufacturers*
(EPA, 1977). These effluent standards call for the discharge of < 0.130 lb
of unreacted benzidine for each 1,000 Ib of benzidine produced; this equals
a benzidine loss of ~ 0.013% of the original quantity of benzidine used.
For purposes of this analysis, it is assumed that this effluent standard
is being met by benzidine based dye manufacturers, and that the emission
level (~ 0.013%) is also being met by manufacturers and users of 3,3'-
dimethylbenzidine and 3,3'-dimethoxybenzidine.
PRODUCTION OF BAB DYES
The most comprehensive source of information on the domestic production
of BAB dyes is the synthetic organic chemicals production data for commercial
forms of dyes published by the U.S. International Trade Commission (ITC).
At this writing, their data are available for 1975 through 1978. There are
-1\
Benzidine manufacturers are defined in this regulation to include
manufacturers of benzidine based dyes.
3-6
-------
major limitations in the use of these data; however, in developing a detailed
materials balance for individual or even major categories of BAB dyes (e.g.,
benzidine-based, 3,3'-dimethylbenzidine-based, and 3,3'-dimethoxybenzidine-
based). This difficulty results from the grouping of specific product and
production data necessitated by the requirement that the ITC maintain confi-
dentiality of individual company figures. for domestic production and sales.
The ITC is also the principal source of information on individual dyes
being produced in the United States. In 1977 the ITC listed over 1,000 dyes
as being produced by 41 domestic companies. Unfortunately, the categoriza-
tion of dyes by ITC is not according to chemical structure nor origin, and
thus does not facilitate development of production data for the specific
BAMB precursors of interest.
The dye production profile developed during this study has been based
at EPA direction on a recently completed survey of benzidine pigments and
dyes (Powell et al., 1979) and modified in accordance with a more recent
report from the Dyes Environmental and Toxicology Organization (DETO, 1979),
an association of dye manufacturers. The survey by Powell et al., was con-
cerned only with the major pigments and dyes and was not concerned with the
numerous low volume dyes reported by DETO. The list of currently available
BAB dyes addressed in this study is given in Table 3-1. Table 3-2 shows
the code letters for manufacturers, importers, and distributors employed in
Table 3~1.
The Powell study also reports data that document a shift in the character
of the BAB dye industry in the United States in recent years. The industry
has changed from 61 products manufactured by 25 companies in 1975 to 32 prod-
ucts produced by only nine companies in 1978. Thus a much smaller number
of individual products is available from a fewer number of manufacturers.
Figure 3-2 depicts another trend that has become more pronounced in
recent years. In 1975, 15 of 61 dyes (24.6%) were manufactured domestically
by only one company. In 1978, however, 21 of 32 (65.6%) of the available
dyes were manufactured by only one domestic firm. These factors compound
the difficulty in obtaining data on the production of specific dyes or
classes of dyes because of confidentiality considerations. .
The available data on U.S. production, imports, and sales of BAMB based
dyes in the United States for 1975 through 1978 are given in Table 3-3.
The overall trend in production of benzidine, 3,3'-dimethylbenzidine and
3,3'-dimethoxybenzidine based dye is depicted in Figure 3-3.
IMPORTS AND TOTAL BENZENOID DYE CONSUMPTION
The data presented in Table 3-3 provide reported quantities of various
benzidine, 3,3'-dimethylbenzidine, and 3,3'-dimethoxybenzidine derived dyes
imported into the United States during 1975 through 1978. It is the opinion
of numerous industry sources, including dye importers, that these quantities
are understated for all years, especially for those dyes derived from benzi-
dine. .
3-7
-------
TABLE 3-1.
BAB DYES ON THE U. S. MARKET IN 1979!/
Dye
Manufacturer, importer,
or distributor
S, CGY, CKC
CGY
S.
AC, ATL, ACY, FRAN, CGY, CKC, BUC,
FAB, HSH, L&R, BAS, S
ATL
AC, JC, ATL, CKC, V, DUP, S
ATL
AC, ATL, FRAN, BAS, FAB, CKC
S
ATL, L&R, BAS, CKC, CGY, S, FAB, V
Benzidine
Direct Black 4
Direct Black 38
JC, FAB, CKC
JC, FRAN, FAB, CKC, BUC,
SSS
JC, FAB, FRAN, L&R, ORC
JC, FAB, CKC,L&R~ SSS
JC , L&R
JC, CKC, FAB, L&R
FAB
FAB, CKC, L&R, JC
JC
FAB, L&R
CKC, FRAN, FAB, L&R, SSS
FAB, CKC, L&R
JC, CKC, FAB, L&R, ORC
JC, CKC, FAB, L&R, ORC
JC
ORC
FAB, CKC, L&R, SSS
JC, CKC, FAB, L&R, ORC
CKC, FAB, L&R, ORC, SSS
JC, FAB, L&R, ORC
JC, L&R
L&R
CKC, FRAN, FAB
Direct Blue 2
Direct Blue 6
Direc t Brown 1A
Direct Brown 2
Direct Brown 6
Direct Brown 31
Direct Brown 59
Direct Brown 74
Direct Brown 95
Direct Brown 154
Direct Green 1
Direct Green 6
Direct Green 8
Direct Orange 1
Direct Orange 8
Direct Red 1
Direct Red 28
Direct Red 37
Direct Violet 1
Direct Violet 22
Acid Red 85
Dimethoxybenzidine
Direct Black 91
Direct Black 114
Direct Black 118
Direct Blue 1
D i rec t
Direct
Direct
Direct
Direct
Direct
Blue 8
Blue 15
Blue 22
Blue 76
Blue 77
Blue 80
(continued)
3-8
L&R, ORC,
-------
TABLE 3-1 (continued)
Dye
Manufacturer, importer,
or distributor
Dimethoxybenzidine (continued)
Direct Blue 80 (s)
Direct Blue 90
Direc t Blue 98
Direct Blue 100
Direct Blue 151
Direct Blue 156
Direct Blue 160
Direct Blue 191 (s)
Direct Blue 218
Direct Blue 218/224 (s)
Direct Blue 224
Direct Brown 200
Direct Yellow 68
Direct Violet 93
Azoic Blue Composition 2
Azoic Blue Composition 3
Azoic Black Composition 4
Azoic Diazo Component 48
Azoic Coupling Component 3
Others
Atlantic Printing Black 2B Pdr.
Atlantic Printing Black FOR Pdr.
Neutrazoic Black 2B Pdr.
Neutrazoic Black FOR Pdr.
Neutrazoic Black GF 167% Pdr.
Neutrazoic Black IN Pdr.
Padazoic Black GLL Pdr.
Padazoic Black RLL Pdr.
Padazoic Black 2G 150% Pdr.
Atlantic Resin Fast Blue ARL
Atlantic Resin Fast Blue BFL
Atlantic Resin Fast Blue BLA 150%
Atlantic Resin Fast Blue BLC
CKC, CGY
S
ATL, FRAN, HSH, BAS, CKC, S, FAB, V
FAB, CKC
ATL, L&R
CGY, CKC
FRAN, S, CGY, CKC
FAB, CKC
AC, ATL, S, L&R, BAS, FAB, CGY, DUP,
S, V, CKC
CKC
ATL
S
CGY, CKC
CGY
ATL
ATL
ATL
ATL, ALL, BUC, PCW, V
ATL, BUC, PCW
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
(continued)
3-9
-------
TABLE 3-1.
(continued)
Dye
Manufacturer, importer,
or distributor
Atlantic Resin Fast Blue BRN
Atlantic Resin Fast Blue 8BGL 200%
Atlantic Resin Fast Blue 3GLL
Atlantic Resin Fast Blue 5GLL
Atlantic Resin Fast Blue 8GLN
Atlantic Resin Fast Blue LBGL
Atlantic Resin Fast Blue 6GKS
Atlantic Resin Fast Blue 8GUM
Atlantic Resin Fast Blue 9GLR
Atlantic Resin Fast Blue UGLL
Atlantic Resin Fast Blue FFBL
Padazoic Blue GP Pdr.
Padazoic Denim Indigo Blue G Pdr.
Padazoic Navy Blue WS EX Pdr.
Pontamine Blue WE Liq.
Padazoic Brilliant Indigo 3B Pdr.
Padazoic Denim Indigo Pdr.
Atlantic Printing Brown GGN Pdr.
Atlantic Printing Brown BR Pdr.
Neutrazoic Brown BR Pdr.
Padazoic Farmer Brown Pdr.
Atlantic Resin Fast Grey LVL
Super1itefast Grey LVL
Super1itefast Rubine WLKS
Dimethy1benzidine
Acid Red 114
Acid Red 167
Acid Black 209
Azoic Coupling Component 5
Azoic Yellow Composition 1
Azoic Yellow Composition 2
Azoic Yellow Composition 3
Azoic Orange Composition 3
Direct Blue 14
Direct Blue 25
Direct Blue 26
Direct Orange 6
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
ATL
DUP
ATL
ATL
ATL
ATL
ATL
ATL
ATL
CKC
CKC
AC, ATL, CGY, CKC, V, FAB, S, ORC
S, ATL, CGY
CGY
BUC, ATL, PCW
ATL, ALL
ATL, ALL
ATL
ATL
S, CKC, CGY
FRAN, CGY, CKC, ATL, S
ATL
JC, ATL
3-10
-------
TABLE 3-1 (continued)
Dye
Manufacturer, importer,
or distributor
Dimethylbenzidine
Direct Red 2
Direct Red 39
Direct Brown 230
Direct yellow 95
(continued)
AC, ATL,
JC, ATL,
ATL
CGY
CKC, CGY, FAB, L&R
S, CKC, L&R, ORC
Others
Diphenyl Green BBN
Pyrazol Dark Green 3B
Direct Fast Brown BCW-NB
Direct Fast Brown BP-NB Cone.
Direct Brown GG-NB
Direct Brown US-NB
Padazoic Yellow G Pdr.
Padazoic Golden Yellow RLL Pdr.
Padazoic Orange GR Pdr.
Penetrating Black AM-NB
Sandolan Red N-3B
CGY
S
ATL
ATL
ATL
ATL
ATL.
ATL
ATL
CKC
S
a/
List derived from compilation by Dyes Environmental and Toxicology
Organization (DETO), July 1979.
3-11
-------
.
,--
TABLE 3-2.
CODE LETTERS OF MANUFACTURERS, IMPORTERS, AND DISTRIBUTORS
AA
AC
ACY
ALL
ATL
BAS
BDO
BER
BUC
BUF
CGY
CKC
DUP
FAB
Fran
GAF
HSH
ICI
INM
JC
L&R
NYA
ORC
PCW
PDC
PEE
S
SSS
STE
TEN
TOM
V
YOU
American Aniline Products, Inc.
American Color and Chemical Corporation
American Cyanamid Company
Alliance Chemical, Inc.
Atlantic Chemical Corporation
B.A.S.F. Wyandotte Corporation
Benzenoid Organics, Inc.
Bernco1ors-Poughkeepsie, Inc.
Blackman-Uhler, Chemical Division of Synal10y Corporation
Buffalo Color Corporation
Ciba-Geigy Corporation
Crompton and Knowles Corporation
E. I. DuPont de Nemours and Company, Inc.
Fabrico1or, Inc.
Franco1or-Subsidiary of Ugine Kuhlmann Company
(importer/distributor)
GAF Corporation
Harshaw Chemical Company
ICI United States
Inmont Corporation
John Campbell and Company (importer/distributor)
L&R International Dyestuffs Corporation (importer/distributor)
(formerly L&R Dyestuffs Corporation)
Nyanza, Inc.
Organic Chemical Corporation (importer/distributor)
Pfister Chemical Ind.
Bernco1ors-Poughkeepsie, Inc.
Peerless Color Company,Inc.
Sandoz Colors and Chemicals
Sidney Springer Company (importer/distributor)
Sterling Drug, Inc.
Tenneco Colors Division, Tenneco Chemical, Inc.
Toms River Chemical Corporation
Verona Dyestuff Division, Mobay Chemical Corporation
Young Aniline Works, Inc.
3-12
-------
W
I
t-'
W
-0
Q)
u
:)
-0
o
...
Q..
on
Q)
(!; 10
'-
o
Qj
.JJ
E
;)
Z
20
15
--
.
.
5
I:I:::::\l::::\::::::'F<\:::::\:I\:\:::\::::d!\::::::::::'1
o
EXAMPLES
15 Dyes, Each of Which
Was Produced by Only
One Company
2 Dyes, Each of Which
Was Produced by 13
Different Companies
h
I 10 I
I 12 I
I 2 I
I 4 I
I 6 I
I 8 I
Source:
Number of Companies
a) 1975
Powell et al. (1979)
-0
Q)
u
:)
-0
o
d:
on
Q)
(!; 10
.....
o
...
Q)
.JJ
E
;)
Z
20
15
5
o
EXAMPLES
21 Dyes, Each of Which
Was Produced by Only
One Company.
One Dye Produced by
8 Different Companies
..
Number of Companies
b) 1978
Figure 3-2.
Characteristics of BAB dye procuction industry.
-------
TABLE 3-3. u.s. PRODUCTION, IMPORT, AND SALES DATA FOR COMMERCIAL BAB DYES
(in 1b), 1975 to 1978
categorya/ 1975 1976 1977 1978
Benzidine-based dyes:
Acid Red 85 P 67,000 72 , 000 72 , 000 39,639
I 500 2,190
S 66,138 75,000
Direct Black 4 P [65,000] [55,000] 45,000 26,444
I
S [65,000] [55,000]
Direct Black 38 P 2,168,000 3,759,000 2,245,000 823,065
I 70,753 49,525 170,442
S 2,167,122 3,923,000
Direct Blue 2 P [250,000] 771,000 522,000 218,435
I 11,023 38,478 30,755
S 242,506 771,000
Direct Blue 6 P [180,000] [140,000] 287,000 61,524
I 4,409
S [180,000] [140,000]
Direct Brown 1A P
I 4,409
S
Direct Brown 2 P 125,000 188,000 47,000 27,725
I 2,205 18,739 2,205
S 125,662 198,000
Direct Brown 6 P [15,000] [13,000] 10,500 8,563
I 5,512
S [15,000] [16,000]
Direct Brown 31 P 73,000 47,000 82,000 37,406
I
S 73,000 42,000
(continued)
~-H
-------
TABLE 3-3 (continued)
Categorya/ 1975 1976 1977 1978
Benzidine-based dyes (continued):
Direct Brown 59 P
I
S
Direct Brown 74 P [50,000] [45,000] 36,000 32,414
I
S [50,000] [45,000]
Direct Brown 95 P 346,000 595,000 495,000 75,953
I 11,023 8,205 15,962 5,512
S 406,000 532,000
Direct Brown 154 p [230,000] [180,000] 231,000 63,816
I
S [230,000] [180,000]
I' Direct Green 1 P 132,000 169,000 12,000 12,666
I I 747
S 110,000 216,000
Direct Green 6 P [135,000] [135,000] 90,000 109,076
I 250 4,659
S [135,000] [135,000]
Direct Green 8 P N/A N/A N/A N/A
I 250
S N/A N/A N/A N/A
Direct Orange 1 P N/A N/A N/A N/A
I
S N/A N/A N/A N/A
Direct Orange 8 P [70,000] [55,000] 12,000 27,208
I 4,066
S 35,000 [55,000]
D.irec t Red 1 P 132,000 62,000 36,500 26,370
I 4,409
S 114,000 [60,000]
(continued)
3-15
-------
TABLE 3-3 (continued)
Categorya/ 1975 1976 1977 1978
Benzidine-based dyes (continued):
Direct Red 28 p [200,000] [150,000] 61,000 37,327
I 33,069
S [200,000] [150,000]
Direct Red 37 P 63,000 N/A N/A N/A
I
S 65,000 N/A N/A N/A
Direct Violet 1 p N/A N/A N/A N/A
I
S N/A N/A N/A N/A
Direct Violet 22 P N/A N/A N/A N/A
I
S N/A N/A N/A N/A
TOTAL p 4,301,000 6,436,000 4,284,000 1,627,631
I 25,748 147,943 72 ,351 253,255
S 4,279,428 6,593,000 N/A N/A
3,3'-Dimethy1benzidine-based dyes:
Acid Red 114 p 258,000 314,000 240,000 308,000
I 3,079 24,200
S 288,000 275,000 163,000 189,000
Acid Red 167 P N/A N/A N/A N/A
I
S N/A N/A N/A N/A
Acid Black 209 p
I
S
Direct Blue 14 p [25,000] [20,000] [15,000] [5,000]
I
S [25,000] [20,000] [15,000] [5,000]
(continued)
3-16
-------
TABLE 3-3 (continued)
Categorya/ 1975 1976 1977 1978
3,3'-Dimethylbenzidine-based dyes (continued):
Direct Blue 25 P [25,000] [20,000] [15,000] [10,000]
I
S [25,000]. [20,000] [15,000] [10,000]
Direct Blue 26 P [50,000] [50,000] [50,000]. [10,000]
I 500 220
S [50,000] [50,000] [50,000] [10,000]
Direct Brown 230 P N/A
I
S N/A
Direct Orange 6 P [10,000] [10,000] [10,000] [15,000]
I
S [10,000] [10,000] [10,000] [15,000]
Direct Orange 10 P [15,000] [10,000] [5,000]
I
S [15,000] [10,000] [5,000]
Direct Red 2 p 53,000 75,000 81,000 [135,000]
I 1,102
S 46,300 57,000 64,000 128,000
Direct Red 39 p 43,000 [40,000] [35,000] [32,000]
I
S 32,000 50,000 [35,000] [32,000]
Direct Yellow 95 P N/A N/A N/A N/A
I 1,234 7,957 3,527 5,290
S N/A N/A N/A ~/A
Azoic Coupling P
Component 5 I 14,409 29,903 6,945
S
Azoic Orange P N/A N/A N/A N/A
Composition 3 I
S N/A N/A N/A N/A
(continued)
3-17
-------
TABLE 3-3 (continued)
Categorya/ 1975 1976 1977 1978
3,3'-Dimethy1benzidine-based dyes (continued):
Azoic Yellow P N/A N/A N/A
Composition 1 I
S N/A N/A N/A
Azoic Yellow P N/A N/A N/A
Composition 2 I
S N/A N/A N/A
Azoic Yellow P N/A N/A
Composition 3 I
S N/A N/A
Other£/ p N/A N/A N/A N/A
I N/A N/A N/A N/A
S N/A N/A N/A N/A
TOTAL P 479,000 539,000 451,000 515,000
I 15,643 41,439 28,829 12,455
S 491,300 492,000 357,000 389,000
3,3'-Dimethoxybenzidine-based dyes:
Direct Black 91 p [15,000] [15,000] [15,000] [15,000]
I 3,527 3,527
s [15,000] [15,000] [15,000] [15,000]
Direct Black 114 p
I 3,306 17,205 14,770 34,613
S
Direct Black 118 p
I 1,971 5,732 3,960
S
Direct Blue 1 p 156,000 236,000 186,000 90,000
I
s 174,000 230,000 145,000 98,000
(continued)
3-18
-------
TABLE 3-3 (continued)
Category!!} 1975 1976 1977 1978
3,3'-Dimethoxybenzidine-based dyes (continued):
Direct Blue 8 P 30,000 [30,000] [27,000] [25,000]
I
S 20,000 [30,000] [27,000] [25,000]
Direct Blue 15 P [325,000] [530,000] 530,000 350,000
I 1,896 5,726 5,393
S [325,000] [530,000] 514,000 327,000
Direct Blue 22 P [20,000]
I
S [5,000] [5,000] [5,000] [5,000]
Direct Blue 76 P [75,000] 58,000 [60,000] 65,000
I 44,000 250 250
S 53,000 41,000 [60,000] 62,000
Direct Blue 77 P
I 3,085 5,952 2,640
S
Direct Blue 80 P 306,000 491,000 472 , 000 293,000
I 250
S 326,000 471,000 441,000 280,000
Direct Blue 80(s) P N/A N/A N/A N/A.
I 250
S N/A N/A N/A N/A
Direct Blue 90 p
I 8,818 12,623 3,960 661
S
Direct Blue 98 p 107,000 139,000 278,000 271,000
I
S 141,000 164,000 203,000 195,000
Direct Blue 100 p N/A N/A N/A N/A
I
S N/A N/A N/A N/A
(continued)
3-19
-------
TABLE 3-3 (continued)
categorya/ 1975 1976 1977 1978
3,3'-Dimethoxybenzidine-based dyes (continued):
Direct Blue 151 p [10,000] [10,000] [10,000] [10,000]
I
S [10,000] [10,000] [10,000] [10,000]
Direct Blue 156 p
I 3,857 17,415 4,630
S
Direct Blue 160 p N/A N/A N/A N/A
I 7,500 3,740 19,836
S N/A N/A N/A N/A
Direct Blue 191(s) p N/A N/A N/A N/A
I
S N/A N/A N/A N/A
Direct Blue 218 p 1,045,000 1,359,000 [1,000,000] 981,000
I
S 1,309,000 1,253,000 888,000 856,000
Direct Blue 218/ p
224(8) I
S
Direct Blue 224 p
I
S
Direct Brown 200 P
I 13,558 1,543 2,204 1,984
S
Direct Yellow 68 p
I 14,993 14,332 14,551 1,000
S
Direct Violet 93 p
I 2,583 5,819 1,983 4,918
S
(continued)
3-20
-------
TABLE 3-3 (continued)
a/ 1975 1976 1977 1978
Category::o ]~'-D~~~~~gxybenzidine-based dyes (continued):
Azoic Blue P
Composition 2 I
S
Azoic Blue P N/A N/A N/A N/A
Composition 3 I
S N/A N/A N/A N/A
Azoic Black P N/A N/A N/A N/A
Composition 4 I
S N/A N/A N/A N/A
Azoic Diazo P N/A N/A
Component 48 I
S N/A N/A
Azoic Coupling P N/A N/A N/A N/A
Component 3 I
S N/A N/A N/A N/A
Other 5:./ P N/A N/A N/A N/A
I N/A N/A N/A N/A
S N/A N/A N/A N/A
Total P 1,783,000 2,377,000 2,106,000 2,100,000
I 45,896 9,503 9,170 63,512
S 2,052,000 2,278,000 1,867,000 1,873,000
Source:
ITC (1976a, 1976b, 1977a, 1977b. 1978a, 1978b, 1979a, 1979b), NIOSH
(1980a) for 1978 benzidine-based dyes, and MRI estimates. These
estimates, given in parentheses, are based on information ob-
tained from industry sources.
P = Production quantity
I = Imports
S = Domestic sales
N/A = Not available
See Table 3-1 for dyes
comprising this category.
~/
b/
s./
3-21
-------
7,000,000
6,000,000
Q)
>-.
o
" 5,000,000
Q)
N
.-
"E
o
"
c
E. .
V)
'*- 4,000,000
o
~
:3
..
c
o
'';: 3 , 000, 000
u
:;)
"
o
...
a...
.
DMOB
o-
j 2,000,009 ~
II>
W
1,000,000
o I
-8- DMB
-8
-8-
1975
1977
1978
Figure 3-3.
1976
Year
Trends in BAB dye production.
3-22
-------
In order to provide a better insight into the actual quantities of dyes sold
in the United States, and hence available for consumption, an estimated in-
crease is required for all of the dyes of interest. Based on information
provided by dye manufacturers and the Dyes Environmental and Toxicology Organi-
zation (DETO, 1980) revised data for production and imports are presented
in Table 3-4 which show a considerably increased role for imports in the
total quantity of dye consumed in the United States.
Estimates of the increased importation of individual dyes are not pro-
vided. . It would follow that those benzidine based dyes which have been con-
sumed in large quantities (e.g., Direct Black 38, Direct Blue 2, Direct Brown 95,
and Direct Red 38) would be the most likely ones to show increased importation
quantities. According to industry sources, imports of dyes based on 3,3'-di-
methylbenzidine and 3,3'-dimethoxybenzidine have been at a level of approxi-
mately 20,000 to 150,000 lb annually since 1975. The very large differential
between actual and reported consumption quantities has resided with the benzi-
dine based dyes. The estimated error limits used to derive the ranges of
quantities shown in Table 3-4 were generally f 10%. This figure is in accord-
ance with the views expressed by DETO and other industry representatives.
For low volume import quantities, the MRI estimated error limits ranged from
f 10% to f 50% with the very low import quantities assigned the higher error
limits.
Benzidine based dyes imported from certain countries have been found
to contain high levels (up to 224 ppm) of residual benzidine (Boeniger, 1979).
Dyes from Belgium, India, Holland, Egypt, and Poland showed levels of free
benzidine greater than 35 ppm. However, ITC import data do not report country
of origin or quantity imported by country. Thus no means are available to
estimate the total imported quantity of the highly contaminated dyes.
MATERIALS BALANCE FOR DYE PRODUCTION
Estimates have been made of the overall materials balance for the three
BAMB raw materials used to make BAB dyes. These estimates have been expressed
in terms of pounds of the original BAMB raw material and are summarized in
Figure 3-4. The estimates presented in this figure, however, should not be
interpreted as being emissions to the environment. Rather, these estimates
represent losses of starting material with respect to the yield of product
dye. The ~ 0.5 ppm BAMB raw material in the filtrate from product filtration,
for example, is typically treated in the production facility's wastewater
treatment system.
Table 3-5 presents a summary of the estimated active dye losses during
the production processes for 1975 through 1978. This balance is based on
the sources/levels of loss previously discussed and summarized in Figure
3-4, the production rates given in Table 3-4, and the specific assumptions
given in Table 3-6.
The data in Table 3-5 are expressed in pounds of active dye. For the
3.8 to 4.6 million pounds of benzidine based commercial dye production in
1975 (1.9 to 2.3 million pounds of actual active dye), for example, it is
estimated that 5,000 to 26,000 lb of active dye were lost due to processing
losses.
3-23
-------
TABLE 3-4.
ESTIMATED QUANTITIES OF BAB DYE CONSUMED IN THE UNITED STATES
Quantity (106 1b)a/
Type of Dye Source 1975 1976 1977 1978
Benzidine U.S. production'E.../ 3.8-4.6 5.8-7.0 4.1-4.55:/ 1. 5-1. 7
Import 0.8-1.0 0.5-0.7 1.4-1.8 2.0-2.4
Consumption 4.6-5.6 6.0-8.0~/ 5.3-6.5 3.4-4. 2!!:..!
3,3'-Dimethoxybenzidine 1.6-2.0 2.2-2.6 1. 4-1. 8-~/ c/
U.S. production 2.5-3.1~/
Import 0.1-0.2 0.1-0.2 0.1-0.2c/ 0 . 2 -0 . 4-
Consumption 2.0-2.4 2.1-2.5 2.5-3.1- 3.5-4. 3.!/
3,3'-Dimethylbenzidine . c/ 0.62-0.76 0.66-0.80 0.63-0.77 0.74-0.90
u.S. productl0n-
Import£/ 0.01-0.03 0.03-0.05 0.03-0.05 0.13-0.17
(.oJ consumption'12/ 0.75-0.91 0.75-0.91 0.63-0.77 0.74-0.90
I
N
.J::--
E:./
All quantities are in terms of standardized commercial dyes; they do not represent 100% dye. To
convert to active dye content, see footnote (b), Table 3-6. Estimated error limits used to de-
rive the consumption ranges were generally + 10%.
Date from Table 3-7.
Data supplied by DETO (1980).
Estimated by DETO (1980) to be 5.9; estimated by MRI to be 7.0 + 1.0.
Estimated by DETO (1980) to be 3.8.
Stated by the U.S. International Trade Commission (letter from J. o. Parker to S. D. Je1~inek,
November 19, 1979) to be 3.925 million pounds for the U.S. production quantity in 1978; estimated
by DETO to be 3.9 million pounds for the 1978 U.S. consumption 1eve1e, including imports.
Includes approximately 340,000 lb of dye used in numerous areas exclusive of textiles, leather,
or paper. Examples of these use areas are lubricant and gasoline dyes (DETO, 1980).
E-/
5;./
d/
e/
i/
E/
-------
\..i.)
I
N
V1
~O.l%in
Process Vent System
BAMB Raw
Material gJ
Synthesis
Process
O. 25 - 1 % in
Processi ng
Losses
Fi Itration
Grinding.
Standardizing
Drying
\.
y
5 -15 % as By-products QI,
1-3% as Dye in Filtrate
«O.5ppm BAMB Raw
Material in Fi Itrate).
l
1-5°/" as Dye in Processing Losses
(~20ppm BAMB Raw Material)
gj Benzidine,3,31-Dimethylbenzidine, or 3,31-Dimethoxybenzidine
!?I Loss of BAMB Raw Material to By-products Can Be Even Higher If Close Control of Process'
Conditions (pH, Temperature, Mixing Times, etc.) is Not Maintained
Packaging:
Figure 3-4.
Materials balance for BAMB raw materials in dye manufacturing.
J
76- 93 % as
Final Product
(Containing
~ 10ppm BAMB
Raw Material)
-------
TABLE 3-5.
BAB DYE LOSSES FROM PRODUCTION PROCESSESa/
--
Active Dye Loss (1,000 II»
----"
1975 1976 1977 1978
Distribution BEttJ mlB£/ DMO#/ BEN DMB DMOB BEN DMB mlOB BEN mrn DMOB
Processing losses (0.21-0.95%)~/ 5-26 < 1-4 1-8 7-40 < 1-4 2-10 5-26 < 1-4 1-7 2-10 < 1-5 2-12
Filtration losses (1-3%) 23-84 4-13 6-24 35-130 4-14 9-32 25-82 4-14 6-22 9-31 4-16 10-38
w Drying, grinding, standardization,
I
N and packaging losses (1-5%) 23-140 4-22 6-40 35-210 4-23 9-53 25-140 4-23 6-36 9-52 4-26 10-63
0'\
al
- These data, which correspond to those given in Table 3-4, are on active dye basia.
yield of 85% (BANB raw material base) has been assumed.
An overall product
QI
BEN = benzidine-based dyes.
£1 DMB = dimethylbenzidine-based dyes.
dl
- DMOB = dimethoxybenzidine-based dyes.
~I
. For the methods of calculation used in this table, see Appendix B,1.
-------
TABLE 3-6.
BASIS FOR MATERIALS BALANCE CALCULATIONS
1.
Raw Materials Balance (% of raw materials)
Range (%)
By-products
Process and vent losses
Filtration loss
Drying, etc., losses
Product yield
5.0 - 15.0
0.25 - 1.10
1 3
1 5
8~/
2.
Filtrate Rate
10 lb filtrate/lb finished (standardized) dye
3.
Presscake Content of Standardized Dy~/
Standardized Dye
Presscake Content (wt %)
Benzidine based
3,3'-Dimethylbenzidine based
3,3'-Dimethoxybenzidine based
60
58
40
4.
BAlm Molecular
BEN 184.2
DMB 212.2
DMOB 244.2
Weights
5.
Average Dye Molecular Weight
Dye
Range (limited sample)
Calculation Value
Benzidine based
3,3'-Dimethylbenzidine based
3,3'-Dimethoxybenzidine based
613 - 1,122
620 - 1,033
775 - 969
800
750
875
2./
Assumed typical product yield.
'pj
Weight percent presscake is standardized dye product. Dye presscake
typically contains from 10 to 15% salt. Thus, actual active dye con-
tent of the press cake is 85 to 90%; a value of 85% has been used for
this analysis. Using this value, the actual active dye content of
the standardized dyes is calculated to be 51, 49, and 34%, respec-
tively, for the BEN, DMB, and DMOB-based dyes.
3-27
-------
An estimated balance has also been made for the unreacted BAMB raw material
from the dye production process, e.g., the unreacted benzidine that is present
in the finished product, filtrate, etc. This balance is summarized in Table 3-7.
The bases for these estimates of unreacted BAMB raw material are given in
footnotes on the table.
The total quantity of standardized commercial dye consumed annually
during the period 1975 to 1978 was presented in Table 3-4. However, it was
further developed in Table 3-6 that the percentage of active dye in the com-
mercial product is variable depending upon whether the dye is based on benzi-
dine, dimethoxybenzidine, or dimethylbenzidine (see Table 3-6 and accompany-
ing footnote b). The estimated quantities of active dye (100% dye) consumed
during 1975 to 1978 are shown in Table 3-8.
3-28
-------
TABLE 3-7.
UNREACTED BAMB RAW MATERIAL IN DYE MANUFACTU~/
Content (111 of unreacted BANB raw material)
1975 1976 1977 1978
Distribution BEN DHB DMOB BEN DMB DMOB BEN DMB mlOB BEN DMB DMOB
Process vent system 5-64 1-13 2-22 8-98 1-13 2-29 6-63 1-13 2-20 2-24 1-15 3-35
Processing losses 13-64 2-13 4-22 20-98 3-13 6-29 14-63 3-13 4-20 5-24 3-15 7-35
w
I Filtration losses 2-23 < 1-4 < 1-4 1-13 2-22 < 1-4 < 1-9 < 1-8 <1-4 1-16
N < 1-10 3-35
\.0
Drying, grinding. standardization, and
packing losses 46-55 7-9 13-16 70-84 8-9 18-21 49-54 7-9 11-14 18-20 8-10 20-25
Product 19-46 3-8 8-20 29-70 3-8 11-26 20-45 3-8 7-18 8-17 4-9 12-31
al
- For the methods of calculation used in this table, see AppendiK B, II.
-------
TABLE 3-8.
ESTIMATED ACTIVE DYE CONSUMPTION IN THE
U.S. DURING 1975-1978
------.--- . - -
Q . a (x 106 lb)
uant~ty
Type of dye 1975 1976 1977 1978
BENb 2.3-2.9 3.1-4.1 2.7-3.3 1.7-2.1
DMO~c 0.7-0.8 0.7-0.9 0.9-1.1 1.2-1.5
DMB 0.37-0.45 0.37-0.45 0.31-0.38 0.36-0.44
a
Quantities in terms of 100% dye; see consumption quantities in Table 3-4
and footnote b of Table 3-6.
BEN = benzidine.
DMOB = 3,3'-dimethoxybenzidine.
DMB = 3,3'-dimethylbenzidine.
b
c
d
DYE USAGE
The dye consumption data for the various use areas were derived from
discussions with industry sources. The data presented for the estimated
percent consumption by area in Table 3-9 are a synthesis of this informa-
tion and do not represent the specific opinion of anyone source. The dye
industry is considerably more diffuse and much less structured than the pig-
ments industry so that a description of the use of each dye by application
is not feasible. Most industry sources agree that the percentage consumption
of dyes based on 3,3'-dimethoxybenzidine and 3,3'-dimethylbenzidine has re-
mained relatively constant from 1975 through 1978 within the three use areas.
The large changes have occurred for the benzidine based dyes. For these
dyes, consumption in the paper industry has declined considerably within
about the last 2 years. A slight increase in usage of some dimethylbenzi-
dine dyes has occurred but, for the most part, the substitutes for the
benzidine-based dyes are not dyes based on benzidine derivatives. Con-
sumption of benzidine based dyes in the textile industry remained rela-
tively constant during the time period covered by this report.
3-30
-------
.- ---..---
APPROXIMATE PERCENT BAB DYE CONSUMPTION BY AREA.
TABLE 3-9.
1977
1978
1975
1976
Benzidine based dyes:
Textile
Leather
Paper
50 - 60
20 -25
20 - 25
3,3'-Dimethoxybenzidine based dyes:
Textile
Leather
Paper
Other
38 - 42
7 - 13
44 - 46
rv 5
3,3'-Dimethy1benzidine based dyes:
Textile
Leather
Paper
Other
44 - 50
6 - 9
3 - 6
rv 41
45 - 55
20 - 25
25 - 30
38 - 42
7 - 13
44 - 46
rv 5
44 - 50
6 - 9
3 - 6
'" 41
45 - 55
25 - 30
20 - 25
33 - 37
7 - 13
49 - 51
'" 5
36 - 41
5 - 8
5 - 8
'" 41
40 - 50
45 - 55
5
33 - 37
7 - 13
45 - 55
'" 5
45 - 50
4 - 9
rv 5
rv 41
3-31
-------
SECTION 4
TEXTILE DYEING
This section deals with textile dyeing processes that use bisazobiphenyl
(BAB) dyes. An initial industry overview is followed by a discussion of
the types bf textiles colored by these dyes, the quantity of the textiles
colored, and the dyes used. The next subsection discusses textile dyeing
processes used in the industry, and the final subsection presents an esti-
mation of losses for the industry. A discussion of the use of pigments in
textile printing is presented in Section 11. .
INDUSTRY CHARACTERIZATION
Major Groups 22 and 23 of the Standard Industrial Code (SIC) cover the
textile industries. Major Group 22 covers the textile mill products, and
Major Group 23 covers apparel and other textile mill products.
Establishments in Group 23 primarily receive woven or knitted fabric
for . cutting, sewing, or packaging. Dry cleaning and auxiliary processing
may be required for the manufactured products, but generally the processing
is dry and involves no coloring. Except for losses of colored material as
scrap when patterns are cut (10 to 20% depending on the type of pattern and
fabric width), most of the losses of the dyes of interest are restricted to
those in Major Group 22.
Manufacturers of textile mill products (Group 22) include 30 separate
industries that manufacture approximately 90 classes of products (EPA, 1979b).
Primary activities of this sector include receiving and preparing fibers;
transforming these materials into yarn, thread, or webbing; converting the
yarn or web into fabric or similar products; and finishing these materials
at various stages of production depending on whether the product is a transi-
tional material for another segment of Major Group 22 or intended for use
by Major Group 23. Other products may be final consumer products (i.e.,
thread, yarn, or bolt fabric). Major Group 22 is made up of approximately
6,000 manufacturing facilities of which 70% perform operations that require
no process water and 10% which require small quantities of process water.
The remaining 20% generally require large quantities of process water (EPA,
1979b).
Nearly 80% of the facilities categorized as being in Group 22 are located
in the Mid-Atlantic and Southern regions of the United States. The New England,
North Central, and Western regions of the United States equally share the
remaining 20%.
4-1
-------
Description of Raw Materials and Fabrics Colored by Bisazobiphenyl Dyes
Fiber is the basic raw material in
not confined to fiber, however, and can
stock, top (wool or wool blends), yarn,
textile manufacturing. Coloring is
be performed while goods are in the
or fabric state.
Fibers can be categorized as natural and man-made. Natural fibers in-
clude wool, cotton, flax, jute, and silk. Man-made fibers can be further
divided into cellulosic and noncellulosic. Noncellulosics include polyester,
spandex, aramid, fluorocarbon, nylon, polyethylene, polypropylene, acrylics,
and glass. Cellulosics include rayon (regenerated cellulose), acetate
(cellulose acetate), and triacetate (cellulose triacetate). In 1974 consump-
tion of cellulosics constituted ~ 15% of domestic man-made fibers and ~ 11%
of total domestic fibers; wool accounted for ~ 1% and cotton ~ 29% of total
fiber consumption (Versar, 1976).
Dyes
Bisazobiphenyl dyes are classed as direct or acid dyes and may be ap-
plied to a variety of fibers. Government reports state that acid dyes are
used primarily to color protein and polyamide (nylon) fibers (EPA, 1979b;
Sverdrup and Parcel and Associates, 1978; Versar, 1976). Contacts with in-
dustry sources confirm this. Direct dyes are being used to color cellulosic
fibers (EPA, 1979b; Sverdrup and Parcel and Associates, 1978). Versar indi-
cates usage in cotton, rayon, polyester/cotton, and nylon/cotton (Versar,
1976). Another report indicates usage in wool, silk, and man-made fibers
(Powell et al., 1979). Based on information obtained by MRI from industry
contacts, it is believed that the large majority of the consumption of di-
rect dyes involves dyeing cotton and some other cellulosics. Minor use areas
might include polyester/cotton and nylon/cotton blends. Use of direct dyes
to color silk could not be verified. Azoic components and compositions are
insoluble pigments which are anchored within the fiber by padding with a
soluble coupling compound and subsequently treating with a solution of sta-
bilized diazonium salt. They are used for dyeing cellulosic fibers when
good wet-fastness and brightness of shade at a reasonable cost is required.
The estimated production of fabric treated by BAB dyes is presented in
Table 4-1. Cotton broadwoven fabric was reported as the amount dyed and
finished. The Bureau of the Census reported the amounts of man-made fiber
broadwoven fabric dyed in combination with the amount that was white finished
(Bureau of the Census, 1978a). Eighty percent of the total amount (dyed
plus white finished) was dyed (RTI, 1979). Total production of man-made
fiber knit, cotton knit, and wool knit was estimated on the basis of the
reported materials consumed in the production of knit fabrics. It was
assumed that 80% of the total cotton and man-made fiber knits were colored
and 100% of the wool knit and wool broadwoven fabric produced were colored
(RTI, 1979). Only a small percentage of the knit fabrics were colored with
BAB dyes.
4-2
-------
TABLE 4-1.
EST]MATED u.s. DYED FABRIC PRODUCTION
(106 1b of fabric.)
Type of fabric 1975 1976 1977 1978
Cotton broadwoven 512.8 541.9 510 514
Man-made fiber broadwoven 1,091.3 1,218.5 1,248 1,342
Rayon and/or acetate 269.6 258.5 258 246
(including blends)
Nylon and chiefly nylon. 86.3 98.8 88 92
Polyester-cotton blends 498.7 660.8 607 688
Other man-made fiber fabrics 236.7 260.4 295 316
Woo 1 b roadwoven 86.2 99.4 104 120
Cotton knit 235.6 272.6 255 244
Man-made fiber knit 1,326.4 1,183.1 1,107 1,061
Wool knit 7.8 13.8 12.3 12.3
-
Total 3,259.7 3,329.3 4,485 4,635
Source:
MRI estimates based on Bureau of the Census Reports, 1976-1979.
As part of these estimates the following conversion factors were
used to convert linear yards to pounds: cotton fabric, 0.43 1b/
linear yard; wool fabric, 1.025 1b/1inear yard; man-made fabric,
0.44 1b/1inear yard (RTI, 1979).
4-3
-------
TEXTILE DYEING AND DYESTUFF PRINTING
Textile Dyeing
The same general dyeing process is used for the dyes of interest. Minor
differences in the process are due to variations in the particular dye used,
the form of the fiber (e.g., loose stock, yarn), and the type of fiber (e.g.,
wool, cotton, synthetic). The general process and potential sources of dye
loss are shown in Figure 4-1. .
The various application classes of dyes of interest are described below.
Particular attention is given to the classes containing BAB dyes and to dif-
ferences which pertain to dye losses.
Acid Dyes--
This class of dye has been traditionally used on wool and other animal
fibers. These dyes are usually small molecules with sulfonic acid groups
attached to an organic substrate. In addition to use on animal fibers, much
larger quantities of acid dyes are used on nylon and other synthetic fibers
for which high washfastness is needed. Exhaustion (the percentage of dye
which adheres to the fabric) is usually high (95 to 98%).
Azoic Dyes--
These dyes are generally used for cellulose fibers. Dyeing with this
class involves two steps: the fiber first is treated with a phenolic com-
pound and then immersed in a solution containing a diazonium salt which
couples to give a colored compound.
Developed Dyes--
This class of dyes is similar to the azoic dyes except that the reaction
steps are reversed. A dye base is used to dye the cotton and rayon fibers
and then is diazotized with sodium nitrite and an acid. The diazotized dye
is then reacted with other chemicals, such as~-naphthol. Direct dyes are
sometimes developed to produce different shades or better washfastness and
lightfastness.
Direct Dyes--
These dyes are used in neutral or basic dyebaths. Although they produce
full shades on cotton and rayon, they are also used to dye wool, and synthetic
fibers. Salts, such as Glauber's salt, are frequently added to increase
the exhaustion of the dyebath. Exhaustion usually ranges from 70 to 95%.
Other classes of dyes that have significant use in the textile
include sulfur dyes, vat dyes, and fiber-reactive dyes; none of the
these classes, however, are the BAB based dyes of interest to this
industry
dyes in
study.
The different stages in fiber processing are shown below:
4-4
-------
Water
.j>
I
\Jl
Greige or
Bleached Fiber
(As Stock, Yarn,
Fabric or Piece
Goods)
Source: MRI
Dye (50% Dyestuff)
Measuring
& Mixi ng
Dust
Particles
Dye Containers
with Residual Dye
Dyebath
Dye
Assistants
Dye i ng
Machines
Exhausted Uquor Water
Liquid Waste (LW) Vapor
LW from Rinsing
Figure 4-1.
Dryer:
Rinse
Water
Extractor
Water
Vapor
LW
LW
Typical textile dyeing process.
Dyed
Fiber
Other
Processes
Misc.
Wastes
-------
Tops
(Untwisted,
Continuous
Strand)
Dyeing may occur at any stage. There are different machines used for dyeing
fabric at various stages, as listed in Table 4-2. The table includes notes
concerning the dye losses that occur.
Dyestuff Printing
In this process, the dyestuff is mixed with water and other components
to give the paste the properties necessary for printing. Although other
types of dyes, such as acid and direct dyes, are stated to be suitable for
dyestuff printing, disperse dyes seem to be the major dye class presently
in use. The disperse dye paste is first printed on the fabric, which then
passes through a steam chamber where the dye is transferred by heat subli-
mation and pressure to the fabric. The fabric is then washed to remove the
excess dyestuff which did not adhere.
For purposes of the materials balance, it is assumed that the vast ma-
jority of the BAB dyes used in the textile industry are used in dyeing and
that very small quantities are used in textile printing. Even though very
small amounts of the dyes might actually be used in textile printing, the
contribution from this area to the overall materials balance is considered
to be negligible for these reasons:
1. While textile printing literature mentions the use of direct dyes
and acid dyes, none of the textile printers stated they were currently using
appreciable quantities of either class of dye. Their use is common but the
quantities used will vary accordin~ to changes in apparel styles.
2. Industry contacts indicate that the dye losses associated with dye-
stuff printing are comparable to losses in the dyeing industry.
ESTIMATED CONSUMPTION
This subsection contains esti~ated consumption data for the BAB dyes
of interest to this materials balance. The complexity of the textile in-
dustry and the variability in annual consumption of specific dyes due to
style change in apparel design make estimation of the consumption of specific
dyes difficult. No published information is available on this subject.
Industry sources were unable to provide information on the consumption of
specific dyes. As a result, consumption could be estimated only by dye type
(i.e., benzidine based, dimethylbenzidine based, or dimethoxybenzidine based).
4-6
-------
TABLE 4-2.
APPARATUS USED IN TEXTILE DYEING
Form of fiber
Description (and name) of dyeing "rparatus
Additional notes
Loose stock
Tops
Machines generally hold stock in a compressed, dense form.
color with circulation of dyebath.
Various "d"ptations occur to produce uniform
Top i9 dyed in a ball. welghing 5 tn 15 lb.
Machines hold balls and circulate dyeb"th through them.
Yarn:
!lank (skein)' These machines are desIgned wIth spect.Al care tAken to ensure uniform colorlng.
PackAge
.8eams
Fabric
.j>
I
-....I
Piece goods
Packages may be yarn wrapped as cones. cheeses (cylinders), rockets. and tops (the form it is in imme-
diately after spinning). The machines generally have the flow of dyebath from the inside to the out-
side of the package. Flow of the dyebath is typically reversed several times during a dye cycle.
The yarn is wound on long beams And dyed'on the beAm.
Winch--A winch fa nsed to carry the fabric into the open and bAck into the dyebath. Uses a continuous
loop of fabric. Used malnly for woven wQolens and knHted fabric. Winch is also known as beck dyeing.
Jig--Puts only a smAll amouot of the fabric into the dye at one time.
and woven goods.
Usually used for cotton. rayon,
A lower liquor ratio (10:1)
may be used, resulting in
better exhaustion.
Liquor ratios tend to be
higher (10:1 to 30:1).
Very low li~uor ratio.
Lower liquor ratio.
SO\lt'ce:
Padding mangle--A continuous dyeing plocess involving drawing the fabric through the concentrated dye
solution and passing it through two rollers to give a uniform squeeze over the cloth.
Jet dyeing machine--A newer mAchine whid, uses a continuous loop of cloth. The cloth passes
venturi tube. The dye liquor is circulated through the tubes And the suction at the venturi
fabric pass thrQugh.
through a
makes the
Continuous dyeing machines--The fabric passes through dip troughs where the fabric is dyed, then
through rinse boxes and heated drying CAns.
Host machines 'H.ve a paddle and move the goods through the liquor.
IIn oval tank; and the goods rotllted around a central ishnd. This
overhead pllddle machine is also available.
The paddle may be on one side of
would be the oval-type Pllddle. An
MRI
-------
Direct Black 38 appears to be the most widely used BAB dye in the tex-
tile industry. This dye has a variety of uses, although the majority seems
to be for coloring materials such as cambric (low grade cotton used to cover
the underside of upholstered furniture). Direct Blue 218 is also widely
used in the textile industry.
The estimated consumption of BAB dyes by the textile industry, developed
from data in Tables 3-8 and 3-9, is presented in Table 4-3.
TABLE 4-3.
ESTIMATED BISAZOBIPHENYL DYE CONSUMPTION IN THE
TEXTILE INDUSTRY
Quantity (106 Ib)a
Dye Type 1975 1976 1977 1978
b 1.2-1.7 1.4-2.3 1.2-1.8 0.7-1.1
BEN -based
c 0.27-0.34 0.27-0.38 0.30-0.41 0.40-0.56
DMOB -based
d 0.16-0.23 0.16-0.23 0.11-0.16 0.16-0.22
DMB -based
Total 1.6-2.3 1.8-2.9 1.6-2.4 1.3-1.9
a
See Tables 3-8 and 3-9; quantities in terms of 100% pure dye.
BEN = benzidine; c DMOB = dimethoxybenzidine; and d DMB = dimethylbenzidine.
b
ESTIMATED LOSSES
This subsection discusses losses of dyes in textile coloration. Specific
loss areas are identified, and estimated percent losses are calculated for
dyes. Losses of the subject compounds are approximated.
Dye losses that occur during textile processing are in the dust from
mixing operations, residual dyes in the original dye containers, and mixing
and holding containers, and the liquid wastes from the dyeing, rinsing, and
water extracting. Because of the low volatility of the BAB dyes, there should
be very little or no loss from evaporation with the water in the dyeing and
air drying stages. Sources of dye loss and estimated magnitude of the losses
are shown in Table 4-4.
In one study on solid wastes from the textile industry (Versar, 1976),
data were obtained on the residual dyestuff in containers for several tex-
tile industry categories. All figures for the percentage of dye loss due
to residual dye in the container range from 0.02 to 0.05%. In order to apply
these data to the BAB dyes, it must be assumed that the percentage of residual
dye in each process category is the same for all dyes.
4-8
-------
TABLE 4-4.
ESTIMATED BISAZOBIPHENYL DYE LOSSES IN TEXTILES
Source of loss
% Lost
Dust particles
0.05-0.1
Residual dye in containers
0.02-0.05
Exhausted liquor
Direct dyes
Acid dyes
5-30
2-5
Unrecycled dye from continuous units
2-10
Water vapor from dyeing machines (open
vessels and pressure venting)
,." 0
Liquid waste from rinsing machines, rinsing
cloth (fiber), and water extraction
(a)
Water vapor from dryer
,." 0
Solid wastes from processing after dyeing
1.0-1.5
Source: Versar (1976); industry sources; MRI estimates.
(a) Included in exhaust liquor.
A small percentage of dye will be lost as dust particles during weighing
of the dry ingredients of the dye mixtures. Since specific data could not
be found for this process, figures for the loss of dye were estimated to be
the same as those for a similar mixing stage in the paint production industry.
The major loss of dyestuff in textile dyeing is the residual dye in
the wastewater from dyebaths. Numerous variables enter into the exhaustion.
These include the particular dye used, the fiber being dyed, the desired
intensity of color, the liquor ratio, and the temperature. The large quan-
tity of information that would be necessary to derive specific data on the
10s5 of these dyes could not be obtained from the published literature or
industry sources. Therefore, only generalizations can be made concerning
the effects of change in these variables.
The desired intensity of the color makes a big difference in the ex-
haustion. Generally, if two batches of the same material at equal weights
are dyed with the same dye but at two different intensities, the batch with
the darker color will have a lower exhaustion.
4-9
-------
The liquor ratio is the ratio of the weight of the liquor (dyebath)
used to the weight of the dry fabric. The equilibrium reached in dyeing
depends on the concentration of dye in the fabric and the concentration of
dye in the liquor. Therefore, a higher liquor ratio tends to produce a
lower exhaustion. .
Although the equilibrium which pertains to the exhaustion rate is tem-
perature dependent, this temperature dependency varies with the particular
dye used. Industry sources state that because temperature also affects
leveling and dyeing rates, the dyer generally does not choose the tempera-
ture of greatest exhaustion.
When used with a suitable type of fiber, direct dyes give 70 to 95%
exhaustion. The exhaustion may be greater than 95% with very weak initial
dye concentrations, but the total quantity of dye consumed at these low con-
centrations is small. Variations in this class of dyes can be attributed
to the frequent use of dye assistants for some direct dyes and to other
special processing such as dye development. Acid dyes usually exhibit higher
exhaustion than do direct dyes. The exhaustion usually ranges from 95 to
98%, but is affected by various factors.
The estimated residual dye in the exhausted liquors were summarized in
Table 4-4. This table includes estimated losses resulting from rinsing,
water extraction, and dyebath cleaning.
The
ations.
used, or
is used.
dyed fabric is occasionally rinsed prior
The rinsing step may occur in the dyeing
it might involve a separate procedure if
to further processing oper-
vessel if batch dyeing is
a continuous dyeing process
Rinsing and cleaning the dye machines would result in small quantities
of dye loss to wastewater. Dyers usually use lighter to darker dyebaths so
less rinsing is required. More extensive cleaning becomes necessary when
the machine is to be used for a light colored dyebath. This cleaning, as
well as the other rinses, is done with water or a cleaning solution contain-
ing bleach.
The fate of all liquid waste is essentially the same for all of the
textile dyeing facilities. All of the waste is treated by water treatment
facilities, either by the company or by the municipality. American Textile
Manufacturers Institute (ATMI) estimates that of the 2,007 textile plants
which generate potentially hazardous waste, 488 plants have wastewater facili-
ties. It is further estimated that the production of these 488 plants accounts
for 65% of the total production of the 2,007 plants (Versar, 1976). Because
no data are available for a detailed evaluation of the distribution in the
use of these dyes, it is assumed that the amount of consumed dye is propor-
tional to the production of the plants. Thus, about 65% of the dye lost in
wastewater is treated by the individual companies.
Some solid waste is created by miscellaneous processing of the dyed
fiber. The percentage loss by this processing is shown in Table 4-5 for
4-10
-------
the typical processes in each of the industry categories. If the percent-
age losses in this table are weighted by the relative production rates for
each industry category, the percentage loss for all textile dyeing and fin-
ishing industries is ~ 1%. Although the average loss of BAB dyes through
these processes, would be about 1.0 to 1.5%, this higher average loss per-
centage is because most BAB dyes are not used in dyeing wool fabrics or
carpeting (the highest loss categories shown in Table 4-5). Much of the
yarn and stock material will be involved in fabric processing which will
produce additional loss. Generally, these wastes are disposed in a land-
fill.
TABLE 4-5.
FIBER LOSSES DURING FINISHING AND OTHER PROCESSING STEPS
Industry category
(dyeing and finishing)
Processing steps
Form of loss
Percent
loss
Yarn and stock
Special and mechanical
finishing
Mechanical finishing
Chemical and mechanical
Selvage trimming and
fluff shearing
Beaming, quilling,
windings, etc.
Flock and fabric
1.8
Wool
Woven fabric
Knit fabric
Carpet
Cloth and fabric
Cloth
Selvage and
flock
Yarn
1.0
0.7
3.0
0.6
Source:
Versar, 1976
Estimated total bisazobiphenyl dye losses in the textile industry are
presented in Table 4-6.
4-11
-------
TABLE 4-6.
ESTIMATED BISAZOBIPHENYL DYE LOSS IN THE TEXTILE INDUSTRY
Quantity (1.000 1b)
1975 1976 1977 1978
1,600-2,300 1,800-2,900 1,600-2,400 1,300-1,900
1-2 1-3 1-2 1-2
1 1 1 1
80-690 90-870 80-720 65-570
32-230 36-290 32-240 26-190
16-35 18-44 16 -36 13 - 2 9
130-958 146-1,208 130-999 106-792
642-2,170 592-2,754 601-2,270 508-1,794
Dye consumed~/
Dye losses£./
Dust (0.05-0.1%)
Residual dye in containers
Exhaust liquor (5-30%)
Unrecycled dye (2-10%)
Solid waste (1.0-1.5%)
Total
(0.02-0.05%)
Dye in final product
.p-
I
I-'
N
~/ Data from Table 4-3.
£./ Data from Table 4-4.
-------
SECTION 5
LEATHER TANNING INDUSTRY
INDUSTRY OVERVIEW
The leather industry is composed of companies which perform a portion
of or all the steps required to produce finished leather from raw hides.
Throughout the 1970 IS, the total number .of plants has been declining. In
1972 there were over 500 establishments in the United States, but by 1977
the number had fallen to about 400 (Radding et al., 1978; EPA, 1979a).
Some of the companies involved in leather tanning are quite large, but many
are small, family-owned businesses. The number of employees per tannery
ranges from 5 to 500, and production rates range from 100 to over 2,500
hides per day (Conrad et al., 1976; Francke et al., 1978).
The U.S. leather industry has traditionally been centered in the north-
eastern states. Although some tanneries have followed the supply of hides
westward, there is still a concentration of tanneries in the New England
and Middle Atlantic states. In 1976 about 30% of all tanneries were located
in Massachusetts or New York, and about 85% were located east of the
Mississippi River (Conrad et al., 1976). Fulton County, New York, provides
an example of a local concentration of leather handling facilities; in 1967,
22 tanneries were located in or around the two small communities of Glovers-
ville and Johnstown (Nemerow and Armstrong, 1967). Farther west, another
concentration of tanneries is located in the Milwaukee-Chicago area. Over-
all tanneries are scattered across the country in 34 states (Conrad et al.,
1976).
Although shoe leather is their biggest single product, a great variety
of goods are marketed by U.S. tanneries. Table 5-1 presents a partial list-
ing of the categories and types of leather available from domestic tanneries.
The tremendous variety inherent in the production of these goods is accented
by the changes in fashion and the multiplicity of manufacturers active in
the market. Popular colors and styles in shoes, handbags, belts, and other
leather goods may vary dramatically over short periods of time. When these
changes do occur, companies make rapid adjustments in their processing and
dye usage depending on the needs of their current clientele. Thus, differ-
ent firms may be quite dissimilar in methodology and/or end products.
5-1
-------
TABLE 5-1
A PARTIAL LISTING OF THE CATEGORIES AND
TYPES OF LEATHER PRODUCED BY
U.S. TANNERS
Belt and watchstrap
Bookbinding
Chamois
Craft
Glove and garment
Handbag
Harness and saddle
Hat, cap, and sweatband
Holster and tool pouch
Lace
Linings
Luggage
Orthopedic articles
Patent
Reptile and sharkskin
Shoe upper and sole
Sporting goods
Transmission belting
Upholstery
Source:
Adapted from Tanners Council of America
(1977) .
Much of the detailed production information is highly proprietary.
The reason for this concern is competition--there are approximately 100 pro-
ducers of glove and garment leather and approximately 80 producers of hand-
bag leather listed in the Tanners Council 1977 Directory (TCA, 1977).
The primary raw material for leather is cattle hide (> 90%). The other
animal hides and skins that are used--sheep, lamb, and pigskin*--contribute
less than 10% of the total hide tanned (Radding et al., 1978). Consequently,
the leather industry is closely linked to the beef industry.
During the 1975 to 1978 period, the annual commercial cattle slaughter
in the United States ranged from about 39.5 to 42.5 million head; the lowest
production occurred in 1978 (U.S. Department of Agriculture, 1979). During
the same period, the annual number of equivalent hides** tanned in the United
States has ranged from 20 to 22 million hides, again with the lowest pro-
duction in 1978 (Radding et al., 1978; Lollar, 1979). The discrepancy be-
tween total cattle slaughter and total hides tanned is due primarily to
A very small quantity of exotic hide and skin is also tanned:
and kid, deer, elk, moose2 reptile, seal, kangaroo, and shark.
One equivalent hide = 3.7 m (40 ft2) of leather.
goat
.'.
"
"it(j'(
5-2
-------
foreign acquisition of U.S. hides. Purchases by tanners in South Korea,
Japan, Spain, and Italy are particularly significant (Harrison, 1979; Gallup,
1974) because after finishing, much of this leather is imported to the U.S.
market for sale (Radding et al., 1978).
LEATHER TANNING AND DYEING PROCESSES
The production of leather involves four principal stages: (a) beam-
house processing, (b) tanhouse processing, (c) retanning, coloring, and fat
liquoring, and (d) finishing.
Typical operations in the initial beamhouse processing include cutting
the hides in half (lengthwise), washing and soaking, fleshing, and hair re-
moval. For the washing, soaking, and chemical loosening and/or dissolution
of hair--as well as many of the subsequent tanning stages--the hides are
placed in processing solutions in vats (with or without paddles), drums, or
hide processors (concrete mixers with special linings). Fleshing is accom-
plished on special machines designed for that purpose (Gallup, 1974).
At the completion of these preparatory steps, the hides are moved to
the second stage in the tanning sequence, the tanhouse where they are sub-
jected to bating, pickling, tanning, and splitting.
I
Bating occurs in vats, drums, or hide processors. A solution of
ammonium salts and enzymes delime the skins (the lime is a residue
from the dehairing solutions), reduce swelling in the leather,
peptize fibers, and remove protein degradation products.
Pickling involves the introduction of an acid and a brine, normally
into the same vessel where bating has taken place. Pickling is
always carried out prior to chrome tanning, and the process is
sometimes also employed prior to vegetable tanning.
Tanning requires the treatment of the hides with chromium sulfate
mixtures or vegetable (plant extract) tanning solutions. Chrome
tanning in drums is the most common procedure. Vegetable tanning
is used primarily in the production of heavy leathers, i.e., shoe
sole leather, mechanical leathers, or saddle leathers; the process
usually occurs in vats.
Splitting involves the splitting of the tanned hide into a grain-
side portion having a constant thickness and a fleshside portion,
also called a "split" (Gallup, 1974).
Retanning, coloring, and fat liquoring make up the third stage in the
tanning procedure.
Retanning is a second tanning step carried out in drums to which
chrome, vegetable, or synthetic tanning agents are added. This
procedure yields a finished leather possessing better character~
is tics than those which would result if tanning was performed in
only one treatment. (At this point, sole leathers are commonly
bleached with sodium bicarbonate and sulfuric acid.)
5-3
-------
Coloring is carried out in the same drums used for retanning.
Dyes may be added before or after fat liquoring. This is the stage
at which the most significant dye use occurs in the leather industry.
Consequently, a more thorough discussion of this portion of the
tanning process is presented following the general description of
the entire tanning operation.
Fat liquoring is the replacement of oils lost from the leather
during tanning. This treatment softens the leather and makes it
pliable. Diffetent quantities of oil are added to le~ther destined
for different end uses (Gallup, 1974).
Finishing operations include drying, wet-in coating, staking or tacking
(a form of massaging), and plating (a surface treatment). Some pigment and
small quantities of dye may be applied to the leather surface during these
operations. However, the quantities of dyes or pigments involved are insig-
nificant compared to dye use in coloring. The finishing procedures complete
the tanning operation and result in products suitable for the manufacture
of leather goods (Gallup, 1974).
The most authoritative current reference on the dyeing of leather is
Radding et al. (1978). Much of the information presented here is derived
from this source.
Leather is dyed in a batch mode process, usually in the same drums in
which the retanning and fat liquoring (addition of oils) takes place. Typi-
cally, the dye is added following retanning and prior to fat liquoring.
During the coloring operation, the hides and the dye solution are mixed,
commonly by the rotation of a drum (Radding et al., 1978).
The dyes used by the tanneries are most often acid or direct dyes.
Basic dyes are also used, as are solvent and sulfur dyes, but acid dyes are
used in the largest overall volume. Direct dyes are somewhat limited by
their inability to penetrate vegetable tanned leather or blue hides (chrome
tanned hides before retanning). Consequently, direct dyes are most suitable
for surface dyeing applications. Both acidic and basic dyes penetrate deeper
into the leather than do the direct dyes. All of the dyes used are formulated
to act as protein binding compounds (Radding et al., 1978).
The predominant colors used by leather tanners are black, brown, and
various other colors which are used with brown to produce shades of brown.
These dyes are acquired by the tanneries in many different forms. The larger
tanneries are frequently able to buy the material directly from the dye manu-
facturer and then formulate their own color compositions. The smaller tan-
neries are more apt to purchase blended dyes from companies which formulate
leather tanning chemicals. Both the large and small tanneries also buy leather
specialty dyes, dye formulations put out by the major dye manufacturers spe-
cifically for use in the leather industry (Lollar, 1979).
5-4
-------
The quantity of dye required for a given application depends on many
factors including color, type of leather (split or grain; cattle, sheep,
etc.), and the mix of dyes. Different colors and intensities are produced
using different dyes or different dye mixtures, but part of this technology
also involves variations in the quantity of dye used. Typical percentages
of commercial dye per wet leather weight range from 0.25 to 5.0% with an
average around 0.7%, which is about 13 Ib of commercial dye per 2,000 Ib of
wet leather (Radding et al., 1978).
The specific bisazobiphenyl (BAB) dyes used in leather tanning are dif-
ficult to pinpoint for any given year due to changes in demand for different
colors on different products. The abundance of proprietary formulations,
whose composition cannot be obtained, is also a major problem (Radding et
al., 1978). However, some BAB dyes are known to have been used in the
leather industry during the 1975 through 1978 period. These dyes are
listed in Table 5-2.
DYE CONSUMPTION
Knowledge of the quantity of dyes used by a tannery can be used to esti-
mate their total production of finished hides. Since this information is
an important marketing tool, the extent and nature of dye utilization within
individual tanneries is highly proprietary. .
Estimates of the quantity of BAB dyes consumed in the leather industry
are presented in Table 5-3. The dyes of interest to this study that are
consumed in the leather industry were presented in Table 5-2.
As a check of the validity of the estimations employed in the deriva-
tion of the quantities in Table 5-3, an alternative method was employed to
estimate the quantities of BAB dyes in the leather industry.
Approximately 85% of all tanned hides are dyed (Lollar, 1979). The
average usage of dye amounts to approximately 0.7% of the weight of hide
dyed, with an average weight per hide of 50 lb (Radding et al., 1978;
Lollar, 1979). Table 5-4 shows the total number of hides tanned from 1975
through 1978 and the corresponding dye consumption based on these estimations.
In order to estimate the fraction of the leather industry's total dye
consumption that was BAB dyes, MRI conducted a literature search and contacted
individuals within the leather industry. Information obtained from these
two sources indicated:
1. Approximately 38%* by weight of the dye sold in 1975 to U.S. tan-
neries was direct dye (Radding et al., 1978).
*
Total dye sales to the leather industry during 1975 were ~ $15 million at
an average price of $3.00/lb. These figures indicate total dye sales of
~ 5.0 million lb. Direct dyes accounted for $3.7 million worth of this
total at an average price of $1.95/lb. Thus direct dye sales are approxi-
mately 1.90 million lb (Radding et al., 1978). Based on these statistics,
direct dye purchases accounted for ~ 38% of total dye purchases by weight
during 1975. .
5-5
-------
TABLE 5-2.
BAB DYES USE9 IN LEATHER TANNING,
1975-l97~
Benzidine-based dyes
CI No. Generic name
o-tolidine-based dyes
(3,3 I -dimethyl. .)
CI No. Generic name
o-dianisidine-based dyes
(3,3 I dimethoxy . .)
CI No. Generic name
Ln
I
0\
22245
302455
30235
22590
22610
22311
30140
35660
36300
30145
30120
30280
30295
22310
Ac id Red 85~/'
Direct Black 4
Direct Black 38~/
Direct Blue 2
Direct Blue 6
Direct Brown 2~/
Direct Brown 6
Direct Brown 3l~/
Direct Brown 74~/
Direct Brown 95
Direct Brown 154
Direct Green 1
Direct Green 6
Direct Red 1
23635
23850
23790
31930
23375
23370
23500
23630
Acid Red 114
Direc t Blue 14
Direct Blue 25
Direct Blue 26
Direct Orange 6
Direct Orange 10
Direct Red 2
Direct Red 39~/
30400
24410
24400
24280
24411
23155
24175
Direct Black 91
Direct Blue 1~/
Direct Blue 15
Direct Blue 22
Direct Blue 76
Direct Blue 98
Direc t Blue 151
~/
~/
Adapted from Powell et ale (1979).
Usage confirmed by industry contacts.
-------
TABLE 5-3.
ESTIMATED CONSUMPTION OF BAR DYES IN THE
LEATHER INDUSTRY
Quantity (1.000 1b)~/
Dye category 1975 1976 1977 1978
BEN.Q/ 460-725 620-1,025 675-990 765-1,155
DMO#-/ 49-104 49-117 63-143 84-195
DMB.M 22-41 22-41 16-30 14-40
Total 531-870 691-1,183 754-1,163 863-1,390
2;./
Data derived from Tables 3-8 and 3-9; 100% pure BAB dye, not standardized
commercial dye.
'EJ
BEN = benzidine-based.
:=./
DMOB = 3, 3 '-dimethoxybenzidine-based.
E-./
DMB = 3,3 '-dimethyl benzidine-based.
2. Approximately 68 to 75% of the direct brown and direct black dye
sold in the United States during 1975 and 1976 was BAB dye (Jenkins, 1978).
Table 5-5 combines the available information and estimates to yield an
approximate total consumption of BAB dye by the leather industry. The total
quantity of dye consumed is calculated using the method of Radding et al.
(1978) with a minor change in accord with comments by Lollar (1979). The
approximate levels shown in Table 5-5 for BAB dye consumption for 1975 to
1978 generally fall within the range estimated by a completely different
method in Table 5-3.
ESTIMATED LOSSES
The discussion which follows presents an estimation of the total quantity
of BAB dye which remains a part of finished leather goods and the quantity
of BAB dye that becomes a constituent of production waste. The estimates
required to quantify dye uptake are taken from Radding et al. (1978). This
source indicates that about 85 to 90% of the dye utilized in leather dyeing
is successfully j oiiled to the leather. In order to allow for trimmings,
5-7
-------
1975
1976
1977
1978
'VI
I
00 ~/
. TABLE 5-4.
OVERALL DYE CONSUMPTION IN THE LEATHER INDUSTRY (1975-1978)
Total number Weight of totac)
of hides dye consumed-
tanned i~/ Number of Weight of (106 1b)
the U. S.- dyed hides~/ dyed hide~/ (0.7% of dyed
(106) (106) (106 1b) hide weight)
22 19 950 6.8
24 20 1,000 7.1
22 19 950 6.8
20 17 850 6.0
Statistics obtained from Radding et a1. (1978) and Lollar (1979).
purposes of this approximation, 1 hide = 40 ft2 of leather.
For
E./
- 85% of the total; obtained from Lollar (1979).
£./
50 lb per hide; method of approximation patterned after Radding et a1. (1978).
-------
j-
TABLE 5-5.
APPROXIMATE CONSUMPTION OF BAB DYE BY THE LEATHER
INDUSTRY (1975-1978)
Quantity of dye
consumeda/
(0.7% of dyed
hide weight)
. (103 lb)
Percent
direct
dye1l-/
(%)
Direct
dye
consumed
(103 lb)
Percent of direct
dyes which ~7e
BAB dyes-
(%)
Standardized
BAB
dye
consumption
(103 lb)
Active
BAB dye d/
consumption-
(103 lb)
1975 6,800 '" 35 2,400 '" 65 1,600 787
1976 7,100 ..... 35 2,500 '" 65 1,620 802
1977 6,800 '" 35 2,400 -- 65 1,600 787
VI 1978 6,000 '" 45 2,700 '" 65 1,750 858
I
1.0
a/
Adapted from Radding et al. (1978) and Lollar (1979); see Table 5-4.
E-/
MRI estimates based partially on Radding et al. (1978).
5:./
MRI estimates based partially on Jenkins (1978). Personal communications with leather industry
sources were inconclusive in regard to changes in BAB dye consumption (Lollar, 1979; anonymous
industry sources). However, one dye manufacturer indicated that the leather industry has been
slower to reduce its usage of BAB dyes than the other major consuming industries.
d/
Active BAB dye consumption derived from the weighted quantity of pure BEN, DMOB, and DMB con-
tained in 1,000 lb of standardized commercial dye. Percentage composition of 1,000 lb of "BAB"
dye obtained from Table 5-3. Percentage of pure dye contained in standardized dye taken from
footnote (b) of Table 3-6.
-------
buffing losses, and other miscellaneous losses, the lower end of this range
is reduced to 80%. Consequently the final range used for the calculation
of BAB dye retention on finished leather goods is 80 to 90%.
The remaining 10 to 20% of the dye consumed in processing enters pro-
duction waste streams (note Figure 5-1). Although no definitive information
is available to provide a quantitative breakdown for the fate of waste dye-
stuffs in leather tanneries, some relevant facts are known. The dyes in
question are protein binding formulations (Radding et al., 1978). Pro-
teinaceous materials abound in the liquid effluents which result from
leather tanning processes (Conrad et al., 1976; MRI, 1977). Aerosol losses
during the mixing of dyes and the drying of dyed leather may account for a
minor loss of dye material, but no evidence is available to quantify these
losses. All of this evidence indicates that the majority of the BAB dye
that is lost in processing will ultimately become a solid waste--either as
a component of a wastewater sludge or as a component of plant buffing dust,
trimmings, or other miscellaneous solid waste residues. Additional losses
to solid waste will occur during subsequent industrial fabrication of
leather products.
Consequently the fate of the BAB dyes lost during the coloring of
lea ther, which represents 10 to 20% of the total dye consumption, is
thought to be greater than 99.8% solid waste, less than 0.1% liquid waste,
and less than 0.1% aerosolized waste. No basis exists for an industry-wide
breakdown specifying the portion of the BAB dye waste that appears in waste-
water sludge, leather trimmings, buffing dust, or other miscellaneous resi-
dues. However, Conrad et al. (1976) suggest that the percentage breakdown
for all tannery solid wastes is as follows:
60%
Wastewater screenings and sludge
35%
Trimmings and shavings
3%
Floor sweepings
2%
Finishing wastes
Dye could be present in small quantities in any of these four categories.
Table 5-6 summarizes the estimated losses of BAB dyes in the leather
industry during the 1975 through 1978 period. The total dye consumption
figures are based on MRI estimates described earlier in this section (Table
5-3).
5-10
-------
Misc. Syntans,
Process i ng Tanning Fat liquor ,
Chemicals Chemicals & Dyes
Cured Beamhouse Tanhouse Retan, C%r
Catt I e Processes Processes and Fatliquor
Hides
LW LW LW
V1
I
f-I
f-I
Pigment
Finishing
Chemicals
Drying, Mechanical Conditioning, & Finishing.
Finished
Leather
LW - Liquid Wastes
Ae rosa I
Wastes
LW
Buffi ng Dust,
Trimmings, &
Other Finishing
V
\}-
Solid Wastes
Source:
Adapted from Conrad et a1. (1976)
Figure 5-1.
A general process flow diagram illustrating tannery inputs and wastestreams.
-------
TABLE 5-6.
ESTIMATED LOSSES OF BISAZOBIPHENYL
DYES IN THE LEATHER INDUSTRY
Quantity (1,000 1b)2./
Loss source 1975 1976 1977 1978
Total dye consumption£/ 531-870 691-1,183 754-1,163 863-1,390
Processing losses 110-20%
of consumption)~
Solid waste (99.8%) 53-174 69-236 75-232 86-277
Liquid waste (- O. 1%) -0.1-0.2 -0.1-0.2 -0.1-0.2 -0.1-0.3
Aerosol waste (-0.1%) -,0.1-0.2 -0.1-0.2 -0.1-0.2 -0.1-0.3
Total 53-174 69-236 75-232 86-278
Total quantity of dye on
finished leather 357-817 455-1,114 522-1,088 585-1,304
a/
Based on 100% BAB dye; not standardized commercial dye.
b/
Taken from Table 5-3.
~/
The 10-20% loss range was derived from average dye uptake percentage
(Radding et a1., 1978) and an MRI estimation of additional processing
losses.
5-12
-------
SECTION 6
PAPER INDUSTRY
INDUSTRY OVERVIEW
The paper industry* is a very large, diversified industry. The American
Paper Institute has over 200 member companies, who together represent approxi-
mately 90% of domestic paper and paperboard production. The industry is
not dominated by a few large companies; the biggest single U.S. paper and
paperboard producer turns out less than 10% of total production. In order
to account for 50% of the total U.S; production, the production of 50 or
more companies would have to be included (Bognar, 1979).
The expense of transporting low cost paper goods great distances prior
to sale is not cost-effective. Consequently, paper mills are scattered across
the country and are located wherever there is sufficient wood fiber and pro-
cessing water. The northeast, north central, southern, and northwestern
states all support significant levels of paper and paperboard production
(Vogt, 1974). .
At various mills, different tree species are harvested for pulp, dif-
ferent types and amounts of recycled paper are included in processing, and
different mechanical and chemical methods are employed (note Table 6-1).
Some companies are small; others are large corporations or subsidiaries
thereof. Thousands of different end products are provided by the diverse
segments of the industry.
Table 6-2 enumerates paper and paperboard production for the 1975 through
1978 period. The following 10 end use categories are listed (Franklin et al.,
1979):
Newsprint - A generic term used to describe paper of the type
generally used in the publication of newspapers. The furnish**
is largely mechanical (ground wood) pulp, along with some chemi-
cal wood pulp.
Printing and Writing Paper - Printing papers are those papers
utilized by the printing industry for mass communications
and other end uses where a multitude of copies are required
'ir
General references to the "paper" industry include the closely associated
paperboard industry.
The "furnish" is the fiber-water slurry which receives the dye.
'i'\1(
6-1
-------
!-
TABLE 6-1.
ORIGIN AND USE OF VARIOUS WOOD PULP
Type Process Wood End uses
Unbleached Ground wood Balsam/spruce Newsprint; board
Bleached Mechanical Balsam/spruce Paper; paperboard;
Thermo- foodboard
mechanical
Unbleached Chemical Pine/spruce/ Paper; paperboard;
sulphate hemlock/fir towels; tissue;
(Kraft) linerboard
Bleached Chemical Pine/spruce/ Fine papers;
sulphate hemlock/fir tissues; toweling;
board; paper
Unbleached Chemical Pine/spruce/ Fine papers;
sulphite hemlock/fir tissues; toweling;
board; paper
Bleached Chemical Pine/spruce/ Fine papers;
sulphite hemlock/fir tissues; toweling;
board; paper
Soda pulp Chemical Cottonwood/ Extender for white
maple/poplar/ papers; tissues;
gum/etc. toweling
Semichemical Secondary Corrugating
fibers (re- medium; linerboard
cycled material)
Source:
Adapted from Continental Forest Industries, Inc. (1978).
6-2
-------
.TABLE 6- 2. PAPER PRODUCTION BY END USE, 1975 TO 1978
Production quantity (106 short tons)
1975 1976 1977 1978
Paper
Newsprint 3.7 3.7 3.9 3.8
Printing and writing paper 11.0 13.2 13.8 14.5
Packaging paper 4.2 4.9 4.9 4.9
Special industrial papers 0.4 0.6 0.5 0.5
Tissue paper 4.0 4.2 4.3 4.2
Total 23.3 26.6 27.4 27.9
Paperboard
Container board 17.4 19.9 20.4 21.5
Boxboard 7.4 8.6 8.5 8.8
Total 24.8 28.5 28.9 30.3
Other
Building paper 1.6 1.8 1.7 2.0
Insulating and hard pressed board 3.0 3.6 3.8 3.6
Wet machine board 0.1 0.1 0.1 0.1
Total 4.7 5.5 5.6 5.7
Grand total 52.8 60.6 61.9 63.9
Sources: Data for 1975 through 1977 taken from Franklin et a1., 1979. Data
for 1978 taken from Funaroff, 1979.
6-3
-------
generally by long press runs on high speed equipment. Printing
papers (such as offset, book paper, and ground wood printing
paper) are frequently printed on both sides. Therefore, opacity
is generally important for products such as magazines, books,
pamphlets, and greeting cards, etc. This paper is made in a wide
range of qualities from chemical and mechanical wood pulp and, in
some products, with a cotton fiber pulp content. Printing paper
may be coated or uncoated.
Writing paper consists of a variety of papers (bond,
ledger, manifold, etc.) suitable for pencil, pen and ink, or for
use with a typewriter, automatic accounting equipment, computer,
etc. The majority of the writing paper is made from chemical wood
pulp. Cotton fiber pulps are used in about 5% of the tonnage.
In addition, mechanical wood pulps may be used in some instances.
The papers are usually uncoated but may be coated for use in
specialized end uses.
Packaging Paper - Wrapping paper; shipping sack; bag and sack other
than shipping sack; and other converting papers 18 Ib* and over.
Special Industrial Papers - Paper and board of all weights, calipers
(thickness), and finishes designed for specialized end uses, such
as abrasive paper, absorbent paper, cable paper, electrical insu-
lation, vulcanized fiber, and resin-impregnating.
Tissue Paper - A general term indicating a class of papers of charac-
teristic gauzy texture, in some ~ases fairly transparent, made in
weights lighter than 18 Ib.* The class includes sanitary tissues,
e.g., toilet paper, wrapping tissue, towels, napkins, facial
tissues, and wipers.
Containerboard - A general term designating: (a) the component
materials used in the fabrication of corrugated paperboard and
solid fiber paperboard--linerboard, corrugating medium, chip-
board; and (b) solid fiber or corrugated combined paperboard used
in the manufacture of shipping containers and related products.
Boxboard - A general term designating the paperboard used in fabri-
cating folding cartons, setup boxes, milk cartons, and foodboard.
It may be made of wood pulp or waste paper or any combinations of
these and may be plain, lined, or clay coated.
Building Paper - Sheathing paper, felts (roofing, floor covering,
automotive, deadening, industrial pipe covering, refrigeration),
asbestos paper and asbestos-filled paper, flexible wood fiber
insulation.
'k
Grading of paper by pound refers to the weight of product
i.e., one 3,000 sq ft ream, or every 500 sheets measuring
per sheet, of "18 lb" paper weights 18 lb.
per ream,
24 x 36 in.
6-4
-------
Insulating and Hard Pressed Board - A group of paper and paperboard
products used in making insulating boards and construction panels.
A fibrous-felted homogeneous panel made by interfelting of the
fibers, e.g., interior building board, wallboard, sound deadening
board, acoustical tile, exterior sheathing board, roof insulation
board, trailer board, etc.
Wet Machine Board - Binders board, shoe board (e.g., counter board,
heel board, and innersole), automotive board, chair seat backing,
. coaster board, luggage, mill board, panel board, table top board,
etc. (Franklin et al., 1979).
PAPER PROCESSING AND DYEING
Though the equipment may vary, over 90% of all colored paper is dyed
in the same manner. The fiber is dyed prior to its aggregation into sheets
while it is in an aqueous bath (Cramsie, 1979).
In one common approach, the dyeing takes place in the beater (note
Figure 6-1). As the name implies, the beater is designed to fragment fiber
bundles and shorten individual fibers in the pulp. A typical beater has
the appearance of an oval-shaped tank. A divider in the center of the tank
produces an oblong channel. The floor of this channel slopes downward from
a backfall immediately behind the beater roll which is suspended across one
side of the oblong channel. The beater roll has a series of longitudinal
blades. As the roll turns, these blades beat the pulp against stationary
blades beneath the roll. The rotating blades also force the slurry to cir-
culate continuously around the tank. After the appropriate preparation of
the fiber, as determined by the nature of the original stock and the type
of end product desired, various papermaking compounds including dye may be
added to the slurry in the beater (Danforth, 1970).
The main alternative to the traditional beater consists of two or three
separate machines--a pulper, which defibers the dry pulp and/or paper in a
water medium; a continuous refiner, in which the various papermaking materials
are added to the furnish; and occasionally, a deflaker added between the
pulper and refiner. The deflaker ensures the reduction of pulp to individual
fibers after the slurry leaves the pulper and before it is fed into the refiner.
(Any remaining flakes of wood or paper are destroyed while the stock passes
through the deflaker.
Though the design details may vary considerably, all three of these
machines consist of containment vessels with rotating and stationary blades.
The purported advantages of the continuous refining technology, compared to
the use of beaters, include the greater ease with which pulpers recycle un-
saleable paper (sometimes referred to as "broke") and other materials which
are hard to defiber; adaptability to automated production; and more efficient,
continuous operation, since dye color changes can be accomplished more easily
and more rapidly (Danforth, 1970; Landerl, 1979). One example of a contin-
uous paper refiner is a conical refiner shown in Figure 6-2.
6-5
-------
Source:
Stock Slurry
Roll
Elevatingj
Lowe ri ng
Mechanism
Midfeather
Backfall
Bedplate
Path of
Stock Flow
\
Stator Blad~:::::-
and Woods
To Dump
Pump
Adapted from Danforth (1970).
Figure 6-1.
Simplified representation of a beater.
6-6
-------
Thrust Beari ng
Thrust/Clearance
Adjustment Mechanism
Sliding Coupling
Thrust/Clearance
Adjustment Mechanism
Blade
Blade~ Rat
Va,
Source:
Adapted from Danforth (1970).
Figure 6-2.
Simplified representation of a
conical continuous refiner.
6-7
-------
Regardless of how the pulp is reduced to the proper consistency, dye
is commonly added to the beater or continuous refiner after the mechanical
breakdown of the fiber has progressed to the appropriate stage for the given
application. The dye may be added as a liquid solution or as a dry powder.
The most important group of dyes used in the coloring of paper is the
direct dye. The affinity of these dyes for cellulose fiber makes them more
versatile and more easy to control than either the acid or the basic dyes
(Lips, 1970).
Because direct dyes are not very soluble, they are generally limited
to less than a 1% aqueous solution. However, the ability to dye fiber
directly allows effective coloring to take place despite these low concentra-
tions. This affinity for cellulose fiber also makes direct dye a logical
choice for the coloring of facial tissue, toilet tissue, and absorbent tis-
sues where size* and alum are not used (acid dye could not be used under
these circumstances).
The two primary limitations of the direct dyes are a lack of brilliance
and the tendency to unevenly dye the paper if used improperly. This latter
problem refers to a difficulty caused by the rapid exhaustion of dye on only
a portion of the fiber being dyed. When this occurs, the paper product does
not possess a uniform color but is speckled because the paper is composed
of both deeply dyed fiber and uncolored fiber. Some direct dyes are much
more prone towards this problem than others. The remedy lies in the use of
cool, dilute dye solutions (Lips, 1970).
The dominance of direct dyes in paper coloring applications may be ex-
plained by the deficiencies of the competing dye classes.
Acid dyes are much more soluble than direct dyes; some exhibit solu-
bilities over 10%. However, acid dyes have very little attraction for the
cellulose fiber. As a result, it is easy to achieve a high concentration
of color in the fiber slurry but difficult to join the color to the fiber.
When acid dyes are used on paper, the color is usually retained in the sheet
by a chemical complex formed between alum and rosin size. Sometimes other
retention aids are also employed. As noted previously, this situation pre-
cludes the use of acid dyes in tissues and absorbent applications. Acid
dyed products are also unsuitable for uses involving direct contact with
moist or wet foods because the highly soluble dye tends to migrate (Lips,
1970).
Although most paper is dyed using the technology just described, some
surface coloring also takes place after the paper sheet is formed. In these
cases, dye may be added to the product via water boxes at the calendar stack
or via the surface sizing solution at the size press. The colorants used
are predominantly fluorescent white dyes and various acid dyes (Lips, 1970).
*
Size refers to finely ground additives (i.e., rosin, paraffin, wax)
which intermingle with the fiber in the production of water-resistant
papers.
6-8
-------
Because these applications are minor with respect to total dye consumption
and because no appreciable quantity of benzidine-related dyes is thought to
be involved in such usage, no detailed discussion of surface coloring or
coating will be undertaken (Lips, 1970).
DYE CONSUMPTI ON
Color is an important sales tool in the paper industry. As such, the
details of dye utilization are proprietary. Despite this information barrier,
some generalizations can be made in regard to dye usage per unit of production
(see Table 6-3). "
TABLE 6-3.
COMMERCIAL DYE USAGE IN PAPER AND
PAPERBOARD
Dye
Consumption ~/
Representative products
0-0.5 lb/short ton
Unbleached kraft products
(brown grocery bags, wrapping
paper, and cardboard boxes);
white paperboard for food
packaging; white papers;
white tissues
0.5-2 lb/short ton
Household tissue, paper towels,
and paper napkins
2-60 Ib/short ton
Miscellaneous uses such as
construction paper, wrapping
paper, writing paper.
60-80 Ib/short ton
Full shade tissues and brightly
colored glassine
~/
MRI estimates derived principally from contacts
with Cramsie (1979, Landerl (1979), and Kasprzak (1979).
These levels represent commercial dyes, not active dye.
6-9
-------
At the lower end of the range where dye consumption is less than 0.5 Ib/
short ton, dye is used to slightly modify existing colors (Landerl, 1979;
Cramsie, 1979). For example, small additions of brown color may be employed
to tint unbleached kraft for grocery bags or to match the color of recycled
fibers with the unbleached kraft in such products. In the manufacture of
white paper or paperboard, reddish-blue is added to tint away a yellowish
cast present in the bleached pulps.
In the intermediate range, 0.5 Ib to 2 Ib/short ton of product, dye is
employed to impart color to many different products, such as paper towels,
tissues, and stationery.
. At the upper end of the range where consumption is as high as 80 Ib/
short ton, dye applications yield maximum color intensities. The products
which commonly receive this level of colorant addition include full shade
tissues and brightly colored glassine (Landerl, 1979; Cramsie, 1979; and
Kasprzak, 1979).
No data were found which allow a quantification of general dye consump-
tion or bisazobiphenyl (BAB) dye consumption in the paper industry. In the
absence of authoritative information, the estimates in Tables 3-9 and 3-14
were used as approximations of the level of consumption by paper and paper-
board producers of the dyes of interest to this study. These estimated con-
sumption quantities are shown in Table 6-4. Consumption quantities derived
by Jenkins (1978) provide a considerably higher estimate of BAB dyes in the
paper industry.
Direct dyes have been the most important class of dyes used in the paper
industry (Lips, 1970). As previously noted in the discussion of paper dyeing
technology, direct dyes are particularly suited to the job of coloring tissues
and other absorbent papers. Full shade tissue and other absorbent paper
(highly colored glassine) requires a much higher level of dye application
per weight of product than any other category of production (Landerl, 1979;
Cramsie, 1979).
In addition to the coloration of tissues, another large use of dye by
the paper industry is the tinting of white paper. In order to yield a white
paper, blues and reds are commonly added to remove the yellow color present
in papermaking fiber. 3,3'-Dimethoxybenzidine-based and other direct blues
receive significant use in this area (Landerl, 1979). Though tinting white
paper represents a low usage per ton, total production of white paper repre-
sents a very large volume (Lips, 1970).
ESTIMATED LOSSES
The discussion which follows presents an estimation of the total quantity
of BAB dye which remains a part of finished paper and paperboard products,
and also the quantity that becomes a constituent of processing waste streams.
The calculations required to quantify dye uptake are taken from comments by
Landerl (1979). This source indicated that about 90 to 98% of the dye em-
ployed for the coloring of paper is successfully joined to the papermaking
materials. In order to allow for losses of dyed furnish and size, trimmings,
6-10
-------
TABLE 6-4. ESTIMATED CONSUMPTION OF BAB DYES BY THE PAPER INDUSTRY
1975 1976 1977 1978
Dye base (103 1b)~/ % (103 1b) % (103 1b) % (103 1b) %
BENE./ 460-725 -62 775-1,230 -73 540-825 -56 85-105 -L2
DMOB£./ 308-368 - 37 308-414 -26 441-550 -42 540-825 -86
D~/ 11-27 -1 11-27 -1 16-30 -2 18-22 -2
Total 779-1,120 1,094-1,671 997-1,405 643-952
~/
Quantities of dyes estimated from Tables 3-8 and 3-9; quantities in terms of active dye (100% dye).
'Q/
Dyes based on benzidine
~/
Dyes based on 3,3'-dimethoxybenzidine
0\ d/
I -
t-'
t-'
Dyes based on 3,3'-dimethylbenzidine
-------
and other miscellaneous losses during production, this range is lowered to
85 to 95% for a calculation of BAB dye retention on finished paper and paper-
board products.
The remaining 5 to 15% of the dye consumed in processing necessarily
enters production waste streams (note Figure 6-3). No definitive informa-
tion is available to provide a quantitative breakdown for the fate of waste
dyestuffs in paper mills. However, some relevant facts are known. The dyes
in question have a strong affinity for cellulose fiber (Lips, 1970). There
is sufficient fiber and size in the whitewater system to absorb and/or adsorb
the vast majority of the dye (especially, direct dye) employed. The direct
dye formulations used in the paper industry are not highly soluble in water
(Lips, 1970). Volatile losses during the mixing of dyes and the drying of
dyed paper may account for a minor loss of BAB material, but no evidence is
available which quantifies these losses. Many modern mills rely on premixed
liquid dye formulations which are automatically metered into processing equip-
ment (Lips, 1970; Landerl, 1979). Changeovers to this production method-
ology have been encouraged because of industrial hygiene considerations.
One of the results of such processing changes is a decline in volatile and
airborne particulate wastes from dye mixing.
All of this evidence indicates that the majority of the BAB dye that
is lost during processing ultimately becomes solid waste--either as a com-
ponent of wastewater sludge, trimmings, plant dust, or other miscellaneous
residues. Additional losses as solid waste will occur from trimmings re-
sulting from industrial fabrication of specific paper products.
Consequently, the fate of the BAB dyes lost during the coloring of paper
and paperboard, which represents ~ 5 to 15% of consumption, is thought to
be greater than 99.8% solid waste, less than 0.1% liquid waste, and less
than 0.1% volatile waste. Table 6-5 summarizes the estimated losses for
these dyes in the paper and paperboard industry during 1975 through 1978.
TABLE 6-5.
SUMMARY OF ESTIMATED BISAZOBIPHENYL DYE
LOSSES FROM THE PAPER INDUSTRY
Loss Source
Quantity (1 ,000 Ib)
1975 1976 1977 1978
779-1,120 1,094-1,671 997-1,405 643-952
39-168 55-250 50-210 32-142
- 0.1-0.2 0.1-0.3 0.1-0.2 -0.1
- 0.1-0.2 0.1-0.3 0.1-0.2 -0.1
39-168 55-251 50-210 32-142
Total BAB dye consumPtion~/
Dye loss during processing:
Solid waste (~9.8%)
Water was te ("-0. 1 %) 'E./
Volatile waste ("-0.1%) E./
Total loss
(~5-15% of total
dye consumption):='/
Dye remaining in finished
paper product
611-1,081
843-1,616
787-1.355
501-920
~/ Quantities are 100% dye; not standardized commercial dyes (see Table 6-4).
E./ MRI estimates
£/ The total percentage of dye loss was derived from information from Landerl (1979)
and an ~mI estimation to allow for additional processing loss~s.
6-12
-------
"
Dye, Alum
and Size
Ca enc er Stac < Dyes
or Pigments and
Size Press Solution
Which Also May Contain
Dye*
Raw
Fiber
Slurry
Beater or
Pulper - Deflaker - Refiner
Fourdrinier or
Cylinder Papermaking
Machine
Pape r
Whitewater Recycle
cr-
.
t-'
lJ.)
LW
LW - Liquid Wastes
V - Sol id Wastes
*
Addition of dye at this point is not the most common practice. The colorants used are
predominantly fluorescent white dyes and various acid dyes (Lips, 1970). No significant
consumption of benzidine-related material is thought to occur here.
Figure 6-3.
A general process flow diagram illustrating papermaking
inputs and wastestreams.
-------
SECTION 7
PIGMENT PRODUCTION
This section discusses the manufacturing process for diarylide pigments,
sources of loss during production and approximate magnitudes of those losses,
published and estimated production quantities, and usage patterns for each
of the pigments. .
MANUFACTURING PROCESS
The manufacturing process consists of two parts: the production of
3,3'-dichlorobenzidine and 3,3'-dimethoxybenzidine and the production of
the various pigments. For pigments based upon 3,3'-dichlorobenzidine, the
dihydrochloride salt is used as the starting material. For pigments based
upon 3,3'-dimethoxybenzidine, either the dihydrochloride salt or the free
base may be utilized. No pigments based on 3,3'-dimethylbenzidine are commer-
cially produced in the United States at the present time.
3,3'-Dichlorobenzidine Manufacture
The commercial scale production of 3,3'-dichlorobenzidine proceeds by
the reduction of o-nitrochlorobenzene followed by acid rearrangement of the
resulting dichlorohydrazobenzene to the desired product (Powell et al., 1979).
Both of the current U.S. producers of dichlorobenzidine (Bofors Lakeway
and Upjohn) employ the o-nitrochlorobenzene reduction process followed by
rearrangement with aCid,-usually hydrochloric (Wolthuis, 1979). The reaction
for the3,3'-dichlorobenzidine production is shown is Equation 7-1. Both
U.S. manufacturers employ a batch process with dedicated equipment. Following
hCl
.tQJ
@- Cl
Reduction 0 -@
> N-N
I I
HH
Cl Cl
HCl ) HCl'H2N -@-@-~'HCl
(7 -1)
the reduction step, the dichlorohydrazobenzene solution may be purified prior
to acid rearrangement. The purified solution is treated with acid to produce
a solution containing approximately 80 to 85% crude 3,3'-dichlorobenzidine
and 15 to 20% other rearrangement products resulting from coupling of the
rings in positions other than the desired one. The rearrangement products
are removed by proprietary purification processes (no further rletai.ls were
7-1
-------
available). Approximately 0.5 to 1% dichlorobenzidine dihydrochloride is
included in the "acid" stream containing the rearrangement products. This
stream is "treated" to reduce dichlorobenzidine levels, and the solid wastes
are transported to an EPA-approved site by a licensed hauler (Wolthuis, 1979;
DCNA, 1980).
The purified dichlorobenzidine is isolated as the dihydrochloride salt
by being either filtered or centrifuged. One manufacturer estimated that
0.5 to 1.5% dichlorobenzidine would be contained in the wastestream following
isolation of the solid dichlorobenzidine dihydrochloride. At Bofors Lakeway,
the wastestream from the isolation procedure is transferred to a recycle
system, which results in a concentration of the waste stream (Wolthuis, 1979).
This concentrated waste stream is then recycled into the process. Period-
ically, the waste stream is purged and the aqueous waste removed to an EPA-
approved disposal site. The other producer sends the wastestream from the
isolation of the solid dichlorobenzidine dihydrochloride to biological waste-
water treatment facilities.
The dichlorobenzidine dihydrochloride is transferred directly into drums
for shipment or storage. Because the product is shipped as a damp material,
minimal losses should occur in the form of dust. Since the entire production
process at each manufacturer utilizes dedicated equipment, dichlorobenzidine
dihydrochloride remaining in equipment such as blenders and packaging machines
is incorporated into the next batch of product.
Pigment Manufacture
A basic flow diagram for the manufacture and processing of pigments
produced from 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine (tolidine), or
3,3'-dimethoxybenzidine (dianisidine) is shown in Figure 7-1.
For 3,3'-dichlorobenzidine, the formation of the tetrazonium compound
would be as shown in Equation 7-2. The dichlorobenzidine dihydrochloride
Cl Cl
HzN-@-@-NHZ + 4HCl + ZNaN0Z
~
Cl Cl
ee ~ ~. e e
Cl N=N~~N Cl + ZNaCl + 4HZO (7-2)
3,3'-Dichlorobenzidine
tetrazonium chloride
is received as a damp or moist powder containing about 10% water. It is
slurried with water and additional hydrochloric acid~ cooled by the addition
of ice, and treated with sodium nitrite to form the water-soluble tetrazonium
compound. Although a filtration step is included in Figure 7-1, industry
sources state that, as a rule, the tetrazonium compound is not filtered.
If the tetrazonium solution appears to require clarification, then the filtra-
tion step would be performed. Losses resulting from filtration were estimated
by industry to be approximately 0.1 to 0.3%. The filter contains some form
of filter aid which would likely be discarded as solid waste after treatment
with sodium hypochlorite or other decontaminating agent.
7-2
-------
DCB, DMB,
or DMOB
Coup ler
2-10% Excess
~
I
W
Caustic
-
H20
DCB= 3,31-dichlorobenzidi
DMB = 3,31-dimethylbenzid
DMOB = 3,31-dimethoxyben
NaN02 T etrazoni um Filter
-;;.
H+ Compound
Pigment Fi Iter - Wet
Formation -- Presscake
Water Wash
H+ - Reprecipitated
Sod i um '" Coupler
Acetate
Buffe r
I Blender I -
I 1-
Packaged - Pulverizer Dryer ...e-
for Shipment -
Packaged ~ Printi ng Oleoresin Flusher
for Shipment Ink Paste - -
ne Packaged for Shipment.
ine
z i dine as T exti Ie Presscake
Figure 7-1.
General flow diagram for pigment manufacture.
-------
Pigment formation occurs upon mixing of a 2 to 10% excess of the coup-
ler and an aqueous solution of the tetrazonium compound. Table 7-1 shows
the couplers and structures of the dyes of interest to this report. Prior
to pigment formation, the coupler may be reprecipitated in a finely divided
form and a buffer added to maintain the pH within the range necessary for
completion of the coupling reaction and to ensure proper color characteristics.
The tetrazonium solution and the coupler slurry are mixed and pigment forma-
tion is initiated. The resultant pigments are insoluble in aqueous solution
and precipitate upon formation. Industry sources state that the reaction
proceeds to basically 100% of the theoretical yield and that losses result-
ing from the pigment manufacture are very small. MRI feels it is probable
that a small amount (0.5 to 1.0%) of dichlorobenzidine tetrazonium chloride
or water soluble by-products remains in solution during pigment manufacture.
The pigment is then filtered and washed with water; the solid pigment remain-
ing on the filter is termed the presscake. Industry sources state that the
presscake remaining after the final water wash contains approximately 20
ppm or less of the dihydrochloride salt of dichlorobenzidine, dimethylbenzidine,
or dimethoxybenzidine. Because the levels adsorbed on the pigments are low,
subsequent discussions in this subsection concerning process losses will
refer to losses of pigment and will not consider the 20 ppm or less of the
adsorbed acid salt of dichlorobenzidine, dimethylbenzidine, or dimethoxyben-
zidine.
The presscake can be treated in three ways depending upon the final
use for the particular pigment: "flushed color," dry pigment, or presscake.
If a flushed color is to be produced, the presscake is transferred from the
filter to a unit called a flusher. In the flusher, an oleoresinous material
is added and the pigment dispersed in the vehicle to form a wet, sticky paste
to be used for lithographic purposes. The flushed color is then transferred
to shipping or storage containers. Pigment manufacturers estimated that
handling losses would be approximately 1 to 3%; these losses would occur
primarily in the transfer of the presscake to the flusher and from the flusher
to the shipment or storage containers.
If the pigment is to be shipped or stored as a dry powder, the wet press-
cake is transferred to a drier. Depending on the volume of the pigment to
be produced, the drying process may be batch or continuous with or without
dedicated equipment. From the drier, the dry presscake is pulverized and/or
blended to produce the finished pigment which is then packaged in drums or
bags for shipment or storage in a warehouse. Finely divided dry pigment as
dust from the pulverizer is vented to a baghouse for collection. Attempts
are made to reclaim as much pigment as possible from the baghouse filters
and the recovered pigment is blended into another batch. Very finely divided
particles, or "fines," remaining in the filters are discarded as solid waste.
Overall losses of pigment resulting from the processing of the dry pigment
are estimated by a major pigment manufacturer to be approximately 1 to 3%,
the principal sources being the pulverizing operation and the various transfer
operations from machines to containers. The pulverizing step is estimated
by MRI to be the largest single loss source, accounting for approximately
50% of the pigment losses resulting from the handling of the dry pigments.
If the equipment, such as driers and pulverizers, is dedicated for the specific
pigment, little, if any, cleaning of the equipment would occur and losses
7-4
-------
TABLE 7-1.
STRUCTURES OF SELECTED DIARYLIDE PIGMENTS
Pi~ment
DCB!/ based
Red 38
MW .. 739.6
Orange 13
MW - 623.5
Orange 34
MW .. 651.5
Yellow pigments
Ye 110101 12
Ye 110101 13
Yellow 14
Yellow 17
Ye l10w 55
Ye 110101 83
x = H; Y 'CI H; Z .. H
X .. C1I3; Y a CH3; z . H
X .. C1I3; y.. H; Z . H
X a OC1I3; y:a H; Z a 11
X .. H; Y .. C1I3; Z a H
X - OCH3; Y - Cl; Z - OCH3 MW= 820.5
Coupler
o
II
H5C2OC-C-C1I2
II I
'~'~
H3C-C-CH2
~ b.o
@
H3C-C-C1I2
II I
N c=o
~.
CH3
X
~ 00
Y0NH~C~~CH3
Z
Structure
Wl
o 11 0
H5C20~-~-IH-NaN 0 0 N=N-I-r~OC2H5
~'~ ~~
C1 Cl
. '1::::\ ~ n ¥
H3C-~-11I-N-N~aN-f-~-C1I3
'~~ ~~
~1
11
H3C-~-IH-N=N O. O=N-1-rC1I3
N ~.O o=<; N
~ ~
X C1 C1 X
Y IQ\NH~yH-N.N IcY ~ u-N-yHHNH I(y Y
\;::Y c.o ~0::!f 0-« ~
z <:H3 H3C Z
MW - 629.4
MW .. 685.6
MW. 657.4
MW D 689.4
MW - 657.5
7-5
-------
TABLE 7-1.
(cone luded)
Pigment
Structure
DMOBl!/ based
Red 41
MW = 642.7
Orange 16
MW = 620.6
Blue 25
)1W = 792.8
DMB's/ based
Orange 15
~F..r = 588.6
Coupler
R)C-C-CR2
II I
N c=o
"N/
@
@ 00
o NH8CR28cR)
o
@NH~ OR
$
@ 00
o NH~CR2~CR)
OCR) OCR)
H3CIl----f"-N"~=N-f----~-CH3
N C=O O=C N
"N/ "N/
@ @
OCR) OCR)
@NRgyR-N=N ~ ~ N=N-yH~NH~
C=O ~ C=O \::::Y
I I
CR3 CH3
@NR8 OR OCR3 OCR3 OR gNH~
~N'N@-@N~
CH3 CH3
@~RgyR-N=N ~ ~ N=N-yH~NH~
C=O . ~ c=o \::::Y
I ' ~
CH3 CH3
~/ DCB = 3,)'-dich1orobenzidine; MW = 253.1)
~/ DMOB = 3,)'-dimethoxybenzidine; MW = 244.29
.s/ DMB = ),)'-dimethy1benzidine; MW = 212.28
7-6
-------
from this source would be extremely small. Additionally, if a light-colored
pigment (e.g., yellow) were to be followed by a dark pigment (e.g., blue or
red), the equipment would generally not be cleaned prior to changing pigments
. since the incorporation of a small amount of light-colored pigment into a
dark shade would have little effect on the overall dark color. The same
would not be true, however, for the reverse situation in which a light shade
followed a dark shade. In these instances, the equipment would likely be
cleaned prior to use with the lighter colored pigment. If cleaning is re-
quired, MRI estimates that pigment losses could be 0.5 to 1%.
On occasion, an off-standard shade of dry pigment may be produced. If
the shade is darker than the standard or specified color, an extender (e.g.,
barium sulfate) is used as an inert diluent to reduce the color intensity
to the specified level. If the shade is lighter than the standard or speci-
fied color, it is blended with a quantity of darker than standard pigment
to produce the correct color. When the blending operation is used and clean-
ing of the blender is required, industry sources state that losses would be
less than 1%. .
The third method of pigment processing is for presscake. For use in
textile printing or water-based paint, ink, or coatings, the pigment is
shipped in the water-wet form of the presscake, which has a dough-like con-
sistency, or as a dispersed slurry. The only losses would result from the
mechanical transfer of the presscake or the slurry from the filter to drums
for shipment. As with the transfer in the formation of flushed colors,
losses resulting from removal of the pigment from the filter could be ap-
proximately 0.5 to 1%.
PRODUCTION HISTORY
The pigments considered in this study were delineated earlier in Table 7-1.
Except for the inclusion of pigment Yellow 83, this listing is virtually
the same as those considered in a previous report (Powell et al., 1979).
Manufacturers of each of the pigments are presented in Table 7-2 for the
period 1975 to 1978. Within this time period, numerous manufacturers of
diarylide pigments have ceased production or have been sold to other com-
panies. In 1975, 29 companies manufactured one or more pigments derived
from 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, or 3,3'-dimethoxybenzi-
dine. Pigments Yellow 13 and 14 had the greatest number of producers, 20;
followed by Yellow 12 with 19, and Yellow 17 with 18. By 1978, the total
number of manufacturers had been reduced to 21. Yellow 14 was produced by
the greatest number of companies, 17; followed by Yellow 17 with 15 companies.
Fourteen companies manufactured Yellow 12 in 1978.
Production, sales, and import quantities of each of the pigments, as
dry, full strength, 100% material, are presented in Table 7-3. For some
pigments, a sufficient number of producers exist to allow a report of the
production and sales data in government publications.
7-7
-------
TABLE
7-2.
PIGMENT MANUFACTURERS,
1975-1978
-...J
I
00
1975
Red Orange Orange Yellow Yellow Yellow Yellow Yellow Yellow Red Orange Blue Orange Total
Producer 38 13 34 12 13 14 17 55 83 41 16 25 15 produced
Allied Chemical Corporation X X X X X X X X 8
Ridgway Color and Chemical X X X X X 5
Hercules, Inc. X X X X X X X X X 9
Chemetron Corporstion X X X X X 5
Harshaw Chemical Company X X X X X X X X 8
Inmont Corporation X X X X X X X X X X 10
M. Kohnstamm and Company X X 2
Max Marx Color and Chemical X X X X X X X X X 9
Ciba-Geigy X X X X X X X X 8
American Cyanamid CorporatioD X X X X X 5
Harmon Color Corporation X X X X 4
Sandoz, Inc. X X X X X X 6
Sun Chemical Corporation X X X X X X X X X 9
Blackman-Uhler X X X X 4
Bostik South, Inc. X X X X X 5
United Merchants and X X X X X X 6
Msnufacturers
Sterling Drug, Inc. X X X X X 5
Verona Division, Baychem X X X X X 5
GAF Corporation X X X X X 5
Paul Uhlich and Company X X 2
Apollo Colors, Inc. X 1
Borden. Inc. X 1
American Hoechst Corporation X X X X X X 6
E. 1. du Pont X X X 3
Sherwin Williams X X X 3
ICI America X 1
Crompton and Knowles X 1
Binney and Smith, Inc. X X 2
Reichard-Coulston, Inc. X 1
Total producers 9 13 8 19 20 20 18 4 3 3 14 6 2
(continued)
-------
TABLE 7 -2.
(continued)
-...J
I
\0
1976 .
Red Orange Orange Yellow Yellow Yellow Yellow Yellow Yellow Red Orange Blue Orange Total
Producer 38 13 34 12 13 14 17 55 83 41 16 25 15 produced
Allied Chemical Corporation X X X X X X X X 8
Ridgway Color and Chemical X X X X 4
Hercules, Inc. X X X X X X X 7
Chemetron Corporation X X X X X X 6
Harshaw Chemical Company X X X X X X 6
lnmont Corporation X X X X X X X X X X 10
H. Kohnstamm and Company X 1
Max Harx Color and Chemical X 1
Sandoz, Inc. X X 2
Sun Chemical Corporation X X X X X X 6
8lackman-Uhler X X X X 4
Bostik South, Inc. X X X X 4
United Merchants and X X X X X X b
Manufacturers
Sterling Drug, Inc. X X X X X X 6
GAF Corporation X 1
Apollo Colors X 1
Borden, Inc. X X X 3
American Hoechst Corporation X X X X X X II
Binney and Smith, Inc. X X 2
Keystone Color Works X 1
Total producers 3 9 4 12 10 16 11 2 4 1 11 1 1
(continued)
-------
TA BLE
7-2.
(continued)
.......,
I
.--
o
1977
Red Orange Orange Yellow Yellow Yellow Yellow Yellow Yellow Red Orange Blue Orange Total
Producer 38 13 34 12 13 14 17 55 83 41 16 25 15 produced
Ridgway Color and Chemical X X X X X 5
Hercules, Inc. X X X X X X X 7
Chemetron Corporation X X X X X X 6
Harshaw Chemical Company X X X X X X 6
Inmont Corporation X X X X X X X X X 9
M. Kohnstamm and Company X 1
Harmon Color Corporation X X X X X X X 7
Sandoz, Inc. X X 2
Sun Chemical Corporation X X X X X X 6
Blackman-Uhler X X X X 4
Bostik South X X 2
United Merchants and X X X X X X 6
Manufacturers
Sterling Drug X X X X X X 6
GAF Corporation X 1
Apollo Colors, Inc. X X X X 4
Borden, Inc. X X X 3
American Hoechst Corporation X X X X X X 6
Binney and Smitb X X 2
Galaxie Chemical Corporstion X X X X X X X X 8
Indol Chemical Company X X X X X X X X 8
Total producers 3 8 6 14 11 19 14 2 7 1 10 3 1
(continued)
-------
':A L ~ 7 - 2 .
(cone .uded)
-....J
I
I--'
I--'
1978
Red Orange Orange Yellow Yellow Yellow Yellow Yellow Yellow Red Orange Blue Total
Producer 38 13 34 12 13 14 17 55 83 41 16 25 produced
Ridgway Color and Chemical X X X X X 5
Hercules, Inc. X X X X X X X X 8
Chemetron Corporation X X X X X X 6
Harshaw Chemical X X X X X 5
Harmon Color Corporation X X X X X X 6
Sandoz, Inc. X X X 3
Sun Chemical Corporation X X X X X X X X 8
United Merchants and X X X X X 5
Manufacturers
Sterling Drug X X X X X 5
Apollo Colors, Inc. X X X X 4
Borden, Inc. X X 2
American Hoechst Corporation X X X X X X 6
Binney and Smith, Inc. X X 2
Indol Chemical Company X X X X X X X 7
Inmont Corporation X X X X X X X 7
Total producers 2 9 5 13 " 12 10 1 7 1 10 )
v
Sources:
Synthetic Organic Chemicals, U.S. 'International Trade Commission, Washington, D.C., 1975-1977; Powell et al., 1979;
industry contacts; MRI estimates.
-------
TABLE 7-3.
u.s. PRODUCTION AND IMPORTS OF SELECTED PIGMENTS
Quantity (1,000 1b)
Pigment Source 1975 1976 1977 1978
Dich1orobenzidine-Based
Red 38 Production~/ [185-190J1?J 141 205 [210-215 J
Sa1es.~/ 161
Import'£/ 4.84 64.24
Orange 13 Production 209 267 230 237
Sales 168 171 186 238
Import 11. 02 2.20 9.48 3.30
Orange 34 Production 99 89 75 83
Sales 97 [89J 75 68
Imports 96.47 13.42 7.7
Yellow 12 Production 6,028 7,830 8,670 11,860
Sales 3,906 5,223 5,768 7,537
Imports 62.12 34.65 28.71 2.26
Yellow 13 Production 240 380 367 511
Sales 166 203 300 386
Imports 2.56 19.98 4.63 9.66
Yellow 14 Production 1,840 3,000 3,248 3,130
Sales 1,646 1,992 2,323 2,475
Imports 11. 06 0.11 5.19
Yellow 17 Production 415 767 1,002 1,370
Sales 280 416 612 816
Yellow 55 Production [50-60 J [50-60 J [90-110 J [140-160J
Yellow 83 Production [600-700 ] [800-900 J [900-1,100J [1, 100-1, 300J
Imports 33.22 58.39 18.99 5.78
Total Production 9,666-9,781 13,324-13,434 14,787-15,007 18,641-18,866
Total Imports 124.82 275.93 75.34 33.89
(continued)
7-12
-------
TABLE 7-3 (concluded)
Quantity (1,000 Ib)
Pigment Source 1975 1976 1977 1978
Dimethylbenzidine-Based
Orange 15 Production [ 40-45 J [40-45J [35-40 J
Import 1.19
Total Production 40-45 40-45 35-40
Total Imports 1.19
Dimethoxybenzidine-Based
Red 41 Production [40-60 J [40-60J [40-60J [40-60 J
Orange 16 Production 377 475 439 465
Sales 279 367 441 468
Imports 2.18
Blue 25 Production [170-1801 J155-1651 1145-1551 J135-1451
Total Production 587-617 670-700 624-654 640-670
Total Imports 2.18
Overall Totals
Production 10,293- 14,034- 15,446- 19,281-
10,443 14,179 15,701 19,536
Imports 124.82 275.93 77 .52 35.08
2./
Data from "Synthetic Organic Chemicals," U.S. International Trade Commission,
Washington, D.C. 20436, 1975-1978. All quantities are in terms of dry, full
strength, 100% pigment. MRI estimates the accuracy of the reported produc-
tion quantities of all yellow pigments to be ~ 10%; all other pigments to
be + 15%.
'E-/
MRI estimates are shown in brackets.
sj
Data from "Imports of Benzenoid Chemicals and Products," U.S. International
Trade Commission, Washington, D.C. 20436, 1975-1978.
7-13
-------
All other production figures were
plied by industry sources. These
proximate quantities.
estimated by MRI based on information sup-
figures should be interpreted as only ap-
Opinions were solicited from pigment manufacturers regarding the ac-
curacy of the data reported by the International Trade Commission (ITC).
One manufacturer stated that in his opinion the reported data for diarylide
yellows were accurate to probably + 10% and somewhat higher for the other
pigments. While other manufacturers declined to state a specific figure,
opinions were that + 10% was probably a "pretty good" estimate for the yel-
low pigments. For the other pigments, the opinion was that an accuracy of
+ 15% is probably a fairly good representation. In 1977, production quanti-
ties of the yellow pigments accounted for over 93% of all ITC data cited in
Table 7-3.
For any given year, the U.S. production quantity plus import quantity
is assumed to be equal to the U.S. consumption of any specific pigment.
The use of sale quantities plus imports is not employed because the sale
quantity reflects only purchases by other companies and does not reflect
quantities of the pigment employed for captive uses. This fact is particu-
larly important for any pigment consumed in the printing ink industry be-
cause two of the pigment manufacturers are also the largest and second larg-
est printing ink manufacturers in the United States. Thus, these two com-
panies consume large quantities of pigments in captive production which are
not reflected in the sales quantities of the ITC data. Industry sources
indicated that, with the possible exception of some very low volume pigments,
quantities of pigment committed to the warehouse for extended periods of
time (years) would be a very minor factor. . For the foregoing reasons, all
U.S. consumption quantities of pigments employed in the succeeding sections
of this report will be the sum of U.S. production plus imports.
ESTIMATED LOSSES
Losses of 3,3'-dichlorobenzidine dihydrochloride can occur during pro-
duction of the material and during its use in pigment production. Data are
presented in Table 7-4 for estimated losses arising solely from the manufac-
ture of DCB, DMOB, and DMB. In Table 7-5, data are given for estimated losses
of these materials during their use in pigment production. For 3,3'-dimethyl-
benzidine and 3,3'-dimethoxybenzidine, either the free base or the acid salt
(usually the dihydrochloride) is produced and used in pigment production.
The production process for 3,3'-dichlorobenzidine dihydrochloride was dis-
cussed earlier in this section. In the previous discussion, it was stated
that losses of the dichlorobenzidine can occur during the purification of
the crude product and during the filtration (or centrifuging) of the 3,3'-
dichlorobenzidine dihydrochloride. Based on the quantities of 3,3'-dichloro-
benzidine required for pigment production, estimated losses (in 1,000 Ib)
for the purification and filtration procedures are shown in Table 7-4. Losses
of 3,3'-dimethylbenzidine and 3,3'-dimethoxybenzidine are also estimated
assuming the same production procedure. Both losses receive pretreatment
prior to discharge or landfill disposal.
Pigment production results in potential loss sources of raw materials,
by-products, and the corresponding pigments. The estimated loss of raw mate-
rials and soluble by-products is presented in Table 7-5. Raw materials include
7-14
-------
TABLE 7 -4 .
ESTIMATED LOSSES OF 3,3'-DICHLOROBENZIDlNE,
3,3'-DlMETHYLBENZIDINE, AND 3,3'-
DIMETHOXYBENZIDINE DURING THEIR
MANUFACTURE
Base
pur~fication
losses- (0.5-1.0%)
Filtration
losses~1 (0.5-1.5%)
3,3'-Dich1orobenzidin~1
1975
1976
1977
1978
19-39
26-55
29-60
37-77
19-60
26-83
29-91
39-116
3,3'-Dimethoxybenzidin~1
1975
1976
1977
1978
1-2
1-3
1-2
1-3
1-3
1-4
1-4
1-4
bl
3,3'-Dimethy1benzidine-
1975
1976
1977
1978
0.1-0.2
0.1-0.2
-0.1
0.1-0.2
0.1-0.2
0.1-0.2
~I
QI
Estimated losses in terms of 1,000 lb.
For methods of calculation used in this table, see Appendix B, III.
7-15
-------
r
TABLE 7 -5.
ESTIMATED LOSSES OF 3,3'-DICHLOROBENZIDlNE,
3,3' -DlMETHYLBENZ IDlNE, AND 3,3 1-
DlMETHOXYBENZ IDlNE DURING PIGMENT
PRODUCTION
Base
Optional titrazonium
filtration! (0.1-0.3%)
Losses in pigment
formatio~/ (0.5-1.0%)
3,3'-Dich1orobenzidin~/
1975
1976
1977
1978
4-11
5-16
6-17
7-22
19-39
26-54
29-60
37-76
3,3'-DimethoxYbenzidine~/
1975
1976
1977
1978
0.2-0.7
0.3-0.8
0.3-0.8
0.3-0.8
1-2
1-3
1-2
1-3
3,3'-DimethY1benzidin~/
1975
1976
1977
1978
0.02-0.05
0.02-0.05
0.02-0.05
0.1-0.2
0.1-0.2
-0.1
2-/
'2-/
Estimated losses in terms of 1,000 lb.
Losses include free base, unreacted tetrazonium compound, and soluble
by-products resulting from the pigment production process.
For methods of calculation used in this table, see Appendix B, III.
~/
7-16
-------
the free base or acid salt of 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine,
and 3,3' -dimethylbenzidine and the corresponding tetrazonium compounds.
Estimated pigment losses resulting from subsequent transfer and handling
procedures are presented in Table 7-6. Percentage loss ranges for each source
of loss were discussed earlier in the pigment manufacture subsection. Once
the pigment presscake is formed, the three processes delineated earlier can
occur. The estimated losses resulting from shipment of the presscake are
less than if the pigment is shipped as a dry toner or flushed color. Data
for the percent distribution among the three processes were available only
for the pigments derived from the dichlorobenzidine. Therefore, in Table
7-6, pigments resulting from either the dimethylbenzidine or dimethoxybenzi-
dine were assumed to be the dry toner or flushed color (loss ranges are the
same). Data from the ITC on the distribution of dichlorobenzidine-based
pigments among the three processes are as follows (lTC, 1976a; 1977a; 1978a;
1979):
1975 1976 1977 1978
(%) (%) (%) (%)
Yellow 12
Dry, full-strength toner 27.3 31.2 36.6 46.7
Flushed color 70.4 67.6 49.1 50.9
Presscake and dispersions 2.3 1.2 14.3 2.4
Yellow 14
Dry, full-strength toner (a) (a) (b) 59.3
Flushed color (a) (a) (b) 4.4
Presscake and dispersions (a) (a) (b) 36.3
All other DCB pigments
Dry, full-strength toner 53.0 58.6 (c) 66.8
Flushed color 14.1 13.0 (c) 12.4
Presscake and dispersions 32.9 28.4 (c) 20.8
(a) Included with all other DCB pigments.
(b) Included with Yellow 12.
(c) Assumed 1976 percentages.
In 1977, Yellow 14 was removed from all the other DCB pigments category and
combined with Yellow 12. The ITC distribution for these two pigments in
1977 was dry, full-strength toner (36.6%), flushed color (49.1%), and press-
cake and dispersions (14.3%). No data were provided for all other DCB pig-
ments; the 1976 percentages were assumed for 1977. The percentages are ap-
plied to the appropriate production quantities presented in Table 7-3. After
the quantity of each DCB pigment is calculated for the processing method
(i.e. toner, flush color, and presscake), the percent loss ranges shown in
Table 7-6 are used to estimate the losses for each method.
A quantity of dichlorobenzidine dihydrochloride normally is present in
the presscake and is incorporated into a flushed color or dry toner. Industry
sources state that the level of dichlorobenzidine dihydrochloride found in
7-17
-------
TABLE 7-6.
ESTIMATED PIGMENT LOSSES DUE TO TRANSFER AND HANDLING AT PRODUCTION FACILITIES, QUANTITY
(1,000 1b)
1975 1976 1977 1978
% Loss miBE/
Source of loss range DcI0.1 DHOB.~/ DCB DHOB DHB DCB DHOB DHB DCB DHOB
Dry toner - handling 36-112.Q.!
losses 1-3 6-19 0.5-1 57-177 7-21 0.5-1 61-191 6-20 0.4-1 99-309 6-20
Flushed color - handling ND~/
losses 1-3 48-148 ND 61-186 ND ND 63-193 ND ND 67-206 ND
Presscake transfer 0.5-1. 0 7-14 ND ND 8-17 ND ND 13-26 I'D ND 11-22 ND
-...J Pulverizer cleaning
I (optiona1)Y 0.5-1.0 (18-37) (3-6) (0.2-0.5) (28-58) (3-7) (0.2-0.5) (30-62) (3-7) (0.2-0.4) (49-101) (3-7)
f-'
00
Blender cleaning
(optional)Y 0.5-1.0 (18-37) (3-6) (0.2-0.5) (28-58) (3-7) (0.2-0.5) (30-62) (3-7) (0.2-0.4) (49-101) (3-7)
Total Loss of Pigment
(excludes optional
sources) 91-274 6-19 0.5-1 126-380 7-21 0.5-1 137-410 6-20 0.4-1 177-537 6-20
Final Quality of Pigment
(sold and for captive 9,666- 587- 40-45 13,324- 670- 40-45 14,787- 624- 35-40 18,641- 640-
use)E.I 9,781 617 13,434 700 15,007 654 18,866 670
~I Pigments based on 3,3'-dichlorobenzidine; for estimated Quantities see Table 7-3.
bl
-I Pigments based on 3,3'-dimethoxybenzidine; for estimated quantities see Table 7-3.
£ Pigments based on 3,3'-dimethylbenzidine; for estimated Quantities see Table 7-3.
~I For methods of calculation used in this table, see Appendix B, IV.
~I ND = Not determined; all pigments derived from dimethoxybenzidine and dimethy1benzidine were
assumed to be sold as dry toner.
ij Data apply only to quantities sold as dry toner (see p. 7-17).
~ See Table 7-3.
-------
most pigments is approximately 20 ppm. These same sources indicated that
imported quantities of pigments appeared to contain approximately the same
level of dichlorobenzidine dihydrochloride as the u.s. material. Based on
information derived from these sources, an estimate of the probable accuracy
of the levels of dichlorobenzidine dihydrochloride in the finished pigment
would be 20.:!: 10 ppm. It is assumed that the levels are the same in the
pigments derived from 3,3'-dimethylbenzidine and 3,3'-dimethoxybenzidine as
they are for pigments based on 3,3'-dichlorobenzidine. Using a 20 ppm level
and data from Table 7-6, the estimated quantities of 3,3'-dichlorobenzidine
dihydrochloride present in the press cake pigments were 90 to 300 lb (1975),
135 to 400 Ib (1976), 150 to 450 Ib (1977), and 190 to 570 Ib (1978). For
dimethoxybenzidine, the estimated quantities present in the presscake pig-
ments were 6 to 20 Ib (1975), 7 to 20 Ib (1976), 7 to 20 Ib (1977), and 7
to 20 Ib in 1978. For dimethylbenzidine, the estimated maximum quantities
were approximately 1 Ib for all 4 years. The above quantities include the
estimated error factor of + 50% for the 20 ppm level.
PIGMENT USAGE
The usage of the pigments within various product areas was derived from
industry sources and a recent report (Powell et al., 1979). Data presented
for the percentage consumption of a given pigment in each area are a synthesis
of the information received and do not represent the specific opinion of
anyone source. The opinions were weighted to a certain extent depending
upon the degree of involvement of the particular source in a specific area
of use. The percentage utilization of each pigment in various applications
is given in Table 7-7.
TABLE 7-7. CONSUMPTION OF PIGMENT BY USE AREA
Percent
Printing TPI!.!
Pigment ink Plastics Coatings Rubber Other
Red 38 75 25
Red 41 . 99 1
Orange 13 45 45 5 5
orange 15 100
orange 16 30 30 6 20 14
Orange 34 100
Yellow 12 97 3
Yellow 13 70 8 7 15
Ye llow 14 60 7 1 30 2
Yellow 17 50 25 25
Yellow 55 70 30
Yellow 83 35 25 10 30
Blue 25 4 96
!oj TPI = textile printing ink.
7-19
-------
~
The percentage distribution for Yellow 17 is for 1978. Prior to that
year, the distribution was printing ink, 40%; plastics, 30%; and coatings,
30%. Aside from the use of the yellow pigments in the printing ink industry,
the percentage application in each area remained essentially the same from
1975 to 1978. In the printing ink industry, yellows have been extensively
employed as a replacement for chromes. In addition, a considerable amount
of interchanging between the various diarylide yellows has also occurred.
It would be very difficult to chronicle the interactions between the various
yellow pigments during the period 1975 to 1978. Therefore, the percentage
distribution shown in Table 7-7 will be employed in the estimation of losses
in Section 9, but it must be recognized that interactions among the yellow
pigments have transpired.
7-20
-------
SECTION 8
PLASTICS AND RUBBER INDUSTRY
This section discusses the use of pigments by the plastics and rubber
industries. The pigments employed to color plastics and rubber and the types
of resins colored are identified. Estimates of the quantities of pigments
consumed by type of resin and total pigment loss (by compounding process)
for each resin are estimated for 1975 through 1978.
INDUSTRY OVERVIEW - PLASTICS
Total plastics sales for the years 1975, 1976, 1977, and 1978 were 23,521
x 106, 29,168 x 106, 31,059 x 106, and 33,995 x 106 Ib, respectively (Modern
Plastics, 1976-1979).
Nine resins were identified that employed, in varying degrees, the pig-
ments Reds 38 and 41, Oranges 13 and 16, and Yellows13, 14, 17, 55, and 83
(Modern Plastics Encyclopedia, 1978-1979). These resins are ABS, nylon,
polyester, low density polyethylene (LDPE), high density polyethylene (HOPE),
polypropylene, polystyrene, polyurethane, and polyvinyl chloride. There
are two types of polyesters: thermoplastic and thermoset. In this report,
the data have been limited only to the thermoset. These resins comprised
~76% of the total plastics production in 1975, ~77% in 1976, and ~80% in
1977 and 1978. Table 8-1 presents data for total production and production
of colored resins for each of the nine resins during 1975 through 1978.
A brief discussion of each resin and the pigments used in the colora-
tion of that resin is presented in the following paragraphs.
ABS
ABS (acrylonitrile, butadiene, and styrene) is a basic three monomer
system that can be tailor-blended to meet a variety of specifications and
as such can be used in a wide spectrum of applications. Red 38 and Yellow
13 are the most commonly used pigments while Yellows 14 and 17 arid Orange
13 find minor usage.
ABS resins can be processed by all techniques common to thermoplastics
although approximately 93% of the processing involves molding or extrusion
(Modern Plastics Encyclopedia, 1978-1979). ABS is slightly hygroscopic,
and drying for 2 to 4 hr at approximately 80°C is required prior to molding
or extrusion.
8-1
-------
TABLE 8-1. PRODUCTION OF SELECTED RESINS, 1975-1978
Quantity (million pounds)
1975 1976 1977 1978
Resin Total Colored Total Colored Total Colored Total Colored
Thermoplastics
ABS 644 419 931 705 1,058 765 1,120 804
:-Iylon 144 (22) 209 (33) 249 (38) 271; (40)
237~/
PVC 3,749 2,931 4,637 3,813 5,243 3,967 5,770 4,210
LDPE 4,736 2,041 5,788 2,698 6,502 2,903 7,025 3,092
HDPE 2,311 1,807 3,124 2,270 3,565 2,374 4,084 2,515
Polypropylene 1,899 1,280 2,597 1,838 2,703 1,871 2,957 1,977
Polystyrene 2,282 1,984 2,655 2,535 2,796 2,601 3,027 2,964
Thermosets
Urethane 1,354 (68) 1,627 (80) 1,733 (87) 1,852 (93)
Polyester/alkyd -1.11:.. ~ ~ (240) ~ ~ ~ ~
Total 17,890 10,740 22,520 14,210 24,890 14,870 27,260 15,980
% of total plastic
production 76% 77% 80% 80%
Source:
~Iodern Plastics, September 1977-1978 and January 1977-1978; MRI estimates are shown in
parentheses.
~/
Industry source.
8-2
-------
Extruded sheet ABS can be thermoformed by heat and pressure/vacuum.
The sheet may be embossed or have a laminate applied as the sheet passes
through calendering/cooling rollers. Processing temperatures of 195 to 233°C
are normally employed.
Nylons
Nylons are any long-chain synthetic polymeric amides with the amide
group recurring as an integral part of the polymer chain. Yellows 14 and
17, and to a lesser extent Yellow 13, are the diarylide pigments used in
nylons.
Nylon 6/6 and Nylon 6 are general purpose resins which are offered in
a wide range of formulations and properties. Both resins can be processed
by injection molding or extrusion. According to a major nylon manufacturer,
industry data indicate that the combined consumption of Nylons 6/6 and 6
accounted for approximately 84% of total nylon consumption in 1978 (134 x
106 Ib of Nylon 6/6 and 66 x 106 Ib of Nylon 6).
Nylons 6/10 and 6/12 are
tion characteristics and are
characteristics are required.
prevalent processes by which
produced.
specialty materials with low moisture absorp-
used in applications where stringent design
Injection molding and extrusion are the most
products containing Nylons 6/10 and 6/12 are
Nylons 11 and 12 are also considered specialty nylons. Like Nylons 6/10
and 6/12, they possess low moisture absorption characteristics. These nylons
are mainly used in extrusion, fluidized bed, and electrostatic coating op-
erations. According to an industry source, 1978 consumption of Nylons 6/10,
6/12, 11, and 12 was 7 to 8 million pounds.
All nylons are naturally hygroscopic (Modern Plastics Encyclopedia,
1978-1979). If supplied in moisture-proof packages, the nylon can be directly
processed. Nylon resins supplied in open packages or regrind (waste resin
processed by reuse) are dried in a vacuum or dehumidifying oven at about
80°C for 3 hr to decrease the moisture content to less than 0.3%.
The 1978 consumption statistics for the nylons varied somewhat accord-
ing to the source. A trade publication (Modern Plastics, see Table 8-1)
stated that 271 million pounds were consumed but an industry source esti-
mated that 237 million pounds were sold domestically in resin form in 1978.
The industry data will be used in this discussion.
Polyester/Alkyd
Alkyd molding compounds are thermoset materials produced by mechani-
cally mixing polyester resins, cross-linking monomers, catalysts, mold re-
lease agents, mineral fillers, and fibrous reinforcements. These materials
are supplied in three forms: a free-flowing granular form used where low
impact strength is required; an extruded form supplied as preweighed logs
or continuous rope used where medium impact strength is required; and bulk,
where compression molding produces parts requiring high impact strength.
8-3
-------
1,_-
Polyester alkyds exhibit good dimensional stability and dielectric proper-
ties, which makes them especially useful in a wide range of electrical appli-
cations.
Granular and extruded forms of polyester can be compression, transfer,
or injection molded. When compression or transfer molding the granular form,
a preforming operation is normally required. Since the extruded material
is not free-flowing and cannot readily be fed by a continuous process, special-
izedmachinery is required to injection mold this resin. The bulk form is
normally compression molded.
Of the pigments under consideration, only Orange 16 is employed in any
extent with polyester/alkyds. Minor usage is found for Red 38, Orange 13,
and all of the yellows.
Polyethylene
The complex reactions by which polyethylene is produced result in the
availability of hundreds of different compounds with widely different prop-
erties. Polyethylene production represents> 30% of the total plastic resin
market. LDPE is normally produced in autoclaves or tubular reactors with
reaction pressures of up to 50,000 psi and temperatures up to 300°C. HOPE
is produced by several low pressure polymerization processes; solution and
slurry processes using Ziegler or Phillips-type catalysts are the two major
methods. A gas-phase process is gaining increased importance; the process
works by continuously feeding gaseous monomer and a catalyst to a fluidized
bed reactor at reaction pressures of only 100 to 300 psi and temperatures
of ~ 100°C (Modern Plastics Encyclopedia, 1978-1979).
Polyethylene products can be fabricated by every processing method used
for thermoplastics, but blow-molding, injection molding, and extrusion account
for the bulk of production.
For LDPE, Orange 13 and Yellows 14 and 17 are the common pigments.
There is minor usage for Reds 38 and 41, Orange 16, and Yellows 13, 55, and
83. In HOPE, Orange 13 and Yellow 17 are widely used, and Orange 16 and
the remaining yellows find minor usage.
Polypropylene
Polypropylene is a thermoplastic consisting of an ordered arrangement
of repeating propylene monomer units in a chain-like configuration. A strip-
ping process at the end of the polymerization cycle is used to reduce an
amorphous portion of the product (~ 10%) which, when present, has a negative
effect on physical properties. Processing techniques widely used with poly-
propylene include extrusion and injection molding.
Yellow 17 is the only diarylide pigment with wide application in poly-
propylene. Oranges 13 and 16 along with Yellows 14, 55, and 83 find minor
usage in this resin.
8-4
-------
Polystyrene
General-purpose polystyrene is a transparent, rigid, glass-like homo-
polymer. When modified with rubber, an opaque and impact resistant resin
is produced.
The predominant industrial processes used to produce polystyrene are
mass (or bulk), solution, and suspension free radical polymerization. A
combination of mass and suspension methods may be employed (Modern Plastics
Encyclopedia, 1978-1979).
Polystyrene can be processed by all conventional thermoplastic fabrica-
tion techniques, but injection molding and sheet extrusion are probably the
two most popular methods. Processes exhibiting significant growth include
structural foam molding, injection- and extrusion-blow molding, profile ex-
trusion, and coextrusion.
Only Orange 13 finds wide usage in polystyrene; Red 38 and all of the
yellow pigments find minor usage.
Polyurethanes
Polyurethanes, also commonly called urethanes, are made
reaction of an isocyanate and a polyol. Flexible foam, rigid
tomers comprise the three broad groups of urethanes.
by chemical
foam, and elas-
Most flexible foam employs toluene diisocyanate (TDI); less commonly,
polymethylenepolyphenyl isocyanate (PMPPI) and polyethers. Continuous lines,
which produce slab flexible foam, are the most common manufacturing process.
Flexible foams produced by this method are the low density and intermediate
density foams. High resilience (RR) foams are produced by filling hot-cure
foam with up to 50% clays, silica, and calcium carbonate.
Rigid foams include isocyanurates as well as urethane products. Appli-
cations are mainly for insulation products. In addition, the foams can be
sprayed, poured in place, frothed, laminated, or foamed into buns which are
cut into broadstock. Orange 13 and Yellow 14 are widely used in polyurethane;
Red 38 and the remaining yellows (13, 17, 55, and 83) find minor usage in
this resin.
Polyvinyl Chloride
Polyvinyl chloride (PVC) is a versatile, widely used polymer finding
application in areas where requirements range from very soft and flexible
to very rigid. Polyvinyl chloride is manufactured by four basic polymeri-
zation processes: suspension, solution, emulsion, and mass t'or bulk).
Major additives used in compounding PVC are heat stabilizers, lubricants,
processing aids, impact modifiers, plasticizers, fillers, and pigmentation
systems.
8-5
-------
PVC resins are available as pellets, powders, or in liquid dispersions.
Powders or dry-blends are normally compounded through the use of ribbon blend-
ers or high-intensity mixers. Optimum mixing is achieved by varying the
time and temperature at which additives are introduced. The powder or dry-
blend can be used directly or compounded into pellets. In the compounding
step the powder or dry-blend is transformed into a melt by heat and mastica-
tion and then pelletized.
Liquid forms include plastisols and organosols. Dispersions of homo-
polymers and vinyl acetate copolymers of vinyl chloride in plasticizers are
termed plastisols; organosols are plastisols containing a volatile diluent
necessary to lower the paste viscosity without increasing the plasticizer
level. Pigments are added to a plastisol in a predispersed pigment--
plasticizer paste prepared on a three roll paint mill.
The majority of the PVC is processed by extrusion, injection molding,
blow molding, and calendering. Powder coating and liquid processing are
less commonly used processes.
Numerous diarylide pigments find wide usage in both flexible and rigid
PVC. Yellows 17, 55, and 83, and Oranges 13 and 16 are widely used in both
types of PVC. In addition, Red 38 and Yellow 13 are widely used in flexible
vinyl but find only minor usage in the rigid vinyl. Red 41 and Yellow 14
find only minor usage in either form of PVC.
PIGMENT CONSUMPTION - PLASTICS
Nine of the diarylide pigments under study are used in the plastics
industry. These pigments were delineated in the previous subsection; esti-
mated consumption of each pigment for 1975 through 1978 is presented in
Table 8-2.
The degree of application for each of these pigments with respect to
specific resins was discussed in the previous subsection.
Colorant Addition
Mixing and compounding are the principal stages in plastics production
during which additives, such as pigments, are incorporated into the resin.
Some resins such as polyethylene and polypropylene use only small amounts
of additives and, therefore, have no separate compounding stage. The addi-
tives are usually incorporated into the resin during an extrusion/compounding
operation subsequent to the reaction process (Modern Plastics Encyclopedia,
1978-1979). Typical machines for this operation are continuous or batch
internal mixers and single or twin-screw extruders. Other resins are com-
pounded during a separate operation.
There are a variety of compounding machines including internal mixers,
Banbury-type mixers, screw extruder (single or twin-screw), and various com-
binations of mixers and extruders.
8-6
-------
1------
!
TABLE 8-2. ESTIMATED CONSUMPTION OF PIGMENTS IN THE PLASTICS INDUSTRY
Quantity (1,000 1b)~/
Pigment 1975 1976 1977 1978
Red 38 (143-146) 154 154 (158-161)
Red 41 (40-60) (40-60) (40-60) (40-60)
Orange 13 99 121 108 108
Orange 16 113 143 132 140
Yellow 13 13 32 40 42
Yellow 14 130 210 227 219
Yellow 17 125 230 301 343
Yellow 55 (15-18) (15-18) (27-33) (42-48)
Yellow 83 (158-183) (216-240) (230-280) (277-327)
Total 842-893 1,161-1,208 1,249-1,325 1,369-1,448
~/
Quantities of 100% pigment derived from Tables'7-3 and 7-7. Values in
parentheses are based on MRI estimates; all others are based on ITC data.
Diarylide pigments may be added to the resin in basically two forms:
color concentrates or dry pigment. The dry pigment is added directly to a
resin during the additive blending process. In a color concentrqte, the
pigment is predispersed in a medium such as the resin itself. Typically,
35 to 50% of the color concentrate is pigment. The ratio of the weight of
the final colored resin to the weight of the concentrate is called the let-
down ratio. This ratio usually ranges from 20:1 to 100:1, which means the
concentration of pigment in the final resin ranges from 0.35 to 2.5% (Modern
Plastics Encyclopedia, 1978-1979). Concentrates are usually supplied in
pellet form but may also be supplied in flake form.
Pigment Usage
Contacts with industry representatives (pigment manufacturers and plastic
formulators) and literature searches failed to provide the data necessary
to complete a breakdown of specific pigment consumption in individual resins.
In the absence of necessary data, several assumptions were made in order to
derive estimations for specific pigment consumption in each of the nine
resins.
One assumption is that approximately 90% of the total quantity of pig-
ment was consumed in those resins for which the pigment found wide usage and
10% was in those resins for which the pigment had only limited usage. As an
example, Yellow 14 is widely used in the following resins: nylon, LDPE, and
8-7
-------
polyurethane. It finds limited usage in ABS, polyester/alkyds, HDPE, poly-
styrene, polypropylene, and PVC. Thus, 90% of the total quantity of Yellow
14 consumed in plastics (approximately 219,000 Ib in 1978) is used to color
nylon, LDPE, and polyurethane; and 10% is used in ABS, polyester, HDPE, poly-
styrene, polypropylene, and PVC. The quantity of each colored resin produced
annually was presented in Table 8-1. From these data, the quantity of each
pigment utilized in the individual resins was prorated on the basis of either
wide or limited usage and the total quantity of colored resin manufactured
for each year. These data are presented in Tables 8-3 to 8-6.
The data in these tables assume no bias towards a specific resin. To
use the Yellow 14 example, it is assumed that 90% of the total quantity of
pigment is prorated on a weight basis between nylon, LDPE, and polyurethane
according to the total quantity produced of each of the three resins. The
. same assumption is made for the area comprising 10% of the total consumption.
ESTIMATED LOSSES - PLASTICS
The majority of pigment losses from plastics is associated with the
ultimate disposal of the consumer product. Few data were obtained from the
plastics industry regarding losses of colorants in the resin compounding
stage (i.e., formation of the colored resin). Based on other processing
information, it is estimated that a 1 to 2% pigment loss occurs due to han-
dling and transfer of powdered colorants or concentrates during the com-
pounding of resins.
Estimates of pigment loss during processing were combined with data
for the total quantity of pigment consumed by specific resins (Tables 8-3
to 8-6). The estimated losses (1-2%) of diarylide pigment due to handling
and transfer of powdered colorants or concentrates from each resin for 1975
through 1978 are presented in Table 8-7.
Information was obtained from the plastic industry trade association
for estimated resin losses during processing by plastics fabricators. Resin
losses represent an additional source of pigment loss although the pigment
has been incorporated into the resin and is not lost as the pure colorant.
These losses range from 5 to 15% for thermoplastics and from 10 to 30% for
thermosets. Of the resins listed in Table 8-1, all are thermoplastics ex-
cept for polyester/alkyd and urethane. Fabrication waste reuse for thermo-
plastic production varies from company to company and from operation to op-
eration. Unless the scrap thermoplastic is captively reprocessed or dis-
carded because of contamination or too small a volume, the waste plastic
from primary production and fabrication is acquired by scrap dealers or
reprocessors. Reprocessing of thermoplastics may entail regrinding, wash-
ing, or reblending the scrap material. The reprocessed material is either
sold or returned to the client in the reground form or converted to colored
or black pellets. For thermoset wastes, those materials, which can be re-
melted, are reused. Those wastes, which cannot be remelted, have tradi-
tionally gone to disposal (SPI, 1979).
8-8
-------
TABLE 8-3.
ESTIMA': ~) AMOUNT OF PIGME~' ~S CONSUMED BY RESIN C .975)
(Quantity in 1,000 1b)~/
Po1yester/ Vinyl
Pigments ABS Nylon alkyd LOPE HOPE PP Po1YRtyrene Urethane Flexible Rigid Comhf.ned Total
Red 38 31-31. 7 0.5 4.9-5.1 4.8-4.9 0.2 97.7-99.7 3.9-4.0 143-146
Red 41 16.4-24.6 23.6-35.4 40-60
Yellow 13 3.6 0.05 0.6 0..5 0.6 0.02 13.7 19
Yellow 14 0.6 1.2 0.3 112.1 2.8 1.9 2.9 3.7 4.4 130
Yellow 17 2.1 0.3 0.9 28.3 25.3 17.9 9.2 0.3 40.8 125
Yellow 55 0.05 0.4-0.5 0.4 0.3 0.4-0.5 0.01 13.5-16.2 15-18
Yellow 83 0.4-0.5 4.4-5.0 3.9-4.5 2.7-3.1 4.2-4.9 0.1 142.3-164.9 158-]83
Orange 13 0.2 1.1 20.2 18.7 7 20.6 0.6 30.5 99
00
I 16 6.3 4.5 4 2.8 95.4 113
\0 Orange
Total 37.5-38.2 1.5 9.6-9.7 191.8-200.9 55.5-56.1 32.6-33.0 42.7-43.6 4.9 111.4-113.4 3.9-4.0 350.5-387.6 842-893
:!/ Quantities in terms of 100% pigment.
Source: Estimates based on Modern Plastics, September issues 1976-1978 and January iRsues 1977-1979; and Modern Plastics Encyc10pedi~. 1978-1979. Data
from Tables 4-3 and 4-6.
-------
TABLE 8-4. ESTIMATED AMOUNT OF PIGMENT CONSUMED BY RESIN (1976)
(Quantity in 1,000 1b)~/
-- -"---------- ------
P01y~ster/ Vinyl
P 19ment ABS Nylon alkyd LOPE HDPE PP Polystyrene Urethane Flexible Rigid Combined Total
Red 38 40.1 0.5 5.5 5.6 0.2 97.5 4.6 154
Red 41 16.6-24.8 23.4-35.2 40-60
Ydlow 13 7.3 0.01 0.1 1.1 0.9 1.0 0.03 21.6 JL
Y~ llO\/ 14 1.3 2.2 0.4 181. 4 4.2 3;5 4.7 5.4 7.0 210
Yellow 17 4.5 0.6 l.5 52.6 44.2 36 ]6.1 0.6 74.1 230
Yellow 55 0.05 .0.5-0.6 0.4-0.5 0.3-0.4 0.2 0.01 13.6-16.3 15-18
Yellow 83 U.7 6.8-7.6 5.7-6.3 4.6-5.2 2.6-2.9 0.2 195.5-217.2 216-240
Ocang~ 13 3 25.8 21. 7 8. 24.2 0.8 36.4 121
Orange 16 7.5 5.6 4.8 3.9 121.1 143
00
I
I-' To ta 1 56.2 2.8 11.8 2Y5.9-J05 81.9- 56.3-57 54.4-54.7 7.2 llY.l 4.6 47l.1-507.3 1,161-1,208
o 82.6
'}../ Quantities in tenus of 100% pigm~nt.
Source: Estimates based on Mod~rn Plastics, September issues 1976-1978 and January issues 1977-1979; and Modern Plastics Encyclopedia, 1978-1979.
-------
TABLE 8-5. ESTIMATED AMOUNT OF PIGMErrS CONSUMED BY RESIN (1977)
(Quantity in 1,000 1b)!.
Po1yesterl Polystyrene Vinyls
Pigment ABS Nylon alkyd LDPE HDPE PP (combined) Urethane Flexih1e Rigid Combined Total
Red 38 41.6 0.5 5.6 5.0 0.2 97 4.2 154
Red 41 17-25.2 23-34.8 40-60
Yellow 13 7.2 0.01 0.1 1.1 0.9 0.9 0.03 20 10
Yellow 14 1.5 2.6 0.5 195.7 4.5 3.6 5 5.9 7.7 227
Vellow 17 6 1 2.2 70.5 57.6 1.5.5 21.1 0.5 96.5 301
Vellow 55 0.1 0.9-1.1 0.07-0.9 0.6-0.8 0.4-0.5 0.03 24.3-29.7 27-33
Vellow 83 0.7-0.8 7.8-9.5 6.4-7.8 5.0-6.2 2.8-3.4 0.2-0.3 207-252 230-280
Orange 13 2.8 0.9 23.5 19.1 22 0.7 32.1 108
Orange 16 7.3 5.4 4.4 3.5 111. 4 132
Total 59.1 3.6 12.3-12.4 327.5- 93.6- 65.2- 57.2-58 7.7-7.8 117 4.2 502-564.2 1,249-1,325
337.6 95.2 66.6
00
I
I-' !!f QuantitIes in terms of 100% pigment.
I-'
Source: Estimates based on Modern Plastics, September issues 1976-1978 and January iaauea 1977-1979; and MO,d,~r,! ,P,lastics Encvc10pedia,
1978-1979.
-------
ex>
I
t-'
N
-----------
Pigments
Red 38
Red 41
Yellow 13
Yellow 14
Yellow 17
Yellow 55
Yellow 83
Onmge 13
Orange 16
ABS
42.4-43.2
10.4
1.2
6.6
2.9
Total 63.5-64.3
Nylon
TABLE 8-6.
Poly~~terl
Alkyd
0.5
0.01
2.1
0.5
ESTIMATED AMOUNT OF PIGME~TS CONSUMED BY RESIN (1978)
(Quantity in 1,000 1b)~
------_. -
----------.. ----~- '-.------- -'--+---------_--_--4_~ --_.__._-------
LOPE
5.6-5.7
]6.4-25.0
0.1
190.0
80."
1.4-1.6
9.3-11.0
23.3
5.7
332.3-342.5
IIDPE
~._-----~---
1.5
1,.3
1>6.2
1.1-1. 3
7.7-9.0
19.0
4.7
101,.5-106.0
PI'
3./,
51.8
0.9-1.1
6.0-7.1
7.0
3.7
72 .8-74.1
PolyRlyrpne
(~omb.ln"d )
5.3-5.5
1.1,
5.2
24.7 .
0.6
3.6-4.3
22.4
63.2-64.1
Urethane
0.2
(), 01,
5.0
0.8
0.05
0.3
0.7
7. I
---.----- Vln:tLs___--_----
Flexible Rig I.d Combl.ned
99.8-101. 7
4.2-1,.3
--~--_.
Tot,,1
-------- --- ---.
]51\-11>1
23.2-35.4
7.2
109.6
37.8-43.2
249.3-294.4
31.8
1l7.9
576.8-639.5
4n-~o
1,2
719
Y,3
42 -."8
277-327
108
140
1,369-1,448
~I Quantities in terms of 100% pigment.
Source: Estimates based on Modern Plastics, Septt'mber issues .1976-1978 and January issues 1977-1979; and Modern Plastics Encyclopedia, 1978-1979.
0.5
2.3
0.1
0.8-1.0
1.0
8.0
2.6
13.2-13.1,
28.6
128.4-130.3 4.2-4.3
-------
TABLE 8-7. ESTIMATED PIGMENT LOSS IN RESIN COMPOUNDING STAGE
Quantity (1,000 1b)
1975 1976 1977 1978
Total pigment used!/ 842 -893 1,161-1,208 1,249-1,325 1,369-1,448
Res in - thermoplastic
ABS 0.4-0.8 0.6-1.1 0.6-1.2 0.6-1.3
Nylon 0.02-0.03 0.03-0.06 0.04-0.07 0.03-0.05
LDPE 1.9-4.0 3.0-6.1 3.3-6.8 3.3-6.9
HDPE 0.6-1.1 0.8-1.7 0.9-1.9 1.0-2.1
Polypropylene 0.3-0.7 0.6-1.1 0.7-1.3 0.7-1.5
Polystyrene 0.4-0.9 0.5-1.1 0.6-1.2 0.6-1. 3
Polyvinyl chloride 4.7-10.1 5.9-12.6 6.2-13.7 7.1-15.5
Total loss 8.3-17.6 11.4-23.8 12.3-26.2 13.3-28.7
Total in resin 810-870 1,118-1,178 1,203-1,293 1,320-1,414
Resin - thermoset
Polyester/alkyd 0.1-0.2 0.1-0.2 0.1-0.2 0.1-0.3
Urethane 0.05-0.1 0.07-0.1 0.08-0.2 0.07-0.1
Total loss ~/ 0.15-0.3 0.17-0.3 0.18-0.4 0.17-0.4
Total in resin 14.2-14.5 18.7-18.8 19.6-20.0 19.9-20.3
a/
'Q../
See Tables 8-3 to 8-6.
Percentage losses are as follows: 1975 (1.0-2.1%); 1976 (0.9-1.6%);
1977 (0.9-2.0%); and 1978 (0.8-2.0%).
8-13
-------
Estimates of the total quantity of pigment in resin developed in Table
8-7 were combined with the percentage resin losses stated by SPI to provide
a basis for the estimated pigment losses as a result of resin losses. These
data are shown in Table 8-8.
TABLE 8-8.
ESTIMATED PIGMENT LOSSES VIA RESIN PROCESSING
1975
Quantity (1,000 1b)
1976 1977
1978
. a/
Total pigment in reS1n-
Thermoplastic
Thermoset
810-870
14 .2 -14 . 5
1,118-1,178
18.7-18.8
1,203-1,293
19.6-20.0
1 , 320 -1 , 414
19.9-20.3
Estimated pigment losses
Thermoplastic (5-15%)
Thermoset (10-30%)
41-131
1-4
56-177
2-6
60-194
2-6
66-212
2-6
Total loss
42-135
58-183
62 -200
68-218
Total quantity of pigment in
finished produc t
689-843
954-1,139
1,023-1,251
1,122-1,366
a/
See Table 8-7.
INDUSTRY OVERVIEW - RUBBER INDUSTRY
Although rubber related industries can be divided into natural and syn-
thetic rubber users, it is more advantageous for the purposes of this discus-
sion to classify the industry according to the Standard Industrial Classifica-
tion (SIC) codes. These are presented in Table 8-9.
The pigments under consideration in this report are probably not employed
by industries in at least two of the five SIC codes listed. Tire and inner
tube manufacturing (SIC 3011) uses small a~ounts of white pigment mainly
titanium oxide, for the white walls on automobile and truck tires, but the
remainder of the rubber is black as a result of the carbon black added to
improve some of the physical properties of the finished rubber. Tire manu-
facturers do not use colored (nonblack) organic pigments.
Processes involved in reclaiming rubber (SIC 3031) could lead to degrada-
tion of the colorants and process wastes which may be different from the rest
of the rubber industry; however, most of the scrap rubber used in this industry
results from discarded tires and inner tubes which do not contain any of the
pigments of interest. Therefore, SIC Codes 3011 and 3031 were excluded from
any further consideration in this study.
8-14
-------
1--
TABLE 8-9.
STANDARD INDUSTRIAL CLASSIFICATION (SIC) CODES FOR
RUBBER AND MISCELLANEOUS PLASTIC PRODUCTS
SIC Code
Industry
3011
Tires and inner tubes
3021
Rubber and plastics
footwear
3031
Reclaimed rubber
3041
Rubber and plastics
hose and belting
3069
Fabricated rubber
products, not else-
where classified
Description of products
Pneumatic casings, inner tubes,
and solid and cushion tires for
all vehicles, and camelback,
tire repair and retreading mate-
rials.
All rubber
waterproof
and rubber
and plastics footwear,
fabric upper footwear,
or plastic soles.
Devulcanized, depo1ymerized or
regenerated rep1asticized prod-
ucts from scrap rubber tires,
tubes and miscellaneous waste
rubber articles.
Industrial hose and belts and
garden hoses.
Industrial and mechanical rub-
ber goods, rubber fabrics, and
miscellaneous rubber goods.
Source:
Statistical Policy Division, 1972
8-15
-------
The remaining industries, rubber and plastics footwear (SIC 3021), rubber
and plastic hoses and belts (SIC 3041), and fabricated rubber products not
elsewhere classified (SIC 3069) are the potential areas for the use of diarylide
pigments.
Other considerations for the use of these pigments result from their
higher cost in comparison to the inorganic pigments and the general lack of
lightfastness displayed by some of the diarylide pigments. The primary use
of the diarylide pigments in the rubber industry probably lies in housewares
(e.g., mats for sinks and tubs) and toys, automobile accessories, and other
household, automotive, or recreational products.
Data for 1978 show that 64.4% of all new rubber was used by the tire
segment; no data were available on the amounts of rubber colored by pigments
other than black or white (Rubber World, 1979). One estimate is that less
than 10% of the rubber used is colored (Bleaskiewcz, 1979). If this estimate
is correct, the total quantity of colored rubber would be approximately 700
million pounds. No data were obtained on the percent of rubber colored with
organic pigments or with diarylide pigments. .
RUBBER PRODUCTION PROCESS
The rubber industry is divided into two segments, natural and synthetic
rubber. The rubber production process basically involves obtaining an elas-
tomer by polymerization of compounds or extraction from rubber plants, mixing
the elastomer with other chemicals, forming this mixture into a desired shape,
and curing or vulcanizing to produce a crosslinked thermoset structure. It
is the crosslinked structure which produces the rubber-like qualities.
Natural rubber is extracted from trees as field latex, a dispersion of
small rubber particles in water, which is then processed into either a latex
form or dry rubber.
The synthetic elastomers are produced by polymerizing various monomers
depending upon the specific properties desired in the final product. The
polymerization may take place in an emulsion or in a solvent which leads to
only slightly different steps in removal of the water or solvent. The syn-
thetic rubber maybe utilized as a latex, but most often it is dried and
used as dry rubber. The production of the various types of rubber for 1975
through 1978 is shown in Table 8-10.
Once the elastomer is produced, the next step is compounding, during
which various additives are mixed with the elastomer to impart specific prop-
erties to the finished rubber. Carbon black and other inorganic fillers
and pigments are sometimes added to the rubber; other chemicals added during
compounding include the vulcanizing agents necessary to produce the cross
linkage characteristics of rubbers, accelerator for vulcanization, and anti-
oxidants and antiozonants.
The next step in rubber production is the shaping or molding of the
rubber. The mixture may be molded by three methods: compression, transfer,
8-16
-------
TABLE 8-10. U.S. RUBBER PRODUCTION BY TYPE, 1975-1978
Quantity (x 106 1b)
Type of rubber 1975!!./ 1976~/ 1977~./ 1978!!/
SBR 2,606 2,979 3,252 2,994
Butyl 183 276 329 340
N-type 119 165 161 161
Po1ybutadiene 655 781 796 856
Po1yisoprene 135 163 137 Q/
EPDM 185 302 348 386
Silicone 31 37 53 78
Styrene-butadiene- 29 31 33 43
viny1pyridine
Urethane type 57 82 93 112
Other 637 650 701 902
Total 4,637 5,466 5,905 5,872
~/
1975-1978 production figures were obtained from lTC, 1976a;
lTC, 1977a; ITC 1978a; and lTC, 1979.
'Q/
Included in Other in 1978.
8-17
-------
-0;"
or injection. Compression molding is the most common and the simpLesL.
Transfer molding transfers the rubber from a larger container into the mold;
the method usually produces more waste but also gives better dimensional
control. Injection molding utilizes a screw device which injects the rubber
into a mold. Rubber can also be treated by other processing methods, such
as calendering. After molding, the rubber is vulcanized to cross link the
molecules.
PIGMENT CONSUMPTION - RUBBER
Industry sources estimate that only two of the pigments being considered
in this study are used in the rubber industry. Approximately 2% of the total
consumption of Yellow 14 and about 5% of Orange 13 are employed in the manu-
facture of rubber products. Table 8-11 presents estimated consumption of
these two pigments from 1975 through 1978. Small quantities of other di-
arylide pigments may be used in the rubber industry; however, Orange 13 and
Yellow 14 were the only two pigments specifically identified in this study
and for which consumption data could be reliably estimated.
TABLE 8-11.
CONSUMPTION OF PIGMENTS - RUBBER INDUSTRY
Pigment
Quantity (l~OOO 1b)~/
1975 1976 1977 1978
Orange 13
yellow 14
11
37
13
60
12
65
12
63
a/
Quantities of 100% pigment derived from
Tables 7-3 and 7-7.
ESTIMATED LOSSES - RUBBER
Although other losses occur during the production of elastomers, the
loss of pigment begins with the compounding of the rubber. One of the pri-
mary considerations in the determination of losses during compounding is
whether the pigment is added in a dry form or as a masterbatch. A master-
batch consists of a quantity of pigment dispersed in an equal amount of dry
rubber, resin, or plasticizer. Although an estimated 45% of the pigment
used by the rubber industry is purchased as dry pigment (Greer, 1979), the
pigment will almost always be mixed by the rubber producer to form a master-
batch (Bleaskiewcz, 1979). Reasons for this include easier measurement of
an exact quantity of pigment, less pigment waste, and less dust to contami-
nate the compounding machines.
8-18
-------
It is estimated that little pigment loss (~ 0.1-0.3%) would occur as
dust during the actual compounding stage. During production of a master-
batch, pigment losses occur as dust from handling and transfer of the pig-
ment. Because specific information could not be identified concerning the
magnitude of these losses, an estimated loss of 0.1 to 0.5% has been assumed
based on similar procedures in the coatings industry (see Section 10). The
dust would likely be collected as floor sweepings or in collection contain-
ers of air filter devices. These solid wastes are disposed by landfilling
(Snell, 1978).
The cleaning wastes in compounding, shaping, and molding are assumed
to be small. The compounding equipment may be cleaned with a solvent or by
the use of excess dry rubber called clean-out rubber. The clean-out rubber
is used repeatedly until it becomes too contaminated for further usage. At
this point the contaminated clean-out rubber is landfilled with the rest of
the rubber waste.
Excess rubber is produced from shaping, molding, and finishing. Losses
due to uncured scraps from the shaping and molding steps are estimated to
be 4.2% for the rubber footwear industry and 2.2% for the rubber and plastics
hose and belting industry (Snell, 1978). Although a composite figure could
be calculated for the loss of uncured rubber stock, a range of 2.2 to 4.2%
loss was utilized due to the very small total consumption of pigments in
this industry. The waste from uncured rubber stock is usually landfilled.
Uncured scraps of rubber are also created in the finishing steps. In
general, these scraps result from flash trimmings (excess rubber in molds),
miscellaneous scraps, and rejects. Estimates of these wastes range from 1
or 2% to approximately 30% (based on Snell, 1978). The general practice is
to landfill this waste.
An estimate of the total quantity of pigment loss in the rubber indus-
try is presented in Table 8-12 for 1975 through 1978.
TABLE 8-12.
ESTIMATED PIGMENT LOSS IN THE RUBBER INDUSTRY
Quant itv (1,000 1b)!!..1
1975 .!ill. !ill ~
Total Pigment in Rubber£/ 48 73' 77 75
Estimated Pigment Losses
Compounding (0.1-0.3%) 0.05-0.1 0.07-0.2 0.08-0.2 0.08-0.2
Masterbatch (0.1-0.5%) 0.05-0.2 0.07-0.4 0.08-0.4 0.08-0.4
Shaping, Molding, and
Finishing (2.2-4.2%) 1.1-2.0 1.6-3.1 1.7-3.2 1.7-3.2
Total Loss 1.2-2.3 1. 7-3. 7 1.9-3.8 1.9-3.8
Total Quantity of Pigment
in Rubber 45.7-46.8 69.3-71.3 73.2-75.1 71.2-73.1
~/ Quantities in terms of 100% pigment.
£/ See Table 8-11.
8-19
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SECTION 9
PRINTING INKS
Printing inks, especially the process inks used in color printing, rep-
resent the major industrial use of the pigments based on 3,3'-dichlorobenzidine
(DCB) or 3,3'-dimethoxybenzidine (DMOB). Approximately 11.5 million pounds,
or 76% of all the diarylide pigments produced in 1977, were consumed in the
form of printing ink. A detailed examination of the patterns of pigment
usage and losses to the environment associated with the production and use
of printing inks will serve to place in perspective the distribution of
diarylide compounds and routes of entry into various media.
INDUSTRY CHARACTERISTICS
The ink industry (SIC 2893) comprises an estimated 460 to 500 manufactur-
ing establishments operated by approximately 200 companies. In addition,
there are estimated to be 100 captive ink manufacturing sites within printing
companies who manufacture inks for their own use. Current data are not avail-
able on the ink production activity within SIC 27, Printing and Publishing.
The 1972 Census of Manufactures placed the number of ink manufacturing plants
at 407 establishments having a total of 9 ,600 production employees. The
1977 Census reported 452 establishments, of which 158 had more than 20 em-
ployees.
The survey conducted in 1978 (Burns and Roe, 1979a) obtained responses
from 460 ink manufacturing sites that reported production and employment on
the basis of 1976 operations. The data obtained through this survey are
considered by MRI adequate to reflect the current characteristics of the
industry.
There are a large number of small ink manufacturing plants. Forty-two
percent of these plants have fewer than 10 employees; and 71%, fewer than
20 employees. However, these smaller plants accounted for only 25.5% of
ink shipments in 1972. The 130 plants (28.3%) having more than 20 employees
shipped 75% of the total ink sold.
A moderate degree of concentration is found in ink manufacture. Thir-
teen companies operate 51% of all plants, and six larger companies (Borden,
Inmont, Sun Chemical, Flint Ink, Sinclair and Valentine, and Kohl and Madden)
account for 37% of all ink manufacturing plants. Ink manufacturing establish-
ments are generally located in metropolitan areas where large volumes of
printing are performed. Slightly over 50% of all large ink plants (> 30
employees) are located in the states of New Jersey, Illinois, Ohio, and
9-1
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California. Sixty-four percent of all plants are branch plants of a multi-
ple plant company (Burns and Roe, 1979a).
Tot41 ink shipments for 1977 were valued at $960.2 million, up 93% over
1972 shipments. . The volume of ink produced in each plant ranges from less
than 200,000 Ibfyear to over 3 million pounds annually (Table 9-1).
TABLE 9-1.
1976 PRODUCTION VOLUME IN POUNDS
Volume pounds Plants Percent of plants
Under 200,000 121 28.8
200,000 to 500,000 76 18.1
500,000 to 1 million 79 18.8
1 million to 3 million 75 17.9
Over 3 million 69 16.4
Source:
Burns and Roe, 1979a.
Due to the increasing demand for commercial printing, the physical output
of the printing ink industry has been growing substantially. Present data
are not adequate to characterize the rate of growth for different types and
classes of printing inks. . The disttibution of shipments of ink in 1977, by
type of ink, is given in Table 9-2.
TABLE 9-2.
1977 INK SHIPMENTS BY TYPE OF INK
Ink type
Value million dollars
Percent of shipments
Letterpress
Lithographic
Gravure
F1exographic
Other types
Not classified
119.6
281.2
194.5
194.7
61.3
108.9
12.5
29.3
20.3
20.3
6.4
11.3
Total
960.2
100.0
Source:
Census of Manufactures, 1977.
9-2
-------
. There have been, and will continue to be, major shifts among the types
of printing processes employed and the kinds of ink used. Gravure and flexo-
graphic ink output has been growing rapidly in recent years. Lithography
has grown steadily and currently represents 56% of all commercial printing.
Letterpress (except for flexography) has continued its downward slide, even
in long run daily newspapers. According to one industry source, the antici-
pated changes among printing processes are shown in Table 9-3. Gravure,
lithography and flexography will account for 89% of press operations by 1990,
while traditional letterpress printing will decline by over two-thirds.
TABLE 9- 3.
DISTRIBUTION BY PRINTING PROCESS
Process 1977 1980 1990
Letterpress 32% 25% 10%
Flexography 11% 12% 15%
Lithography 38% 40% 40%
Gravure 14% 17% 25%
Screen printing and 5% 6% 10%
other processes
Source:
Bruno, 1978.
INK PRODUCTION BY TYPES
The wide variety of printing inks employed ranges from newspaper inks
to specialized electrostatic jet printing inks. However, most of the inks
produced for printing can be classified into two viscosity ranges and four
main types of inks:
Paste Inks
Fluid Inks
Letterpress
Lithographic
Flexographic
Gravure
Letterpress inks are viscous, tacky, resinous pastes, typically made
using vehicles that are oil and varnish based, and solvent thinned. Drying
occurs by the oxidation of the varnish type vehicle.
Lithographic (sometimes called offset inks) are viscous inks with an
oleoresinous, varnish-based vehicle, generally thinned with organic solvents.
Because lithographic inks are applied in thinner films, the pigment content
9-3
-------
is higher than in letterpress inks, and pigments of high tinting power and
good color saturation are employed. Lithographic inks are designed to be
water resistant and to run in the presence of water since a water film is
used to create the nonimage areas of the printing plate.
Flexographic inks (a subcategory of letterpress printing in which
raised rubber type carries the ink to the surface) are liquid inks which
dry by evaporation of the carrier and by absorption into the substrate.
Both waterborne and solvent vehicles are used in flexography; water inks
are used on absorbent paper, and solvent inks are used on packaging films
and nonabsorbent surfaces.
Gravure inks are liquid inks which dry by evaporation of the solvent
carrier. Three subtypes of gravure inks are recognized. "Publication" inks
used for catalogs and magazines are designed to have superior color charac-
teristics and sharp printing properties. "Supplement" inks used for adver-
tising supplements to newspapers employ less costly pigments and are designed
to perform high speed printing on more absorbent papers. Both publication
and supplement inks have fairly well standardized properties. "Packaging"
inks, the third subtype, are much more varied and are formulated individually
for printing on films, foils, coated papers, and the variety of materials
used in the packaging field (Welch, 1979).
Table 9-2 gave the relative percentage of each of the main types of
ink used in 1977 in terms of value of shipments. Letterpress inks are less
costly than the other three types of ink. Although 32% of all printing is
performed with letterpress inks, the value of the ink represents less than
13% of total dollar volume of all printing inks. Lithographic inks represent
30% of the total value, and because ink "mileage" is greater with litho-
graphic inks (thin ink films are laid down), nearly 40% of all printing is
run on lithographic presses.
The Gravure Technical Association survey team reported (Maida, 1978)
that a conservative estimate of gravure ink consumption in 1976 could be
broken down as follows:
Subtype
Million pounds
Value (million dollars)
Publication inks
Packaging and specialty
Total
180
150
330
90
120
210
Most gravure printing is in color; the distribution of ink colors are:
black, 32.0%; magenta (red), 23.5%; cyan (blue), 25.9%; and yellow, 48.9%.
A large proportion of the diarylide yellow pigments are used in the produc-
tion of gtavure inks. '
Other types of ink such as screen process printing inks, metallic inks,
magnetic inks, virkotype and electrostatic jet printing inks are very diverse
and specialized. Ink experts generally agree that specialty inks do not
consume significant quantities of the diarylide organic pigments. Textile
9-4
-------
printing inks, although sometimes considered as part of the printing ink
field, were discussed in the textile dyeing and printing section.
MANUFACTURE OF PRINTING INKS
Virtually all printing inks are produced in batches--sometimes large
batches exceeding 10,000 Ibj more often in batches ranging from 100 to 500
Ib at a time.
The essential steps in the production of printing inks generally include:
1.
Weighing the ingredient for a batch into a mixing tub.
2.
Dispersing (grinding) the pigments into the vehicle.
3. Adjusting the properties of the ink to final specifications (e.g.,
adding thinners, additives, tinting colors, and blending to uniformity).
4.
Packaging for delivery to the user.
5.
(Sometimes) cleanup of equipment.
It is convenient to discuss the handling of diarylide pigments, the
range of losses of ink and pigment during production, and the levels of pig-
ment discharged to environmental media in terms of these basic steps in pro-
duction.
Pigment Usage
For purposes of detailing the fate and distribution of pigments based
on DCB or DHOB, only the organic pigments used and the types of vehicles
employed--paste or liquid, solvent or water-based--will be considered.
The diarylide pigment yellows and oranges are used extensively in the
manufacture of printing inks. For many years the diarylide yellow pigments
have dominated the market for organic yellow toners. As early as 1969, di-
arylides accounted for 84% of total U.S. organic yellow pigments (Patton,
1973). By 1978, total diarylide production in the United States had risen
to an estimated maximum of 19.5 million pounds, with the distribution shown
in Table 4-6. Yellow 12 is still the dominant pigment at 11.9 million pounds
(61.0% of all diary1ide pigments). Yellow 14, with an estimated production
of 3.1 million pounds, accounts for 15.9% of all diarylides. Since 1976,
Orange 13 has generally declined in usage, and Yellow 17 has almost doubled
in production volume. The only significant addition since 1969 has been
Yellow 83, which was not reported separately prior to 1976, and had an esti-
mated production volume of 1.2 million pounds in 1978.
Total consumption of diary1ide pigments in printing inks amounted to
an estimated maximum of 15.2 million pounds in 1978. This usage accounted
for 77.9% of all the diarylide pigments under consideration in this study.
Table 9-4 presents the best available industry data regarding printing ink
9-5
-------
TABLE 9-4. ESTIMATED DIARYLIDE PIGMENT CONSUMPTION IN PRINTING INKS
Percent Quantity~/ (1,000 1b)
Pigment in ink!./ 1975 1976 1977 1978
Orange 13 45 99 121 108 108
Orange 16 30 113 143 132 140
Ye llow 12 97 5,907 7,629 8,438 11,506
Yellow 13 70 170 280 260 . 364
Yellow 14 60 1,111 1,800 1,949 1,881
Yellow 17 40 166 307 401
(1975-1977)
50 685
(1978)
Ye 11 ow 55 70 (35-42) (35-42) (63-77) (98-112)
\0 Yellow 83 35 (222-257) (300-335) (322-392) (387-457)
I
0\
Total 7,823-7,865 10,615-10,657 11,673-11,757 15,169-15,253
!./
See Table 7-7.
~/
See Table 7-3; all quantities in terms of 100% pigment.
-------
usage of eight diarylide pigments for the past 4 years. From 1975 through
1978, between 72 and 80% of all pigments of interest to this study (produc-
tion plus imports) were consumed in ink making. The pigment yellows and
some orange pigments are used extensively in inks, whereas the reds, blues,
and certain orange pigments rarely find application in ink production.
The diarylide yellow pigments are of great economic importance in the
printing ink industry. The major reasons for the widespread reliance on
these pigments are the combination of high tinting strength (much higher
than the Hansa yellows, pigments based on substituted anilines), good bleed
resistance, almost perfect chromaticity for color printing, and excellent
printing characteristics. According to industry sources, the 1ightfastness
of Yellows 12 and 14 is only fair, and the rapid growth in consumption of
Yellow 17 and Yellow 83 is partly due to their superior resistance to fading.
SOURCES OF PRODUCTION LOSS
In ~he manufacture of printing. inks, material losses and waste genera-
tion are unavoidable. These sources of losses can be related to the basic
steps in the production of printing ink.
Overall Losses
Many ink makers allow for an "overage" of 4 to 5%; that is, to mix a
batch of 1,000 Ib of finished product, sufficient resins, pigments and other
additives will be employed to produce 1,040 to 1,050 Ib of ink. This is a
generous allowance for production losses and wastage; industry sources state
that actual material lost in production is considerably less than 5% (Sutt,
1979; Barnett, 1979; Gilbert, 1979). Few plants, however, maintain detailed
records of their losses.
Several ink plants were able to supply estimates of typical total produc-
tion losses over the recent past:
Average:
1.5% (1973-1977)
4.0% (1977-1978)
2.6% (since 1970)
3.0% (1974-1976)
2.5% (last 20 years)
2.4% (1977)
2.7 Ib per 100 Ib of ink
These losses typically include all shrinkage from the purchase of raw mate-
rials to shipment of the finished ink. Individual sources of loss of ink
ingredients were considerably more difficult to define; only a few produc-
tion managers were able to estimate the incidence of broken shipping con-
tainers, spillage, off-specification materials not salvageable, clean-up
residues, and end-of-run ink sent to waste.
The extent of production losses are markedly affected by such factors
as batch size, type of ink produced (paste or liquid), the form of pigment
9-7
-------
used (dry toner or flushed color), solvent or water-base vehicle, type of
production equipment, and the frequency and kind of cleaning system used
(Sutt, 1979). Each of the sources of pigment 9r ink loss will be considered
in turn for a typical (medium size) ink plant.
Weigh Station Losses
Dry diarylide toners are most commonly received in 25 or 50 lb plastic-
lined shipping sacks, or in fiber drums. Ink makers estimate that from 1/4
to 1 oz may remain in the folds and crevices of sacks and drums after empty-
ing into a mixing tub (Barnett, 1979; Vathako, 1979). MRI estimates that
approximately 0.05 to 0.125% of organic pigments remain in the original ship-
ping package. The ink industry recognizes that residues in shipping contain-
ers pose one of the biggest sources of material losses (Anon, 1979).
A few ink plants report the use of returnable shipping containers to
reduce raw material losses and minimize contamination. At least one plant
has installed a special "air pallet" system that uses shipping containers
which fluidize finely divided materials to ensure almost complete discharge
of the contents (Anon, 1978a).
Predispersed pigments (flushed colors, dry dispersions, and liquid dis-
persions) are much more widely used in the United States than in other
countries (Patton, 1973). In 1977, only 2,961,000 Ib (or 36.6%) of Yellow
12 or Yellow 14 were sold as dry, full strength color (Anon, 1978b). The
balance was used as flushed colors (49.1%) and as aqueous dispersions, dry
dispersions, or dry extended toner (14.3%). In using flushed colors there
is no dust and little spillage. Usually the shipping containers are rinsed
into the ink batches, so pigment loss in raw material handling is estimated
to be 40% lower than for dry toners (Gilbert, 1979; Vanderhoff, 1979). MRI
estimates that losses are approximately 0.075 to 0.10% of pigment content,
mostly as container residues. .
Losses in Ink Processing and Packaging
Depending on the type of inks being produced, there are several process-
ing steps that generate wastes or pigment losses. Initial pigment dispersion
is accomplished using high speed dispersers, sand mills, or quite commonly,
a three roll mill. High speed, sawtooth dispersion mills can be used in
the mixing tubs and the dispersion head washed into the batch after mixing.
Hence, very little waste is associated with this type of dispersion. A few
older plants use old style pebble mills to grind their inks. Where separate
pebble mills are dedicated to use with one color of ink, virtually no waste
occurs in the dispersion step, and the mills are only rarely cleaned out
(Renson, 1979).
Roll mills and sand mills require cleaning before switching to a differ-
ent color or pigment. Grinding on a three- or five-roll mill continues until
a plate test for fineness of grind shows only one or two scratches. Quite
frequently, the grind will be completed with 1 to 2% of the original mix
9-8
-------
still working at the feed roll. At this stage, the mill is stopped and the
unground paste is removed (Barnett, 1979). Sometimes this paste can be added
to the next similar batch, but among ink plants contacted, the most frequent
practice was to place the residue in cans that are sent to ink waste (Vathako,
1979; Sutt, 1979; Barnett, 1979).
Mixing tubs used in ink making are cleaned with varying frequency and
by several methods. All plants conduct some dry cleanup by wiping or scrap-
ing. Tubs can be rinsed with water, solvent or caustic, or some combination
of methods. Water rinses are normally used following water base ink batches;
solvent rinsing after oil base or solvent ink batches; and caustic rinsing
may be used for either. Many plants routinely use caustic rinsing for smaller
portable tubs and clean fixed tubs with caustic only when required because
of heavy buildup of ink residue.
Batches of solvent base or oil base ink are usually rinsed with solvent
and do not generate wastewater. The dirty solvent is generally handled in
one of three ways:
1.
Used in the next compatible batch of ink as part of the vehicle.
2. Collected and redistilled either by the ink plant or by an outside
contractor for subsequent reuse or sale.
3. Reused as wash solvent with or without settling until considered
spent, then sealed in drums for disposal. If a settling tank is used, the
settled sludge is periodically removed for disposal as solid waste.
Plants that employ caustic washing systems clean the tanks and mixing
tubs in several ways:
Hot caustic from a holding tank is pumped through spray nozzles
into the tub being cleaned and the caustic is returned to the hold-
ing tank.
Tubs are filled with caustic wash and soaked until clean. The
caustic is then transferred to the next tub to be soaked and even-
tually either stored for disposal or discharged as waste.
Small portable tubs may be soaked in a caustic vat until clean or
they may be washed in a machine like a large dishwasher which cir-
culates hot caustic spray followed by a water rinse.
Both fixed tanks and portable tubs that are cleaned with caustic receive
a water rinse. Rinse water is most commonly added to the caustic solution
as makeup water, although some plants discharge rinse water to a sewer.
The quantity of water used to clean tubs in those plants that employ
water rinsing is partly determined by the water pressure used in washing.
Plants employing high pressure rinses tend to generate less tub cleaning
wastewater per batch of ink (Burns and Roe, 1979a).
9-9
-------
Sources of ink loss other than equipment cleaning vary widely among
ink plants but often include residues from spills which may be hosed into
floor drains; wastewater from cleaning tank trucks used to deliver raw
materials; off-specification or spilled ink batches which cannot be re-
worked and are usually discharged as solid waste; residues from laboratory
testing; wastewater from laundering shop rags that are used to clean ink
tubs and other equipment; and ink washed from employees' hands.
The ink industry, as a whole, generates approximately 40,000 gal. of
process wastewater daily, about 75% of which is actually discharged. The
remaining water is reused in ink making, evaporated, or drummed for disposal
as solid waste (Burns and Roe, 1979a).
After the initial dispersion of pigments and resins into the vehicle,
ink batches are diluted to the required viscosity, checked and adjusted for
tint, and the necessary additives are incorporated. Following this quality
control step, the ink is ready for packaging or shipment. Larger ink mak-
ing facilities may use packaging equipment to load ink into cans, tubs, or
pails. Many plants, however, package inks directly from the ink mill. Be-
cause ink batches are normally initially formulated with sufficient raw
materials to produce 4 to 5% excess ink that will be shipped, some residual
ink remains at the end of packaging. Depending on the circumstances, these
residues are added to the next batch or are drained into drums or holding
tanks as waste ink (Barnett, 1979; Gilbert, 1979).
Based on discussions with ink production specialists and observation
of ink making and equipment cleaning practices in typical plants, MRI esti-
mates losses associated with the various processing and packaging steps as
follows:
Paste Inks
Oil base or solvent base, ink residue
Oil or solvent base, water or caustic wash
Water base, ink residue
Water base, water or caustic wash
Liquid Inks
Oil base or solvent base, ink residue
Oil or solvent base, water or caustic wash
1.5%
1.0%
1.0%
3.0%
1.2%
1.0%
Water base, ink residue
0.8%
Water base, water or caustic wash
2.5%
9-10
-------
WASTE HANDLING AND TREATMENT
Wastewater containing ink from floor and equipment cleanup is most com~
monly discharged to a sewer; no plants are known to discharge waterborne
waste directly to a receiving stream (Burns and Roe, 1979a).
Less than 15% of all ink plants employ some form of wastewater treat-
ment prior to discharge. Since these plants are typically the larger facili-
ties, it is assumed that about 30% of all wastewater receives at least minimal
treatment. The most common methods used by ink plants for pretreating waste-
water prior to disposal are gravity separation or settling. A few plants
also neutralize the caustic and skim water before discharge. Relatively
few ink plants are known to employ sophisticated wastewater treatment. The
number of ink plants that employ some form of wastewater treatment prior to
discharge is shown in Table 9-5.
TABLE 9-5.
WASTEWATER PRETREATMENT PRIOR
TO DISCHARGE
Type of treatment
Percent
No. plants
Neutralize
Settle
Flotation
Polymer
Lagoon
Carbon adsorption
Equalization
Evaporation
Lime addition
Trickling filter
Primary gravity separation
Filtration
Alum addition
Ac ti va ted s Iud ge
Any form of pretreatment
9
36
o
o
3
o
3
11
o
o
19
4
2
7
30
2.0
7.8
o
o
0.7
o
0.7
2.4
o
o
4.1
0.9
0.4
1.5
13.0
Sourc e :
Appendix I - Questions 120 to 141 (Burns
and Roe, 1979a).
9-11
-------
Analysis of the wastewater from ink plants clearly shows the presence
of the pigments generally used in inks. Typical data for wastewater from
several plants are given in Table 9-6 (Burns and Roe, 1979a). Plant No.7
did not treat wastewater. Plant Nos. 10 and 23 used only gravity sedimenta-
tion. Plant No. 22 used settling, neutralization and surface skimming of
caustic wash and condensate from steam cleaning of ink tubs and tanks.
Levels of barium, chromium, lead, and zinc indicate that the pigments are
carried into the waste and washing water. Relatively simple gravity settling
at Plant No. 22 shows the removal of 75% of total solids and somewhat higher
removal of most heavy metal pigments.
All of the plants sampled used the diarylide pigments based on 3,3'-
dichlorobenzidine as one of their raw materials. About 85% of all plants
surveyed reported the use of various diarylide pigments:
69.1% used yellow toner
44.3% used orange toner
3.9% used yellow toner with copper
30.2% used nonaqueous diarylide dispersions
19.6% used yellow aqueous dispersions
6.1% used red aqueous dispersions
0.7% used orange aqueous dispersions
In the wastewater samples from ink plants, 3,3'-dichlorobenzidine was
found in only one treated effluent sample at a concentration less than 10
~g/liter (Burns and Roe, 1979a). This finding is somewhat unexpected be-
cause the extensive dilution of ink residues in the wastewater should have
been sufficient to reduce the levels of free 3,3'-dichlorobenzidine in
diarylide pigments below the unit of detection. Diarylide pigments typi-
cally contain about 10 ppm of free 3,3'-dichlorobenzidine base as an impur-
ity. The wastewaters, both raw and treated, showed total suspended solids
concentrations (chiefly resins, pigments, and fillers) ranging from 200 to
800 ppm.
Since it is evident that ink plant wastewater contains traces of other
pigments, failure to detect 3,3'-dichlorobenzidine in the effluent does not
indicate that diarylide pigments are not present in the discharge.
For plants that do not discharge wastewater to a city sewer, the most
common method of disposal is contract hauling. Nearly 34% of plants surveyed
had wastewater and/or spent 'caustic sludges handled by contract hauling.
Most contract haulers used by ink plants discharge the sludge to a landfill
although a small number incinerate or reclaim the wastes (Bratchler, 1979).
Discussions with salvage haulers of ink plant wastes revealed that the
vast majority of sludges and ink residues from ink plants find their way into
9-12
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TABLE 9-6. ANALYTICAL DATA FROM INDIVIDUAL PLANT SITES
(Selected Compounds Only)
Parameter
measured Plant number
(all units j1g/f 7 .
unless noted) (Batch No. 2) 10 23 22 (raw) 22 (treated) % removal
pH 8.8 7.6 12.9 12.9 12.5
T8 (mg/1. )2:./ 11,840 3 ,900. 1,100 22,600 5,600 75.2
TSS (mg/1. )Q/ 1,310 480 120 1,600 110 93.1
Aluminum 30,000 2,000 1,000 20,000 600 97
\0
~ Barium 30,000 900 500 20,000 100 99.5
w
Chromium 30,000 20,000 200 10,000 50 99.5
Molybdenum 6,000 1,000 100 700 50 92.9
Lead 40,000 50,000 4,000 90,000 200 99.8
Titanium 70 300 80 3,000 3,000 0.0
Zinc 3,000 600 1,000 1,000 1,000 0.0
Source:
Appendix H.
Burns and Roe, 1979a.
2:./
TS = total solids.
Q/
TSS = total suspended solids.
-------
landfills (Taylor, 1979). Significant quantities of ink wastes from equip-
ment cleaning are also discharged to sewer systems.
There is no evidence of airborne pigment dust emissions from ink making.
Special tests for pigment dusts have been conducted in one ink production
plant (MRI, 1979a). Sampling pumps were attached to the clothes of workmen
at the pigment weighing station to determine whether the lead base pigments
being used created a dust hazard. Neither lead nor chromium was detected.
Because tests were being conducted, it is possible that greater care may
have been exercised here than is typical in production plants. However,
these tests and on-site observations by MRI in several ink manufacturing
plants indicate that airborne pigment dust from raw material handling repre-
sents a negligible route of discharge to the environment.
ESTIMATED LOSSES
The flow chart in Figure 9-1 is an example of a materials balance for
diarylide pigments in printing ink and is based on a consumption in 1978 of
15,253,000 lb, which is the maximum quantity of diarylide pigments believed
to be used (production plus imports). Although 9.6 million pounds of flushed
color and dispersions were used, compared to 5.6 million pounds of dry toner,
pigment losses in shipping containers and weighing and handling losses are
about equal for the two types of pigments. Total pigment losses prior to
grinding are only about 14,000 Ibfyear.
Waste ink residues generated in ink processing, packaging, dry cleanup,
and solvent washing are generally sent as solid waste in landfills.
About 143,000 Ib of residue and sludge pigments are generated annually
from paste inks. Liquid inks are made in smaller volumes and also produce
less waste; about 60,000 lb of pigments enter solid waste from this source.
Wastewater represents a major source of pigment discharge. Approxi-
mately 86,000 lb of pigment from paste ink making and about 61,000 lb of
pigments from liquid ink waste are discharged to sewers. Of the total pig-
ment load in wastewater (~ 210,000 lbfyear), an estimated 30% is pretreated
prior to discharge, with a removal efficiency of approximately 75% or more.
From this treated wastewater, about 47,000 lb of pigments are contained in
sludges disposed in landfills. An additional 16,000 Ibfyear is discharged
with the treated wastewater. Of the initial 15.25 million pounds of diarylide
pigments, about 14.83 million pounds of pigment (97%) is contained in finished
inks sent to printing shops. These computed losses of 3% compare favorably
with the mean overall ink loss rate of 2.7% reported by experienced ink makers.
A summary of the estimated losses of diarylide pigments for the period
1975 to 1978 is shown in Table 9-7. These estimated losses are based on
pigment consumption ranges presented in Table 9-4.
INK LOSSES IN PRINTING
Following manufacture, printing inks are used primarily in commercial
printing. The diarylide pigments of interest are used almost exclusively
9-14
-------
Source:
Total Diarylide Pigments
Used in Ink Manufacture
15.253.000 Lb.
63% Flushed and Dispersed
Shipping Contoiner and
Handling Losses
0.125% -
Shipping Container and
Handling Losses
0.075% -
65% Paste Ink
35% Liquid Ink
88%
Oil and Solvent
Base Pas te
8.716.600 Lb.
42%
Water Bose
Paste
1. 188. 600Lb.
Processing,
Packaging,
and C lean UP. Lasses
1.5%
Processing,
Packaging,
and Clean UP. Losses
Sa lid Waste
130.700 Lb.
11.900 Lb.
142.600 Lb.
Wastewater and
Caustic Wash
\Nastewoter .Jnd
Caustic Wash
1.0%
2.5%
1.0%
3.0%
Finished Ink Shioments
Containing 14.826.800 Lb.
Diarylide Pigments
30%
15 Percent of Plants Pr,,-treat
30% of Wostewater 75°S Removal
25% Discharged
75% Sludge
I
I
60.aoo
70%
63.000 Lb. I
Sedimentation
Pre - Treatment
700{..
Solid Waste
86.000
47.200 lb.
Discharge to Sewer
86.000 Lb. from Paste
60.800 lb. from Liquid
i5.800 lb. from Waste Treatment
162.600 lb. to Water
.I I
MRI estimates.
Figure 9-1. Sample
inks
Materials b~lance for diarylide pigments in printing
in 1978.
9-15
-------
TABLE 9-7.
ESTIMATED LOSSES FROM THE PRINTING INK INDUSTRY
Quantity (1,000 Ib)~/
.-.-,-
1975
1976
1977
1978
----.--.--.-
Solid Waste
Shipping container and
handling loss 7.3 9.9 10.9-11.0 14 . 2 -14 .3
Processing, packaging,
and cleanup 103 . 7 -104 . 2 140.6-141.3 154. 7 -15 5 . 9 201. 0-202.1
Sludge from wastewater 24.2-24.4 32.8-32.9 36.1-36.4 47.0-47.2
Subtotal solid waste 135.2-135.9 183.3-184.1 201. 7-203.3 262.2-263.6
Air 2,/ 2,/ 2,/ 2,/
\,Tastewater
Caustic wash and water
rinse; discharged with-
out pretreatment 75.3-75.7 102.2-102.6 112.4-113.2 146.0-146.8
Effluent from pretreatment 8.1 11.0 12.0 -12. 1 15 . 7 -15 .8
Subtotal to water 83.4-83.8 113.2-113.6 124.4-125.3 161. 7 -162.6
Total pigment loss 218.6-219.7 296.5-297.7 326.1-328.6 423.9-426.2
Ink shipments (pigment
content) 7,603.3-7,646.4 10,317.3-10,360.5 11,344.4-11,430.9 14,742.8-14,829.1
Total pigment c/ 7,823.0-7,865.0 10,615.0-10,657.0 11,673.0-11,757.0 15,169.0-15,253.0
use -
~/ All pigments used in printing inks are derived from 3,3'-dichlorobenzidine (DCB) except
~range 16, which is derived from 3,3'-dimethoxybenzidine. Since Orange 16 contributed
only 1.1-1.5% of the total quantity in anyone year from 1975-1978, it is included with
the DCB pigments and not presented separately.
2,/ Minute quantities.
~/ See table 9-4.
9-16
-------
in process color printing, printing colored materials used in packaging,
newspaper supplements, and specialty color reproduction processes.
Regardless of the printing process, certain types of ink losses have
been identified:
Ink not removed from shipping containers;
Ink from supply fountains;
Press and plate washing;
Press overruns and misruns; and
Trim, broke and waste.
Little or no airborne pigment loss occurs even with steam or heat-set
inks. Most color printing plants are carefully controlled in terms of tem-
perature, humidity, and ventilation; exhaust air is often minimal.
Minor amounts of ink enter wastewater from the cleaning of equipment
using water based printing inks. For those classes of printing processes,
the volume of ink removed in washing equipment is generally less than 1% of
ink consumption. Printing companies contacted reported that wash-water from
equipment cleaning was very often discharged into city sewers (Peters, 1979;
Fagan, 1979; Schafer and Bastin, 1979). A limited survey did not find any
printing shop having any type of special treatment or disposal methods for
ink contaminated washwater.
The majority of the ink discarded or wasted in printing is placed in
trash containers and handled as commercial solid waste. Ink cans, contain-
ing residues not readily removed by spatulas or draining, are discarded in
the trash. This is said to represent by far the largest single loss of ink
in most printing plants (McGrew, 1979). Small ink cans (1 to 5 lb) typically
contain from 10 to 55 g of ink when discarded, averaging 2.3%. Tubes and
cartridges retain up to 20 g when empty and thrown away. Larger ink contain-
ers are estimated to have residues of about 1.5% of the original contents,
or up to 3/4 lb in a 50-lb pail. Fluid inks used in gravure and some flexo-
graphic processes were found to have residues in the range of 1 to 2 fl oz/gal.
or 0.8 to 1.6%, which is comparable to losses with larger size cans of paste
ink. Hence, discarded ink in containers may range from about 1.5 to 4.4%
of purchases (MRI, 1979b).
With paste inks, some ink skinning and splatter occur at the ink supply
fountains. Small quantities are periodically removed with spatulas or wiped
up with shop wipes and thrown into trash drums. Printers estimate that up
to 1% of paste ink is lost through this route (Fagan, 1979). Fluid ink
losses are lower. When standard process colors are used, ink fountains may
require complete cleaning out only once each week. Ink removed from press
cleaning and fountain cleaning is estimated to account for 1.5 to 2.7% of
ink purchased. All plants contacted reported that these cleaning wastes
were either placed in general trash, or temporarily stored in safety cans
before being emptied into plant trash (Schafer and Bastin, 1979).
9-17
-------
The printing waste allowance varies with the type of press operation
and the nature of the material being printed, but is always substantial.
Sheet-fed color lithography often allows for the spoilage or discard of 500
sheets from a standard 3,600 sheet run (12.2%) (Peters, 1979). The U.S.
Government Printing Office reported that the built-in losses often run close
to 20 to 25% for broke, trim misruns, and overruns (Materozzi, 1976). A
few large establishments separate out recoverable paper waste for recycling,
but most smaller printing plants treat printing waste as general trash to
be hauled away by commercial waste firms.
Since the preponderance of printing ink lost in printing enters the
solid waste stream, losses may be summarized as:
Discarded in ink containers
Removed in press cleaning
Discarded as printing waste
1.5 to
1.5 to
9.5 to
12.5 to
4.4%
2.7%
13.0%
20.1%
Wastewater discharge originating from cleanup of wa~er base ink printing
machines is estimated to contain ~ 2% of the water base printing ink. In
1978, ~ 3.3 million pounds of diarylide pigments were used in water base
inks, which means waterborne discharge is approximately 66,100 lb annually.
POSTPRINTING DISPOSITION
The useful life of printed matter is fairly short.
pigments are consumed in printing newspaper supplements,
ing matter, catalogs, and packaging. It is assumed that
materials are discarded within 1 year after printing.
The bulk of diarylide
magazines, advertis-
90% of these printed
Waste paper recycling is currently limited except for newsprint and
corrugated boxboard. About 3.1 million tons of newsprint were recovered in
1977 or about 30% of total production (Franklin et al., 1979). Of the 22
million tons of boxboard produced, 7 million tons were reclaimed. Only about
4% of newsprint is deinked in recycling and none of the corrugated is deinked.
Recycled paper is used primarily in paperboard packaging, gypsum board, and
some tissue products.
Most of these products have a short life cycle and are ultimately dis-
posed in mixed solid wastes. Since 1975 approximately 93% of mixed solid
wastes have been landfilled; currently only about 7% is incinerated. Using
the ink and printing waste factors estimated in this section and an assumed
discard rate of 90%, the estimated fate of diarylide pigments in printed
materials is summarized in Table 9-8.
9-18
-------
TABLE 9-8.
ESTIMATED FATE OF DIARYLIDE PIGMENTS IN PRINTED MATERIAL
Quantity (1.000 1b)
1975 1976 1977 1978
Total pigment employed 7,603-7,646 10,317-10,361 11,344-11,431 14,743-14,829
(see Table 9-7)
Wastewater loss
Cleanup of water-base ink 33.9-34.1 46.0-46.2 50.6-51.0 65.8-66.1
(-2'70 loss)
Solid waste loss
\0 Container residue (1. 5-4 .4%) 114-336 155-456 170-503 221-652
I
...... Press loss (except water-base) 114-206 154-279 169-307 220-399
\0
(1. 5-2.7%)
Printing waste discard 722-994 980-1,347 1,078-1,486 1,401-1,928
(9.5 -13.0%)
Printed material disposition
Prompt waste 950-1,536 1,289-2,082 1,417-2,296 1,842-2,979
Discarded within 1 yr (90%) 5,430-5,996 7,370-8,123 8,097-8,967 10,528-11,629
Landfilled (93%) 5,050-5,576 6,854-7,555 7,530-8,339 9,791-10,815
Incinerated (7%) 380-420 516-569 567-628 737-814
-------
SECTION 10
PAINT AND COATINGS INDUSTRY
INDUSTRY CHARACTERISTICS
Paint, varnish, lacquer, and other protective coatings are manufactured
domestically in approximately 1,400 establishments operated by about 1,300
companies. Total industry employment is 65,000, of which approximately
36,000 are involved in paint production. The 1972 Census of Manufactures
showed 1,599 establishments, 687 of which had more than 20 employees.
A recent survey of the paint and coatings industry obtained responses
from 1,374 establishments (Burns and Roe, 1979b). The geographic distribu-
tion of paint manufacturing plants obtained from this survey shows the larger
paint plants tend to be concentrated in major centers of manufacturing and
population. Approximately 45% of all plants having more than 100 employees
are located in just four states (New Jersey, Illinois, Ohio, and California).
The states containing the major percentage of all paint plants are shown in
Table 10-1.
The principal products of the paint industry (SIC 2851) are consumer
paint products called "trade sales," which are sold primarily off the shelf
for exterior and interior painting of buildings, and industrial finishes
sold to manufacturers for factory application to products such as automo-
biles, furniture, appliances, and machinery.
The output of the paint industry in 1977 was approximately 1 billion
gallons of product valued at slightly more than $4 billion. Growth in paint
production is modest, about 3% annually in volume and about 5% annually in
value of shipments (Census, 1977).
, PAINT MANUFACTURING
Production Processes*
Paints can be classed as either solvent base or water base (also called
latex base), but there is little difference in the production processes used.
*
This brief characterization of paint production processes, focusing upon
pigment usage, sources of waste and equipment cleaning practices, is
based in part on a recent report on the paint manufacturing industry
(Burns and Roe, 1979b).
10-1
-------
TABLE 10-1.
DISTRIBUTION OF LARGE PAINT
PLANTS, BY STATE
State
% of all paint
plants
Illinois
California
New Jersey
Ohio
New York
7.7
14.3
8.2
7.5
7.9
Pennsylvania
Texas
Michigan
Missouri
Georgia
4.8
4.2
3.4
3.7
2.5
Indiana
Kentucky
North Carolina
All others
2.5
1.6
1.5
31. 2
Total
100
Source:
Burns and Roe (1979b).
The major production difference is in the carrying agent; solvent base paints
are dispersed in an oil mixture, while water base paints are dispersed in
water with a surfactant used as the dispersing agent. Another significant
difference is in the cleanup procedures used. As the water base paints con-
tain surfactants, it is much easier to clean up the formulating tanks with
water. The tanks used to make solvent base paint are generally cleaned with
an organic solvent, but cleaning with a strong caustic solution is also a
common practice (Barrett, 1973; EPA, 1973).
Major raw materials used in paint manufacture in terms of pounds con-
sumed are oils, resins, pigments, and solvents. Alkyls and drying oils,
such as linseed oil, are used as the film forming binder in some solvent
base paints. Semidrying oils and water soluble alkyls are used in the manu-
facture of water base paints.
Pigments are used to impart opacity and color to the coatings. The
four basic types of pigments are: (a) prime white pigments, such as titanium
dioxide and zinc oxide, (b) colored inorganic and organic pigments, (c) filler
and extender pigments, and (d) metallic powders.
Practically all paints are produced using a batch process. The major
difference in the size of a paint plant is in the size of the batches. A
small paint plant will produce batches from 100 to 500 gal. while a large
plant will manufacture batches up to 6,000 gal. In general, there are too
many color formulations to make a continuous process feasible.
10-2
-------
Solvent Base Paint Operations--
There are three major steps
process: (a) mixing and grinding
and (c) filling operations. The
these steps.
in the solvent base paint manufacturing
of raw materials, (b) tinting and thinning,
flow diagram in Figure 10-1 illustrates
The mixing and grinding of raw materials for solvent base paints are
accomplished in one production step. For high gloss paints, the pigments
and a portion of the binder and vehicle are mixed into a paste of a speci-
fied consistency. This paste is fed to a grinder, which disperses the pig-
ments by breaking down particle aggregates rather than by reducing the.
particle size. Two types of grinders are ordinarily used for this purpose:
pebble or ball mills, and roll-type mills. Other paints are mixed and dis-
persed in a mixer using a saw-toothed dispersing blade commonly referred to
as a high speed disperser.
In the second production stage, the paint is usually transferred to
tinting and thinning tanks by gravity feed or occasionally by means of port-
able transfer pumps. At this stage, the remaining binder and liquid, along
with various additives and tinting colors, are incorporated. The paint is
then tested and the composition is adjusted as necessary to obtain the cor-
rect specifications for the type of paint being produced. The finished prod-
uct is then transferred to a filling operation where it is filtered, packaged,
and labeled (EPA, 1976; Barnett, 1979).
The paint remaining on the sides of the tanks may be allowed to drain
naturally and the residue, or clingage as it is called, may be cleaned from
the sides with a squeegee during the filling operation until only a small
quantity of paint remains. The final cleanup of the tanks generally consists
of flushing with a solvent until clean. The dirty solvent is treated in
one of three ways: (a) it is used in the next paint batch as a part of the
formulation; (b) it is placed in drums that are sold to a company where it
is redistilled and resold; or (c) it is collected in drums with the cleaner
solvent being decanted for subsequent tank cleaning and returned to the drums
until only sludge remains in the drum. The drum of sludge is then sent to
a landfill for disposal (Hine, 1971, Barnett, 1979; EPA, 1976).
Some plants clean solvent base paint tanks and equipment with hot caustic
either on a regular or periodic basis. The caustic is generally recycled
and is followed by a water rinse. Part of this water is returned to the
caustic tank as makeup, and any remaining water is disposed of by (a) dis-
charging to the sewer, (b) holding, treating, and discharging to a sewer,
(c) drumming and landfilling, or (d) reusing as rinse water (Bruhns, 1971).
In plants that manufacture both solvent base and latex base paints, this
rinse water is often combined with the wastewater from latex base paint op-
erations.
Water Base Paint Operations--
Water base paints are produced
vent base paints. The pigments and
because they are received in proper
in a slightly different manner from sol-
extending agents do not require grinding
particle size. Hence, the dispersion of
10~3
-------
,~
r
Oils Tints and
Pigments and Resins Thinners
Solvents
I ~ I
.
Mixing
Tank
,Ir . ,
Stone Pebb Ie Dispersing
or
Roller or Tank
Mill Ba II Mill
,
Thinning --
and
Tinting -
Tank
,
Filling
Packaging
and
Shipment
Figure 10-1.
Flow diagram of solvent base paint manufacturing process.
10-4
-------
the pigment, surfactant and binder into the vehicle is accomplished with a
saw-toothed high speed dispenser. In small plants, the paint is thinned
and tinted in the same tank, while in larger plants the paint is transferred
to special tanks for final thinning and tinting. Once the formulation is
correct, the paint is transferred to a filling operation where it is filtered,
packaged, and labeled in the same manner as for solvent base paints. The
production process for water base paints is diagrammed in Figure 10-2.
As in the solvent base paint operation, as much product as possible
may be removed from the sides of the tub or tank before final cleanup starts.
Cleanup of the water base paint, tubs is done simply by washing the sides
with a garden hose or a more sophisticated washing device. The washwater
may be: (a) collected in holding tanks and treated before discharge; (b)
collected in drums and taken to a landfill; (c) discharged directly to a
sewer; (d) reused in the next paint batch; or (e) reused in the washing
operation (Miller, 1979).
Some paint plants may regularly or occasionally rinse latex base paint
tanks and equipment with hot caustic in a similar manner to that described
for solvent base paints. Any rinse water generated is combined with the
regular cleanup water and disposed of by one of the same methods.
PIGMENT USAGE
The pigments used in paint production cover a wide range of materials.
One medium size manufacturer reported that they maintain over 8,000 paint
formulations on a computer listing, and annually manufacture more than 4,500
different production formulas, many of which differ primarily in pigmenta-
tion (Johnson, 1979).
Inorganic pigments are most widely used in white and tint base paints;
barium, titanium, calcium, and zinc pigments are prominent in this class of
product. Inorganic pigments also tend to dominate the colored paint field
because they are more stable and less expensive than most organic toners.
Inorganic extender pigments, such as the silicates, are also widely used in
both white and colored coatings.
Data from a recent study show that the paint industry relies heavily
on inorganic pigments. Half of the plants that responded to a survey indi-
cated that they use over 70% inorganic colorants (Burns and Roe, 1979b).
Diarylide Pigments
The pigments derived from 3,3'-dichlorobenzidine and 3,3'-dimethoxy-
benzidine represent a small portion of all pigments used in the paint industry.
This small usage of the diarylide pigments is fairly widespread--roughly
one-third of all plants.
The paint industry accounts for less than 6% of the total consumption of
diarylide pigments. Diarylide pigments tend to be more widely used in solvent
base coatings than in water base paints; and more extensively in industrial
coatings than in trade sales products, as shown in Table 10-2. The table
10-5
-------
Res i ns Water Ti n ts
Pigments Oils
Surfactants
1 ..
1
Dispersing
Tank
Tinting -
and
Thinning -
'r
Packaging
and
Fi I ling
Figure 10-2.
Flow 4iagram of water base paint manufacturing process.
10-6
-------
TABLE 10- 2.
DIARYLIDE PIGMENTS IN PAINT PRODUCTION
Plant characteristics
Diary1ide pigments usage
Number of plants Percentage
All plants
Paint production
90+% solvent base
90+% water base
Paint sales
90+% industrial
90+% trade .
412 30
156 34
19 17
167 37
62 18
Source:
Burns and Roe, 1979b.
shows that the use of these pigments is twice as frequent among solvent paint
producers as it is for water base paint producers and twice as common in
industrial paints as in consumer paints.
Usage of diarylide pigments in exterior paints is limited because most
of these pigments fade in sunlight. Although some diarylide pigments are
used in tinting interior latex paints, the inorganic color pigments (such
as inorganic oxides or the titanated pigments) are more generally used be-
cause they perform well and are less costly. Diarylide pigments find their
greatest application in brightly colored lacquers, enamels and specialty
coatings where high tinting strength and color saturation are desired. The
use of diarylide pigments allows production of bright coatings with high
hiding power at relatively low pigment loadings. This is a characteristic
of considerable value in some industrial finishes and consumer products,
such as aerosol spray enamels.
The approximate consumption of diarylide pigments by the paint industry
is estimated in Table 10-3. These estimates by MRI are based on discussions
with pigment sales departments, the purchasing agents and formulation special-
ists for six diversified paint producers, and available statistics on pigment
consumption (Byrd, 1979; Richardson, 1979; Miller, 1979; Asher, 1979).
Annual consumption of diarylide pigments in paints is estimated to ac-
count for approximately 6% of total diarylide pigment consumption. The pig-
ment based toners are seldom, if ever, used as the sole color pigment; they
are ~sually used to enhance the saturation and chroma of other pigments.
The paint industry relies far more heavily on inorganic colors. Over 62%
of plants use chrome yellow, compared with 10.5% using yellow. toners. Some
52% report use of molybdate orange, versus 22% using Oranges 13 and 16. The
10-7
-------
TABLE 10-3. ESTIMATED DIARYLIDE PIGMENT CONSUMPTION IN PAINTS
Quantity (1,000 1b)~/
Pigment 1975 1976 1977 1978
Yellow 12 182 236 261 356
Yellow 13 17 28 26 36
Yellow 14 19 30 32 31
Yellow 17 125 230 300 343
Yellow 83 63- 7 5 89-96 92-112 111-131
Orange 13
11
14
12
12
Orange 16
23
29
26
28
Red 38
48-49
51
51
53-54
Red 41
0.4-0.6
0.4-0.6
0.4-0.6
0.4-0.6
Blue 25
7
6-7
6
5-6
Total
495-507
710-722
806-827
975-998
Source:
MR.I estimates.
2-./
Quantities derived from Tables 4-3 and 4-6.
10-8
-------
phthalocyanine blues and greens are among the more widely used organic pig-
ments; nearly 60% of paint prants use these pigments (Burns and Roe, 1979b).
Use of diarylide pigments in aqueous and nonaqueous dispersions is small
but significant, with about 6% of all plants employing these predisposed
colors. Nonaqueous dispersions or flushed toners are employed more than
aqueous dispersions. This is probably due to less demand for intense color-
ation in water base paints. Table 10-4 presents a comparison of the fre-
quency of usage of different types and classes of pigments.
ESTIMATED LOSSES IN PAINT MANUFACTURE
In the manufacture of paint several principal sources or points exist
at which pigments or pigment-containing paint can enter waste streams and
possibly be discharged to the environment.
~k
Shipping container residues and pigment handling loss.
I~
Spills of product.
-!(
Solvent washing and cleanup.
"k
Water or caustic equipment cleaning.
"I(
Overage or packaging residues.
Other minor sources'of discharge include laboratory paint samples and
residues, laundering of shop cloths used in cleanup, cleaning of truck tanks
of incoming raw materials, and production work hand washing (Mellan, 1979;
Asher, 1979).
The levels or magnitude of losses throughout production and cleanup
are directly affected by factors which include size and scale of operations,
specialization in water base or solvent paints, use of dedicated tanks and
equipment, type of equipment cleaning practiced, and the availability of
suitable waste disposal systems. No satisfactory data were found from which
the industry norms for loss rates could be derived. It was necessary, there-
fore, to obtain estimates of the probable range of losses from a number of
experienced paint production managers. The consensus among 11 producers of
both solvent and water base paints resulted in estimates for overall industry
loss factors for the principal sources identified as follows:
~k
Pigment shipping container residues, plus spills and loss in pig-
ment handling and weighing--0.2%; all treated as solid wastes.
I';
Processing and packaging waste in solvent base coatings, including
off specification or spoiled batches that are not reused in subse-
quent paint batches--0.8 to 1.4%, average 1.0%. Over 80% treated
as solid residue from solvent recovery or discard; 20% maximum
may enter wastewater system, of which less than half will be dis-
charged with treatment.
10-9
-------
TABLE.lO-4.
RELATIVE USAGE OF COLOR PIGMENTS BY PAINT PLANTS
A.
Inorganic color
pigments
Percent
usage
Percent
usage
B.
Organic pigments
Percent
usage
C.
Organic pigment dispersant
f-'
o
I
f-'
o
Zinc yellow
Cd yellow-orange
Antimony Pb or Zn
yellow
Chrome yellow
Chrome orange
Molybdate orange
Lead yellow or red
Cd red
Iron blue
Chrome blue
Cd blue
Silver blue
46.1
11.6
4.4
62.4
13.0
52.5
29.0
13.0
39.5
2.0
0.7
15.1
DCB orange toner
DCB yellow toner
Pyrazalone red
DCB yellow withCu
DCB yellow with Ni
Phthalocyanine blue
Phthalocyanine green
22.1
10.5
4.2
1.7
11.4
57.9
56.2
DCB yellow non-aqueous
DCB yellow aqueous
DCB orange aqueous
Compare with:
Lead or chrome yellow non-
aqueous
Lead or chrome orange non-
aqueous
Lead or chrome green non-
aqueous
Green (Cu or CN) non-aqueous
Blue (Cu or CN) non-aqueous
5.9
5.5
3.7
25.1
21.6
10.8
38.4
38.3
Source:
Burns and Roe.. 19 79b .
-------
*
Processing, packaging, and waste in water base paint may exhibit
lower levels of losses because the batch sizes tend to be consider-
ably larger--0.6% average. At least 75% enters wastewater, while
the balance is handled as solid waste. Approximately half the
water containing paint residues is recycled; the remaining half
of these wastes will be discharged in wastewater with or without
treatment.
*
Solvent washing of equipment for oil and solvent base coatings
accounts for 1.0 to 1.5% overall losses, average 1.2%. All of
these residues eventually are handled as solid waste.
*.
Water
water
water
water
or caustic washing of equipment used for either solvent or
base paints carries away 1.6% of production. About 30% of
wash is reused in paint. All caustic and the balance of
wash becomes wastewater.
*
Miscellaneous losses are estimated to account for less than 0.1%
of production; half solid, half wastewater.
*
The diarylide pigments of interest are estimated to be consumed
65 to 80% in solvent base coatings.
Determination of paint losses is complicated considerably by the divers-
ity of equipment cleaning practices used. Both solvent washing and water
washing are extensively employed. The use of caustic cleaning is signifi-
cant but is much less commonly used than in the printing ink industry.
The study by Burns and Roe (1979b) presents information on the distribu-
tion of tank cleaning methods within the paint industry (see Table 10-5).
Most of the large plants that produce only water base paints use water wash-
ing as virtually the only cleanup technique. When making latex base paints
on a large scale, most producers report that all of the wash water cannot
be reused in paint making. Even with effective preservatives and biocides,
the risk of biological contamination is so great that only washing residues
from certain stages of production can feasibly be reused (Walanski, 1979).
Further, the volumes of water wash employed in specialized latex paint plants
is quite large. For these reasons, most large latex paint plants have con-
structed some type of wastewater treatment system. A small number of water
base paint plants report that they have been able to operate without generat-
ing any wastewater. Table 10-6 compares the wastewater production of solvent
base and water base plants. The plants making water base paint generate,
on the average, about 1,650 gallons per day (gpd); solvent base plants typi-
cally generate about 1,700 gpd. Actual discharge of wastewater follows a
different pattern. Over two-thirds of the solvent base paint plants did
not discharge any water. The remaining one-third of plants had an average
discharge of 2,600 gpd. Those water base paint plants that discharge water
averaged 1,360 gpd or about 82% of wastewater generated.
Small plants are much more likely than large plants to reuse wastewater
as part of product formulation. Only 1.1% of the large plants indicated
reusing wastewater in product all of the time versus 16% of small plants
and 13% of all plants that use a water rinse.
10-11
-------
TABLE 10-5.
METHODS OF TANK CLEANING
Rinsing method
Number of plants
surveyed
Percent of
plants
Water rinse only~/
143
10.4
Solvent rinse on1y~/
383
27.9
Caustic rinse or soak on1y~/
14
1.0
Dry cleaning only
24
1.7
Water and caustic rins~/
30
2.2
Water and solvent rins~/
491
35.7
Solvent and caustic rins~/
40
2.9
Water, solvent and causti~/
187
13.6
Not answered
62
4.5
Total using:
Water 851 62
Solvent 1,101 80
Caustic rinse 163 12
Caustic soak 164 12
Dry cleanup 189 14
Source:
Burns and Roe, 1979b.
~/
With or without dry cleaning of tanks.
10-12
-------
TABLE 10-6.
VOLUME OF WASTEWATER GENERATED
BY PAINT PLANTS
Wastewater Plants producing over Plants producing over
generated 90% water base paint 90% solvent base paint
(gpd) (%) (%)
0 11.0 44.7
1-100 56.9 21.1
101-500 9.2 6.3
501-1,000 2.8 2.6
1,001-6,000 11.9 4.4
6,001-12,000 - 1.7
Over 12,000 4.6 5.4
Not answered 3.7 13.7
Total 100.0 100.0
Source:
Burns and Roe (1979b).
Wastewater from paint plants is infrequently discharged directly. The
most widely used methods of disposal are discharge to city sewer, contract
hauling, evaporation, and landfill or impoundment (EPA, 1976; Bruhns, 1971).
Some type of treatment or pretreatment of wastewater prior to discharge
is used by 355 plants (Burns and Roe, 1979b). Settling and gravity separa-
tion are most commonly used. Some of the larger plants, especially those
producing mostly water based paints, have installed physicochemical treatment
systems. Advanced treatment with coagulants to aid precipitation of suspended
matter typically shows greater than 95 to 98% removal of total suspended
solids and 60 to 85% removal of metals found in pigments (Desoto, 1974).
Analysis of wastewater from paint plants shows the presence of pigments.
Barium, cadmium, chromium, copper, molybdenum, lead, and titanium are almost
always found in raw wastewater and at reduced levels in most treated discharge.
No samples of wastewater tested were found to contain benzidine or 3,3'-di-
chlorobenzidine. Failure to detect 3,3 I -dichlorobenzidine in wastewater
from paint plants does not mean that diarylide pigments are absent.
Estimates for diarylide pigment losses and disposition from paint manu-
facture were derived from data on total diarylide toner use in paints together
with loss factors supplied by industry (see Table 10-7). Largely because
the diarylide pigments are used more in solvent base and industrial finishes
10-13
-------
TABLE 10-7.
ESTIMATED PIGMENT LOSS FROM PAINT MANUFACTURE - 1978
Source of loss
Diary1ide Di~ent consumed in paints~/
(975,000-998,000 lb)
70% Solvent base 30% Water base
682,500-698,600 292,500-299,400
Shipping container and pig-
ment handling
0.20% - solid
0.20% - solid
Processing and packaging
0.8 - 1.4%- 80% solid
20% water
0.60% - 25% solidb/
75% water-
Equipment cleanup
1.0 - 1.5% - solid
1.60% - 80% washwater£/
20% caustic wash
Miscellaneous sources
0.1% - 50% solid
50% water
0.1% - 50% solid
50% water
Summary of losses
So lid was te
1b
1. 9 - 2.9%
12,968 - 20,259
0.4%
1,170-1,198
Water waste
1b
0.2 - 0.3%
1,365 - 2,096
1.5%
4,388-4,491 (3,072-3,144)Q/
Total losses:
Solid waste -- 14,138 - 21,457 lb
Water waste -- 4,437 - 5,240 1b
Total paint shipment:
948,303 - 979,425 1b
a/
See Table 10-3.
~/
Of the losses during processing and packaging of water base paints, 25% are
solid waste and 75% are in wastewater. Fifty percent of the wastewater
is recycled and 50% discharged without further treatment.
c/
30% - recycled; 70% - discharged.
-~/
70% discharged with no treatment; 30% treated to achieve 75% solid removal.
The solid removal figure is not included in the total range for solid
waste.
10-14
-------
which generally employ solvent cleanup methods, the largest fraction of pig-
ment residue is discarded as solid waste. The distribution of diarylide
pigments associated with paint manufacture for 1975 to 1978 is shown in
Table 10-8. Estimations employed in these calculations were presented earlier
in this subsection. Using these industry estimations, the following percent-
ages can be computed. Of the total quantity of pigment employed in solvent
base paints, 1.9 to 2.9% (2.4% average) is disposed as solid waste, 0.2 to
0.3% (0.25% average) is discharged in wastewater, and 96.7 to 97.9% (97.3%
average) is contained in paint shipments. For pigments in water base paints,
0.4% is disposed as solid waste, 1.5% is discharged in wastewater, and 98.1%
is contained in paint shipments.
TABLE 10-8.
ESTIMATED PIGMENT LOSS FROM
PAINT MANUFACTURE
Quantity (1,000 1b)
Loss category 1975 1976 1977 1978
Maximum total consumptio~1 495-507 710-722 806-827 975-998
Pigment discharged in 2-3 3-4 -4 4-5
wastewaterQI
Pigment . l.d t bl 7-11 10-16 12-18 14-21
1n so 1 was e-
Pigment contained }n 481-498 690-709 784-811 949-980
paint shipments£
~I See Table 10-3.
~I See Table 10-7 for percentage losses from solvent base and water
base paints.
~I Quantities obtained by difference.
LOSSES IN PAINT APPLICATION
The application of protective coatings is accompanied by significant
losses due to unused paint, overspray, drop and spillage, and the cleaning
of equipment used to apply the coating. The fraction of paint usefully ap-
plied to the intended surface may range from less than 75% for unskilled
brush painting to more than 90% for electrocoating and industrial fused
powder coating methods (Mullen, 1979). Hence, a substantial proportion of
pigments used in paint making do not enter the environment directly because
they are contained in surface coatings which have a useful life of several
years.
Of the total quantity of diarylide pigments in paint shipments, approxi-
mately 30% are incorporated into water base paints and 70% into solvent base
10-15
-------
paints. Within the water base category, 28% are industrial sales and 72%
are trade sales. For solvent base paints, 29% are trade sales, 62% are in-
dustrial sales, and 9% are other sales, which includes powder coatings, elec-
trodeposition, dip coating, and other special application techniques. The
distribution among the sale categories is accurate to ~ 5%. However, within
each of the sale categories, it is difficult to estimate painting losses
with any degree of accuracy. Industrial coating operations using solvent
base materials generally achieve a coating efficiency of 80 to 85% (Hahn,
1979). Makers of industrial painting equipment estimate that 8 to 10% of
paint purchased is disposed of as solid residue and overspray collection,
with another 7 to 10% collected in water curtain or scrubbing systems or
through water washing (Maas, 1972). Most large industrial coating opera-
tions that generate waterborne paint wastes employ some type of concentra-
tion and treatment before discharging wastewater. MRI estimates that
roughly 35% of industrial water contaminated with paint is treated at a re-
moval efficiency of 75%.. Sludges are widely removed by contract hauling.
For trade sales of solvent base coating, the coating efficiency is esti-
mated to be about 65 to 80% with approximately 15 to 25% discarded as solid
waste and the remainder discharged as water waste. Other solvent base paint
applications are estimated to show about 90% coating efficiency, with approx-
imately 8% of the residue as solid waste and 2% as water waste.
Only wide approximations could be made for painting losses from water
base industrial sales or trade sales. An approximate coating efficiency of
70 to 85% was assumed for both areas. Solid waste was estimated at 5 to
15% and water waste at 10 to 15%.
A summary of estimated diarylide .pigment losses resulting from paint
application processes is presented in Table 10-9.
10-16
-------
TABLE 10-9.
ESTIMATED PIGMENT LOSS FROM PAINT APPLICATION
Quantity (1,000 lb)
Loss category 1975 1976 1977 1978
Total diarylide pigment 481-498 690-709 784-811 949-980
(see Table 10-8)
Water base (30%) 144-149 207-213 235-243 285-294
Industrial sales 41-42 57-59 66-68 79-82
Trade sales 103-107 150-154 169-175 206-211
Solvent base (70%) 337-349 483-496 549-568 664-686
Trade sales 98-101 140-144 159-165 193-199
Industrial sales 209-216 299-307 340-352 411-425
Other 30-31 44 50-51 60-62
Pigment in coatings 355-423 508-601 579-688 684-824
Pigment in solid waste 40- 71 58-104 67-117 80-139
Pigment in wastewater 35-55 50-78 56-88 76-126
discharge
10-17
-------
SECTION 11
TEXTILE PRINTING
This section describes the textile printing processes that employ pig-
ments based on 3,3'-dichlorobenzidine, 3,3'-dimethoxybenzidine, and 3,3'-
dimethylbenzidine. An overview of the textile industry was presented in
Section 4; the reader is referred to that section for a detailed industry
characterization. The brief industry characterization is followed by a dis-
cussion of textile printing processes, specific type and estimated quantities
of diarylide pigment used, and an estimation of losses for this industry.
INDUSTRY CHARACTERIZATION
Except for losses of colored material as scrap when patterns are cut
(10 to 20% depending upon the type of pattern and fabric width), most of
the losses of the pigments are restricted to those in Major Group 22 of the
Standard Industrial Code (SIC). Major Group 22 is comprised of about 6,000
manufacturing facilities (EPA, 1979b). The primary activities of this sector
include receiving and preparing fibers; transforming these materials into
yarn, thread, or webbing; converting the yarn or web into fabric or similar
products; and finishing these materials at various stages of production.
Fiber is the basic raw material in textile manufacturing. The fibers
used to form the fabric or web can be either natural or synthetic. Natural
fibers include wool, cotton, jute, silk, and flax. Synthetic fibers are
cellulosic (e.g., rayon, acetate) or noncellulosic (e.g., polyester, nylon,
spandex).
PRINTING PROCESSES
There are three basic textile printing processes: roller printing,
screen printing, and transfer printing~ Screen printing may be further di-
vided into rotary screen or flat bed screen printing. The estimated quan-
tity of fabric printed by each process is presented in Table 11-1. There
are also printing classifications based on the type of printing paste used
in a process: (a) pigment printing uses a color paste containing insoluble
colorants; (b) dyestuff printing uses a paste containing soluble colorants;
and (c) thermosol treatment uses a disperse dye which is applied to paper
or fabric and diffused into the fabric by means of heat or steam. The ther-
mosol process is used primarily for dyeing of polyester fabric and does not
employ bisazobiphenyl dyes. Processing of the fabric after it has been
printed with the paste varies according to the classification of the color-
ant and the fibers which are used.
11-1
-------
TABLE 11-1.
ESTIMATED QUANTITY OF FABRIC PRINTED BY
PROCESS (1975-1978)
Fabric printed~/ (106 Ib)
Printing process 1975 1976 1977 1978
Rotary screen 458 505 557 614
Flat bed screen 298 301 302 301
Roller 199 215 232 251
Transfer 40 54 70 88
Total 995 1,075 1,161 1,254
~/
These data are based on 1976 estimates by RTI (1979).
An 8% growth rate for total textile printing industry
was applied (RTI, 1979), with the following estimates
of changing market shares for the different processes:
rotary screen - up 1% annually; flat bed screen - down
2% annually; roller - no change; transfer - up 1% annu-
ally (RTI, 1979).
The methods for printing colors are described in the following subsections.
Figure 11-1 shows the typical printing process.
Roller Printing
Roller printing uses engraved rollers which are coated with the print
paste. The paste is removed from the surface of the roller by a knife, called
the color doctor, but paste is left in the engraved regions. This paste is
then transferred by pressure to the fabric being colored. The equipment
and material used in the process are a color pan to hold the printing pastes,
a furnishing roller to transfer the paste from the color pan to the engraved
roller, the engraved roller, color doctor, the pressure cylinder to back up
the cloth while it is printed, and a back-grey, which is fabric to absorb
any excess paste which goes through the fabric being printed. Different
colors are printed with additional rollers.
Screen Printing
There are two types of screen printing. Rotary screen printing is a
continuous process with the screening material stretched on a circular frame
within a cylinder. Flat bed screen printing is a slower process with the
screen tacked onto a flat rectangular frame.
Rotary screen printing
expensive because the added
ever, the screens cannot be
is almost as fast as roller printing but not as
cost of engraved rollers is not required. How-
used for as high volume printing as the rollers.
11-2
-------
Solvents
Woter
t-'
t-'
1
W
Source: MRI
Dye or Pigment
and Contoiners
Resi n Bi nders.
Thickeners. and
Other Additives
Mixing
Dust
Containers with
Residual Dye
and Pigment
Color Paste
Fabric
Printing
'Cleaning Wastes
(From Equipment
and Paste Containers)
Fi gure 11-1.
Excess Paste
Thermosol
Pigment
Pri nti ng
Voloti Ie Wastes
Volatile Wastes
Wet Printing
Paste Not
Recycled
To Mixing
Volatile
Wastes
Liquid
Wastes
Volatile
Wastes
Typical printing process.
Pri nted
Fabric
Misc. Wastes
(Cloth)
-------
The process consists of covering portions of a porous screen, most commonly
nickel, with a resistant material. The printing paste is then forced through
the material onto the cloth while the resistant material blocks the printing
paste from being printed. In this way the screen is similar to a simple
stencil. A separate screen is required for each color in the design.
Flat bed screen printing is similar to rotary screen printing except
the silk or synthetic cloth screen is stretched across a rectangular frame.
The process may be manual, semiautomatic, or automatic. In the manual pro-
cess the design is printed by forcing the paste through the screen with a
squeegee. The pattern is then repeated by moving the squeegee along the
fabric. The semiautomatic process differs from the manual process in that
the fabric is automatically moved and positioned while the screen is kept
in place but the paste is still applied manually. The automatic process
does the positioning and the application automatically, but the process is
virtually the same as the manual process. Although flat bed screen print-
ing is relatively slow, the low equipment expenses make it quite economical
for small shops.
Transfer Printing
Transfer printing is a dry printing technique which can refer to one
of two commercially viable processes. One process is known as Thermachrome,
the other as dry heat transfer (sublimation). The dye in the dry heat trans-
fer method must vaporize rapidly at temperatures less than 150° to 220°C to
avoid fabric damage. The dye must not sublime too readily, however, and
must have good light and wash fastness. Disperse and basic dyes have found
application in this area.
The fabric which is printed is usually a satin or glazed surface type
weighing 50 to 60 g/m2. It must have a uniform fiber structure and must
not be excessively absorbent. Dyes are first dispersed in solutions of bind-
ing and thickening agents which have no affinity for the dye. Printing is
typically done by conventional paper-printing methods.
Fabrics in garment or piece form printed at temperatures of 1850 to
210°C and dwell times 20 to 30 sec include cellulose di- and tri-acetate;
acrylics; Nylon 6 and 6/6; polyester; polyester/cotton; polyester/wool; and
polyester elastane.
Thick masses of garments or fabrics can be uniformly heated and dyed
by use of a press employing radio-frequency heating.
No subsequent treatment is required following printing.
Pigment Printing
The steps for pigment printing are printing of the fabric with a pig-
ment paste and then heat curing the coloring paste. Essential constituents
of the paste are the pigment and a binder to bind the pigment to the fabric.
These, and other chemicals needed to give good working properties to the
11-4
-------
paste, are added to an oil-in-water or water-in-oil emulsion. One typical
formulation for an oil-in-water paste contains 15% pigment (Hochberg, 1979);
however, one printer stated that an average pigment concentration might be
about 6% (Glick, 1979). The pigment described for these formulas is commer-
cially available with only a 7 to 10% actual colorant concentration; there-
fore, the concentration of colorant in the paste would be about 0.42 to 1.5%
by weight. This paste is applied to the fabric with a weight ratio of about
1:1 (RTI, 1979). The fabric is then heat cured. The only washing of the
fabric is done to check the curing of the binder. If properly cured, no
pigment loss should occur. .
ESTIMATED PIGMENT CONSUMPTION
Pigments produced from benzidine congeners used in textile printing
include: Oranges 16 and 34; Yellows 13, 14, and 83; and Blue 25. Print
color is applied to specific areas of the cloth to achieve a planned design;
this is often referred to as localized dyeing.
Pigments do not react chemically with the fiber to which they are being
applied. Instead, a binder acts as an interface, linking the molecules of
the fabric to the dye molecule. Pigment systems are easier to apply and
lower in cost than dye systems (Patton, 1973).
The volume of pigments estimated to be consumed in textile printing is
listed in Table 11-2. The quantities shown in this table were derived from
data presented in Tables 7-3 and 7-7.
TABLE 11-2.
ESTIMATED DIARYLIDE PIGMENT CONSUMPTION IN TEXTILE PRINTING
Quantity (1 ,000 lb)
Pigment 1975 1976 1977 1978
Orange 16 75 95 88 93
Orange 34 99 186 88 91
Yellow 13 36 60 56 78
Yellow 14 555 900 974 941
Yellow 83 190-220 257-287 276-336 332-392
Blue 25 163-173 147-158 139-149 130-139
Total 1,118-1,158 1,645-1,686 1,621-1,691 1,665-1,734
11-5
-------
PIGMENT LOSSES
Roller printing pigment losses occur when the paste ink is left on the
equipment before it is cleaned and by paste ink loss from the back-grey when
it is washed and dried for further use. Estimates of these losses could
not be obtained from industry sources because of the lack of uniformity on
the number of rollers, engraving depths, and cleaning procedures. The losses
are mainly solid wastes, such as paste left in the color pan, but small
amounts of liquid waste result from the final equipment cleaning.
Pigment losses that occur in rotary screen printing are a result of
the cleaning of the screens and other equipment. Flat bed screen printing
results in pigment and dye losses during the cleaning of the equipment and
paste containers. Pigment losses in transfer printing should occur only in
the printing stage of the paper.
For all pigment printing processes, liquid wastes from the cleaning of
the equipment were estimated to be 1 to 2% of the total amount of pigment
consumed in textile printing. This range is based on information from in-
dustry sources.
For printing from a paste ink, minor miscellaneous losses will occur;
the most important of these are losses from the mixing of the paste and the
disposal of excess pigment. In the mixing of the dry pigments prior to
paste formation, very small quantities of dye are estimated to be lost as
dust particles. It is estimated that the percentage of pigment lost as dust
through mixing is close to the percentage of dye dust particles (see
Table 4-4).
For printing a specified amount of fabric, the printer can only esti-
mate the amount of pigment paste required; however, the printer usually com-
pounds an excess quantity of paste to ensure that all of the fabric can be
printed. One company estimated that an average of about 10% excess pigment
paste is made for each lot of fabric (Glick, 1979). Other industry sources
state that excess paste loss could reach 20% for each lot. Although much
of the excess paste can be incorporated into black pastes and the shading
of other colors, a quantity of residual paste is discarded as solid waste.
It is estimated that less than 50% of the excess paste can be recycled.
Although much of the printing is done in the same textile plants as
dyeing and the colorants are packaged in a similar manner, pigment pastes
are very viscous and losses from residual pigment paste remaining in their
shipping or other containers are much higher than the dye losses. It is
estimated that 0.5 to 2% of the pigment pastes are lost in container wastes.
Loss of dye and pigment also occurs from the final finishing of the
fabric. One report stated that for the typical woven fabric dyeing and fin-
ishing processes, 1.0% of the fabric is lost in finishing after the dyeing
and finishing have taken place. For the typical knit fabric dyeing and fin-
ishing process, 0.7% of the fabric is lost in finishing (Versar, 1976). It
is assumed that this loss applies to the pigment and dye as well as to the
cloth. This solid waste is either sold as rags, recycled and reprocessed
for other end uses, or landfilled.
11-6
-------
A summary of the sources of pigment loss and the estimated magnitude
of these losses for textile printing processes is presented in Table 11-3.
TABLE 11-3.
ESTIMATED DYE AND PIGMENT LOSSES IN THE TEXTILE PRINTING
PROCESS
Source of loss
% Loss
Dust from mixing
Cleaning wastes from rollers, screens, squeegees,
accessory equipment
Excess paste (not recycled)
Residual pigment paste in shipping containers
Volatile wastes from heat curing (pigment printing)
Colorant in waste cloth from other finishing steps
0.05-0.10
1-2
5-20
0.5-2
~ 0
0.7-1.0
The estimated pigment losses resulting from the textile printing pro-
cesses are presented in Table 11-4.
11-7
-------
TABLE 11-4. ESTIM\ TED DIARYLIDE PIGMENT LOSS IN TEXTILE PRINTING
Quantity (1,000 1b)
Source of loss 1975 1976 1977 1978
To ta 1 pigment consume~/ 1,118-1,158 1,645-1,686 1,621-1,691 1,665-1,734
Pigment loss.!?/ 6-23 8-34 8-35
Residual in shipping 8-34
container (0.5-2.0'/0)
Mixing (0.05-0.1%) 1 1-2 1-2 1-2
Cleaning wastes (1. 0-2.0%) 11-23 16-34 16-34 17-35
Excess paste (5-20%) 56-232 82-337 81-338 83-347
(not recycled)
Waste cloth from finishing 8-12 12-17 11-17 12-17
steps (0.7-1.0%)
t-'
t-'
I To ta 1 82-291 119-424 117-425 121-436
00
Total pigment in finished 827-1,076 1,221-1,567 1,196-1,574 1,229-1,613
cloth
2../
Data from Table 11-2.
'EJ
Data from Table 11-3.
-------
SECTION 12
MISCELLANEOUS USES
This section presents a brief discussion of a number of miscellaneous
uses of benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, and 3,3'-
dichlorobenzidine and the dyes and pigments derived from these compounds.
The areas of interest generally focus on those uses which were outside the
scope of the major segments presented earlier in the report. In some in-
stances, the areas represent a very small percentage use of certain materials
while for others they may represent the sole use.
LABORATORY AND TEST APPLICATIONS
Benzidine was employed for many years in analytical and medical research
laboratories for occult blood determinations, metal ion detection, chlorinated
organic pesticide detection, and other analytical procedures. The advent
of replacements in occult blood tests such as phenophthalein, tetramethyl-
benzidine, 3,3'-dimethylbenzidine, and others resulted in a gradual cessa-
tion of benzidine consumption approximately 3 to 4 years ago. The data con-
cerning the potential health effects of benzidine were probably a major factor
in the cessation of its usage. The use of benzidine as an analytical reagent
for metal ions and chlorinated organic pesticides also has decreased severely;
it would be currently employed only in very rare circumstances. One chemical
supplier estimated that less than 1,000 lb of benzidine is currently sold
for testing or other similar applications.
According to the report by Powell et al. (1979), approximately 5%
(~ 10,000 Ib) of the domestic usage of this compound is for various labora-
tory procedures such as occult blood testing or chlorine detection.
The Ames Company produces an occult blood test kit, Hematest@, that
uses 3,3'-dimethylbenzidine in a tablet form. This product is sold over
the counter in drugstores and similar. businesses that sell medical supplies
to the general public. The Ames Company declined to estimate the total con-
sumption of the dimethylbenzidine to produce the kits or the total sales of
these test kits. The company source estimated that only 1 to 2% of these
kits would be used in crime laboratories, hospital laboratories, or medical
research facilities.
Although no data are available regarding total consumption of the di-
methylbenzidine for the various test procedures, it can be estimated that
production of this material as a pellet would generally result in formulation
12-1
-------
losses of 5% or less, probably as solid waste. This estimate would include
the losses resulting from blending of the dry ingredients and the pressing
of the pellets. Since the pellets are dispersed into a liquid, it would
appear that the vast majority of this material consumed for testing purposes
would be discharged to wastewater.
HOME USE DYES
These dyes are sold in powder and liquid forms in supermarkets, drug-
stores, variety stores, fabric stores, and other consumer outlets. Powders
are sold in packets ranging in weight from 0.5 to 2.125 oz with the commer-
cial dye content ranging from 1% (light colors) to 45% (dark colors). Dark
colored .dyes dominate the market. Powdered dye packets are usually formu-
lated to dye 1 Ib of fabric. The liquid forms are sold in 8-oz containers
and are formulated to dye 2 Ib of fabric. Liquid dyes are much less popular
than the solid dye products.
The major manufacturers of home use dyes are RIT Dyes (Best Foods Di-
vision, CPC International), Tintex (Division of Kuomark, Inc.), and Putnam
(Dick Blick Materials, Inc.). An industry source estimated that RIT controls
approximately 90% of the home use dye market.
Formulation
All three current manufacturers stated that benzidine based dyes are
no longer used in the formulations of home use dyes. Putnam and RIT ceased
using benzidine based dyes in 1976; RIT had exhausted all stock containing
benzidine based dyes by 1977. Tintex ceased formulation with these dyes in
late 1977 and had exhausted all stock by October 1978. All three producers
stated that they currently formulate their products using dyes based on 3,3'-
dimethylbenzidine and 3,3'-dimethoxybenzidine in conjunction with other dyes.
NIOSH (1980b), however, found that 13 of 15 samples of retail dyes bought
in the fall of 1978 in New York City contained benzidine-based dye. The
dye samples were chemically reduced and analyzed for benzidine, 3,3-
dimethylbenzidine, 3,3'-dimethoxybenzidine, and analine. The relative per-
cent benzidine (percent of the total reduced components) averaged 57% (range
1 to 100%).
Consumption
Dyes based on 3,3'-dimethylbenzidine which are currently employed in
home use products are Direct Blue 14, Direct Orange 6, Direct Red 2, and
Direct Red 39. Dyes that are based on 3,3'-dimethoxybenzidine are Direct
Blue 1, Direct Blue 218, and Direct Blue 80 (Battelle, 1979). Between 60
and 70% of all colorant packets in the home use market contain dyes based
on 3,3'-dimethy1benzidine or 3,3'dimethoxybenzidine.
All three formulators were contacted but could provide no information
on the total consumption of the dyes of interest during the period 1975
through 1978. Data in the Battelle report show that for 1978, an estimated
12-'2
-------
400,000 lb of all dye types were consumed to produce home use dye packets.
Of this quantity, an estimated 33% (~ 130,000 lb) were dyes based on dimethyl-
or dimethoxybenzidine. The total number of dye packets produced in 1978
was 25 to 30 million. Approximately 50 million packets of dye were produced
in 1975 (Jenkins, 1978).
No data were available for the total number of packets produced in 1976
or 1977; prorated production figures for these 2 years estimate the number
of packets in 1976 at 40 to 45 million and at 30 to 40 million in 1977.
Using 1978 data for dimethyl- or dimethoxybenzidine-based dye consump-
tion (130,000 lb) and the average total number of packets produced (27.5
million), an average quantity of dye per packet can be obtained. This aver-
age quantity per packet was used to estimate quantities for 1975 (230 to
255,000 lb), 1976 (190 to 215,000 lb), and 1977 (140 to 195,000 lb). No
information could be obtained from industry sources which would permit any
further evaluation of these quantities with respect to the percentage based
on dimethylbenzidine or dimethoxybenzidine.
Estimated Losses
For the purposes of these estimations, it is assumed that all dye is
formulated into dry packets. This assumption is ba~ed on the knowledge that
liquid dye products represent a small percentage of 'the market and that for-
mulating losses for the liquid would likely be equal or less than losses
for a dry packet.
No data were available from home dye manufacturers concerning-formula-
tion losses. In most of the industries discussed earlier in this report,
the formulation of dyes into dry mixes resulted in average losses of approx-
imately 2 to 3% as residual dye in the shipping containers, handling losses,
dust losses from mixing, and other losses. This loss range, then, will be
assumed for these products. For the dyeing process in the home, an exhaus-
tion (uptake of dye on fabric) of about 25 to 40% was assumed. The remain-
ing 60 to 75% of the dye was discharged to the sewer. These estimated losses
are summarized in Table 12-1.
TABLE 12-1.
ESTIMATED LOSSES FROM HOME DYES
Quantity 0,000 lb)~/
Loss source 1975 1976 1977 1978
Total dye used 115-128 95-108 70-98 60-65
Formulation losses (2-3%) 2-4 2-3 1-3 1-2
Wastewater loss (60-75%) 69-96 57-81 42-74 36-49
Dye on finished fabric 15-57 11-49 ' 10-55 9-28
~/
Based on 100% dye; for method of calculation, see Table 5-5, footnote d.
12-3
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ARTS AND CRAFT DYES
The market for arts and crafts dyes is very fragmented with respect to
both the supply and demand segments. Most of the dyes used in crafts are
either the industrial dyes which have been specially packaged for craft use
or the home-use dye (see preceding subsection). The specially packaged craft
dyes are more concentrated than the home-use dyes. Potential users of the
specially packaged dyes are reached by direct mail advertising, craft oriented
magazines, or through specialty shops. Distributors of the dyes may employ
imported, prepackaged dyes or may purchase bulk quantities. The bulk quanti-
ties may be repackaged directly for resale or used in the formulations of
dye mixture for resale.
Fifteen consumer retail dyes were bought at arts and crafts shops in
New York City and analyzed for BEN, DMB, and DMOB. All 15 samples were shades
of blue, black, or brown (NIOSH, 1980b). It is unknown whether these are
the only BEN, DMB, or DMOB dyes available or only the ones selected for anal-
ysis.
Arts and crafts dyes are used for a multitude of coloring applications
with textiles, wood, paper, glass, metal, and other materials. The degree
of dye absorpton into the material ranges from very high (e. g., textiles)
to very low (e.g., glass, metal).
The annual consumption of dyes based on dimethyl- or dimethoxybenzi-
dine in this area is very small. Estimates of total annual consumption range
from 10,000 to 20,000 lb of commercial dye and consumption has remained in
this range since 1975 (She1drick, 1979). It is estimated that approximately
20% of the total quantity is discarded as solid or liquid waste during formu-
lation and consumer use of these products and that about 80% of the total
quantity is contained in the finished product. Of the 20% which is discarded,
75% is estimated to be solid waste and 25% wastewater. Thus, for each year
since 1975, approximately 4,000 to 8,000 lb of 100% dye were contained in
the finished product and 1,000 to 2,000 lb of 100% dye were discarded. Of
these estimated losses, 750 to 1,500 lb. are estimated to be solid waste and
250 to 500 lb discharged to the sewer.
MARKING INSTRUMENTS
Pigments derived from dimethylbenzidine (Orange 15) and dimethoxybenzidine
(Orange 16) were used in the production of children's crayons, lumber marking
crayons, china marking pencils, paint sticks, carpenter markers, and other
similar products. Orange 15 is no longer produced in the United States,
and in 1978 import quantities were very small.
Formulation
Most of these products are formulated in basically the same manner.
For children's crayons, a mixture of paraffin and stearic acid is melted in
a steam kettle, the colorants added, and the liquid wax mixture poured into
molds. Circulating cold water chills the molds and solidifies the wax mix-
ture. The crayons are ejected, trimmed, and paper wrapped.
12-4
-------
Industrial crayons are produced in a slightly different manner. The
most popular type of industrial crayons is composed of kaolin, color pigment,
and either natural or synthetic gum as the binder. All ingredients are mixed
with water to form a mass with dough-like consistency. This mass is extruded,
dried, and then impregnated with wax. Other methods of production include
dry pressing with a powdered wax mixture and the use of melted wax mixtures
as described for children's crayons. .
Consumption
Orange 15 and Orange 16 are the only two pigments of interest consumed
in this area. Estimated total quantities of the two pigments were derived
from Tables 7-3 and 7-7. The estimated total annual consumption is as fol-
lows: 1975 (93,000 to 98,000 Ib), 1976 (107,000 to 112,000 Ib), 1977 (96,000
to 101,000 Ib), and 1978 (66,000 lb).
Estimated Losses
Estimated losses during the production of the hot wax mixture should
be very small. The only anticipated losses result from the handling of the
dry pigment during weighing, and very small losses due to residual pigment
in containers. In previous sections of this report, these losses have been
estimated to be less than 0.5%. The only other production losses would be
due to trimmings from the cast or extruded crayons. It is estimated that
these losses would not be greater than 2.5 to 3.5%. All losses from the
production process would likely be treated as solid waste. The estimated
quantities of loss are presented in Table 12-2.
TABLE 12-2.
ESTIMATED LOSSES FROM CRAYON PRODUCTION
Quantity (1,000 lb)a
Loss source 1975 1976 1977 1978
Total pigment used 93-98 107-112 96-101 66
Pigment loss
Mixing and handling (0.5%) ~ 0.5 ~ 0.5 ~ 0.5 ~ 0.3
Trimming (2.5-3.5%) 2.5-3.3 2.7-3.9 2.4-3.5 2.3
Total 3-4 3-4 3-4 ~ 3
Pigment in finished crayon 89-95 103-109 92-98 63
a Derived from Tables 7-3 and 7-7.
12-5
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OTHER BAB DYE USES
In addition to the information presented in this report on uses of BAB
dyes, quantities are also used in other areas for which little or no infor-
mation could be developed. The lack of data is a result of either signi-
ficant uses in specific areas considered to be proprietary or very small
usage in a multitude of areas.
Information from DE TO (DETO, 1980) indicates that approximately
340,000 lb of dye based on 3,3'-dimethylbenzidine has been consumed annu-
ally since at least 1975 for miscellaneous uses in the coloration of lubri-
cants, gasoline, and other fuels. The specific dye or dyes are manufactured
by one company and all information concerning these products is proprietary.
No further information could be derived for these products.
It is recognized that quantities of BAB dyes are sold through formu-
lators or repackagers (companies who purchase in bulk and repackage in
smaller quantities) for a variety of uses. Little information is known con-
cerning the total quantity of dyes employed in these uses, the specific dyes
being employed, or the uses for the dyes. In general, the quantities employed
are small and the uses are extremely varied. However, the cumulative quan-
tity of a specific type of BAB dye (e.g., 3,3'-dimethoxybenzidine-based)
.could reach 4 to 5% of the total quantity consumed in 1 year. Due to the
diversity of the uses and the quantities of dye involved with each use, no
information was developed for these areas.
12-6
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SECTION 13
PRELIMINARY MATERIALS BALANCE
This section contains a preliminary overall materials balance for BAB
dyes and for selected pigments produced in the United States from 1975 to
1978.
The overall balance has been divided into two parts, BAB dyes and pig-
ments. In each balance the size of the range reported for each value is
indicative of the uncertainty associated with the specific estimate. De-
tailed descriptions of the technique used to generate individual estimates
as well as the uncertainties involved are contained in the appropriate sec-
tions of this report.
BAB DYES
Table 13-1 provides estimates of the losses of BAB dyes during the dye
production processes. These losses result from processing and filtration
losses during dye production, and product losses during drying, blending,
and final packaging.
Table 13-2 summarizes a materials balance for the BAB dyes in specific
use areas. Estimates are provided for the quantitities of dye production
resulting in the final products (commercial products or end uses), solid
waste, liquid waste, and losses to the air. All data are expressed in
thousands of pounds of dye. The data are presented in terms of ranges
rather than single values. This results because in the calculations,
ranges were employed for the percentage use in specific areas and for the
magnitude of the various sources of BAB dye loss during manufacture and
consumption. As a result, the data in Table 13-2 represent minimum and
maximum levels rather than average levels, which would have been the result
if single values had been employed.
As stated in Section 12, all uses of BAB dyes have not been character-
ized in this study and are not represented in Table 13-2. These uses, al-
though very small individually, can cumulatively account for up to 4 to 5%
of the total annual use of a type of BAB dye (e.g., benzidine-based). Thus,
the material balance accounts for the significant major uses of BAB dyes
but does not present a complete accounting for all losses resulting from
all possible uses.
13-1
-------
TABLE 13-1.
BAB DYE LOSSES FROM PRODUCTION PROCESSES
Active Dye Loss (1,000 1b)
1975 1976 1977 1978
Distribution BEN!?.! -DMBE/ DMOB~/ BEN DMB DMOB BEN DMB DMOB BEN DMB DMOB
Processing losses (0.21-0.95%)~ 5-26 < 1-4 1-8 7-40 < 1-4 2-10 5-26 < 1-4 1-7 2-10 < 1-5 2-12
Filtration losses (1-3%) 23-84 4-13 6-24 35-130 4-14 9-32 25-82 4-14 6-22 9-31 4-16 10-38
......
W Drying, grinding, standardization,
I
N and packaging losses (1-5%) 23-140 4-22 6-40 35-210 4-23 9-53 25-140 4-23 6-36 9-52 4-26 10-63
a/
- These data, which correspond to those given in Table 3-4, are on active. dye basis.
yield of 85% (BAMB raw material base) has been assumed.
Q/ BEN = benzidine-based dyes.
An overall product
~/ DMB = dimethy1benzidine-based dyes.
d/
- DMOB = dimethoxybenzidine-based dyes.
e/
- For the methods of calculation used in this table, see Appendix B,l.
-------
TABLE 13-2.
ESTIMATED MATERIALS BALANCE FOR B~ DYES BY USE AREA
Final Product
1975
1976
1977
1978
Losses
Solid waste:
1975
1976
1977
1978
Liquid waste:
1975
1976
1977
1978
Air losses:
1975
1976
1977
1978
Total dye in final
products
Losses
So lid
Liquid
Air
Total Losses
Textile
642-2,170
592-2,754
601-2,270
508-1,794
18-38
20-48
18-39
15-32
112-920
126-1,160
112-960
91-760
c/
neg.-
neg.
neg.
neg.
1975
1,629-4,133
113-386
181-1,016
neg.
294-1,402
Quantities (1,000 1b)~/
Leather Paper
-357-817
455-1,114
522-1,088
585-1,304
53-174
69-236
75-232
86-277
0.1-0.2
0.1-0.2
0.1-0.2
0.1-0.3
0.1-0.2
0.1-0.2
0.1-0.2
0.1-0.3
Sunnnary
1976
1,905-5,538
147-539
183-1,241
neg.
330-1,780
611-1,081
843 -1 , 616
787-1,355
501-920
39-168
55-250
50-210
32-142
0.1-0.2
0.1-0.3
0.1-0.2
0.1
0.1-0.2
0.1-0.3
0.1-0.2
0.1
~977
1,924-4,776
145-486
154-1,034
neg.
299-1,520
Home dyes£/
19-65
15 - 54
14-63
13-36
3-6
3-5
2-5
2-4
69-96
57-81
42-74
36-49
neg.
neg.
neg.
neg.
1978
1,607-4,054
135-455
127-809
neg.
262-1,264
~/ Quantities are in terms of 100% dye, not standardized commercial dye.
~/ Includes arts and crafts uses.
£/ Negligible losses.
13-.3
-------
PIGMENTS
Table 13-3 presents an estimate of the losses of 3,3'-dichlorobenzidine
(DCB), 3,3'-dimethoxybenzidine (DMOB), and 3,3'-dimethylbenzidine (DMB) oc-
curring during the manufacture of these three materials and during reactions
consuming these materials to form the desired pigments. For example, in
1978 it is estimated that 7,445,000 to 7,531,000 lb of DCB were produced.
Of this total quantity, 78,000 to 196,000 lb were lost in wastewater from
various stages of the manufacturing process and 38,000 to 77,000 lb were
lost in wastewater from various stages of the pigment production process.
All wastewater from both the manufacturing process and pigment production
process is treated prior to disposal. Thus, 7,258,000 to 7,329,000 lb were
estimated to be used to produce all DCB-based pigments in 1978.
Losses of pigment occur due to handling and transfer during the process
of transforming the pigment into a packaged, finished pigment ready for ship-
ment to the user. These estimated losses of pigment are shown in Table 13-4.
The losses presented in Table 13-4 are based on the maximum estimated annual
pigment production levels presented earlier in Section 7.
The estimated materials balance for pigments based on DCB, DMOB, and
DMB in specific use areas is shown in Table 13-5. As with the BAB dyes,
the data are presented in terms of ranges rather than single values. In
the calculations, ranges were employed for the percentage use in specific
areas and for the magnitude of the various sources of pigment loss during
manufacture and consumption. As a result, the data in Table 13-5 represent
minimum and maximum levels rather than average levels, which would have been
the result if single values had been employed.
OVERALL PERSPECTIVE
This subsection presents a brief discussion of the availability and
reliability of data on the production and use of BAB dyes and on the data
for pigments. Needs for additional information in each of these areas are
defined.
Dye and Pigment Production
In an overall perspective, more data are available and the sources of
loss are better defined for this area than any other general area considered
in this material balance. The production processes are fairly well defined
as are the relevant sources of loss in the BAB dye production process. How-
ever, additional detailed information is required for pigment production
since only a rather generalized procedure is described.
Pigment production quantities and the extent of pigment usage by the
various industries are considerably better defined than the corresponding
information for dyes. The percent utilization of a given pigment or BAB
dye by various industries will, of necessity, be a matter of conjecture
since estimates obtained from various manufacturers will differ.
13-4
-------
'-
TABLE 13-3. ESTIMATED LOSSES OF RAW MATERIAL DURING
MANUFACTURE AND PIGllliNT PRODUCTION
Losses (x 103 1b) Consumed in
Pigment pigmentgQ./
Base Manufacture prod .~/ (x 103 1b)
DcB£/
1975 40-102 20-40 3,762-3,799
1976 56-140 27-54 5,180-5,215
.1977 62-155 30-61 5,742-5,811
1978 78-196 38- 77 7,258-7,329
DMOB~/
1975 2-6 1-2 215-226
1976 2-7 1-3 250-261
1977 2-7 1-3 233-244
1978 2-7 1-3 240-251
D~/
1975 0 . 2-0 . 5 0.1-0.2 14-16
1976 0.2-0.5 0.1-0.2 14-16
1977 0.2-0.4 0.1-0.2 13-14
~/
Excludes optional processes.
'pj Excludes the "",20 ppm of base dihydroch1oride salt
remaining on pigment.
s/
DCB = 3,3'-dich1orobenzidine.
~/
DMOB = 3,3'-dimethoxybenzidine.
!:../
DMB = 3,3'-dimethy1benzidine.
13-5
-------
TABLE 13-4. ESTIMATED PIGMENT LOSS IN PRODUCTION PROCESS
Quantity (1.000 1b)
1975 1976 1977 1978
Total pigment production
DC B!./ 9,875-10,056 13 , 565 - 13 , 815 15,147-15,417 19,050-19,404
DMOB~/ 623-636 707-722 661-674 677-691
mm£./ "-' 4 6 "-' 4 6 "'46
Estimated pigment losses
DCB 91-274 126 -380 137-410 177-537
DMOB 6-19 7-21 6-20 6-20
DMB 0.5-1 0.5-1 0.4-1
Total pigment for sale
or captive use
f-' DCB 9,666-9,781 13,324-13 ,434 14,787-15,007 18,641-18,866
w
I DMOB 587-617 670-700 624-654 640-670
0'\
DMB 40-45 40-45 35-40
!./ DCB = 3,3'-dich1orobenzidine.
~/ DMOB = 3,3'-dimethoxybenzidine.
£./ DMB = 3,3'-dimethy1benzidine
-------
, ~A ~ L ~ 1: - 5 .
~S' ~n A' :ED M: nIALS ~A ~CE FOR 3,31 -DICHLOROBENZIDIN ~, 3,31 - LMETI Y ~ mNZIDINE
AND 3,31-DIMETHOXYBENZIDINE BASED PIGMENTS IN USE AREAS
Ouantities (1,000 1b)
Textile Misca/
Printing ink printing Plastics Coatings Rubber Uses-
Final product
1975 6,033-6,662 827-1,076 689-843 481-498 46-47 89-95
1976 8,189-9,026 1,221-1,567 954-1,139 690-709 69-71 103-109
1977 8,997-9,963 1,196-1,574 1,023-1,251 784-811 73-75 92-98
1978 11,698-12,921 1,229-1,613 1,122-1,366 949-980 71-73 63
Losses
Solid waste:
1975 1,085-1,672 71-268 42-135 7-11 ",1-2 3-4
1976 1,472-2,266 103-390 58-181 10-16 '" 2-4 3-4
1977 1,619-2,499 101-391 62-200 12-18 '" 2-4 3-4
1978 2,104-3,243 104-401 68-218 14-21 "'2-4 "'3
Liquid waste: Neg.P..!
...... 1975 117-118 11-23 2-3 Neg. Neg.
LV 1976 159-160 16-34 3-4
I :;reg. Neg. Neg.
-....J 1977 175-176 16-34 Neg. -4 Neg. Neg.
1978 228-229. 17-35 Neg. 4':'5 Neg. Neg.
SUMMARY
1975 1976 1977 1978
Total production range
including imports 10,418-10,568 14,310-14,455 15,510-15,765 19,316-19,571
Total pigment in
final products 8,165-9,221 11,226-12,621 12,165-13,772 15,132-17,016
Losses
Solid 1,209-2,092 1 ,648-~, 863 1,799-3,116 2,295;3,890
Liquid 130-144 178-198 195-214 249-269
Air Neg. Neg. Neg. Neg.
Total 1,339-2,236 1,826-3,061 1,994-3,330 2,544-4,159
J!/ Crayons and other marking instruments.
]2./ :;reg1igib1e.
-------
The information obtained for this report for the dye production pro-
cess was more detailed than for pigment production so that fewer assumptions
and estimations were necessary. On balance, these data are better defined
than for the pigment manufacturing process. Analytical data for the quan-
tities of 3,3'-dimethoxybenzidine and 3,3'-dimethylbenzidine currently being
discharged in wastewater would be of interest to better define the magnitude
of these losses during the manufacturing process.
One of the major areas of estimation in this report is the production
and import of the BAB dyes of interest. Since very few data were available,
gross estimates of the U.S. production and import quantities of the specific
BAB dyes were necessitated. Because these data are one of the keystones
for estimating potential losses from user industries, more detailed informa-
tion is critically required in this area.
BAB Dye Consumption
With the BAB dye industry, it is extremely difficult to evaluate with
any degree of accuracy the consumption of specific BAB dyes by a particular
user industry. In many respects, this inability arises from the wide diver-
sity observed among the various manufacturers in the textile, leather, and
paper industry. Another contributing factor, especially in the leather in-
dustry, is the use of prepackaged dye formulations which are prepared by
small speciality businesses for the particular tannery.
In the report, the estimated losses resulting from BAB dye consumption
in the leather, textile, and paper industries have the largest degree of
uncertainty of all the inputs to the material balance.
Losses resulting from the various processes employed within a specific
industry (e.g., textiles, leather, etc.) are extremely difficult to ascer-
tain with any degree of accuracy primarily because of the multitude of var-
iations employed by the individual companies. Because of this, generalized
processes were employed to estimate overall losses that might be anticipated.
One of the major deficiencies in the available data is the lack of in-
formation concerning the levels of BAB dye being discharged by these user
industries. If such data were available, the assumptions employed to obtain
the estimated data could be reevaluated and the degree of accuracy refined.
Sampling studies have been performed at sites in a number of different in-
dustries but very few data are available concerning specific effluent levels.
At the various sampling sites, the parent compound is the species under in-
vestigation, not the discharged BAB dye. Reliable data are necessary for
the quantities of BAB dyes being discharged from the various user facilities
before an accurate evaluation of the processes occurring within an industry
can be completed.
Pigment Consumption
On the surface, it appears that the major pigment users have a more
refined estimation of the sources of pigment loss and the magnitude of each
13-8
-------
'-
loss. The printing ink industry totally dominates the user market for pig-
ments; in 1978 they accounted for the use of approximately 74% of the total
quantity of all pigments of interest to this study. Most printing ink com-
panies purchase either dry toner or flushed color pigments and develop the
printing ink. Because of this practice and the methodology of ink produc-
tion, this industry appears to be able to define pigment losses within a
much more narrow range than those industries associated with BAB dye con-
sumption. The paint and coatings industry appears to be very similar to
the printing ink in the ability to define the sources and magnitude of pig-
ment loss. Other industries consuming pigments were not able to define the
losses to the same degree of accuracy. For the plastics industry, the very
diverse nature of that industry probably contributes to a large degree to
the overall inability to be more definitive. In addition, some of the me-
chanical processes used lead to wide variations in the magnitude of the
losses.
As with the area of BAB dye consumption, the major deficiency in the
data available on pigment loss lies with the lack of data on the quantity
of pigments discharged from the user facilities. To a large degree the
statements made previously with respect to data needs for a more definitive
evaluation of BAB dye consumption are equally valid for the area of pigment
consumption. Since the major consumers of pigments appear to have more re-
fined estimates of pigment loss, the need for quantitative data on pigment
discharges may not be as critical as for the BAB dye consuming industries.
13-9
-------
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1978a.
American Ink Maker.
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p. 24.
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Anon. 1979. Cradle to Grave Waste Disposal.
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American Ink Maker.
Asher, D. 1979. DeSoto Coatings, Chicago, Illinois.
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Personal communi-
Barnett, S. 1979. General Printing Ink Company, Kansas City, Missouri.
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Tele-
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Bruno, M. H. 1978.
1978. p. 19.
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R-1
-------
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Current Industrial Reports. MQ-22K(76)-5. U.S. Department of Commerce,
Washington, D.C. November 1977.
Bureau of the Census. 1977c. Wool Broadwoven Goods: 1976. Current In-
dustrial Reports. MA-22T.3(75)-5. U.S. Department of Commerce,
Washington, D.C. September 1977.
Bureau of the Census. 1978a. Finished Broadwoven Fabric Production:
1977. Current Industriai Reports. MA-22S(77)-1. U.S. Department of
Commerce, Washington, D.C. August 1978.
Bureau of the Census. 1978b. Knit Fabric Production: Summary for 1977.
Current Industrial Reports. MQ-22K(77)-5. U.S. Department of Commerce,
Washington, D.C. November 1978.
Bureau of the Census. 1978c. Knit Fabric Production: Second Quarter 1978.
Current Industrial Reports. MQ-22K(78)-2. U.S. Department of Commerce,
Washington, D.C. September 1978.
Bureau of the Census. 1979a. Knit Fabric Production: Fourth Quarter 1978.
Current Industrial Reports. MQ-22K(78)-4. U.S. Department of Commerce,
Washington, D.C. March 1979.
Bureau of the Census. 1979b. Finished Broadwoven Fabric Production: 1978.
Current Industrial Reports. MA-22S (78)-1. U.S. Department of Commerce,
Washington, D.C. August 1979.
Bureau of the Census. 1979c. Broadwoven Fabrics (Gray): Summary for 1978.
Current Industrial Reports. MO-22T (78)-5. U.S. Department of Commerce,
Washington, D.C. December 1979.
Burns and Roe. 1979a.
facturing Industry.
January 1979. .
Effluent Limitations Guidelines for the Ink Manu-
Environmental Protection Agency, Washington, D.C.
Burns and Roe. 1979b. Effluent Guidelines for the Paint Manufacturing
Industry. Burns and Roe, EPA Draft, January.
R-2
-------
Byrd, R.
Kansas.
1979. Enmar-Wichita Division of Ameron Corporation, Wichita,
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Tele-
Danforth, D. W. 1970. Beating and Refining Equipment. Handbook of Pulp
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Dr. Patrick A. Florio, American Hoechst Corporation,
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1980. Letter from
as a spokesman for
April 10, 1980.
Ensminger, C., and M. Culp. 1979. Enmar-Little Rock, division of Ameron
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R-3
-------
Environmental Protection Agency (EPA). 1976. Assessment of Industrial
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spokesman for dyes). Personal communication to Dr. Thomas W. Lapp.
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Francke, D. W., R. E. Seltzer, and D. J. Wissman. 1978. Economic Impact
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Tele-
Gallup, J. D. 1974. Development Document for Effluent Limitations Guide-
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Gilbert, W. 1979. General Printing Ink Division of Sun Chemical Company,
Kansas City, Missouri. Personal communication to H. Gadberry. July 19.
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Communication to B. Thompson. July 2.
Telephone
R-4
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Greer, B. 1979. Harwick Chemical Corporation, Akron, Ohio.
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Telephone
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Textile
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Imports of Benzenoid Chemicals
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and Products, 1978. Washington, D.C.
Imports of Benzenoid Chemicals
Jenkins, C. L. 1978. Scientific Basis for the Proposed Regulation of Dyes
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Toxic Substances, Environmental Protection Agency, Washington, D. C.
November 15.
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R-5
-------
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(7th
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Metal Finish-
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P. 19.
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In: Environ-
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Packages of Cream, Yellow, Gold, and Orange Paints were Inspected to Deter-
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Miller, E. 1979. Glidden Division of SCM, Inc., Cleveland, Ohio.
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Tele-
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R-6
-------
,-
Modern Plastics. 1977a. Plastics Sales Data, 1976 vs. 1975: Back Over
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Modern Plastics, September 1977. pp. 52-55.
Colorants.
Modern Plastics. 1978a. Market 1978.
1976. Modern Plastics, January 1978.
U.S. Plastics Sales Data; 1977 vs.
pp. 49-55.
Modern Plastics. 1978b. Opening the Doors to New Markets:
Modern Plastics, September 1978. pp. 54-57.
Colorants.
Modern Plastics.
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1979.
Materials 1979.
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1978.
Modern Plastics Encyclopedia 1978-
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Telephone commun-
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Report: The Carcinogenicity and Metabolism of Azo Dyes, Especially Those De-
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Washington, D.C.
Patton, T. C. 1973. Pigment Handbook, Vol. I and II.
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Wiley Interscience
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Personal
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Benzidine, Related Substances, and Related Dyes and Pigments. EPA-560/
13-79-005, EPA, Washington, D.C. 212 pp.
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Industry Dyeing Operations. EPA 600/2-78-315. EPA, Cincinnati, Ohio.
64 pp.
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letter to H. Gadberry, July 17.
R-7
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1-
Research Triangle Institute (RTI). 1979. Final Report Prioritization of
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April.
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1979. Battelle, Columbus, Ohio.
August.
Personal communication to
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LMS-226.
April.
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Philadelphia, Pennsylvania. Telephone communication to H. Gadberry.
June 19.
R-8
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~
Vathako, G. 1979. International Printing Ink Division of Inmont Corpora-
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June 11.
Versar, Inc.
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1976. Assessment of Industrial Waste Practices, Textiles
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Vogt, C. 1974. Development Document for Effluent Limitations Guidelines
and New Source Performance Standards for the Unbleached Kraft and Semi-
chemical Pulp Segment of the Pulp, Paper, and Paperboard Mills Point
Source Category. EPA 440/1-74-025-a. EPA, Washington, D.C. May. p. 21.
Walanski, K. 1979. Environmental Engineer, DeSoto Coatings, Inc.
Des Plains, Illinois. Telephone communication to H. Gadberry and letter
to H. Gadberry. July 26.
Welch, W. 1979. Gravure Research Institute, Port Washington, New York.
Telephone communication to H. Gadberry. June 7.
Wolthuis, R. J. 1979. Bofors Lakeway Inc., Muskegon, Michigan.
conversation and letter to T. W. Lapp, August 10.
Telephone
R-9
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APPENDIX A
REPORT REVIEWERS
A-I
-------
The following companies, organizations, and trade associations were pro-
vided draft copies of this report for their review and comments.
Al Schneid
Inmont Corporation"
150 Wagaraw Road
Hawthorne, NJ 07506
Frank Vincent
American Can Co.
1915 Marathon Ave.
Neenah, WI 54956
John L. Waldo
Saugatuck Dye & Chemical
P.O. Box 97
Saugatuck Station
West Port, CT 06880
Dr. Barry Bochner
Atlantic Chemical
10 Kingsland Road
Nutley, NJ 07110
Corporation
Dr. Roderick H. Horning
Crompton & Knowles Corporation
Dyes and Chemicals Division
500 Pear Street
Reading, PA 19603
Gilbert Bassett
Graphic Arts Technical
Foundation
4615 Forbes Street
Pittsburgh, PA 15213
Mr. Frank T. Ryan
Rubber Manufacturers
Association, Inc.
1901 Pennsylvania Avenue, NW
Washington, DC 20006
Dr. Robert M. Lollar
Tanners' Council of America 14
University of Cincinnati
Cincinnati, OH 45221
James E. Renson
National Association of
Printing Ink Manufacturers
500 Manaroneck Avenue
Harrison, NY 10528
Donald L. Morgan
Cleary, Gottlieb, Steen & Hamilton
1250 Connecticut Avenue, NW
Washington, DC 20036
Ralph Harding
Society of the Plastics
Industries, Inc.
1101 17th Street, ffi~
Washington, DC 20036
Dr. Harshad Vyas
Mobay Chemical Corporation
Verona Dyestuff Division
P.O. Box 385
Union Metropolitan. Park
Union, NJ 07083
Dr. P.S. Stensby
Ciba-Geigy Corporation
Dyestuffs & Chemicals Division
P.O. Box 11422
Greensboro, NC 27409
Dr. Hugh Smith
Sun Chemical Corporation
Pigments Division
4526 Chickering Avenue
Cincinnati, OH 45232
Mr. Raymond J. Connor
National Paint and Coatings
Association, Inc.
1500 Rhode Island Avenue, NW
Washington, DC 20005
Dr. John Festa
American Paper Institute
1619 Massachusetts Avenue, NW
Washington, DC 20036
Mr. John Tritsch
American Textile Manufacturers
Institute, Inc.
1101 Connecticut Avenue, NW
Washington, DC 20036
Richard Alsager
BASF Wyandotte Corporation
Pigments Division
491 Columbia Avenue
Holland, MI 49423
A-2
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APPENDIX B
SAMPLE CALCULATIONS
B-1
-------
SAMPLE CALCULATIONS
The following procedures and sample calculations are provided for
Tables 3-5 (p. 3-26), 3-7 (p. 3-29), 7-4 (p. 7-15), 7-5 (p 7-16), and
7-6 (p. 7-18).
1.
Table 3-5, p. 3-26
Procedure and Sample Calculation
A.
From p. 3-5:
Process Losses = ~ 0.25 to 1.0% (based on BAMB
raw material).
By-Products = 5 to 15%; 85 to 95% active dye
(based on BAMB raw material).
Filtration Losses = 1 to 3% (based on BAB dye)
Drying, Grinding, Standardization, and Packag-
ing = 1 to 5% (based on BAB dye).
B.
From Table 3-6:
(p. 3-27)
Product Yield = 84% (based on BAMB raw material).
Active Dye Content of Presscake (Footnote b)
= 85 to 90% (85% used in all calculation).
C.
Convert process losses from a BAMB raw material basis to an active
dye basis.
From (A):
(Total percent process 10ss)(Percent
dye from production process)
(0.25%)(0.85) = 0.21%
(1.0%)(0.95) = 0.95%
active
Lower Percentage:
Upper Percentage:
The process losses stated in (A) are now 0.21 to 0.95% based on
BAB dye.
D.
Sample calculations for benzidine-based dyes in 1975 are as follows:
Estimated total U.S. production = 3,800,000 to 4,600,000 pounds
(Table 3-4, p. 3-24)
Benzidine-based dye presscake content of standardized dye is
60% (Table 3-6, p. 3-27)
Estimated Loss = (Production rate) (product yield factor)(loss fac-
tor)(fractional presscake content of standardized dye)(fractional
active dye content of presscake).
% loss
Loss factor = 100
B-2
-------
II.
1.
Processing losses
Estimated loss =
(lower limit)
Estimated loss =
(upper limit)
2.
Filtration losses
Estimated
loss =
(lower limit)
Estimated
loss =
(upper limit)
Table 3-7, p. 3-29
1
(3,800,000)(0.84)(0.0021)(0.6)(0.85)
= 4,845 Ib
1
(4,600,000)(0.84)(0.0095)(0.6)(0.85)
= 26,532 Ib
1
(3,800,000)( 0.84)(0.01)(0.6)(0.85)
= 23,071 Ib
1
(4,600,000)( 0.84)(0.03)(0.6)(0.85)
= 83,786 Ib
Procedure and Sample Calculations
A.
Assumed Product Yield = 84% (see Table 3-6, p. 3-27).
B.
Process Vent Loss = 0.1%, either as unreacted starting material
or as decomposition products (p. 3-5).
Assume 1 to 10% of the total net losses are unreacted BAMB raw
material.
Thus, process vent loss of unreacted BAMB raw material is
0.001 to 0.01%.
1.
Processing Loss = 0.25 to 1.0% of the BAMB-based material (p. 3-5).
Assume that 1% of this loss is unreacted BAMB raw material.
Thus, processing losses are 0.0025 to 0.01% as unreacted BAMB
raw material.
2.
Filtration Losses: Assume 1 to 10 lb of filtrate per pound
of standardized dye and a filtrate content of 0.5 ppm of
unreacted BAMB raw material (p. 3-5).
3.
4.
Drying, grinding, standardization, and packaging losses: Assume
an unreacted BAMB raw material content of 20 ppm in each
pound of filter presscake for each BAB dye (p. 3-6).
5.
Product losses: Assume an unreacted BAMB raw material content
of 5 to 10 ppm in each pound of standardized dye (p. 3-6).
B-3
-------
c.
Sample calculation for benzidine-based dyes in 1975 are as follows:
Estimated total U.S. production = 3,800,000 to 4,600,000 pounds
(Table 3-4, p. 3-24).
Molecular weight of benzidine = 184.2.
Average molecular weight of benzidine-based dyes = 800 (Table 3-6,
p. 3-27).
Estimated loss = (Production rate) (product yield factor)(fractional
presscake content of standardized dye)(fractional actual dye
benzidine mol. wt.
content of presscake)( d 1 t)
. average ye mo . w .
Fractional presscake content of standardized dye = 0.60 (Table 3-6,
p. 3-27).
Fractional active dye content of presscake = 0.85 (Table 3-6, p. 3-27).
1.
Vent losses (lower limit):
Estimated loss = (3,800,000)(0.~4)(0.00001)(0.6)(0.85)(1~~o2)
= 5 Ib
2.
Processing losses (lower limit):
Estimated loss = (3,800,000)(0.~4)(0.000025)(0.6)(0.85)(1~~02)
= 13 Ib
3.
Filtration losses (lower limit):
Estimated loss = (Production rate)(filtrate weight)(level of
raw material in filtrate)
= (3,800,000)(1)(0.5 x 10-6) = 2 Ib
4.
Drying, grinding,
(lower limit):
standardization,
and packaging losses
Estimated loss = (Production rate) (fractional presscake content
of standardized dye)(level of raw material in
presscake)
= (3,800,000)(0.6)(20 x 10-6) = 46 Ib
5.
Product loss (lower limit):
Estimated loss
= (Production rate)(level of raw material in
standardized dye)
= (3,800,000)(5 x 10-6) = 19 Ib
B-4
-------
III. Table 7-4, p. 7-15 and Table 7-5, p. 7-16.
Procedure and Sample Calculation
3,3'-dichlorobenzidine in 1975
A.
From Table 7-6:
Examples
Total loss range of DCB-based pigment due to
transfer-and handling is 91,000 to 274,000 lb.
Calculate the range of percent contribution of
each DCB-based pigment to the total production
figures.
Yellow 12-(6028000)(100) = 62.4%; (6028000)(100) = 61.6%
,- 9666000 9781000
B.
From Table 7-3:
C.
1840000 - o. 1840000
Yellow 14 (9666000)(100) - 19.0%, (9781000)(100) = 18.8%
Multiply the percentage range for each DCB-based pigment (from B)
and the estimated losses of DCB-based pigment (from A). This pro-
rates the losses according to production volumes. Add losses to
annual production figures in Table 7-3.
Example
Yellow
12 (91,000)(0.616)
estimate)
(274,000)(0.624)
estimate)
= 56,000 lb (lower
= 171,000 Ib (higher
Estimated total Yellow 12 production =
6,028,000 + 56,000 = 6,084,000 lb
(low)
6,028,000 + 171,000 = 6,199,000 lb
(high)
Repeat this procedure for all DCB-based pigments.
D.
Calculate the quantity of free amine required for the total
of each DCB-based pigment. The molecular weight of DCB =
DMOB = 244.3; and DMB = 212.3. Pigment molecular weights
in Table 7-1.
production
253.2;
are given
Example
Yellow 12 253.2 = 0 402
629.4 .
(0.402)(6,084,000) = 2,446,000 Ib (low estimate)
(0.402)(6,199,000) = 2,492,000 Ib (high estimate)
The calculated range of DCB required to produce Yellow 12 in 1975 was
2,446,000 to 2,492,000 lb.
E.
Repeat this procedure for each DCB-based pigment. Sum the weights
of DCB required for each pigment to obtain the total DCB require-
ment of 1975. This sum is estimated to be 3,797,000 to 3,907,000 lb.
B-5
-------
F.
IV.
A.
Use the total DCB requirement obtained in (E) to calculate the
estimated losses in Tables 7-4 and 7-5.
For Table 7-4:
Purification losses = 0.5 to 1.0%
In 1975:
1.000 - 0.005 = 0.995
1.00 - 0.01 = 0.99
3,797,000 = 3 816 000 lb. 3,907,000 = 3,946,000 lb
o .995 " , 0.99
Therefore purification losses are:
(3,816,000)
(3,946,000)
(3,797,000) = 19,000 lb
(3,907,000) = 39,000 lb
G.
Use same procedure as shown in (F) to calculate purification losses
and filtration losses in Table 7-4 and the optional tetrazonium
filtration losses and pigment formation losses in Table 7-5.
Table 7-6, p. 7-18
Procedure and Sample Calculation
3,3'-dichlorobenzidine-based pigments in 1975
From Table 7-3:
Total production range of DCB-based pigments in
1975 was 9,666,000 lb to 9,781,000 lb.
Of this total quantity, Yellow 12 production was 6,028,000 lb and
all of the other DCB-based pigments were 3,638,000 to 3,753,000 lb.
B.
Data on p. 7-17 provides percent distribution of DCB-based pigments
between the three processing forms. Calculate distribution using
total production figures in (A).
Yellow 12:
(0.273)(6,028,000) = 1,646,000 lb
(0.704)(6,028,000) = 4,244,000 lb
. Dry toner
Flushed color
Presscake and
dispersions
(0.023)(6,028,000 = 139,000 lb
All other DCB-based:
pigments
(0.53)(3,638,000) = 1,928,000 lb
(0.53)(3,753,000) = 1,989,000 lb
Dry toner
Flushed color (0.141)(3,638,000) = 513,000 Ib
(0.141)(3,753,000) = 529,000 lb
Presscake and (0.329)(3,638,000) = 1,197,000 lb
dispersions (0.329)(3,753,000) = 1,235,000 lb
B-6
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,-
Total DCB-based pigments as:
3,574,000 to 3,635,000 Ib
Dry toner
Flushed color
4,757,000 to 4,773,000 Ib
Presscake and
dispersions
1,336,000 to 1,374,000 Ib
C.
Loss ranges are presented in Table 7-6 for each processing form
(i. e., dry toner, flushed color, and presscake).
Apply these loss ranges to totals for each processing form derived
in (B).
Example - Dry toner:
loss range = 1 to 3%
total production = 3,574,000
3,635,000 Ib (from B)
to
The total quantity of DCB-based pigment processed as dry toner
before any transfer and handling losses are as follows:
3,574,000 -
0.99 -
3,635,000 -
0.97 -
3,610,000 Ib (lower limit)
3,747,000 Ib (upper limit)
Losses due to transfer and handling are:
(3,610,000) - (3,574,000) = 36,000 Ib
(lower
limi t)
(3,747,000) - (3,635,000) = 112,000 Ib
(upper limit)
D.
Use same procedure in (C) to calculate other losses in Table 7-6.
B-7
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50272 -101
REPORT DOCUMENTATION
PAGE
i.1::....REPORT HO.
I EPA-560/2-81-001
'2-
!
3. Recipient's ACCOl1llion No.
.. rrtte and Subtitle
Materials Balance for Dyes and Pigments from Benzidine and
Three Benzidine Derivatives
5.. Report Date
Mav 1981
6.
7. AuthOr(s) Thomas W. Lapp, Thomas L. Ferguson, Howard Gadberry,
Fritz Hoffmeister, Fred Hopkins
iJ. Perform;"c O,.anization Name and Address
Midwest Research Institute
425 Volker Boulevard
Tr-.sas City, Missouri 64110
~
a. Performi"C Oraa"ization Rept. No.
10- ProjectlTuk/Wortc Unit No.
Task V
11. eo"tntct(C) tK~~ No.
(C) 68-01-3896
(G)
- - Soonsonna Orcanization Name and Address
Environmental Protection Agency
Office of Pesticides and Toxic Substances
Washington, D.C. 20460
11. Type of Report & Period Covered
Final Report
14.
-
15.. Supplementa" Not"
Roman Kuchkuda, Project Officer
.16. Abstract (Limit: 200 words) The processes - for and losses resulting from-the" manufacture of dyes and
pigments are presented. Consumption profiles and estimated losses are summarized for bis-
azobiphenyl (BAB) dyes in the textile, leather, and paper industries and for pigments in
the rubber, plastics, printing ink, textile printing, and coatings industries. During
dye production, losses occur in by-products, process venting, process losses, product fil-
tration, and transfer and handling of solid dyes. For 1978, about 80% of the total BAB
dye use in the testile, paper, and leather industries was incorporated into the final
product and 20% was lost to solid waste or wastewater. Losses in wastewater were about 50%
greater than in solid waste. During pigment production, losses result from soluble by-
products and handling and transfer losses. In 1978, estimated total losses due to handling
and transfer of pigments during production were 190,000 to 558,000 lb. The printing ink
industry consumed the majority of the total pigment production. In 1978, about 75% of the
total pigment used in the five industries was incorporated into the final product and 25%
was lost to wastewater or solid waste. Essentially all of the pigment loss was as solid
waste with very small quantities in wastewater.
17. Document An..)'Si. .. Descriptors
Benzidine
Dichlorobenzidine
Dimethylbenzidine
"-Tolidine
Dimethoxybenzidine
Dianisidine
Materials Balance
Direct Dyes
Diarylide Pigments
Production
Exposure
Solid Waste
Industrial Waste
Water Pollution
b. Identifiers/Open. Ended Terms
Materials Balance
Solid Wastes
c. COSATI Fil'ld/Group
18. Availability Statement
Unlimited Distribution
119. Security Class (This Report)
I UNCLASSIFIED
I 20. SKU"ty Clan (Tho. Pace)
UNCLASSIFIED
21. No. 0' Paies
217
I Z2. Price
. .0"'-'0...... ~ORIIoII 272 (4-77'
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