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United States

Environmental Protection
Air and Energy Engineering
Research Laboratory
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Agency Research Triangle Park NC 2771 1
Research and Development EPAIGOOIS2-851010 Apr. 1985

GEPA Project Summary

Textile Dyes and Dyeing


Equipment: Classification,
Properties, and Environmental
Aspects

S. V. Kulkarni, C. D. Blackwell, A. L. Blackard, C. W. Stackhouse, and


M. W. Alexander

N e w dyes are continuously being equipment described. All information


developed t o meet the demands of was collected on an as-available basis
new technology, new fabrics, ad- and included data generated by site
vances i n dyeing equipment, and t o visits and discussions with other in-
overcome the serious environmental dividuals familiar with this industry.
concerns associated w i t h some ex- Information o n air emissions t o the
isting dyes. The impact of these new ambient environment from textile dye-
replacement dyes o n the environment ing operations was collected and
and workers can be assessed by com- reported; however, little data were
paring them w i t h similar existing available o n air emissions of dyestuffs
dyes. For this study, information was t o the ambient air. For data on worker
collected from the open literature, exposure t o airborne dyes, four 1978
product technical brochures, trade studies by the National Institute for
association studies, and visits t o t w o Occupational Safety and Health were
textile dyeing operations. The col- consulted. U n f o r t u n a t e l y , these
lected i n f o r m a t i o n w a s used t o studies were of limited use since they
characterize the physical, chemical, dealt only with benzidene-based dyes
and application properties of 14 w h i c h have been curtailed f r o m
classes of textile dyestuffs. Informa- widespread use by the industry.
tion collected on textile dyeing equip- Where possible, worker exposure
ment was studied t o describe dyeing times were recorded during the plant
procedures, the operation of various visits.
types of textile dyeing equipment, and A data base f r o m E P A s Effluent
t o estimate both the amount o f textile Guidelines Division was accessed:
dyestuff released t o the environment results of a brief analysis of this base
from a typical dyeing operation and are reported. Information extracted
t h e e x t e n t o f w o r k e r exposure from the data base included the
associated w i t h each operation. These number and size range of wastewater
estimates were made on a weight-per- treatment and pretreatment plants of
weight basis of dyestuffs to fabric various textile dyeing operations. This
dyed for typical operations. The plant information, separated into direct and
visit information was used t o verify indirect wastewater discharges, was
data obtained from the literature and presented for small, medium, and
t o fill data gaps. This information large textile dyeing operations.
enabled estimates t o be made of Since there were data gaps in the
dyestuff releases from actual dyeing area of the emission/release of textile
operations for each type of dyeing dyestuffs t o the environment, addi-
~

tional areas of possible investigation Dye Class Categorization the fiber to form an insoluble color
are identified, including data t o Using general dye chemistry as the molecule. These dye components, sold as
characterize worker exposure time basis for classification, textile dyestuffs paste-like dispersions and powders, are
and dyestuff concentration levels, are grouped into 14 categories or classes: used chiefly for cellulosics, especially cot-
quantities o f drestuffs purchased b y (1) acid dyes, (2) direct (substantive) ton. Dyebath temperatures of 16-27OC
textile dyeing operations, and updated dyes, (3) azoic dyes, (4) disperse dyes, (5) (60-80°F) are generally used to the shade.
plant size data specific t o dyeing sulfur dyes, (6) fiber reactive dyes, (7) Disperse dyes are colloidal and have
operations. This information would basic dyes, (8)oxidation dyes, (9) mor- very low water solubilities. Most of these
create a larger, more comprehensive dant (chrome) dyes, (10) developed dyes, dyes are used for polyester, nylon,
data base f r o m which t o obtain a (11) vat dyes, (12) pigments, (13) op- acetate, and triacetate fibers. They are
more realistic profile o f the textile tical/fluorescent brighteners, and (14) sol- usually applied from a dye bath as dis-
dyeing industry. vent dyes. persions by direct colloidal absorption.
Six of the above dye classes (1-61, Dye bath conditions (temperature, use of
This P r o j e c t S u m m a r y w a s carrier) are varied based on the degree of
selected by EPA's Office of Toxic
developed by EPAIS Air and Energy difficulty encountered by the dyes in
Substances, were the focus of intensive
Engineering Research Laboratory, penetrating the fiber being dyed. They are
data collection efforts in an attempt to
Research Triangle Park, NC, to an- s o m e t i m e s a p p l i e d dry a t h i g h
describe each class, its chemistry, and
nounce key findings of the research temperatures by means of a sublimation
chemical and physical properties as fully
project that is fully documented in process followed by colloidal absorption.
as possible. Information collected for the
separate report of the same title (see High temperature sublimes the dye and,
remaining eight classes (7-14) was similar,
Project Report ordering information a t once it is inside the fiber, the dye con-
but not as detailed. Selection of these
back). denses to a solid colloidal state and is ab-
classes (1-6) was based in part on a pro-
jection of new dye development activities sorbed on the fiber.
Introduction and concerns about the health and en- Sulfur dyes are used primarily for cot-
In 1980, 111 million kg (245 million Ib) vironmental effects of these dyes. The ton and rayon. The application of sulfur
of synthetic organic dyestuffs were pro- following paragraphs briefly identify these dyes requires carefully planned trans-
duced in the U.S. The U.S. imported six classes of dyes and describe their use formations between the water-soluble re-
another 13 million kg (29 million Ibl, or 12 by the textile dyeing industry. duced state of the dye and the insoluble
percent of the domestically produced Acid dyes are typically used to dye oxidized form. Sulfur dyes can be applied
amount of synthetic organic dyestuffs. acrylics, wool, nylon, and nylon/cotton in both batch and continuous processes;
About two-thirds of the dyestuffs pro- blends. They are called acid dyes because continuous applications are preferred
duced in the U.S. were used by the tex- they are normally applied t o the because of the lower volume of dye re-
tile industry for dyeing. Until recently, nitrogenous fibers of fabrics in organic or quired. These dyes generally have a poor
azo-type acid dyes, direct dyes, and inorganic acid solutions. Chemical reac- resistance to chlorine. In general, sulfur
pigments based on benzidine and ben- tions between the dye and fiber form an blacks are the most commercially im-
zidine congeners were commercially im- insoluble color molecule on the fiber. In portant colors and are used where good
portant and very popular dyestuffs. 1980, acid dyes accounted for 10 percent color fastness is more important than
However, recent health and environmental of total U.S. dye production. The three shade brightness. Sulfur dyes are not ap-
concerns about benzidine-based dyes most commercially important acid dyes plicable to wool or silk because the fibers
have caused dyestuff manufacturers and are azo, anthraquinone, and tri- are chemically damaged by the dyeing
dye users to seek less toxic and en- arylmethane. These dyes are generally ap- process.
vironmentally safer replacements. In addi- plied as a liquid at elevated temperatures Fiber reactive dyes derive their name
tion, new technology, new fabrics, and of greater than 39OC (102OF). Although from the fact that they form covalent
advances in dyeing equipment provide in- acid dyes may be used for transfer print- bonds with the fiber molecules to be
centive to develop new dyes. ing, this use is not commercially im- dyed. Molecules of fiber reactive dyes are
Knowledge of the physical, chemical, portant. In general, these dyes have poor much smaller than the complex molecules
and application properties of new data wet fastness. Molecular weights range of direct dyes. Fiber reactive dyes are
can provide valuable information about from 200 to 900, and the higher the unique in that they become an integral
the dye's environmental release and molecular weight, the poorer the leveling part of the textile fiber that is dyed.
worker exposure effects. One method (uniformity of dye uptake) property. Although more expensive than direct
used to determine this information for dyes, advantages of reactive dyes are ex-
Direct dyes are applied in an aqueous cellent shade reproducibility and good
new and replacement dyes is by compar-
bath containing ionic salts and elec- leveling properties. These dyes also have
ing the properties of new dyes with
trolytes. These dyes are normally used to outstanding wet fastness. In 1980, about
similar dyes within the same dye class for
dye cotton and other cellulosic fibers; 2 percent of the total dyestuffs produced
which such information is already known.
they bond to fibers by electrostatic forces. in the U.S. were fiber reactive dyes.
This report provides a basis upon which
In 1980, 13 percent of the dyes produced These dyes can be subdivided into either
such a comparison can be made.
in the U.S. were direct dyes. These dyes "hot" or "cold" dyeing groups, based on
are highly soluble even in cold water; the temperature of application. Although
Summary most have solubilities in water from 8 to silk and nylons can be dyed with fiber
40 gif. A few have solubilities up to 80 reactive dyes, the chief fibers dyed are
Three major areas of the study relate to
dye class categorization, dye equipment glP. cellulosics and wool. These dyes are also
categorization, and wastewater treatment Azoic dyes are applied by combining popular for printing textiles, since even
plant size. two soluble components impregnated in the brightest colors are wet fast.
2
Fiber reactive dye products were first tions are presented for the currently where machine tension on the fabric
introduced in 1956; by 1980 there were 66 available dyeing equipment, and dyestuff could cause damage. Pressure becks
on the market. Of these, 59 represent use requirements were estimated for each typically use 3,300P (858 gal.), or 3,245 kg
about equal numbers of yellow, orange, machine, based on typical fabric/dye (7,153 Ib), of water per 454 kg (1,OOO Ib)
red, and blue dyestuffs. The remaining in- combinations. These estimates were of fabric dyed; an atmospheric beck uses
clude black, brown, green, and violet verified with information collected during twice this volume of water to dye the
shades. By 1982, the number of fiber two plant visits. same quantity of fabric. The typical fabric
reactive dyestuffs listed for sale had in- Two textile dyeing operations were dyed in an atmospheric beck is cotton;
creased to 139, more than twice the visited to verify information collected in polyesters generally are dyed in a pressure
number available in 1980. This increase, the literature search and to verify actual beck. Dye exhaustion rates of 90 to 100
along with the fact that the dye shades dyeing procedures, attainable dye exhaus- percent were achieved depending on the
are very reproducible and wash fast, in- tion rates, and drug room procedures, dye class used and the shade of color
dicates a continued increase in impor- and to determine the typical quantities of desired. For example, a medium to light
tance of fiber reactive dyes in the future. dye and fabric used in dyeing operations. color was found to exhaust 100 percent;
Based on a linear regression projection of The two plants visited were selected whereas, a dark color would only achieve
the past 10 years' production volumes of because: (1) small and large dyeing opera- 90 percent exhaustion.
fiber reactive dyestuffs, this class of dye tions were represented; (2) four types of
A typical atmospheric beck using sulfur
is expected to show a 56 percent increase dyeing equipment of interest were in use;
dyes on cotton fabric releases about 0.5
in production volume by 1990 to a level of (3) a commission dyeing operation involv-
kg (1.2 Ib) of dye solids per 454 kg (1,000
approximately 19.7 million kg (49.3 million ing several dye products was represented;
Ib) of fabric dyed in its rinse water ef-
Ib). The fiber reactive dye class is ex- and (4) the distance from Research
fluent. This amount depends on the ex-
pected to experience the largest percent- Triangle Park, NC, was less than a day's
haustion and dye shade desired. An addi-
age increase in production of any of the drive. Information obtained from these
tional 4.8 kg (11 Ib) of dye per 454 kg
14 dye classes by 1990. two plant visits was used to develop a
(1,OOO Ib) of fabric dyed leaves the dye
mass balance f o r t y p i c a l d y e operation with the fabric, depending on
Dye Equipment Categorization equipment/fabric/dyestuff combinations. the exhaustion and dye shade desired.
Ten major types of dyeing equipment The mass balance estimates indicate Pressure becks (or jet machines) typically
are now in use by the textile dyeing in- the amount and manner in which a dye apply disperse dyes on polyester. This
dustry. Some of these machines required substance is released to the environment
operation releases 1.2 kg (2.7 Ib) of
minor operational modifications to accom- from specific types of dye equipment. The
disperse dyes per 454 kg (1,OOO Ib) of
modate the newer dyes and to take ad- dyestuff release from the fabric and rinse fabric dyed in water effluent, depending
vantage of recent advances in dyeing water was found to vary widely for the
on the exhaustion and shade desired. The
equipment technology. The 10 general different types of dyeing equipment and dyed fabric typically contains 11.2 kg
types of dyeing equipment are: (1) beams, the fabric dyed. The total amount of
(24.5 Ib) of disperse dye solids per 454 kg
(2) becks, (3) jigs, (4) jets, (5) package dyestuff can be accounted for in the
(1,OOO Ib) of polyester fabric, but this can
units, (6) vats, (7) semicontinuous (pad- fabric, in the rinse water, and in the at- vary depending on exhaustion and desired
batch dye machines), (8) continuous dye- mospheric environmental release. shades.
ing (TAK dyeing, space dyeing, thermosol Therefore, rinse time, rinse volume, and
dyeing, and pad-steam dyeing), (9) dye exhaustion rates are important Pad-batch dyeing is accomplished with
transfer printers, and (10) direct textile parameters for estimating environmental a padding machine that is equipped with
printers. release. The following descriptions of a set of wringers which force the dyestuff
Four of the 10 classes (2, 7, 9, and 10) each type of dyeing equipment and its through the fabric. Once the fabric has
were selected by EPA's Office of Toxic typical mass balance illustrate the variabili- been saturated with dye, the fabric is
Substances for detailed study. Selection ty of dyeing equipment. developed in a batch immersion operation
was based on the predicted continued Beck dyeing takes place in a U-shaped to exhaust the dye onto the fabric. This
and predominant use of the equipment in box or trough with a gradually curved process can be used for vat, sulfur, azoic,
the textile dyeing industry. bottom. The fabric to be dyed is placed solubilized vat and diazotized, and
The four types of dyeing equipment are on a driven reel above the box and is developed direct dyes. Exhaustion rates
fully described with respect to operation allowed to slide down the back of the for this type of equipment range from 60
methods and procedures, physical box, travel through the dye liquor in the to 95 percent, and depend on the amount
features, and the dyeing processes for box, and then continually return to the of process time and the fabric/dye class.
which they are suitable. Machine types reel. This procedure is continued until Rinse time for this process ranges from 1
also are categorized by the fabric which dyeing is completed. Beck dyeing is best hour to 4 or 5 hours. Because of the
can be dyed and then related to the dye suited to woolen knit and woven goods numerous steps required, this process is a
classes that typically would be used with as well as heavyweight fabrics such as large user of water compared with other
the various machine/fabric combinations. carpets, twills, and satins. wet dyeing operations. Water use ranges
Detailed time/temperature dyeing profiles Beck dyeing utilizes the exhaustion dye- from 6,240 to 9,1201 (1,648 to 2,409 gal.),
also were developed for numerous ing method which is aided by heating the or 6,232 to 9,110 kg (13,739 to 20,084 Ib),
fabric/machine/dyestuff combinations. dye liquor with steam. In order to per 3,175 kg (7,000 Ib) of fabric dyed in a
The important advantages and features decrease the dyeing time, beck dyeing batch.
of these classes of dyeing equipment machines are pressurized to accelerate the The third type of dyeing equipment in-
were identified along with their limitations exhaustion process. These h i g h vestigated in detail was a transfer printer.
and disadvantages in dyeing different temperature and high pressure becks The method most commonly used in the
types of fabric. The equipment specifica- (jets) are best suited to elasticized fabrics transfer printing process involves the
3
direct transfer of a pattern or Color from a Wastewater Treatment million gpd); and large, 0.05 m3/s (1.1
printed paper to the fabric. This is a dry Plant Size million gpd). The design flow of the
process and achieves almost complete Data from EPA's Effluent Guidelines respective POTWs that received the
color exhaustion onto the fabric. A typical Division were analyzed to characterize the typical dyeing plant effluent averaged:
transfer printing ,operation purchases its volume of wastewater effluents from tex- small, 0.73 m3/s (16.70 million gpd);
supply of transfer paper and therefore tile dyeing operations and the general medium, 0.83 m3/s (18.90 million gpd);
does not generate any dye waste at the methods of treatment. Although this is and large, 1.20 m3/s (28.40 million gpd).
textile printing facility. The expended the most current data available, it does
transfer paper minus its dyestuff coating not reflect any changes since it was com- Conclusions
is discarded with the plant's refuse. piled in 1977. The data are based on infor- Based on the information collected for
Transfer printing is accomplished by a mation provided by textile operations from this study, new dyestuffs will continue to
sublimation process in which the solid two standard industrial classifications replace older dyes. In the textile industry,
(dye) is vaporized by heat and condenses (SIC): 223 and 226. These classifications, the two dye classes that will experience
into a solid on the fabric when cooled. covering wool weaving and finishing mills the most growth are fiber-reactive and
Disperse dyestuffs are the dye class most and textile finishing (excluding wool) disperse (sublimable) dyes. A concurrent
typically used for transfer printing onto a plants, were selected for analysis because increase in the use of new dyeing equip-
polyester fabric. Transfer printing uses most dyeing operations fall into one or ment (e.g., the pressure beck (jet) and
about 0.5 kg (1.1 Ib) of disperse dyestuff the other. transfer and direct printers) is expected
per 45 kg (100 Ib) of fabric. Some other The data provided by 494 plants per- because of their high dyeing efficiency
methods of transfer printing use a wet or forming textile dyeing were analyzed. Of and exhaustion rates. For these reasons
semiliquid process, but the dry process these, about 30 percent (only 147 plants) and since this type of equipment uses lit-
described above is becoming predominant discharge their wastewater effluent after tle or no water compare with other equip-
because it is unique, uncomplicated, and on-site wastewater treatment. The rest ment (e.g., the beam, pad-batch opera-
and requires less skill to operate than pretreat their wastewater and discharge it tion, and atmospheric beck), many dyers
other types of dyeing equipment. In addi- to publicly owned treatment works will reduce the quantity of wastewater
tion, the dry process is suitable for (POTW). and dye solids discharged to the environ-
polyester fabric, which has traditionally ment. However, because the new dry
Both the indirect and direct discharges
been one of the most difficult fibers to printing method (transfer printing) uses
were separated into three plant size
dye. This process also can be used on categories (small, medium, and large) dyes that sublime, use of this method
acetate, triacetate, and nylon; its use with may transfer dye emissions from a water
based on their daily fabric production
disperse dyes is limited because of the rates. These categories were determined medium to the atmosphere surrounding
high temperature involved. Its use on cot- by selecting the medium-sized plant pro- the machine. Use of this method could
ton, wool, or silk is limited by the lack of duction rate range to be between 0.75 have a greater impact on worker exposure
affinity and/or fastness properties for and 1.25 times the overall average daily than wet dyeing methods. In addition,
disperse dyes and because of cylinder production rate. Plants with higher pro- both plant visits conducted for this study
head temperatures as high as 230OC duction rates were considered to be large; revealed that dye operations can, with
(446OF) that will scorch these delicate those with lower production rates were proper machine operation, achieve a very
fibers. considered to be small. From this distribu- high degree of dye exhaustion onto the
The fourth type of textile dyeing equip- tion, typical average plant production fabrics. Based on observations at the two
ment that was investigated in detail was rates and wastewater volumes were deter- plants visited, this effort is already being
direct textile printing. This method uses a mined for each plant size. made to maximize the effective use of
combination of mechanical and chemical A typical small plant, directly discharg- dyestuffs and minimize the cost of dye
means to dye the fabric substrate. The ing to the surface waters after on-site purchases.
two primary methods of direct printing are waste treatment, produces 14,000 kg
roller and screen: in both, the dyestuff is (31,000 Ib) of fabric per day and generates Recommendations
applied as a print paste or printing ink. 0.02 m 3 / s (0.40 million gpd) o f Several areas were identified where in-
The paste or ink is dispersed and either wastewater. The typical medium-sized formation was incomplete or unavailable
rolled directly onto the fabric (roller print- plant produces 44,000 kg (97,000 Ib) of on textile dyeing operations. In most in-
ing) or extended (screen printing) from a fabric per day with a resultant wastewater stances, the unavailable information was
circular or flat perforated screen onto the discharge of 0.04 m3/s (0.90 million gpd). nonexistent; obtaining it would require
fabric. Acid dyes are typically used in this The typical large direct discharging plant detailed research efforts. In other in-
process and are applied to nylon knit produces 107,000 kg (236,000 Ib) of fabric stances, the information was available,
fabrics; pigments and reactive dyes are per day and discharges an average of 0.08 but the database was incomplete or insuf-
used for cottons. In actual printing opera- m3/s (1.90 million gpd) of wastewater. ficient t o establish reliable emis-
tions, 100 percent of the dye is applied to Typical daily production rates for the sion/release estimates and trends. The
the fabric; consequently, the only en- small, medium, and large plants discharg- areas of textile dyeing operations requiring
vironmental dyestuff release is via the ing their wastewater to a POTW were additional study are:
printed fabric. However, some of the 6,000 kg (14,000 Ib), 23,000 kg (50,000 Developing Information on Properties
dyestuff on the printed fabric will be Ib), and 86,000 kg (189,000 Ib), respective- of Dyestuffs- Most information
released during rinsing. Since this printing ly. Pretreatment facilities for these typical available o n physical/chemical
method results in high quality designs, it plants were found to have the following dyestuff properties is general and
is becoming the most appealing method design capacities: small, 0.01 m3/s (0.26 does not describe the properties of
for coloring designer and fashion apparel. million gpd); medium, 0.02 m3/s (0.52 specific large volume dyestuffs now

4
in use. The use of chemical property quantity of dyestuffs transferred to
estimation techniques and/or actual the residual wastes from treatment of
testing of specific dye substances textile dyeing wastewater.
could develop detailed information in Compiling Information on Dyeing of
this area. vThis effort could also be Leather and Non-woven Textile Prod-
enhanced by preparation of en- ucts-Data on these topics were
vironmental fate and accumulation available, but were not a major focus
estimates for the dyestuffs, using of this study.
recently published estimation Additional Plant Visits to Textile Dye-
methods. ing Operations-Additional plant
Characterizing the Size, Capacity, visits to collect similar information
and Dye Use of Textile Dyeing Opera- would broaden the data base for
tions-The most recent data available plant operations and dyestuff release
was from EPA's Effluent Guidelines estimates. This study investigated
Division and was about 6 t o 10 years only two plants; more such visits
old. Since that time, new dyes and would be useful in obtaining a
fabric combinations have replaced realistic profile of the textile dyeing
older dyestuffs, fabrics, and industry.
machines. This currently available in-
formation primarily focuses on textile
finishing operations, rather than dye- S. Kulkarni, C. Blackwell, A. Blackard, C. Stackhouse, and M. Alexander are with
ing operations. Additional data collec- Radian Corporation. Research Triangle Park, NC 2 7709.
tion efforts could focus on textile J. S.Ruppersberger is the EPA Project Officer (see below).
dyeing operations, rather than on tex- The complete report, entitled "Textile D yes and Dyeing Equipment: Classification,
tile finishing operations as past data Properties, and EnvironmentalAspects,"(Order No. PB 85- 173 771 /AS; Cost:
collection efforts did.
Developing Data on Worker Exposure
$3 1 .OO, subject to change) will be available only from:
National Technical Information Service 8' \ . 4
r

to Dyestuffs- Little information was 5285 Port Royal Road


available in the literature on worker Springfield, VA 22 16 1
exposure to dyestuffs, except for Telephone: ZU-487450 &'do ?-$ I 6 z PI
benzidene-based dyes which have The EPA Project Officer can be contacted at:
been largely dropped from use by the Air and Energy Engineering Research Laboratory
industry. Parameters t o be considered U . S . Environmental Protection Agency
include: frequency, duration, and ex- Research Triangle Park, NC 2771 1
posure concentrations for workers. I 1
No data were found to characterize
the type and concentrations of
volatilized dye or solvent emissions
from dry transfer printing operations
t o the atmosphere or dyestuff
releases via the expended transfer
paper. This, as well as other batch
and continuous dyeing methods,
could be investigated with respect to
worker exposure.
Studying Advanced Wastewater
Treatment of Dyes-Much informa-
tion was available in the open
literature on wastewater treatment of
textile effluents. However, these data
did not focus on removing specific
dyestuffs by these technologies, nor
did they address the removal efficien-
cy of advanced technologies; e.g.,
reverse osmosis and hyperfiltration
for specific dyestuffs.
Investigating Multimedia Transfer of
Dyestuffs-Both existing and ad-
vanced candidate wastewater treat-
aU.S.Government Printing O f f i c e : 1985 - 559-111/10819
ment technologies produce waste-
water sludge or other liquid concen-
trates that must be disposed of. Vir-
tually no data were available for the

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