Zero Discharge In Textile Processing

Through TDS Control

By B.D. Thakur, M. Joshi, M.

Chakraborty, S. Pathak, Northern India
Text. Research Assns., Ghaziabad, India

Abstract Table I: Dye removal from colored effluent using three different coagulant systems.
The requirement of a high concen-
tration of soluble inorganic salts in the System-l System-Ii System-Ill
dyebath recipe in cotton reactive reac- % Dye Removal % Dye Removal % Dye Removal
tive dyeing causes the eventual dis- Metal Before After Metal Before After Metal Before After
charge of intensely colored dye effluent ion Polishing Polishing ion Polishing Polishing ion Polishing Polishing
that contains a high level of total dissolv- (Fe +2 ) (Al + 3) (Fe +3 )
ed solids (TDS). The limitation of a con- (ppm) (ppm) (ppm)
ventional treatment scheme in remov- 50 80.7 99.76 21 83.5 99.90 21 83.8 99.8
ing the inorganic TDS has restricted the 100 83.4 99.69 32 84.6 99.89 41 85.1 99.8
recovery and reuse of water from the 151 84.9 99.81 43 86.5 99.85 83 86.8 99.8
resultant combined stream in other 202 86.0 99.55 53 87.7 99.86 129 88.2 99.8
252 87.0 99.56 107 88.5 99.88 259 89.0 99.8
processing. Also, the repeated recir- 388 89.5 99.8
302 89.0 99.58 214 89.8 99.81
culation of conventionally treated water 352 91.5 99.63 428 90.6 99.87 517 90.9 39.8
causes a further enhancement of in- 403 92.4 99.68 - - - 647 91.6 99.8
organic TDS during the process recir- 504 93.7 99.83 - - - 776 92.7 99.8
605 94.4 99.89 - - - - - -
culation and treatment stage.
This article explores an appropriate
treatment scheme for removing the dye-
stuff and other impurities from the
segregated dye effluent by adopting
physico-chemical and tertiary polishing bility of good quality water, especially in Moreover, an increased use of cotton
treatments. This process helps in the arid regions of the developing coun- in textile products has significantly in-
achieving commercial zero hardness tries, have magnified the already exist- creased the use of direct, vat, sulphur
and low level of metal content in the ing water crisis in the industrial sector. and, especially, reactive dyes. These
recovered water, providing an excellent This has made it an imperative for the dyeing processes require large quant-
scope for its reuse in the dyeing process industry to try to adopt such waste ity of salts to achieve good exhaustion
itself. water treatment schemes where recov- of the dye bath. As a result, the content
The waste inorganic chemicals were ery and reuse of the treated water is of total dissolved salts (TDS) in these
also recovered in the concentrated form envisaged. textile effluents is very high. Hence,
or in pure crystalline form and were Textile wet processing is a highly reactive dyebaths are not amenable for
reused in the dyeing operation. The water intensive operation. The various reuse due to the presence of unabsorb-
fastness properties such as light, chemicals like starch, dye-stuff, aux- ed dye along with other contaminants
washing and rubbing of the yarn after iliaries, alkalies, acids, detergents etc., and high TDS present in the bath at the
dyeing with recovered water and salt that are used in the processing contam- end of the cycle.
have been found comparable to the inate the water and cause pollution in Several techniques investigated by
original samples dyed using fresh terms of BOD, COD, pH, TDS, color, earlier workers have been reported in
chemicals and soft water. hardness etc., in the discharged efflu- review papers1-4 on handling such efflu-
The repeated recirculation does not ent. ents, especially for the removal of col-
cause any significant enhancement of Unexhausted soluble reactive dyes or from the dyeing effluent. These are
TDS or metal content in the recirculated present in the textile dyeing effluent as under:
water. This helps in the indirect control exhibit their color which is highly objec-
of TDS limit for the remaining major tionable from the environmental and
segregated water as prescribed by the aesthetic point of view. Particularly, the
concerned pollution boards in its dis- reactive dyes or their hydrolyzed form i) activated charcoal (adsorption
posal into the outside environment, after hardly undergo biodegradation and thus technique)
repeated recycling. pass through the treatment plant, caus- ii) membrane technology
lntroductlon ing serious contamination of natural iii) ozone treatments
The increasing cost and non-availa- water. iv) coagulation/flocculation.
 Although these treatments are effec-
Shade: Red; M:L = 1:30 Note:
tive in color removal, each technique
Depsoluble ACA- Fiber lubricant
has its associated problems, and all of
them, except the coagulation technique, Dyebath constituents which also mini-
Depsoluble ACA (ICI) 1.0 g/l mizes the risk of
involve high cost and are, therefore, not
Matexil PA-L (ICI) 3.0 g/l dye stains.
techno-economically viable for the tex-
Calgon (ICI) 1 .0 g/l Matexil PA-L Anti-reducing
tile industry.
Common salt 60.0 g/l agent
Newer technologies have also been
Dye Reactofix Calgon Water softener + -
reported in recent literature where
Brill HE-8B 8% (owf) sequestrant
specific dye adsorbers-e.g. polyamide
Soda Ash 5.0 g/l All of the chemicals such as sodium
-ipichlorohydrin-cellulose polymer have
Caustic soda 0.2 g/l
been used for acid dye removal.5 chloride, sodium carbonate, sodium
Another such example is the use of 85°C 60 min hydroxide etc., used were of analytical
cellulose based cation exchange com-
posite for color removal of some basic
dyes.6
The conventional treatment scheme
generally employed in the textile in-
dustry though removes color and
reduces the BOD/COD level to permis-
sible limits, but it fails to control the total
dissolved solids (TDS) level. Such water
increases the tendency to form incrusta-
tions in sewers due to the high amount
of dissolved salts. This also reduces the
calcium and magnesium contents of
soil, hardens the texture of soil, prevents
penetration of roots and affects the sub-
soil water.4
Various techniques such as reverse
osmosis, demineralization etc., have
also currently emerged to reduce the
TDS level in such salt rich effluent
streams, but limitations of such proc-
esses are exposed after attaining a cer-
tain concentration level.
It is, therefore, time to search for
other techno-economically viable alter-
native devices in order to recover and
reuse the waste inorganic chemicals so
that the remaining water can be recov-
ered and recirculated without any tech-
nical hurdles.
This article deals with an in-depth
study of a physico-chemical treatment
scheme of removing color from the
reactive cotton dyeing effluent having a
high level of TDS (60,000 to 80,000 ppm)
and the possibility of recirculation of
treated water in the process house.
Recovery of salt from the segregated
dye effluent which is only about 10% to
20% of the total combined effluent will
make this process highly cost-effective.
The remaining effluent can be treated
using a simple technique at a compar-
atively low cost.
An attempt has also been made to
critically evaluate the various problems
encountered in the reuse of water and
recovered salt.

Experimental
In all the experiments the dye recipe
used is presented in tabular form as:
grade. A pH meter (Electronic India, Table II: Dye removal from simulated effluents of varying colors.
model 121E) was used for measuring
the pH.
Dye Used Characteristics of Treated Effluent
In the physico-chemical treatment
commercial grade metallic salts and After Physico-chemical After Polishing
flocculating aids were used. The reac- Treatment Treatment
tive dyes used in the experiments were Dye cone % Dye Dye cone % Dye
as under: (ppm) Removal (ppm) Removal
l-For red shade, Reactofix Brill Red.
Red ( HE-8B) 18.021 90.98 0.7856 99.61
HE-8 B (Jaysynth) Dyechem Pvt
Ltd) Golden Yellow 16.585 91.71 0.2336 99.88
2-For golden yellow shade, Thalac- HE-RB)
tive golden yellow HE-RB (Goldpal
Green (HE-4BD) 10.2282 94.89 0.2506 99.87
Chem. Industry)
S-For navy blue shade, Navy blue Navy Blue (HE-2R) 6.4370 96.78 0.1050 99.95
HE-2R (Serene Dyestuff Industries
Mixture of Dyes - - Colorless
Ltd)
4-For green shade, Thalactive green
HE-4BD (Goldpal Chem. Industry) Table III: Dye removal from simulated effluent of varying concentrations.
Dye concentration in the effluent and
Original Metal ion Dye removal % in treated water
treated water was measured using op- Cone
Dye* Cone % Dye Removal % Dye Removal
tical density method by UV/VIS spectro- (ppm) (ppm) After Physico- After Polishing
photometer (Model-ShimadzuUV160A) Chemical (ppm)
and respective dye concentration eval- Treatment
uated using a calibration curve.
8 50.4 87.7 98.25
Effluent and treated water character-
100.8 89.4 99.75
istics such as pH, color, COD, TDS,
hardness and iron content were deter- 20 50.4 87.4 98.25
mined using the respective BIS speci- 100.8 89.75 98.20
fications. 98.87
40 50.4 88.5
The experimental recipe was used for 100.8 90.12 98.95
dyeing scoured yarn with reactive dye
HE-8B (red shade) in experiments, and 80 50.4 93.52 99.71
the actual effluent thereafter obtained 100.8 93.9 99.69
was used. For other shades, simulated 100 50.4 93.18 99.37
effluent was prepared to study the effec- 100.8 97.74 99.40
tiveness of chemical treatment for all
types of dye structures. 125 100.8 94.70 99.70
The effluent thus received was ini- 151.1 95.82 99.72
201.5 98.44 99.84
tially given physico-chemical treatment
after which it was polished in order to 150 100.8 96.41 99.87
ensure the removal of iron and hard- 151.1 97.11 99.93
ness, etc. Thus, the final treated water 201.5 98.99 99.93
was directly employed in the experi-
200 100.8 92.25 99.95
ments or salts were recovered from the 151.1 92.88 99.93
treated water and reused in the dyeing 201.5 93.17 99.91
operation.
The different dyed yarns using 'Using Navy Blue HE-2R
original dye solution, recovered water
and chemicals and those using only
recovered chemicals were subjected to special recipe formulation depending on order to maintain the desired pH
light and wash fastness tests etc., ac- the type of shade desired. Such recipe range from 9 to 10.
cording to BIS specification for color has the special characteristics as men- Dye concentration and
fastness to light (IS: 2454:1967) and col- tioned below:
Auxiliary Chemicals
or fastness to washing, test no. 3 (IS:
764-l 979). Inorganic Salts The concentration of reactive dye
(a) The presence of inorganic salts depends on the type and depth of
Results and Discussion like sodium chloride or sodium product shade. The reactive dye
The major bottleneck encountered in sulphate at a level varying from concentration varies from 2% to
the recovery and recirculation of treated 2 % to 8 % i.e., 20,000 to 80,000 8% (on the weight of fabric/yarn
water from the segregated textile dye ef- ppm. to be dyed). The presence of ad-
fluent is its high TDS content and the (b) The requirement of soda ash ditional chemicals like water
possible contamination by iron ions. In /caustic soda varying from 0.5% softener, fiber lubricant and anti-
reactive cotton dyeing, it requires the to 2.0% (5,000 to 20,000 ppm) in reducing agents are also present.

34 American Dyestuff Reporter August I994

 Although the undesirable properties
of water containing aluminum are less Figure P-Effect of metal ion concentration on percentage of dye removal.
serious, excess iron present in process
water can lead to staining and is there-
fore objectionable. Excess iron in
Fe( + 2) or reduced state is soluble and
thus must be converted to Fe( + 3) or an
oxidized state, as the Fe (OH), formed
is insoluble and can be removed
easily.7
Excess iron [Fe( + 2)] removal was
ensured in the experiments by maintain-
ing a pH above 6 and providing proper
aeration so that all iron in ( + 2) state is
oxidized to Fe( + 3) and precipitates in
the form of insoluble Fe(OH), which may
be removed easily.
The reuse of such treated water and
its further recirculation will lead to the
gradual enhancement of TDS value,
which ultimately makes it unfit for fur-
ther recirculation and needs inevitable
disposal into the outside drain. 10 60 110 I60 210 260 310 3 6 0 410 4 6 0 510 560 610 660 710 750
EFFECTIVE ION CONCENTRATION (PPm)
Consequently, strict maintenance of
TDS level (e.g. 2100 mg/l) as prescribed
by concerned pollution control boards
is a difficult task unless the problem is
tackled by alternative ways and means,
Table V: Evaluation of fastness properties.
giving a major thrust to the recovery and
reuse of spent waste inorganic chemi-
cals following a suitable techno-eco- Test Conducted Samples
nomically viable process. Initial Redyelng Dyeing Redyeing
With this objective in view, the initial Dyeing After with re- After
experiments deal with the critical evalu- sample using covered using
ation of the dye effluent characteristics treated salt treated
water by water by
and the necessary treatments to be Al3+ Fe2 +
provided. system system

Color fastness 7 6/7 6/7 6/7

Treatment Scheme
As per the scheme, the dye effluent
is segregated from the other wash
streams and subjected to the physico-
chemical treatment until final polishing
as shown in the schematic flowdiagram
in Figure 1.
The dye concentration in the effluent
has been found to vary from 16 ppm to
400 ppm, depending on the depth of the
shade of the fabric being dyed and the
type of dye used.
Figure 2 shows the effect of metallic
ion concentration on the percentage
removal of reactive dye while dealing
with the actual dyeing effluent with the
dye concentration of 212 ppm where
mare than 90% of dye could be re-
moved. After further polishing of the
treated water it is observed that dye
removal could be achieved more than
99.5%, as shown in Table I.
Table II shows the type of different
reactive dyes used in the experiments
and the percentage removal of dye from
their simulated effluent having an initial
dye concentration of 200 ppm before
to light
Color fastness to
washing (Test No 3)
- Change in shade 4/5 4/5 4
- Staining on 4 4 4 4
white cloth
Color fastness to
Rubbing
3/4 3/4 3/4
Dry 3/4
Wet 3 3 3 3
treatment at a constant level of directly proportional to the dye concen-
chemical dosing. This implies the effect tration present in untreated effluent.
of chemical dosing is equally effective Figure 3 shows the variation of per-
for most of the reactive dyes commonly cent dye removal as a function of initial
employed in the dyeing. dye concentration. This also indicates
Table III shows the degree of chemi- that the efficiency of dye removal in-
cal dosing to be maintained according creases as the original dye concentra-
to the initial level of dye concentration tion in the effluent is enhanced.
which varies from 8 to 200 ppm. This Table IV shows the initial and final
shows the degree of chemical dosing TDS values, pH, color, hardness, COD
and coagulant aid concentration re- and iron content present in the effluent
quired for complete removal of dye is before and after the chemical and pol-

American Dyestuff reporter August 1994

 ishing treatment. Figure i-Effect of dye concentration in the effluent on the percentage of dye
As shown in Table IV, the final recov- removal.
ered water after treatment satisfactor
ily meets the standards specified for it:
use in the dyeing operation. But as dis
cussed earlier, the dyeing recipe formu
lation also depends on the time se,
quence of the addition of various salts
Therefore, the reuse of such treated
(recovered) water is limited to its appli-
cation where the dye bath recipe is
formulated for dyeing deeper shade:
only, as in a case where the presence
of a high quantity of salt in the initial dye
ing water is acceptable.
Such recovered water has been used
in the dyeing operation. The light, wash.
ing and rubbing fastness of dyed yarn
using fresh and recovered water are
shown in Table V. However, such
treated water containing a high amount
of dissolved salts can be reused only Acknowledgement (1993) 23.
when deeper shades need to be dyed. The authors are high/y grateful to Dr. Jai (4) Sharma, M., Tecoya Technical Update,
In the case of lighter shades, an alter. Prakash, Director, NlTRA for his constant en- Aug. (1993) 10.
couragement and support in carrying out this (5) Hwang, M.C., and Chen, K.M.. J. Appl.
native scheme was tried where the work. Our thanks also to Mr. Maheshwar Polymer Sci., 49 (1993) 975.
treated water is concentrated, and the Singh and Mr. H.S. Yadav for their he/p in the (6) Abo-shosha, M.H., Ibrahim, N.A., and
recovered salts were reused in the experimental work. Halwagi, A.EI. American Dyestuff Re-
subsequent dyeing operations using soft porter, February (1993) 41.
References (7) Kirk-Othmer Encyclopedia of Chemical
water. The salt was recovered from the (1) Cooper, P.. J. Soc. Dyer and Co/., 109 Technology, ed. Mark, H.F., Othmer. D.F.,
highly salt rich treated water using a (1993) 97. Overberger, C.G., Seaborg, G.T.. John
multiple vacuum evaporator. (2) Sampath, MR., Colourage, July (1993) 37. Wiley &Sons, 3rd Ed. (1984) Vol. 24, pp.
The salt recovery by this technique is (3) Sharma, F?., Textile Dyer & Printer, Sept. 397.
expected to be quite economical and
comparable to the cost of commercial
salt of the same purity, as available in
the market.
The possible contamination of recov-
ered salt by iron ions was cross-
checked by an optical density method
using a calorimetric method of iron
determination. Iron content in the
recovered salt was found to be in the
range 0.00125% which is very much
within the safe limit prescribed for salt
water to be used in the process houses.

Conclusions
The recovery and reuse of inorganic
salts has significant importance as far
as the water recovery and its reuse in
the process is concerned. It is quite ob-
vious that the recovery cost of the salt
in crystalline form exceeds the cost of
commercial salt, but its reuse in con-
centrated form up to a certain level is
very much techno-economically feas-
ible.
Perhaps the most prominent feature
of this study is that the TDS level of
discharged water is maintainable within
pollution control board limits without any
harmful effect on the environment with
a scope of repeated recycling of recov-
ered water.

August 1994 American Dyestuff Reporter