War. Res. Vol. 28, No. 2, pp. 277-282, 1994 Printed in Great Britain.

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0043-1354194 $6.00+0.00 Copyright 1993 Pergamon Press Ltd

TREATMENT OF TEXTILE WASTEWATER BY ELECTROCHEMICAL METHOD

SI~NG H. Ln~ and CHI F. PENG Department of Chemical Engineering, Yuan Ze Institute of Technology, Neili, Taoyuan 320, Taiwan, Republic of China
(First received November 1992; accepted in revisedform May 1993)

Aiwnct--Treatment of textile wastewaters from several dyeing and finishing mills by an electrochemical method is investigated. The batch experimental results are assessed in terms of color (turbidity) and COD reductions. Several operating variables, such as the wastewater conductivity, pH, power requirement and amount of polyelectrolyte added, are explored to ascertain their respective effects on the treatment efficiency.Optimum operating ranges for each of these operating variables are experimentally determined. The electrochemical method is found to be quite effective and is highly competitive as an alternative chemical method for treating textile wastewater. A continuous experimental apparatus is designed and test runs are performed using the operating conditions obtained in the batch experiments. The preliminary data show similar satisfactory results to those of the batch runs.
Key words--electrochemical method, textile wastewater, color and C O D reductions, conductivity effect

INTRODUCTION

Dyeing and finishing processes are two important steps in the textile manufacturing process. These steps involve the dyeing of man-made or natural fibers to the desired permanent colors and processing of these fibers into final commercial products. Hence dyeing and finishing processings have become an integral part of the textile manufacturing process. However, in the dyeing and finishing processes, a considerable amount of wastewater is generated. Textile wastewater is notoriously known to contain strong color, a large amount of suspended solids, a highly fluctuating pH and a high temperature and COD concentration (Gurnham, 1965). Because of these characteristics, treatment of this textile wastewater has been rather difficult. Traditional methods for dealing with textile wastewater consist of various combinations of biological, physical and chemical methods (Hamza and Hamoda, 1980; Groves and Buckley, 1980; McKay, 1980, 1984; Brower and Reed, 1987; Paprowicz and Slodczyk, 1988). Because of the large variability of the composition of textile wastewaters, most of these traditional methods are becoming inadequate. Furthermore, treatment cost of textile waste effluents has been escalating fairly rapidly in recent years. Hence a search for more cost effective treatment methods is in order. Ozonation has been proposed in recent years as a potential alternative (Snider and Porter, 1974; Beszedits, 1980; Green and Sokol, 1985; Gould and Groff, 1987; Lin and Lin, 1992). This latest method has been shown to be quite effective in decolorizing textile wastewater. However, the cost of ozonation for such purposes needs to be further

ascertained to insure the competitiveness of this method. A method that has never been considered before for dealing with textile wastewater is the electrochemical method. This method has been successfully tested to treat various industrial wastewaters (Beck et al., 1974; Ramirez et al., 1976; Biwyk, 1980; Matis, 1980; Ramirez, 1981; Cenkin and Belevtsev, 1985). However, it has never been attempted to use it for dealing with textile wastewater before. The purpose of this study is to conduct experimental investigations of treating textile wastewater using the electrochemical method. Several fundamental aspects regarding the effects of wastewater conductivity, pH, power requirement and chemical coagulants (polyaluminum chloride) on the treatment efficiency are explored. As will be seen later, the electrochemical method is quite effective and is at least as promising as the ozonation method.
CHARACTERISTICS OF TEXTILE WASTEWATERS

The characteristics of textile wastewater have been discussed in detail before (Lin and Lin, 1992). Here only several key aspects are highlighted. The most notorious part of textile wastewater is its strong color. Depending on the type of dyestuff used, the color of the textile wastewater varies from red, brown, blue, purple and black due to their intensified and dark varieties. Textile wastewater can change color from day to day, or even several times a day because the dyestuff used in the dyeing process changes frequently due to customers' requirements. The variation of color also causes frequent fluctuation in the COD content of the textile wastewater.

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SHENG H. LIN and CHI F. PENG m e d i u m strength wastewater may also have a very strong color. The degree of difficulty in treating these wastewaters is largely in p r o p o r t i o n to their relative strength. Fortunately, most textile wastewaters belong to the medium a n d low strength varieties. The majority of textile wastewaters employed in this study belonged to these two types.
EXPERIMENTAL STUDIES

Such a strong color, if untreated, would have a m a r k e d negative impact o n the e n v i r o n m e n t o f the receiving water body. The large p H swing in the textile wastewater is a n o t h e r strong negative point. The p H variation is primarily caused by different kinds o f dyestuff used in the dyeing process. The pH of the wastewater can change from 2 to over 12 ( G u r n h a m , 1965). Such a big pH variation is particularly troublesome because of the rather limited p H tolerance of the activated sludge process or chemical treatment process. Hence p r o p e r pH a d j u s t m e n t has become a necessary part of the textile wastewater treatment process. In comparison to most industrial wastewaters, the t e m p e r a t u r e of textile wastewater is unusually high. During the dyeing process, rinse waters of up to 90C are used in various steps. The near 40C temperature of the textile wastewater is a t t r i b u t a b l e to these hot rinse waters. The high t e m p e r a t u r e renders immediate treatment of the textile wastewater released directly from the dyeing process impractical a n d usually entails proper prior heat dissipation to lower the temperature to 30C or below. O t h e r i m p o r t a n t pollutants of textile wastewater may consist of small a m o u n t s of polyvinyl alcohol (PVA), carboxymethyl cellulose ( C M C ) a n d starch used for sizing of the chemical or m a n - m a d e fibers. The sizing agents have a very high C O D content of over 10,000 mg/1, depending on their concentrations. They enter the wastewater after the desizing process and contribute significantly to the C O D content of the textile wastewater. A l t h o u g h the pH, BOD, total solids a n d the a m o u n t o f wastewater produced vary widely from one operation to another, mixing of these wastewaters in the equalization tank forms a final waste effluent which possesses more stable physical and chemical properties. In general, the final textile waste effluent can be broadly categorized into three types o f wastewater according to their C O D content a n d the color intensity (Lin a n d Lin, 1992), these are the high, medium and low strength wastewaters. The high strength wastewater has a C O D concentration exceeding 1600 mg/l and a strong dark color with very low transparency. The m e d i u m strength wastewater has a C O D content between 800 a n d 1600 mg/l while the low strength wastewater has the lowest C O D concentration o f less t h a n 800 mg/1. Table 1 lists the average characteristics of these three textile wastewaters. The color in the wastewater usually varies in intensity according to the above strength classification. But in m a n y circumstances, the low or

The batch experimental apparatus is shown in Fig. I. The cathode and anode consist of four pieces of cast iron each, situated approx. 1.5 cm apart from each other and dipped in the wastewater. The power input was controlled by an ammeter and the total power consumption was integrated and registered by a power integrator. In each run, approx. 1000 cm 3 of textile wastewater was placed in the electrolytic cell. The total effective surface area of the cast iron electrodes was 324 em 2. The initial pH of most of the textile wastewaters in the electrolytic cell was adjusted to around 7, except for those samples intended to investigate the pH effect on the COD removal efficiency. The conductivity of raw textile wastewater was adjusted by dilution with deionized water or by adding sea water. Experimental runs using the same wastewater and operated under the same operating conditions were repeated for a complete set of color and COD measurements at various treatment times. The color of the treated textile wastewater was determined using an apparatus similar in basic structure to the candle turbidimeter (APHA, 1985) which is used for measuring the Jackson unit. The color (or turbidity) of the raw and treated wastewater was determined in terms of its transparency (centimeter). According to the Taiwan EPA stipulations, the acceptable transparency of all treated industrial wastewaters needs to exceed 15 cm. The COD was measured by the standard method (APHA, 1985). After the batch experiments were completed, a continuous electrolytic reactor system was designed based on the experiences gained in the batch studies. The continuous system was intended to investigate the performance of the electrochemical treatment for potential practical implementation. The experimental setup is shown in Fig. 2. The electrolytic reactor was made of Pyrex glass with the dimensions 17.5 17.5 x 25 era. With the wastewater flow rate kept at 0.75 l/rain, the reactor permits an equivalent residence time of about t0 rain. The pH of the textile wastewater was monitored continuously and adjusted if necessary. PAC was then added before the wastewater entered the electrolytic reactor. Before the continuous experiments were started, the system was filled with raw textile wastewater. Hence samples taken at the exit of the electrolytic cell showed a transient period. The COD and other parameters were measured using the same methods as the batch runs. DISCUSSION OF RESULTS The mechanism o f the electrochemical process in aqueous systems is quite complex (Pietcher and Walsh, 1990). It is generally believed t h a t there are three possible mechanisms involved in the process: electrocoagulation, electroflotation a n d electrooxida-

Type High strength Medium strength Low strength

Table 1. Characteristics of typical textile wastewater BOD COD SS Temperature (rag/l) (rag/I) pH (mg/l) (C) 500 1500 10 250 28 270 970 9 137 28 100 460 10 91 31

Oil (mg/l) 50 21 10

Conductivity (#S) 2900 2500 2100

Electrochemical treatment of textile wastewater

279

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1. D.C. power supply 2. Digital ammeter
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4. Parallel iron-anodes

5. Parallel iron-cathodes 6. Magnetic bar-stirrer 7. Sampling valve 8. Electrolytic cell 9. Digital magnetic stirring controller Fig. 1. Batch experimental setup. tion. Oxidation and reduction of the electrochemical process occur, respectively, at the anode and cathode of the iron electrodes according to (Pletcher and Walsh, 1990): Anode: 4Fe~-4Fe 2+ + 8 e4Fe 2+ + 10H20+ O 2~,-~4Fe(OH)3 + 8H + Cathode: 8H + + 8 e-~-4H2 With sufficient power supply, the dye molecules are reduced at the cathode to small organic molecules. Some of the small organic molecules and the suspended solids are captured by Fe(OH)3 which is removed by sedimentation or by H 2 flotation. This perhaps accounts for the rather satisfactory decolorization and COD reduction of the textile wastewater by the electrochemical process. In fact, during the experiments, either batch or continuous, small amounts of sludge were scraped off from the top and the bottom of the electrolytic cell, evident of the sedimentation and flotation actions. The textile wastewater samples were obtained from three large dyeing and finishing mills in northern Taiwan. The wastewaters had a COD within the range of 800-1600mg/l and were strongly colored with a transparency invariably less than 4 cm. The suspended solids were consistently less than 200 mg/1 due primarily to partial sedimentation occurring in the equalization tanks. The pH of the wastewater was also partially adjusted in the equalization tanks and was usually within the range of 6-9. Due to significant heat dissipation in these tanks, the wastewater temperature had been maintained below 35C which facilitates the ensuing treatments. Figure 3 displays the transparency of the treated wastewater as a function of time for a typical run of medium strength wastewater. The transparency improves slowly with treatment until 6min. Marked improvement was then observed up to l0 min and beyond that not much improvement was realized. In fact, the color of the treated wastewater had become

Textile

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Electrolytic cell Fig. 2. Continuous experimental setup.

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of textile wastewaters is not needed in most practical applications. Hence, in all subsequent tests, the pH of e l e the samples was not adjusted except for some unusual 30 cases in which the pH fell out of this range. The conductivity of raw textile wastewaters was 25 found to vary from as low as 1000 to over 3000 #mho/cm. In order to examine the effect of ~ 20 o conductivity on the COD removal efficiency, the textile wastewater was artificially adjusted to the g- 15 range between 1000 and 6000#mho/cm using sea 'water or deionized water. Results of a typical run are [lO displayed in Fig. 5. COD removal is seen to increase rapidly with increasing conductivity between 1000 and 2000#mho/cm. It increases mildly beyond 2000 #m.ho/cm and peaks out at 3000 #mho/cm. It is I I I I I I also apparent that corresponding to the range of 2 4 6 8 10 12 conductivity between 2000 and 3000 #mho/cm, there Time (rain) is a rapid decrease in power requirement. Hence, it Fig. 3. T r a n s p a r e n c y as a function o f time. can be concluded that a conductivity in the range between 2000 and 3000 #mho/cm appears to be the optimum operating range in terms of optimum COD very light with a transparency over 20cm. This removal and power utilization. CoincidentaUy, over corresponds to about 8 min of electrolytic treatment. 80% of the textile wastewater samples gathered The Taiwan EPA stipulates that treated industrial from the various dyeing and finishing mills fell within wastewater needs to meet the requirement of 15 cm this range of conductivity. Hence adjustment of transparency, as mentioned earlier. Hence electrolytic the conductivity is usually not necessary. Only on treatment of 8 rain amply satisfies this requirement. rare occasions did the wastewater samples have a Due to the potential pH variation in the textile conductivity much more than 3000 or less than wastewater, the effect of pH on the electrochemical 2000 #mho/cm. In these cases, the conductivity could treatment efficiency was examined next. Figure 4 be easily adjusted to the optimal operating range. shows the results of a typical run on the pH effect. Figure 6 displays the COD removal as a function The pH of the raw textile wastewater collected from of time and power requirement. Two plateaux apparthe textile mills was adjusted using sodium hydroxide ently exist in this figure. The first plateau of COD or sulfuric acid to the desired pH for each experimenremoval occurs at 4 rain after the electrolytic process tal run. It is apparent that the pH effect of the began and with a COD removal efficiency of about wastewater on the COD removal is not very signifi50%. The measured transparency, not shown in the cant within the range of 5-10. This result is particufigure, barely reached 15 cm even at 8 min. However, larly meaningful since the majority of textile beyond that time, considerable improvement in the wastewaters from the equalization tanks have a pH within that range, implying that adjustment of the pH

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Fig. 4. Effect o f w a s t e w a t e r p H o n the C O D removal.

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Fig. 6. COD removal as a function of time. wastewater transparency was observed to begin and at 10 min the transparency far exceeds 25 cm. This is also reflected by a corresponding increase in C O D removal in this figure. In comparison, the improvement in C O D removal does not seem to be as pronounced as that o f the transparency between 8 and 10min. As a consequence, 8-10 min are deemed necessary to achieve good color and C O D reductions. Polyelectrolytes are widely used as a synthetic coagulant in chemical treatment o f wastewaters. To test whether it helps improve the electrochemical treatment, a small a m o u n t o f polyaluminum chloride (PAC) was added to the electrolytic cell in several runs. Figure 7 demonstrates the results with addition o f 5 mg/l PAC. Comparison o f Fig. 5 indicates that the P A C significantly improves the C O D reductions. The transparency was observed to reach 15 cm in less Power (Wh) 0 60
50

than 5 rain for this case and by 8 min it far exceeded 25 cm. The encouragingresults prompted us to explore further the effect o f P A C on this process. Figure 8 shows the C O D removal as a function of the P A C concentration. A P A C concentration o f 40 mg/l appears to yield the optimum results in terms o f c o l o r and C O D reductions. Besides, the power requirement for this case is at least 30% less than that without PAC. The current density was observed by the previous investigators to influence the treatment efficiency o f the electrochemical process (Biwyk, 1980; Matis, 1980; Cenkin and Belevtsev, 1985). Hence, the current was varied to determine its effect on the C O D removal in the present work. F r o m Fig. 9, it is apparent that the C O D removal improves steadily with increasing current and peaks at around 3 amps. With a total electrode surface area of 324 cm 2, this Power (Wh)

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Fig. 9. Effect of current on COD removal.

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Sr~NG H. LI~ and Cm F. I~NG about 92.5 amp/m 2 is also found to yield a maximum C O D removal. A continuous experimental setup is also designed to test the applicability of the process. The continuous runs operating at the optimum operating conditions obtained above show equally satisfactory results as those of the batch runs, indicating the strong potential of the electrochemical process for the textile wastewater treatment.
Acknowledgements--The authors wish to sincerely thank the Far Eastern Textile Company, Republic of China for financial support of this project. Technical help by the personnel of the Far Eastern, Hoyu, Wufon and Yang Ming Textile Companies is greatly appreciated.

~ 3o
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REFERENCES

Fig. 10. COD removal of the continuous run. optimum current is equivalent to a current density of 92.5 amp/m 2 which is within the range of the operating range of current density adopted by the previous investigators (Biwyk, 1980; Matis, 1980; Cenkin and Belevtsev, 1985). The power requirement is also seen to follow the same pattern. In fact, all experimental runs discussed in the previous figures were conducted with this optimal current density. Typical results of C O D removal for the continuous runs were demonstrated in Fig. 10. To attain the best results, the optimum operating conditions determined in the batch experiments were adopted. It is apparent that a transient period of about 50 min existed at the beginning as anticipated. The steady C O D removal fluctuated around 51% which is in line with that obtained in the batch runs operated under similar conditions. The transparency of the treated wastewaters at the steady state was consistently above 20cm. The satisfactory results clearly reflect the applicability of the electrochemical process for continuous treatment of textile wastewater. CONCLUSIONS The electrochemical method has been employed in the present study to treat the textile wastewater. Several aspects, such as the wastewater conductivity, pH, power requirement and addition of polyelectrolyte, are explored to determine their effect on the treatment efficiency. It has been observed that most of the textile wastewaters gathered from the dyeing and finishing mills have a conductivity within the optimum operating range and hence adjustment of the conductivity is usually not necessary. The pH effect of the textile wastewater on the treatment efficiency is found not to be significant when it is within the range between 5 and 10 and hence in the majority of cases, adjustment of the pH prior to electrochemical treatment is not necessary. Addition of a small amount of polyaluminum chloride (PAC) up to 40 mg/l has been observed to significantly enhance the treatment efficiency. A current density of

APHA (1985) Standard Methods for Examination Water and Wastewater, 16th edition, American Public Health Association, Washington, D.C. Beck E. C., Giannini A. P. and Ramirez E. R. (1974) Electrocoagulation clarifies food wastewater. Fd Technol.
28, 2.

Beszedits S. (1980) Ozonation to decolor textile effluents. Am. Dyestuff Rep. 69, 38. Biwyk A. (1980) Eleetroeoaguiation of biologically treated sewage. In 35th Purdue Indust. Waste Conf., Lafayette, Ind. Brower G. R. and Reed G. D. (1987) Economic pretreatment for color removal from textile dye wastes. In Proc. 41st Purdue Indust. Waste Conf., Lafayette, Ind. Cenkin V. E. and Belevtsev A. N. (1985) Electrochemical treatment of industrial wastewater. Eft. Wat. Treat. J. 25, 243. Gould J. P. and Groff K. A. (1987) Kinetics of ozonolysis of synthetic dyes. Ozone Sci. Engng 9, 153. Green J. M. and Sokol C. (1985) Using ozone to decolor dyeing plant wastewater. Am. Dyestuff Rep. 74, 67. Groves G. R. and Buckley C. A. (1980) Treatment of textile effluents by membrane separation p ~ e s . In Proe. 7th
Int. Syrup. on Fresh Wat. from the Sea.

Gurnham C. F. (Ed.) (1965) Industrial Waste Control. Academic Press, New York. Hamza A. and Hamnda M. F. (1980) Multiprocess treatment of textile wastewater. In Proc. 35th Purdue Indust. Waste Conf., Lafayette, Ind. Lin S. H. and Lin C. M. (1992) Decolorization of textile waste effluents by ozonation. J. envir. Syst. 21, 143. Matis K. A. (1980) Treatment of industrial liquid wastes by electro-flotation. Wat. Pollut. Control 19, 136. McKay G. (1980) Color removal by adsorption. Am. Dyestuff Rep. 69, 38. MeKay G. (1984) The adsorption of dyestuffs from aqueous solutions using the activated carbon adsorption model to determine breakthrough curves. Chem. Engng J. 28, 95. Paprowicz J. and Slodczyk S. (1988) Application of biologically activated sorptive columns for textile wastewater treatment. Envir. Technol. Lett. 9, 271. Pletcher D. and Walsh F. C. (1990) Industrial Electrochemistry, 2nd edition. Chapman & Hall, London. Ramirez E. R. (1981) Physicoehemical treatment of rendering wastewater by electrocoagulation. In 36th Purdue Indust. Waste Conf., Lafayette, Ind. Ramit~z E. R., Johnson D. L. and Clemens O. A. (1976) Direct comparison in physicochemical treatment of packinghouse wastewater between dissolved air and electrocoagulation. In 31st Purdue Indast. Waste Conf., Lafayette, Ind. Snider E. H. and Porter J. J. (1974) Ozone treatment of textile wastes. J. War. Pollut. Control Fed. 46, 886.