Integrated Management of Mercerizing Wastewater from a Denim Fabric Manufacturing Industrial Facility Akepati S. Reddy', Vishal Duggal’, J. Nagendra Babu', Mukesh Aggarwal’, Rabindra K. Patel! and Harpreet Singh! ‘Department of Analytical Services, Thapar Center for Industrial Research and Development, Thapar Technology Campus, Bhadson Road, Patiala, Punjab - 147 004 INDIA Alliance Engineers, Patiala, Punjab - 147 001 INDIA : ABSTRACT Mercerizing of dyed denim fabric generates highly alkaline coloured wastewater. Discharge of this wastewater both upsets functioning of the industrial facility’s Effluent Treatment Plant and makes compliance with the effluent discharge standards very difficult. Because of the colour, the industry could not practice the usual strategy of segregation and recovering alkali (through concentrating in multiple effect evaporator and clarification/filtration) for the wastewater management. This study proposes an environmentally sound, chemical saving and economically viable scheme for the management of the mercerizing wastewater. The wastewater is first neutralized and concentrated with acidic flue gases of a petcoke fired industrial boiler. The wastewater is then causticized with slacked lime and clarified for removing colour and recovering the caustic. Lime sludge generated from the process could be used for the control of emission of acidic flue gases from the petcoke fired industrial boiler. Water and energy conservation and waste minimization measures within the mercerizing unit are supposed to further add to the economic feasibility of this mercerizing wastewater management scheme. This scheme has already been successfully evaluated at the laboratory scale. 100 gpl (as CaCO) strength alkali with 1380 P-Co Unit (PCU) colour and 9930 mg/L COD has been recovered from the mercerizing wastewater of 93 gpl strength, 4000 PCU true colour and 14000 mg/L COD. Lime consumption was 2.5 times the stoicheometric requirement. The wastewater is neutralized cold with commercial carbon te pilot scale evaluation is currently in progress. INTRODUCTION Textile is a very diverse sector in terms of raw materials, processes, products & equipment and has very complicated industrial chain. Textile industries in India have great economic significance by virtue of its contributions to overall industrial output and employment regeneration. There are about 2324 textile industries in India out of which the Punjab state shares 19% of the Indian textile industrial establishments.’ The impacts on the environment by these textile industries have been recognized for some time, both in terms of the discharge of pollutants and in consumption of water and energy.’ Environmental problems of the textile industry are mainly caused by discharges of wastewater. The textile sector has a high water 652demand, with primary water consumption (80-100 m‘/ton of finished textile) and waste water discharge (115-175 kg of COD/on of finished textile, a large range of organic chemicals, low biodegradability, colour, salinity).’ Therefore, reuse of the effluents represents an economical and ecological challenge for the overall sector." The textile industrial process involves the following processes, desizing, scouring, mercerization, bleaching, dyeing, printing, finishing, garment manufacturing ete.® Various modern effluent treatment and reeycling methods have been reviewed in the past for the textile effluent as a whole and in part.° Mercerization is a treatment process specific to cotton.” It improves tensile strength, lustre, and ability to take up dyes. This process utilizes very concentrated solutions of sodium hydroxide (20- 30%) followed by washing the caustic used. The effluent generated from this process is highly alkaline in nature and contains phenolics, lignins and other fibre residues. This effluent may either, be recycled and reused or the NaOH recovered and employed in other pre-treatment steps.* However, the discharge of this effluent requires neutralization of alkali, leading to high TDS of the effluent. There are few specifically designed process modifications and treatments or reuse of mercerizing waters, which can be summarized under one or more than one of these categories as : 1. Liquid ammonia is a low pollution substitute for conventional mercerization (NaOH). Heavy cotton fabrics treated with liquid ammonia require less dye for a given depth of shade.” ‘ouring, bleaching or dyeing Dilute alkali from mercerizing can be reused in 16 operations, so that discharges from alkaline treatment can be minimized. Alkali could be recovered and recycled or reused after regenerative treatment to remove dirt (coagulation, flocculation, microfiltration, nanofiltration) and after concentration,'! 4. The non-recoverable fraction of the mercerizing wastewater could be neutralized by mixing with acid effluents or by CO) as acid. '"” Utilizing the last method and upon further recovery of caustic by electrochemical method." Herein we are interested in mercerization effluent of denim jeans industries, where mercerization with 14-18% of caustic alkali is carried out after the dyeing of the fabric. Thus, in addition to the waste generated in normal mercerization process (4-10% caustic alkali), there is an additional waste of dyes present in the effluent. The presence of dye in the mercerization waste makes the caustic reuse impossible. In the present work, we report an integrated industrial environmental management process using flue emission from a pet-coke fired boiler for the neutralization of the caustic alkali in a wet scrubber, followed by regeneration of the caustic with lime dosing of the carbonated effluent and simultaneous color removal. The lime mud thus obtained is used for the reduction of sulphur oxides in flue emissions. The caustic recovery method used is long practiced in recaustisizing of black liquor from kraft pulp & paper industry."* Recently, Raghu ef ai. have reported a clectrochemical-membrane process for dye destruction and simultaneous generation of sodium hydroxide. The process uses an electrolytic divided céll, with Ti/RuO,/IrO> anode and a stainless steel cathode.'! The present work would provide a better and effective method for the treatment of the effluent with significant cost and pollution reduction in a textile industry environment using the closed loop recycling. Thus, the results of our findings from the laboratory scale and the pilot scale experiments on caustic recovery and a complete cycle of integrated environment management is presented herein. 653METHODOLOGY Analysis of the effluent: CaQ used in the analysis was of analytical grade purchased from $. D Fine Chem, Ltd., New Delhi. pH measurement was carried out on an ELICO L1-127 pH meter with Pt glass electrode. Chloride was determined using ion analyzer 940 Expandable lon Analyzer Thermo Orion Pvt, Lid., USA. Color characterization of the effluent and treated effluent were established on HACH DR/2000 and SPECROD-200 UV-Vis spectrophotometer. The characterization of metal ion was carried out using Analytical Jena Nova 330BU spectrophotometer afier digestion as per the standard methods. Aluminium block COD digester irom Spectralab, Mumbai, INDIA was used for the COD digestion. Whatman Filter Paper No. 41 was used for normal filtration and for suspended solid analysis Whatmann glass microfiber filter paper was used. The analysis of various parameters for the effluent and the treated effluent, were carried out according to the standard methods." Neutralization of the Effluent: Neutralization of the effluent was carried out using commercially available carbon dioxide. Carbon dioxide was flushed for 12-18 hrs per SL of the effluent sample. The pH of the solution was checked periodically using a pH meter. The flushing was stopped upon the effluent attaining a pH in the range of 7.0-8.0. This neutralized effluent was further analyzed for alkalinity and pH before the start of the dosing experiment CaO Dosing of the neutralized/carbonated effluent: To a \L of carbonated effluent was added CaO (76.2 gm, 200% dosing) portion wise at an elevated temperature of >90°C (Ideally in our case at 92-95°C). After addition of CaO, 25mL of the treated effluent was collected in separate glassware and kept at the same temperature till the completion of the experiment. 3.8 gm of CaO was added at 5 minutes time interval with collection of 25 mL. sample of treated effluent before addition of the next lot of CaO. Upon addition of 114.3 gm of CaO (300% Dosing), the experiment was terminated. The cleven treated effluent sample obtained were at once centrifuged and filtered through whatmann filter with collection of the filterate. The obtained filterate obtained was subjected to the analysis of pH, total and phenolphthalein alkalinity. Scaleup of CaO Dosing of the neutralized/carbonated effluent: Scaleup of the condition was carried out upon addition of CaO (95.0 gm, 250% dosing) with 2L of aerated effluent in case of the second experiment. The aerated effluent was kept at temperature >90°C. Slow addition with shaking was carried out till complete addition of CaO, There is a complete removal of the color of the solution. The treated effluent was again lefi for 5 minutes at >90°C. This treated effluent was then cooled to room temperature, centrifuged and filtered. The filtrate was then analyzed for various parameters as for the untreated effluent RESULTS AND DISCUSSION Case Study of the Wastewater generation in Merce ing Process Before the discussion of the results and the optimization of the process and wastewater reutilization, it is necessary to understand the mercerizing process employed in the present industry. Mercerising includes the following processes (Figure 1) (a) Brushing (b)_ Impregnation () Stabilizing 654(d) 3-stage w: (ec) Neutrali (1) Multiple drum drying hing and washing (g) Drum cooling ravie —[ ewating Jf stwer [fetes | —evertaas Caustic si Fibrouswaste_ + | impesnater | bosngtane {Dosing ta fabric water be e ‘Causticwash ‘tabi at Steam ue fabric eel ‘Water J aaa if |. caustetastwater [Lean i : - i Washwater Washanter Wiasnuaterovetoue {I wate vashualet recite al camestensing Rinsing? | —Steam Wsrwatrovetone{ | Water insngs }—Seom Acete aed alton Navtataer |— stam ; seam cooing (7 Water a water 2 eat Washwater overtone —I t costing Steam condensate water 2, 1: Showing the present process and material low details in mercerizing process ‘The mercerizing process runs at the rate of 1200 m/hr, using caustic, acetic acid, steam, w water and cooling water. In the stabilizer, steam is directly injected for maintaining the temperature. In the rinse tanks it is condensed into rinse water. Water is consumed at the stabilizer, rinse tanks -1 to 3 and at the post neutralization rinse tank, and the consumption rate is almost same at all the places, Water is also consumed for diluting the acetic acid at the neutralization step. The rinsing currently practiced is not actually a counter-current rinsing. At of rinsing fresh process water is used (applied as water jets on the fabric, prior to the associated squeeze press) and from cach stage excess water is taken out as wash water overflows. For regulating the fiber accumulation, rinse water tanks contents are pumped through a filter and taken back to the rinse tank, Wastewaters generated from the mercerizing include Wastewater draining from the stabilizer (it is collected into an underground sump and part of iv is used in the preparation of 150-200 gpl caustic from 720 gp! caustic, and the rest is allowed to overflow as wastewater) Washwater overflows from rinse tanks -1 to -3 655Washwater overflows from post neutralization rinsing Steam condensate generation at the cylinder driers Cooling water at the cylinder coolers Recommeded Measures for Minimized Energy and Water Utilization Wastewater generation rate must be equal to the consumption of process water, direct injection steam and caustic and acetic acid (including water used for diluting the acid), Very small quantity of the used water (80% by weight of the fabric being mercerized) goes with the fabric to the drum driers and this does not become part of the wastewater generated. Water can be conserved, wastewater generation can be minimized and steam requirements can be minimized by implementing the following |. Practice counter-current rinsing starting from the post neutralization rinsing and ending in the stabilization, while bypassing the neutralization tank. 2. Rinse wastewater overflowing the post-neutralization rinse tank may be heated to the desired temperature in an external heat exchanger prior to using for rinsing in the third rinse tank. 3. Pump contents of a rinse tank through a filter and collect into a overhead tank. Use liquid of the overhead tank in the shower of the previous rinse tank. Allow excess liquid of the overhead tank to fall back into the rinse tank 4. Introduce a squeeze roll between the neutralization tank and post-neutralization tank, which can reduce the acetic acid consumption. 5. Draw cooling water for the cooling of the dried fabric from the circulating cooling water system and afier use, take back the cooling water into the circulating cooling water system. 6. Segregate the steam condensate generated at the cylinder driers and at the external heat exchanger used for heating the rinse water and send to the boiler house for the reuse as boiler feed water. Thus apart from these recommended measures, the alkaline mercerizing effluent produced can be reutilized as caustic in the very process. The caustic regeneration was studied in detail as discussed below Caustic Recovery from Mercerizing Effluent The recovery of caustic from mercerizing effluent was carried out in laboratory using carbonation/neutralization of the caustic effluent. Lime dosing of the neutralized effluent furnished the desired recovered caustic which could be readily used in mercerization process. Before discussing the details of the caustic recovery it is essential to understand the characteristics of the mercerizing effluent. (A) Charaete ¢ Effluent from Rainbow Denim Ltd. Ludhiana ition of Merceri The effluent obtained from’ the mercerizing process was characterized for the following parameters as given in Table-1. The alkalinity of the solution shows a major contribution from hydroxide alkalinity (77000 mg/L as CaCOs) with a carbonate alkalinity of (14000 mg/L. as 656CaCO). The results also show expected high TDS and high organic content with exclusive presence of Na’ ions in the effluent. The color characteristic of the effluent was established using the UV-Vis absorption spectroscopy. The effluent was deep blue coloured with a strong absorption with a nay = 680 nm as shown in the UV-Vis spectrum (Figure 2), Table-1 Showing the results of the analysis of mercerizing effluent Parameters Units Effluent Inlet 128 mg/l. 4020 mg/L. 105890 mg/l. 8025 mg/L 14000 mg/L. 38792 Ca mg/l 35.62 Mg mg/L 3.43 Sulphate 2531 Chloride 307 Total Alkalinity 93000 Phenolphthalein Alkalinity 85000 | Total Hardness mg/L as CaCO, _ | 162 Calcium Hardness mg/L as CaCO, | 139 Colour True PL-Co Unit 4000 Apparent PLCo Unit 8100 io mo Waele inan} is spectrum of a ten time diluted (a) mercerizing effluent (-) and (b) treated effluent (-) 657(B) Characterization of carbonated effluent Flushing CO» into the effluent furnished the neutralized/carbonated effluent. The pH of the effluent was brought down to 7.6-7.8, where the hydroxide alkalinity was completely converted to bicarbonate alkalinity i.e., NaOH was converted to NaHCO. The carbonate effluent showed no phenolphthalein alkalinity. However, the total alkalinity of the carbonated effluent was found to be 68000 m indicating exclusive conversion of hydroxide and carbonate alkalinity to bicarbona alkalinity Optimization of CaO dosing The neutralized effluent was studied for the optimum dosing of CaO. The dosing of CaO was based on the stoichiometric chemical equation (Eqn. 1) and assuming that the total alkalinity being due to the presence of sodium bicarbonate. 2NaHCOs (aq.) + CaO(s) + H3O ———® 2NaOH (aq) + CaCOs () + HO + COs (g) .Eqn. (1) Total alkalinity of neutralized effluent = 68000 mg/L as CaCO; Assuming total alkalinity to be due to the presence of sodium bicarbonate Then, [NaHCOS Irena of otal Alkalinity (mg/L. as CaCOs) X 2 X Mol. Wt. of NaHCO; (in g/L) Mol. Wt. of CaCO; X 1000 [NaHCO renin eg, = (68000 X 2 X 84)/(100 X1000) = 114.24 g/L Thus, CaO required [CaO] = [NaHCO,] X 56 (in g/L) 2X 84 [CaO] = (114.24 X 56) / (2 X 84) = 38.08 y/L culation the dosing of the neutralized effluent was carried out in ¢ batches with CaO dosing ranging from 90% - 300 %. The dosing of the solution was carried out at 93-95°C with portion wise addition of the weighed amount of CaO. Upon completion of addition, the colour of the effluent turned brown to pale yellow. Further, the te that the optimum dosing for the conversion of the bicarbonate alkalinity to hydroxide alkalinity was achieved at 250% (95 gm/L) dosing of CaO (Figure 3). Upon addition of CaO >200%, the alkalinity of the treated effluent showed an increase particularly in case of the phenolphthalein alkalinity, indicative of an increased formation of caustic alkali. results indi 250% dosing he residue left was quant parameters and the characteristics of the treated s carried out. Afier dosing, the ed and the filterate Thus, a scaleup of the optimized procedure a ‘ed and filtered. effluent was cooled, centrifug was subjected to various wastewater a effluent were ascertained (Table 2). 658Seas ioe es ee re “Bots ntsinty nat 0 10 10180 20 Mo Mo 760 200 ‘SéOoting of E90 wt bicarbonate aatntye the carbonated effluent Showing the change in the total alkalinity and phenolphihlein alkalinity as a function of % dosing of CaO Table 2: Showing the result of analysis of the treated effluent ___ Parameters Units ‘Treated Effluent | pll Bo cop mg | 9930 4 Na mel 31100 Ga malt 20 Me mei. 3.49 Sulphate mel. 753 Chloride mil 237 Total Alkalinity mg/l as aco, | 100000 Phenolphthalein Alkalinity | mgil.asCaCo; | 100000. Total Hardne mg/L as Caco; | 100 Calcium Hardness mg/L asCacoy | 10 Colour True Peco 1380 Apparent PLCoL 1380 [ Sludge Formed al. vt Characterization of Treated Effluent The results of the analysis of the treated effluent show complete removal of colour as shown by the UV-Vis spectra (Figure 3). COD and sulphate in the effluent were reduced by 33% cach. No significant Ca or Mg ion concentration in the effluent was detected, which might be accounted to the alkaline nature of solution with pH >13. The alkalinity of the solution showed a complete conversion of bicarbonate alkalinity to hydroxide alkalinity at 250% dosing of CaO. The concentration of the treated effluent is found to be 80.0 g/L, indicating a 89% recovery of the recaustisizing process in laboratory conditions. Thus, the modified process after all the recommendations would be as follows (Figure 4) 659Fabric Brushing Blower Bag filter | —* Vent gas Caustic} CAUSE | ln pregnator Fibrous waste Dosing tank [oar fabric water Oa ra Caustic wash] oF Steam ee =] Stabilizer ——tank _ ers (Overhead pie Rinsing-1 Steam + ee Washwater Washwater ~ overflow for counter [Overhead Rinsing-2 Sica current rinsing tank_}—4 (Overhea = Rinsing-3 Pa in e Steam TF acetic acid solution Heat Neutralizer +—g team exchanged Steam Cooling Tp water “| [water Rinsing Drum drying —*|Drum colin penal, t T, Cooling Steam condensate water Process flow diagram of the mercerizing process after incorporation of the recommendations CONCLUSION unit for wastewater and energy minimization ns. The results indicate a simple and efficient We have presented an account of the merceri with ins ition to petcoke flue emis: method of treatment, used in paper and pulp industries, for the recy om the pet coke fired boilers with the , ant remedi of the mercerizing caustic using wet-scrubbing of the flue gas emission: effluent and recaustisizing of the neutralized effluent. Thus, a complete inhouse integrated environmental management solution for a textile industry mereerizing waste has been accomplished using flue gas emission and lime. REFERENCES 1. Advanced Method for Treatment of Textile Industry RERES/7/2007, Central Pollution Control Board — Mi April 2007. Correia, V. M.; Stephenson, T.; Judd, S. J. Characterization of textile wastewater: A review, Environ, Technol. 1994, 15, 917-919. (b) Germirili, F.; Tunay, O.; Orhon, D. 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