Professional Documents
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Paradise Prints
Desai Street, Sagrampura
Surat 395002, GUJARAT, INDIA
Ph. :- 0261-631965
by
Chittaranjan Desai
Introduction :- After Rio De Janeiro's epic meet on environment, ecology & environment have become quite sensitive issues. Surat being the largest syn-
thetic fabrics center, with more than 200 process houses, can cause considerable pollution problems as wet processing consumes sizeable amount of wa-
ter & materials, but the Gujarat Pollution Control Board has actually gone overboard by coming up with norms which are even more stringent norms than
many of the highly developed European countries & USA. Besides the limits of pollutants are the same for effluent disposal to inland surface waters as well
as public sewers, which is not the case in any other country as seen in Table 1 [1].
TO TO
COUNTRY BOD COD BOD COD
GUJARAT State 30 100 30 100
SACHIN (G.I.D.C.) 15 30
BELGIUM 30 400 300 750
DENMARK 1 70 --- ---
0-20 -100
FRANCE 40 --- 500 ---
/100
GERMANY 25 160 *
*
ITALY 40 160 250 500
SPAIN 40 160 300 500
U.K. 3 ---
0-70 * *
N. CAROLINA, USA NA 250 * 60
NA 0*
* Charges are levied on polluters according to the concentration of pollutants.
Under these stringent regulations, two fundamental approaches to pollution control are available. a) Waste treatment & b) Source Reduction of pollutants.
Many waste treatments simply remove an undesirable process waste from one media to another. e.g. Dyes & chemicals in the effluent are converted to
sludge, which has to be disposed either by landfilling or incineration. This may contaminate the ground water. An important alternative to treatment is
waste minimization. This concept looks to textile processes itself to determine what changes can be made to reduce pollution at source. Waste minimiza-
tion becomes critical to centers like Surat, where most of the process houses & for that matter even municipal sewerage treatment plants have only
primary effluent treatment plants. Besides it requires little or no capital investment & often results in substantial cost savings in the processes.
Various techniques employed to reduce pollution at source are :-
2) Inventory management.
5) Water conservation.
6) Process modifications.
7) Equipment modifications.
1) Quality control of Dyes / Chemicals :- A Laboratory, which is still absent in many of the Surat process houses, becomes the first step towards pollu-
tion reduction. Strict control on the quality can be maintained by testing supplies of Dyes & chemicals. This would result in lower reprocessing & improved
product consistency. This would naturally increase profits as well as reduce wastes associated with reprocessing.
2) Inventory management :- A process house dyes chemicals store generates three kind of major wastes : excess, out of date & no longer used raw ma-
terials. These obsolete items are more often than not, directly dumped into the drain. To avoid this situation, inventory control techniques like ABC analysis,
FSN analysis, etc. can be employed effectively. Excess inventory often results from "getting a good bargain" by purchasing a tanker load where only a drum
is required. This is where Economic order quantity (EOQ) & order levels system would be of immense value. At times surplus stocks of dyes do accumulate
due to the changing fashion trends. Under these circumstances Colour computer matching system can be a used to formulate new recipes using these non
moving dyes or they can be sold back to a willing supplier or another process house using those dyes.
3) Waste Audit:- From Sep '93, complete environmental waste audit statement has been made mandatory by the Pollution Control Board. A complete
waste audit of all the processes & machines in terms of water consumption, COD, BOD, Suspended solids & pH should be carried out to get a complete pic-
ture of major trouble spots. All the above parameters except BOD, can be easily tested in the process house laboratory. BOD values can be obtained from
an environmental lab. Besides COD, BOD values of all the auxiliaries & dyes used can also be obtained, which can be than be used for substitution. This
database can be further enhanced by adding data like Biodegradability, Fish toxicity, Metal content, from Safety Data Sheets supplied by environmentally
aware companies like Sandoz. The process wise effluent analysis is shown in the table no. 2.
The auxiliaries consumption / month, their respective COD, BOD loads & other environmental data are as shown in the Table 3. As seen, many gaps exist
for information like bioelimination, fish & oral toxicity as they are not readily available with the manufacturers.
Table 2
Table 3:-
NO. AUXILIARY ORAL TOXICITY BIO EL. % FISH TOXICITY QTY./MON COD BOD COD/MON. BOD/MON % COD % BOD
.
1 Indrez AG 4800 0.97 0.22 4636.8 1041.6 66.9% 51.9%
2 Acetic Acid LD0 = 100, 380 1.04 0.85 395.2 321.1 5.7% 16.0%
LD100=200
3 Ethyl Acetate NA 200 1.54 0.29 308 58 4.4% 2.9%
4 Non Ionic Deter- >2000 50-100 12 125 1.76 0.47 220 58.4 3.2% 2.9%
gent
5 Oxalic Acid 50-500 Ld0 = 20 1100 0.18 0.14 195.8 154 2.8% 7.7%
6 Hicoklarin KD NA 165 0.95 0.2 156.1 32.2 2.3% 1.6%
7 Sandopur PCI >500 80 1.28 0.18 102.4 14.2 1.5% 0.7%
8 Formic Acid LD0 = 100, 270 0.35 0.15 94.5 40.5 1.36% 2.02%
LD100=200
9 Silicone De- NA 250 0.37 0.03 91.5 7.3 1.3% 0.4%
foamer
10 Lyogen DFT >5000 50-100 >500 45 1.95 0.54 87.6 24.2 1.3% 1.2%
11 Sodium Hydro- NA 250 0.33 0.22 83.3 55 1.2% 2.7%
sulfite
12 Urea LD0 = 16000, 850 0.09 0.09 76.5 76.5 1.1% 3.8%
LD100=30000
13 Ginasol 6836 150 0.5 0.15 75.6 22.7 1.1% 1.1%
(Godrej)
14 Shidofix N 65 13 80 0.91 0.25 72.5 19.8 1.0% 1.0%
15 Sandacid PBI >2000 50-100 >100 40 1.57 0.22 62.7 8.7 0.9% 0.4%
16 Sudirol K 60 0.9 0.2 53.8 12 0.8% 0.6%
17 Diosyn HF 200 0.21 0.15 41.6 30 0.6% 1.5%
18 Sequacel HD 90 0.4 0.1 35.6 9 0.5% 0.4%
19 Catalyst DD 200 0.15 0 29 0.8 0.4% 0.0%
20 U.D.A. Powder >5000 50-100 >100-500 35 0.77 0.23 27 8.1 0.4% 0.4%
21 HicoleveIer BJD 45 0.59 0.09 26.5 3.9 0.4% 0.2%
22 Mercerine PES NA 80 0.32 0.06 25.8 4.7 0.4% 0.2%
23 Lyogen PA 66 35 0.51 0.02 17.9 0.8 0.3% 0.0%
24 Citric W 800 0.02 0.01 16 4 0.2% 0.2%
25 Diaton PR (Hico) 35 0.07 0.02 2.6 0.7 0.04% 0.03%
26 Ammonium 58 TLm = 1290 (96 1100 0 0 0 0 0.0% 0.0%
Sulfate hrs)
27 Caustic Soda 1100 0 0 0 0 0.0% 0.0%
28 Soda Ash 400 0 0 0 0 0.0% 0.0%
29 Hydrochloric Acid 100-330 275 0 0 0 0 0.0% 0.0%
30 Citric Acid LD0 = 625, 0 0.69 0.4 0 0 0.0% 0.0%
LD100=894
31 Diethylene Glycol >5000 0 1.49 0.12 0 0 0.0% 0.0%
32 Phenol 5-10 0 2.28 1.4 0 0 0.0% 0.0%
33 Sarcol DBN 105 0 0.28 0.09 0 0 0.0% 0.0%
Chemical Substitutions :- Several chemical alternatives exist for various wet processing processes. The following factors should be considered to select
1) Biodegradability / Bioeliminability,
2) Aquatic Toxicity,
Scouring :- 1) Majority of the scouring pollutant load comes from the sizes, coning oils, fillers & impurities, which many times are added by the weaver just
to improve the profitability in these hard times ! A processor cannot do much about it, but a composite mill can definitely select sizes & coning oils having
lower COD, BOD value. 2) More than 600 tonnes / Year of non-ionic detergent based on Nonyl phenol ethoxylate is currently being used in Surat. This
product on biodegradation gives toxic metabolites, which are highly poisonous to the fishes. Hence German manufacturers had voluntarily stopped it's
manufacture from 1988. Now it can be substituted even in India, by Alfa Olefin Sulfonate, marketed by Gujarat Godrej as Ginasol 6836. It is easily biode-
gradable, non toxic & cheaper as well. Besides fatty alcohol ethoxylates, which are also biodegradable, are also available. 3) Many stain removers contain
solvents like Carbon tetrachloride. The harmful effect of CFC's like Freon on Ozone layer is causing lot of concern, what is less known is, that Carbon tetra-
chloride has ten % more Ozone depletion capacity than CFC! Thus CCl4 based products should also be eliminated immediately. 4) Oxalic acid used for re-
moving of rust stains is also quite toxic to aquatic organisms & besides has a considerable COD, BOD. It can be replaced by Catalyst D (Dharamsee Morar-
jee). 5) Hydro causes huge depletion of dissolved oxygen in the water. Considerable reduction in COD can be achieved by replacing Hydro which has a COD
of 333 mg/g by 1/5th qty. of Thiourea Dioxide (Diosyn-HF) having COD of 208 mg/g, thus effectively reducing COD by 87.5% & Hydro costs by 43%.
Dyeing :- 1) Acetic acid alone can contributes to more than 20% of a Synthetics process house COD, BOD load. It can be substituted by Formic acid result-
ing in 83% & 91% COD & BOD reductions respectively. COD, BOD can be further reduced by 93% & 99% respectively if Catalyst D (Dharamsee mORARJEe)
is used instead. Similarly S-acid PBI has much higher COD, BOD values & hence should be used only when it is absolutely essential. 2) Carriers based on
chlorobenzenes are highly toxic & even carcinogenic & hence should be eliminated from dyeing process. Thus a few manufacturers like Sandoz (India) have
voluntarily renunciated their chlorobenzene based carriers. Many -PJD type leveling agents contain chlorobenzene as well as perchloroethylene or trichloro-
ethylene, which are again potential carcinogens. 3) The leveling agents also contribute heavily to the process house's effluent load. The conventional level-
ing agent for polyester based on castor oil ethoxylate has COD, BOD values of 1947 mg/g & 537 mg/g, it can be replaced by Hicoleveller BJD (Hico) having
COD, BOD values of 588 & 150 mg/g only. Again this turns out to be the more economical alternative. 4) High quantities of Sequestering agents are required
in Surat due to the very hard water. Poly phosphates like TSPP & Sodium Hexa meta phosphate, which have been banned in Europe since long, are still be-
ing used as water softeners & even in household detergents. They are not easily biodegradable & hence large amounts end up in the river & ocean. Here
they are hydrolyzed to orthophosphates, which promote the growth of algae. Since algae are known for their high oxygen demand, which they withdraw
from the water, & hence most of the algae will begin to rot. This will cause the river to die off. The whole process is known as "Eutrophication". Thus these
products should be voluntarily banned by the processors. Other popular sequesterants are EDTA & NTA based products are also non biodegradable but un-
like polyphosphates, have a strong affinity for Heavy metals & thus could release them later on in the river. Recently phosphonates (Sequacel HD - Excel)
have been introduced in the market. They are more effective than EDTA & their complexes are even more stable than EDTA & thus again could remobilise
heavy metals in the environment later on. The brighter side is that very small quantity is sufficient & they do not promote algae growth. 5) Hydro in reduc-
Printing :- 1) Major environmental problem caused by printing emanates from Pentachlorophenol, used as a preservative in the Printing gum. It has a TLV
value of 0.5 mg/meter of Skin & causes dermatitis, it's chronic exposure can lead to liver & kidney damage & it's also carcinogenic. PCP has been banned
from January 1993 in India but the Gum manufacturers, barring IGI, are still blatantly using it. 2) Considerable Phenol is used for nylon printing, which can
be substituted by Diethylene glycol. This substitution would take care of GPCB's phenol limits. 3) Citric acid contributes quite a bit to the plant COD, BOD
levels (686 & 400 mg/g respectively). Substantial reduction in these levels can be obtained (more than 97%) by using Citric - W (Riddhi Rasayan). 4) Ginasol
6836 can also be used for washing of prints instead of non-ionic detergent, as discussed earlier. 5) Zinc sulfoxylate formaldehyde (Safolin) & tin chloride
used for discharge printing, increases the metal content of the effluent. Many innovative processors have substituted these products with Sodium
sulfoxylate formaldehyde(Rongalite -C) under alkaline conditions to eliminate these metals as well as reduce costs.
Finishing :- 1) The biggest environmental threat comes from Formaldehyde, which has been found to be carcinogenic in some studies. Hence European
countries have set quite stringent standard for free formaldehyde of less than 75 ppm for clothes close to skin & 20 ppm for baby clothing [2]. Recently
Sandoz has come up with low formaldehyde & formaldehyde free products. 2) Cationic softeners based on quaternary ammonium compounds & silicone
polyquats have less biodegradability & are also toxic to aquatic organisms.
The following table shows reduction in COD, BOD levels & costs achieved by some chemical substitutions. A list of chemicals banned, due to their harmful
Table 4
No. Chemical Qty. COD BOD Substituted COD BOD COD BOD Cost Cost
Used Kgs/Mon Kgs/Mon by Redn. Redn. Redn. % Redn. % Redn. Redn.
. . Kgs/Mon. Kgs/Mon %
.
1 Acetic Acid 1250 1300 1056 Catalyst DD 1209 1054 93% 99% Rs33,750 71%
2 Citric Acid 900 617 360 Citric W 599 356 97% 99% Rs32,850 43%
3 N.I. Detergent 300 528 140 Ginasol 6836 377 95 71% 68% Rs12,900 54%
4 Castor oil Eth- 250 487 134 Hicoleveller 340 112 70% 84% Rs11,750 42%
oxylate BJD
5 Phenol 100 228 140 Eliminated 228 140 100% 100% Rs5,500 100%
6 Hydro 1000 333 220 Diosyn HF 324 192 97% 86% Rs26,00 40%
0
7 EDTA Na4 150 240 52.5 HEDP 226.1 45.5 94% 87% Rs5767 77%
G.Total 3950 3733 2102.5 3303.1 1994.5 88.5% 95.1% Rs1,2851
7
Dyes :- The following dyes used in Surat are known to be carcinogenic & hence should be voluntarily discontinued by processors, if not the dyestuff manu-
facturers [3].
Table 5
No. C.I. Generic Name C.I. Number Chemical Class Diazo Component
1 Direct Blue 6 22610 Azo Benzidine
2 Direct Blue 14 23850 Azo Tolidine
3 Direct Blue 15 24400 Azo Dianisidine
4 Direct Blue 53 23860 Azo Tolidine
5 Direct Orange 1 Azo Benzidine
6 Direct Brown 2 Azo Benzidine
7 Direct Black 38 30235 Azo Benzidine
8 Acid Red 26 16150 Azo Xylidine
9 Acid Red 85 22245 Azo Benzidine
10 Acid Red 114 23635 Azo Tolidine
11 Acid Violet 49 42640 Triphenyl Methane ---
12 Basic Yellow 2 41000 Ketonimin ---
13 Basic Orange 14 46005 Acridine ---
Many other toxic & dyes allergic to skin have been listed in the earlier paper [3].
Optimization of chemicals & dyes :- Very often, we processors are used to working with unnecessarily high quantities of auxiliaries & chemicals. They
needlessly increase costs as well as effluent load. e.g. Leveling agents above 0.5 g/l can reduce 10% - 15% colour yield of dyes like Brown 3REL [4]. Many
dyes having good leveling property can be dyed without the addition of leveling agents. Similarly a lot can be done on the dyestuff front. High dyestuff per-
centages, without any consideration for the optimal concentration are a norm in Surat. A colour computer can do wonders for predicting optimum & eco-
nomical dyeing recipes. Besides saturation values of dyes can also be computed from it as follows :- A particular dye should be dyed at different concentra-
tions from 0.1% to 5%. Then their K/S values are computed & plotted versus their concentrations . The slope tends to be almost linear till it reaches a cer-
tain concentration, after which the curve flattens out. This particular concentration is known as saturation value, above which no appreciable increase in
visual depth is perceived. Colourtex & Sandoz have prepared special saturation curves shade cards for their products which can be used to greatly reduce
dyestuff consumption. Hence all the process recipes should be optimized & standardized on the basis of " Three E's" viz. Environment, Efficiency & Eco-
nomy.
Water Conservation :- The following table shows the average water consumed per day in a medium sized process house.
Table 5
more economical low liqour ratio machines(M:L=1:3). They require less than 1/3 rd of water & energy of the conventional machines. The condensate, which
goes down the drain in many process houses, should be collected & reused as boiler feed water. Besides as seen in the table, lots of water is required for
cooling of Jets & vacuum hydroextractors on stenters. This water can be collected in tanks & reused effectively. As seen in the table, printing machines
consume 43% of the total water. Lot of water is wasted on printing machines as the water flow remains on, even when the machine is stopped. This can be
curtailed by attaching solenoid valves to the water valve & automating the flow only when the machine starts. One innovative unit is reusing treated efflu-
ent for printing machine blanket washing operations. Hence, lot of scope exists in reducing the water requirements of a process house.
this aspect some how remains neglected. 2) Reuse of left over finishing liquors.
3) Dyebath Reuse :- Generally almost 95% of dye exhaustion takes place in Polyester dyeing. Hence an alternative to the discharge of this exhausted bath
is to collect it in an over head tank, analyze it for remaining dyes/chemicals quantities & then reconstitute the bath for further use. In this manner, a single
bath is currently being reused for more than twelve times for Optical Whitening & three times for light shades, in our unit & yielding significant savings in
water, energy, chemicals & effluent treatment are achieved by this relatively simple technique.
Role of Dyes / Chemicals Manufacturers in Waste Minimization :- Manufacturers will play a very vital function in environmental protection. They
can make a start by supplying Safety Data Sheets containing data on environmental & toxicological information like Biodegradability, Heavy metal content,
Fish toxicity, carcinogenicity, COD, BOD values. Currently, only ETAD members like Sandoz pass on the SDS to the actual users. We processors can then se-
lect eco friendly products from this information (after verification). By this environmental oriented product selection (rejection !), we can start a new trend
in our industry & forcefully influence manufacturers to develop more "Green" products. Besides voluntary renunciation of many carcinogenic & toxic dyes &
chemicals banned in Europe ( As listed in Apppendix) & now even in India, should be another priority. Many times toxic pollutants observed in the process
house effluent, are impurities occurring in the dyes & chemicals itself. e.g. Mercury comes as an impurity from Caustic Soda manufactured by Mercury cell
method, as very few Chloralkali manufacturers have shifted to the cleaner membrane technology. Cadmium occurs as an impurity from the detergents.
Thus clean technology should evolve right from the raw materials manufacturing end. They should come up with new eco friendly products, which can then
Formation Of Waste Minimization Group of Surat :- Waste Minimization Group has been formed by the local process houses, dyestuff manufacturers
& academicians, voluntarily to propogate Cleaner technologies & Waste Minimization in our Industry. The main objectives of WMG are :-
1) To create awareness about Environmental issues of our Industry & how Cleaner technologies can be implemented;
1) Inform Industry about the Cost benefits achieved from Environmental Audits & Waste Minimization in the form of a Newsletter.
2) Check 200 Chemicals & Dyes commonly used in Surat, for Environmental & Toxicological properties like Biodegradability, Heavy Metal content, BOD,
COD, Carcinogenicity, Fish Toxicity by the Environmental Engineering Department & BioSciences Department. (Safety Data Sheets).
3) Prepare lists of Environmentally friendly & Harmful items from the above study.
5) Study on Environmental Impact of our Industry to be jointly undertaken by Environ. Engg. Dept. & our process house.
these years. Environmental aspects of wet processing will gain more importance in the coming years. The standards to which the industry will have to work
,will become more stringent & clearly effluent treatment costs will increase substantially. Under these circumstances, Waste Minimization can reduce the
enviironmental impact of wet processing as well as be a productive & cost reduction tool for the management.
Appendix
1) Arsenic compounds.
2) Cadmium compounds. *
3) Chromium compounds.
4) Copper compounds.
5) Lead compounds.
6) Mercury compounds. *
7) Silver compounds.
9) Flourides.
1) Carbon Tetrachloride. *
2) Chlorinated paraffins.
4) Dibutylphthalate.
6) Hexachlorobutadiene. *
7) Halon - Hexafluroethane. *
9) Octachlorostyrene.
10) Pentachlorophenol. *
11) Pentachlorobiphenyl.
12) Polychlorinated Biphenyls (PCB's).
14) Trichlorobenzene.
16) Trichloroethane. *
1) Benzidine.
2) Benzopyrine.
3) Hexa Chloropentadiene.
4) Chloroaniline.
5) Dichloroaniline.
D) Miscellaneous :-
References :- 1) "Europäische Abwasserregelungen im Vergleich" - Hartmut Reetz, Mellliand textilberichte 11/1991 pg 632.
2) "Eco standards as a new challenge for industries inn developing countires, The case for India - T. Bunning et al. German Development Institute report.
3) "The ecological & toxicological properties of dyestuffs" - Chittaranjan Desai, Colourage Dec 1992 pg. 51.
4) "Application of Disperse Dyes" - Edited by R.M. Mittal, ATIRA publication pg. 15.