Recycling of wastewaters of textile dyeing industries using advanced treatment technology and cost analysisCase studies

K. Ranganathan , K. Karunagaran, D.C. Sharma

Central Pollution Control Board, Southern Zonal Ofce, Rajajinagar, Bangalore 560 086, India Received 30 January 2006; received in revised form 22 June 2006; accepted 22 June 2006 Available online 26 July 2006

Abstract Textile dyeing industries in Tirupur and Karur of Tamil Nadu (India) usually discharge efuents ranging between 80 and 200 m3 /t of production. Dyeing is performed either by conventional winch process or by advanced soft ow reactor process. Hypochlorite, the commonly used bleaching chemical is being gradually phased out by alkaline hydrogen peroxide solution that generates less efuent and fewer solids in the efuents. Coloring of yarn/cloth takes place in the presence of high concentration of sodium chloride or sodium sulphate (2575 kg/m3 ) in dye solutions. Dye bath wastewaters and wash waters are the process efuents of dyeing industry which are collected separately or together and follow the advanced treatment for maximum recycling of recovered waters. Dye bath water after treating by sand and nanoltrations (NF), the permeate is used in process for dye bath preparation and the reject of about 2030% is sent to multi effect evaporator (MEE)/solar evaporation pond (SEP). Wash waters treated using a sequence of physicochemical and biological unit processes are passed into two stages reverse osmosis (RO) membrane systems and then the permeate is reused in the processes. The rejects about 1520% of the inlet volume is subject either to nanoltration for salt recovery or sent to evaporators. The nal rejects from nanolter systems is directed to multi effect evaporator system where condensed waters are recovered. The removal of total dissolved solids (TDS), chemical oxygen demand (COD), chloride and sodium are in the range of 8097%, 9197%,
Abbreviations: INR, Indian rupees (one USD equal to INR 44); CPCB, Central Pollution Control Board; APHA, American Public Health Association; RO, reverse osmosis; NF, nanoltration; MEE, multiple effect evaporators; TDS, total dissolved solids; BOD, biochemical oxygen demand; COD, chemical oxygen demand; SAR, sodium absorption ratio; TH, total hardness Corresponding author. Tel.: +91 80 23495981; fax: +91 80 23498207. E-mail address: rangacpcb@yahoo.com (K. Ranganathan). 0921-3449/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.resconrec.2006.06.004

7697% and 96%, respectively. Multiple effect evaporators out ows of about 23% of the efuent volume are allowed for solar evaporation and the solids are disposed off. The cost of operation of MEE is about INR 400/m3 of the rejects. The cost of water recovery is about INR 6080/m3 including commissioning and maintenance whereas price of raw-water in Tirupur is about INR 100/m3 . 2006 Elsevier B.V. All rights reserved.
Keywords: Dyeing industry; Wastewater recycling; Reverse osmosis; Membrane process; Nanoltration

1. Introduction Next to food the second basic needs of man cloth is supplied by processing of natural and synthetic bers in the industries called textiles. Increased population and modernized civilization trend gave rise to blooming of textile sectors in India. An estimate shows that textiles account for 14% of Indias industrial production and around 27% of its export earnings. India is the second largest producer of cotton yarn and silk and third largest producer of cotton and cellulose ber (Report of Business India, 2004). The total production of yarn during the year 20032004 was 3051 kt (Annual Report of Ministry of Textiles, 2004). There are about 10,000 garment manufacturers and 2100 bleaching and dyeing industries in India. Majority are concentrated at Tirupur and Karur in Tamil Nadu, Ludiyana in Punjab and Surat in Gujarat. The processes followed in textile industries are spinning of ber to yarn, sizing to improve stiffness, scouring, kiering and desizing to remove excess sizing materials, bleaching to remove pectin and wax from the yarn and fabric and coloring and printing to provide desired color and design to the cloth. Dyeing is a combined process of bleaching and coloring, which generates voluminous quantities of wastewaters and in turn causes environmental degradation. The efuents consist of high TDS, sodium, chloride, sulphate, hardness and carcinogenic dye ingredients. High BOD efuents are generated from the sizing and desizing processes and treated by conventional anaerobic and aerobic biological methods (Tchobanoglous and Burton, 1995). Coimbatore district of Tamil Nadu is well known for cotton production and also called as Manchester of Southern India. Tirupur, one of the towns in Coimbatore District is located at the bank of river Noyyal, a tributary to river Cauvery. The quality of Noyyal river water and climatic condition of Tirupur has been ideal for dyeing operation of yarn and fabric since long time. Presently there are 712 dyeing and bleaching industries in Tirupur that generate 87,000 m3 /d of wastewater. Out of this a total of 281 industries are attached with common efuent treatment plants (CETP) and others are having their individual efuent treatment plants. Presently adopted technology is able to remove the color and other organic impurities to the stipulated standards but failed to arrest the inorganic contaminants. Continuance of efuent discharges has caused gross damages to the nearby aquatic systems receiving body like Orathupalayam dam located at the down stream of river Noyyal and as such the water quality has become unt for irrigation. The reservoir waters TDS, chloride and sodium were reported as high as 5054, 2869 and 1620 mg/L, respectively (Central Pollution Control Board, 2005). Also the concentration of dissolved solids in the ground and river water is reported in the range of 50007000 mg/L i.e. almost ten times higher than the desirable drinking water standard (Indian Standard, 1991). A study carried out by Rajaguru

et al. (2002) indicates that the ground water in the Tirupur area is also contaminated with substances capable of inducing DNA damage in human cells. One more town Karur located at the bank of river Amaravathy, another tributary to river Cauvery is also concentrated with 600 bleaching and dyeing industries. Advanced treatment technologies are imperative to protect the water resources in these areas. Membrane technology for treatment of dye house efuents was studied by Bucklay (1992) and reported 95% color removal. Vandevivere et al. (1998) and Ciardelli et al. (2000) have reviewed and studied successful application of membrane technology in textile wet processing industries. In view of the above impacts of the dyeing efuents on the environment, the industries in Tirupur and Karur are also forced to adopt technology leading towards zero discharge systems. There are 20 dyeing industries that have already installed efuent treatment technologies with advanced techniques and attained zero discharge. Four industries adopted such technologies are extensively studied and the results are discussed in this paper.

2. Materials and methods Four dyeing units namely M/s. Sivasakthi Textile Processors, Tirupur, M/s. Rennaisance Creations Processing Division, Tirupur, M/s. Leeds Spinning Mills (P) Ltd., Tirupur and M/s. Karur Amaravathy Textiles Industry, Karur were visited and information on manufacturing process, production status and wastewater quantity were collected. Waste water samples from the dye bath collection tank and wash water collection tanks, intermediate points and at the outlets of efuent treatment plants were collected and analyzed at mobile as well as stationary laboratory using standard methods. Eight hourly composite and grab samples were collected for the rst two units and other two units, respectively. The samples were preserved and analyzed as per the standard methods (APHA, 1995; CPCB, 2001). Percent sodium and sodium absorption ratio (SAR) values were calculated using the following formulas: percent sodium = concentration of Na 100 concentrations of Na + K + Ca + Mg concentration of Na (concentration of Ca + concentration of Mg)/2

sodium absorption ratio (SAR) =

where the concentrations of the ions are expressed in mequiv./L. All the chemicals used were of analytical and laboratory grades.

3. Results and discussion 3.1. M/s. Sivasakthi textile processors M/s. Sivasakthi Textile Processors engaged in dyeing of yarn (cotton and polyester) is located at Mangalam, Tirupur. Six numbers of soft ow reactors (batch process) with

different capacities are used for dyeing including wetting, bleaching, neutralizing, washing, coloring, washing, etc. In the reactors, 1 t of cotton yarn requires 10 m3 of water whereas 1 t of polyester yarn consumes only 4 m3 in each steps. Dye bath solution requires dyes, alkali and sodium salt in the process. Quantity of salt (sodium chloride) used usually depends on the requirement of color shade. The total quantity of yarn/fabric processed in the unit is 15002000 kg/d and the volume of efuent generated is of the order of 100200 m3 /d. Efuents are segregated into dye bath wastewater and wash water and treatment is effected accordingly. Wash water is collected in holding tanks and pumped to primary treatment unit (lime and ferrous sulfate slurries are ash-mixed with efuent and allowed for settling). Following primary treatment the efuent is carried to pressure sand lter, iron removal lter, ion exchange lter and reverse osmosis (RO) system. Double stage RO system (each with six membranes) with spiral wound membrane is in operation. Pump pressure is maintained in the range of 21.228.2 kg/cm2 . Rejects of rst RO is sent to second RO and the nal reject (20%) is sent to MEE. Condensate water is recycled in the cleaning operations. Outlet with 100 g/L solid content is allowed for solar evaporation and the combined permeate is used in the process. Dye bath water is collected in a separate tank and are subject to nanoltration after following pre-ltration. Total reject of about 30% is sent for multi effect evaporation and solar evaporation systems. The permeate is used for preparation of dye bath solution. The characteristics of the raw efuents, intermediate efuents and permeate are presented in the Table 1. The low hardness of permeate is an added advantage in the process. Permeate of NF ltration contains 4.8% of salts that is mixed with more salts and used in the process. Salt recovery from the dye bath alone has 50% returns. 3.2. M/s. Renaissance creations processing division M/s Renaissance Creations is located at Kuppandampalayam, Tirupur. Dyeing of cloth and garment of cotton is practiced in the unit. The both Winch and soft ow reactors (batch process) are used for dyeing. The process includes wetting, bleaching, neutralizing, washing, coloring, washing, etc. Dye bath solution requires dyes, alkali and sodium salt (sulphate and chloride) in the process. Quantity of the product is 3000 kg/d and the volume of efuent generated is 600 m3 /d. Efuent is segregated into dye bath wastewater and wash water, which is generally in the ratio of 1:10. Wash water equalized in a holding tank is subject to primary treatment by ash mixing with lime and ferrous sulfate and are allowed for settling. Primary treatment is followed by the secondary treatments such as biological oxidation through Tricking lters, chlorination, activated carbon bed and pressure sand lter before entering into reverse osmosis (RO) system. Double stage RO is followed with a feed water ow rate of 27.5 m3 /h. High pressure pumps used to feed the ltered water to the rst array of the RO and the reject of rst RO to second RO and the nal reject (1215%) is sent for multi effect evaporator. Permeate is used in the process after passing through degasser tower. Whereas dye bath water is collected in a separate tank and allowed for lime and ferrous sulfate occulation to remove the color. These light color efuents mixed with the rejects of RO are sent to evaporation system (MEE). Condensed water is recycled in the process and the rejects are diverted to crystallizing system for recovery of Glaubers salt which

Table 1 Characteristics of efuents of M/s. Shivasakthi Textile Processors, Tirupur Parameter Wash water Inlet to ETP pH Electrical conductivity (mS/cm) Total suspended solids (mg/L) Total dissolved solids (mg/L) BOD (mg/L) COD (mg/L) Total hardness (mg/L) as CaCO3 Ca-hardness (mg/L) as CaCO3 Sulphate (mg/L) Chloride (mg/L) Sodium (mg/L) Potassium (mg/L) Percent sodium Sodium absorption ratio (SAR) 9.76 6.80 47 4280 80 317 320 272 75 1912 1600 38 90 39 Outlet of chemical treatment 9.78 6.63 26 3620 63 204 141 104 116 1771 RO permeate 7.52 0.77 BDL 474 10 24 3 3 8 184 RO reject 8.21 32.1 46 21670 450 1143 728 687 328 10756 9280 208 95 146 Dye bath water Dye bath wastewater 10.42 53.9 76 39179 180 909 88 68 174 19179 NF reject 8.21 63.55 60 48294 100 402 45 22 362 26432 20480 62 100 1329

Note: BDL, below detection limit; , not analysed.

is used in the process. The characteristics of efuents are presented in the Table 2. The quality of permeate shows that is suitable for dye house processing. The high TDS and chloride contents in the permeate indicates that the RO membrane has to be either cleaned or replaced. 3.3. M/s. Leeds spinning mills Ltd The industry which process 4000 kg of yarn and fabric per day generates 3000 m3 /d of wash water and 30 m3 /d of dye bath water. The wash efuents and bath efuent are collected separately and treatment is effected. The dye bath efuents are subject to nanoltration after gravitational settling. NF modules are extremely sensitive to fouling by colloidal materials and polymers. It can be used to separate ber reactive dyes and cationic dyes from the salt. The permeate collected contains merely NaCl that is used in the dyeing process. The rejects are diverted to solar evaporation ponds. The wash waters after treating with lime and ferric chloride is passed to sand ltration followed by iron removing cartridges. It is then subjected to double stage reverse osmosis system and 80% of permeate is used in the industrial process and the reject are sent for nanoltration and solar evaporation. Solar evaporation pond is designed keeping water evaporation rate of 4 mm/d. To minimize the area requirement for solar evaporation, the industry has proposed to install one more RO system in conjunction with treatment plant. The results of treated and untreated waters are presented in the Table 3. The permeate has shown the lowest TDS concentration of 212 mg/L out of the studied industries. Due to scarcity of fresh water in the area, the unit had purchased 400 m3 /d of water through tankers. After installation of the advanced water recovery system, the unit is purchasing only 34 m3 /d. 3.4. M/s. Karur Amaravathi textiles industry The unit located at the bank of river Amaravathy processes yarn and fabric dyeing with production capacity of 4000 kg/d and generates efuent of about 400 m3 /d. Both wash waters and dye bath waters are collected together in a tank and subject to advanced treatment. There is no system for BOD, color and other impurities removal. The efuent is sent directly to the disc type RO membrane after settling. There are four modules in the RO system wherein the rejects of rst module is sent to second module and so on. Permeates from the each module are collected together and recycled back in the industrial processes. The rejects of the last module are subject to nanoltration and permeate is used for making dye solution and the reject is sent for solar evaporation. The characteristics of efuent, inlet to RO, individual permeate, combined permeate and rejects are shown in the Table 4. The BOD of permeate is high due to no prerequisite of primary and secondary treatment of wastewaters. 3.5. Comparison of the ROs performance in the studied textile dyeing units The characteristics such as TDS, chloride, percent sodium and SAR show that the untreated and primarily treated wastewaters are unt for irrigation and their discharge into river may further aggravate the problem. Therefore, the advanced treatments such as reverse

Table 2 Characteristics of efuents of M/s. Renaissance Creations, Tirupur Parameter Wash water Inlet to ETP pH Electrical conductivity (mS/cm) Total suspended solids (mg/L) Total dissolved solids (mg/L) BOD (mg/L) COD (mg/L) Total hardness (mg/L) as CaCO3 Ca-hardness (mg/L) as CaCO3 Sulphate (mg/L) Chloride (mg/L) Sodium (mg/L) Potassium (mg/L) Percent sodium Sodium absorption ratio (SAR) 9.28 8.99 90 5072 107 288 121 66 309 2161 1880 40 96 74 Outlet of chemical treatment 7.36 8.64 24 4862 47 154 101 24 451 2336 Inlet to RO 7.68 8.47 8 4764 24 108 141 61 470 2325 RO permeate 7.88 1.97 BDL 1032 2 27 9 5 43 528 RO reject 7.77 19.85 23 12138 13 135 182 131 1748 5373 3760 74 97 121 9.78 17.35 57 10522 45 240 606 343 171 4766 Dye bath wastewater

Note: BDL, below detection limit; , not analysed.

Table 3 Characteristics of efuents of M/s. Leeds Spinning Mills (P) Ltd., Tirupur Parameter pH Electrical conductivity (mS/cm) Total suspended solids (mg/L) Total dissolved solids (mg/L) BOD (mg/L) COD (mg/L) Total hardness (mg/L) as CaCO3 Ca-hardness (mg/L) as CaCO3 Sulphate (mg/L) Chloride (mg/L) Sodium (mg/L) Potassium (mg/L) Percent sodium Sodium absorption ratio (SAR) Note: , not analysed. Inlet to ETP 9.92 7.09 41 4218 360 695 278 91 139 1820 Outlet of chemical treatment 9.08 6.50 23 3904 330 563 364 364 133 1713 Inlet to RO 8.85 6.59 20 4300 350 504 404 364 150 1860 RO permeate 7.32 0.44 2 212 7 18 6 6 13.5 103 RO reject 7.09 31.7 66 23070 800 3243 2323 2283 1019 10510 7360 328 86 67 Nanoltered RO reject 7.22 40.90 147 33180 925 4549 3909 3798 2803 15430 2840 208 Nanoltered dye bath water 10.03 68.7 11 56428 450 1802 182 81 1219 25257 18800 184 99 605.5

Table 4 Characteristics of efuents of M/s. Amaravathy Textiles, Karur Parameter pH Electrical conductivity (mS/cm) Total dissolved solids (mg/L) BOD (mg/L) COD (mg/L) Total hardness (mg/L) as CaCO3 Ca-hardness (mg/L) as CaCO3 Sulphate (mg/L) Chloride (mg/L) Sodium (mg/L) Potassium (mg/L) Percent sodium Sodium absorption ratio (SAR) Note: , not analysed. Holding tank efuent 8.9 19.30 13770 213 702 192 115 1419 5715 3900 84 97 122 Inlet to RO 7.8 > 20.0 15396 163 154 1486 6268 4146 86 98 194 RO permeate 6.3 0.66 364 14 26 3 2 38 166 140 10 95 36 RO reject 8.2 > 20.00 29356 600 1535 317 307 2254 12443 13000 230 98 317 NF permeate 7.6 > 20.00 28594 180 351 107 88 154 14931 12000 300 98 229 NF reject 7.8 > 20.00 54734 1320 3290 518 499 5655 22674 22000 415 98 419

Fig. 1. Removal of pollutants using advanced treatment process in different textile dyeing units.

osmosis and/or nanoltration separation technologies are essentially used to remove the inorganic (mainly) and organic constituents from aqueous solution and non-aqueous solution by membrane (polyamide). The principle followed in all the units are same where as different module such as disc type module and spiral wound module membrane are housed in the RO system. Before charging into RO membrane it is important to remove impurities such as suspended and colloidal impurities of organic and inorganic compounds and dissolved polyvalent ions to extend the life of the membrane. Almost all the systems attained complete removal of suspended solids. Fig. 1 shows the percent removal of major pollutants such as BOD, COD, TDS, total hardness, sulphate and chloride. The industry referred at 3.4 has disc type membrane module showed better performance in terms of TDS and other ions removal. The life of the membrane would be reduced due to the absence of preliminary treatment. The water regenerated using the advanced technology is found good quality and could be directly used in the dyeing process. A typical schematic diagram of the efuent treatment plant provided with primary, secondary and advanced treatment technologies for recycling of wastewater is exhibited in the Fig. 2. To extend life of RO membranes, ushing the membrane periodically with clean water and occasional chemical cleaning is required. The pH around 56 is desirable to prevent both hydrolysis of membrane and precipitation of calcium carbonate (CaCO3 ). A model ow chart of zero discharge scheme for the textile dyeing units is shown in the Fig. 3. Solar evaporation is followed in the units referred above namely M/s. Sivasakthi Textile Processors and M/s. Leeds Spinning Mills (P) Ltd. Solar evaporation pond is lined with a concrete layer and arrangements are made to avoid ground water inltration. An area of about 1000 m2 is required per 4 m3 of wastes for solar evaporation. The nal dried salts are packed in polythene bags for nal disposal. 3.6. Cost analysis of the water recycling process Wastewater treatment plant installation and commissioning cost is in the range of INR 40100 lacs, INR 100200 lacs and INR 200300 lacs for small (below 300 m3 /d), medium

Fig. 2. Typical schematic diagram of advanced wastewater treatment technology for recycling of textile dyeing wastewaters.

(300600 m3 /d) and large (above 600 m3 /d) scale textile dying industries. The maintenance and operation cost is as below:
Chemical cost Power cost Sludge handling Manpower Filters/cartridges (spares) RO/NF membrane maintenance Interest and principal paid on the loan (one USD is equal to INR 44) INR 78 m3 INR 23 m3 INR 0.751 m3 INR 12 m3 INR 510 m3 INR 1520 m3 INR 4050 m3

Total expenses incurred for the water treatment and recovery is about INR 80/m3 of the efuent. Due to non-availability of good quality water for dyeing processes in Tirupur, it is purchased from villages 15 km away from the towns and hence the cost of the water is approximately INR 100/m3 including transportation. Hence, the technology is also economically viable in the studied area.

Fig. 3. Flow diagram of conceptual zero discharge in textile dyeing unit using advanced wastewater treatment.

The bottlenecks in adopting the technology are high cost of operation for MEE and maintenance of RO membrane module. Multi effect evaporation is a costly system for concentration of the efuents before crystallization. It requires more maintenance in terms of consuming more fuel and an average of INR 400 is required per m3 of rejects. The recovered salt has poor purity and market value of salt is also very less i.e. INR 4 per kg. When the availability of land has become constraint, the MEE would be preferable. A common MEE set-up as joint ventures may be an economical recommendation. Proper preliminary treatments should be followed to reduce the maintenance cost of RO membrane.

4. Conclusion The study shows the recycling of treated wastewater and zero wastewater discharge concept are found technically feasible and economically viable in the textile dying industries located in the area of Tirupur and Karur, Tamil Nadu. The average percent removals of BOD, COD, TDS, Sodium and Chloride in the advanced treatment technology are in the range of 8898%, 9197%, 8097%, 96% and 7697%, respectively. The most attracting part of water recovered from these membranes is its extremely low hardness, which is always demanded in textile sector for an improved nish and better quality dyeing. The treatment and maintenance cost INR 80/m3 is cheaper than the water cost INR 100/m3 in Tirupur and Karur areas. Common facility for Multistage Evaporator would be economical.

Acknowledgements The authors are thankful to Dr. V. Rajagopalan, Chairman, Central Pollution Control Board, Delhi for his keen encouragement, Mr. Sunnel Dave, Environmental Engineer for valuable suggestions and Laboratory members of CPCB, Bangalore for their kind cooperation in sample analysis.

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