io

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Copyright 1993 Pergamon Press Ltd

TREATMENT OF TEXTILE WASTE EFFLUENTS BY OZONATION AND CHEMICAL COAGULATION

SHENG H. Lm and Cm M. LIN Department of Chemical Engineering, Yuan Ze Institute of Technology, Neili, Taoyuan, Taiwan 320, Republic of China (First received July 1992"accepted in revisedform March 1993) Abstract--Ozonation experiments in a multiple reactor system were conducted to investigate the efficiency of this process in reducing the color and chemical oxygen demand of the textile waste effluents. It has been observed that decolorization of those waste effluents can be achieved in less than 10 rain in all tested cases. In conjunction with chemical coagulation, the chemical oxygen demand of those waste effiuents can be consistently reduced by up to 70% or more. Ozonation is capable of decomposing the highly structured dye molecules into smaller ones which can be easily biodegraded in an activated sludge process. Hence combination of ozonation, chemical coagulation and the activated sludge processes can provide a very effective means for dealing with this particular type of industrial waste effluent. Key words--chenfical coagulation, color reduction, ozonation, textile waste effluent

INTRODUCTION The textile waste effluents are one of the wastewaters that is very difficult to treat satisfactorily because they are highly variable in composition (Gurnham, 1956). The common methods employed for treating textile wastewater include various combinations of the biological (activated sludge), physical and chemical processes (Souther and Alspangh, 1980; Hamza and Hamoda, 1980; Groves and Bucldey, 1980; McKay, 1980; Ginocchinio, 1984; Brower, 1987; Paprowicz and Slodczyk, 1988). The dye molecules are highly structured polymers, hence they are very difficult to break down biologically and cannot be treated efficiently by an activated sludge process or any combination of biological, chemical and physical methods. Moreover, the cost of textile waste treatment is increasing rapidly and this has prompted further research efforts to identify other more efficient treatment methods in an attempt to lower the treatment cost. Strong color of the textile wastewater is the most notorious characteristic of the textile waste effluent. The color, if not properly dealt with, would have a strongly negative impact on the aquatic environment caused by its turbidity and high polluting strength. Hence decoiorization has become an integral part of the textile waste treatment process. Ozonation represents perhaps the latest method ever attempted for such a purpose of the textile waste effluent (Snider and Porter, 1974; Beszedits, 1980; Green and Sokol, 1985; Gould and Groff, 1987). These studies have shown the potential of this method. Scrutiny of these previous investigations has indicated that there is a lack of more systematic decolorization studies of the textile waste effluents. Furthermore, no works have

been attempted to combine decolorization of textile waste effluent by ozonation with treatment by chemical coagulation. The main reason for considering such a combined method is due to the fact that combination of the biological treatment and ozonation alone is insufficient to deal with decolorization, and COD and SS reductions of the textile wastewater to meet discharge requirements. This paper reports the results of our experimental studies using the textile waste effluents from four large dyeing and finishing plants. The results have indicated that decolorization of the textile waste effluents can be accomplished in no more than 10 rain. Also up to 70% in COD reduction can be realized, when ozonation of the textile waste effluent is followed by chemical coagulation. CHARACrERISTICSOF TEXTILEWASTEEFFLUENTS The fibers used in the textile industries can be divided into two types: natural and man-made. The two major natural fibers are wool and cotton. The most important man-made fibers include polyester, rayon, nylon, polyacrylic and polyamide. Table 1 shows the characteristics of typical textile wastewater samples collected from several dyeing and finishing plants. It appears that most of the textile efltuents do not have high BOD content, but they do have large pH and color variations. Besides, polyvinyl alchohol (PVA), starches and various surfactants may also appear in many dyeing waste effluents. These compounds are chemicals widely used in the dyeing and sizing operations. They have a high COD content of over 10,000 mg/l and can contribute considerably to overall COD content of the textile waste effluents.

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St~NO H. LIN and C-'mM. LtN single parameter, i.e. transparency to light (in centimeters), which will be elaborated in further detail later. The transparencies o f the textile wastewater samples obtained from the various dyeing and finishing plants were typically about 2, 4 and 7 cm, respectively, for the high, medium and low strength wastewaters. The high strength waste effluent was found to be considerably more difficult to deal with than the other two, as will be seen later. Fortunately, most o f the waste effluents from the dyeing plant belong the two latter types.
EXPERIMENTAL STUDIES

Table I. Characteristicsof a typical textile wastewater T Conductivity Type BOD COD pH SS (C)Oil ~m/cm) High strength 500 1500 10 250 28 50 2900 Medium strength 270 970 9 137 28 21 2500 Low strength 100 460 10 91 31 10 2100 Note: all quantitiescarrya unit ofppm exceptfor those as indicated.

The normal dyeing operations of a textile plant are such that the dye used varies from day to day and sometimes even several times a day, primarily because of the batchwise nature of the dyeing process. Dye changes cause considerable variation in the waste characteristics, particularly pH. A large p H swing is especially troublesome primarily because the pH tolerance of conventional biological and chemical treatment systems is very limited. Hence without proper pH control, normal operation of these treatments is essentially impossible. Along with the high pH variation, the textile waste effluents also have a relatively high temperature. In several steps of the dyeing operation, hot rinsewaters of up to 90C are used, resulting in a final effluent temperature between 35 and 40C. This necessitates proper heat dissipation of the hot effluent prior to other treatments. Strong color is the component of the textile waste effluent which is the most difficult to treat, as mentioned earlier. The combination of strong color and high dissolved solid content leads to high turbidity o f the waste effluent. The dyestuffs are highly structured polymers and very difficult to decompose biologically. Hence there is little decomposition o f these molecules in the activated sludge process. A strong effluent color, if not removed, will cause considerable disturbance to the ecological system of the receiving waters. Color removal capabifities of activated carbon, hydrogen peroxide and other decolorizing agents are well known to the industries, however, the cost of polishing processes using these chemicals is high. Ozonotion is a technique that has been suggested in the literature in recent years as a potential alternative. Depending on the sources, the dye waste effluent varies considerably in color, suspended solid content and COD concentration. The dye waste effluents collected for the present experiments varied in color from purple, dark red, brown, grey, dark blue or black. The COD concentration went from 300 to over 2000 mg/l. Hence, according to their C O D content and color and/or turbidity intensity, the dye waste effluents could be approximately classified into three major groups. The high strength waste effluent had a COD concentration over 1600 rag/! and the medium strength one had a COD concentration within the range between 800 and 1600 rag/1. Other textile waste effluents with a COD concentration less than 800 rag/1 fell in the category of low strength effluent. The color and turbidity of the textile wastewater samples were quantified in the present study by a

The present experimental investigations were conducted in a batch multiple reactor system. The experimental schematic is shown in Fig. 1. The ozone generation system consists of two parts. A pressure swing adsorption (PSA) apparatus was used to process the incoming ambient air for the ozone generator. The PSA unit is capable of cleaning and drying (to a dew point of -55C) the ambient air and elevating its oxygen content of over 80%. The dry and oxygen-rich air was then fed to the Sumitomo SG-PSA-01A ozone generator (Sumitomo Electric, Osaka, Japan). The ozone generator is rated at 30 g/h as the maximum generation capacity. The ozone/air mixture from the ozone generator was spargad to the textile waste effluent in the first reactor. The gas effluent exiting the first reactor flowed to the second reactor and then the third before being vented to the KI absorption unit for determination of the amount of unused ozone. Such a multiple reactor system considerably enhanced the ozone utilization. The textile waste effluent was obtained from four major dyeing and finishing plants in northern Taiwan. In all experimental runs, it was very ~ t to know, or even determine, what type of dyestuffs were in the waste effluent because very often several dye waste effluents were mixed together in the equaliT~tion storage tank. The raw effluent obtained was first filtered through a screen filter with 0.3 mm openinss to t~nove the large suspended particles. One fiter of the filtered effluent was placed in each reactor before ozonation began. The batch experiments were repeated for different ozonation times. At the end of each experimental run, the treated waste effluent from the three reactors were mixed together for their COD and turbidity measurements. The mixed waste effluent was then treated with various dosages of aluminum sulfate or combined PAC (polyaluminum chloride) and polymer. The turbidity, COD and pH were measured after chemical coagulation. It is not easy to represent precisely the color and/or turbidity of the dye waste effuent by a simple measurable quantity. One possible method is to measure the fight absorption of the due waste effluent using a spectrophotometer. The problem with this measurement is that the textile waste effuent represents a mixture of different dyestuffs and hence it is difficult to select the right wavelength

To vent

To vent

Ozone generator

K1 solution

Fig. 1. Schematic of the experimental setup.

Ozonation

and coagulation

of textile waste effluent

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for such a measurement. In addition, sizing agents and suspended and dissolved solids in the wastewater add considerable complication to the measurement. Hence, it was decided to determine the transparency of the waste effluent by a visual method (APHA, 1985). An apparatus, similar in basic structure to the candle turbidimeter (APHA, 1985), was thus employed for determining the modified Jackson turbidity unit (Yru). Such a measurement has been widely accepted in Taiwan as the discharge standard for the treated due waste effluents. The acceptable level is 15 cm. RESULTS AND DISCUSSION As mentioned earlier, the treatment of dye waste effluent consists of two steps. In the first step, ozonation was employed primarily for breaking down the large dye molecules and thus for decoiorization. After ozonation, the waste effluent was further treated by chemical coagulation using aluminum sulfate or a combination of polymer and PAC to remove COD. Various ozonation times and different dosages of coagulants were experimented to compare their effects on the color (or turbidity) and COD reductions of the textile waste effluent. Before the experimental studies, the Sumitono ozone generator was first calibrated to determine the true ozone production rate. Figure 2 shows the calibration curves of the ozonator with 1.2 and 2.4 A current inputs. This indicates a good linear ozone production vs time with ozone production rates of 13.25 and 20.49 g/h, respectively. The two calibration curves were employed for determining the amount of ozone consumption in the ozonation experiments.

20
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4 -2 -I I I t I I I I I I

4 5 6 Time (min)

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Fig. 3. The JTU change of low strength waste effluentduring ozonation. Taiwan EPA. In less than 10 rain, the color of the waste effluent had practically disappeared. The COD change of the waste effluent during ozonation is shown in Fig. 4. The COD reduction is seen to be slightly better than 16% during the same period even if the color had faded. The low COD reduction is attributable to the fact that the structured polymer dye molecules are oxidized by ozonation to small molecules, such as acetic acids, aldehyde, ketones, etc., instead of CO2 and water (Rice, 1981). These small molecules still possess a considerable amount of COD. Figure 5 shows the COD changes of the same waste effluent dosed with different amounts of aluminum sulfate with 5-min ozonation and without. Three milliliters of the coagulant appear to be the optimum dosage for the low strength waste effluent. The COD reductions at this point are 46 and 54%, respectively, 400 --

Low strength waste effluent

The turbidity change of the waste effluent during ozonation is demonstrated in Fig. 3. The initial JTU of the waste effluent was low because of its relatively strong color and significant amount of suspended solids. It took just 5 min to reach the discharge requirement of 15 cm JTU, as stipulated by the 2000 1800 1600 O ~ 1400 ~ 1200
0

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6

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7

I
8

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4 5 6 Time (rain)

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Time (min) Fig. 4. The COD change of low strength waste effluent during ozonation.

Fig. 2. Ozonation production as a function of time.

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400

SHENO H. LIN and Cm M. LIN

10 -9

350 300 -~ 250 200 r~ 0 L~ 150 100

50

8 7 3 5rain 6
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0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 Ai 2 (SO4) 3, (ml)

0.5

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t 2.0

I 2.5

I 3.0

J 3.5

J 4.0

(rain)

Fig. 5. The effect of aluminum sulfate dosage on the COD change of low strength waste effluent. for waste effluent with and without 5-min ozonation. The latter appears to have a better C O D reduction. In this case, however, a strong color still existed after aluminum sulfate coagulation. In the former, the treated waste effluent was rather clearer. The slightly higher COD in this case was due to the contribution of small molecules generated by ozone decomposition o f the dyestuffs. Apparently, these small molecules were not completely removed in the coagulation process. It should be noted however that the small molecules can be fairly easily digested in the activated sludge process. The suspended solids concentration of the waste effluent as a function of ozonation time is displayed in Fig. 6. Sixty percent o f the SS reduction was achieved in just 8 min. This SS reduction can be further enhanced by aluminum sulfate coagulation.
100 -

Fig. 7. The JTU change of medium strength waste effluent during ozonation.

Medium strength waste effluent

The medium and high strength waste effluent were characterized by a much higher COD content and a significantly intense color. The turbidity was high
also leading to a greater difficulty in color reduction, as shown in Fig. 7. The JTU reached nearly 8.9 cm after 3.5 min of ozonation. At this level o f JTU, the color o f the waste effluent was significantly lighter but still existed. Chemical coagulation by aluminum sulfate or polymer/PAC can help further reduce the residual color. The COD reductions were seen to be slight as displayed in Fig. 8. Here the ozonations were conducted using 1.2 and 2 . 4 A of current input. The slight C O D reductions however did not reflect the color change in the waste effluent, as shown in Fig. 7. It is of interest to note that an increase in the current 1400
o'o--o
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I I I I I I I I I I

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I I l 4 5 6 Time (rain)

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Fig. 6. The SS change of low strength waste effluent during

ozonation.

Fig. 8. The COD change of medium strength waste effluent during ozonation.

Ozonation and coagulation of textile waste effluent 1400 -1200 ~ 1900 1ooo
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1747

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0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 PAC (ml) Fig. 9. The effect of PAC dosage on the COD change of medium strength waste effluent. input (i.e. increased ozone production rate) considerably shortens ozonation time to bring about the same COD or color change. The low COD reduction was not unexpected because of the generation of small molecule organic compounds mentioned earlier. The more significant COD reduction of the waste effluent by coagulation is demonstrated in Fig. 9. Without ozonation, 1.5 ml of PAC brought about a drastic 65% COD reduction and additional dosage of PAC did not seem to improve the situation, as shown by the solid curve in this figure. After 7 rain of ozonation at a 1.2 A current input, the COD reduction reached nearly 60% at 2.5 ml of PAC dosage. Again the color in the former case was still very strong while that in the latter was considerably lighter. Besides, the residual COD contributed by the small molecules generated during the ozonation can be easily biodegraded in a biological process.

2 3 4 5 6 7 8 9 10 11 12 13 14 15 Time (min) Fig. 11. The COD change of high strength waste effluent during ozonation.

High strength waste e~O~uent

The color and the COD content of the high strength waste effluent was observed to be even stronger than those of the previous two waste effluents. The initial JTU was seen to be quite low, as shown in Fig. 10. The JTU improvements by ozonation at 1.2 and 2.4 A current inputs appeared to be slight. Visual oly'~ervation, however, revealed that there was significant change in the color of the waste effluent. But the JTU variation in this figure did not completely reflect this fact. The main reason for such a small JTU variation is not known. One possible explanation is that some dissolved solids in the original wastewater were converted into suspended solids during ozonation, leading to little change in the wastewater transparency. The wastewater transparency, however, could be drastically improved

1800

1600
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~, 1200

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400

200 o
I 1 I 2 I 3 I 4 I 5 I 6 I 7 I 8 I I I I I I I 9 10 11 12 13 14 15 I I I I I I t I l I

Time (min) Fig. 10. The JTU change of high strength waste efltuent during ozonation.

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 PAC (ml) Fig. 12. The effect of PAC dosage on the COD change of high strength waste effluent

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SHENG H. LIN and Cm M. [diN

by chemical coagulation using aluminum sulfate or polymer/PAC in our experimental tests. The COD reductions by ozonation were expected to be slight again for this case, as demonstrated in Fig. 11. Figure 12 displays the effect of PAC dosage on the COD changes for the cases with and without 10-rain of ozonation. At 3 ml dosage of PAC, the COD reductions were approx. 45 and 50%, respectively, for the cases without and with ozonation. The optimum PAC dosage to realize the most COD reduction appeared to be around 2-2.5 ml of PAC. Again, it should be emphasized that the waste effluent treated by PAC but without ozonation still possessed a very strong color. With ozonation and PAC treatment, the original color had largely disappeared and the waste effluent was considerably cleaner. Furthermore, the residual COD can be easily biodegraded.

generated by ozonation decomposition of the dyestuffs and can be degraded effectively in an activated sludge process. Hence, ozonation in conjunction with proper chemical coagulation and an activated sludge process could provide a potent combination for dealing with this type of difficult waste effluent.
Acknowledgements--The authors wish to sincerely thank

the Far Eastern Textile Company, Taiwan, Republic of China for financial support of this study. Technical help provided by the personnel of the Far Eastern, Holm, Wufon and Yang Ming Textile Companies, is greatly appreciated.

REFERENCES

APHA (1985) Standard Methods for the Examination of Water and Wastewater, 16th edition. American Public Health Association, Washington, D.C. Beszedits S. (1980) Ozonation to decolor textile effluents. Am. Dye. Reptr. 69, 38. CONCLUSIONS Brower G. R. (1987) Economic pretreatment for color removal from textile dye wastes. In Proc. 41st Purdue Ozonation experiments of dye waste effluents were lndust. Waste Conf., West Lafayette, Ind. conducted in the present study. The waste effluent Ginocchinio J. C. (1984) Elimination of dyes and pigments in municipal sewage treatment plants. Chem. Ing. Tech. samples tested were gathered from four different 56, 310. dyeing and finishing plants over a one year period. Gould J. P. and Groff K. A. (1987) Kinetics of ozonolysis The waste effluents could be approximately divided of synthetic dyes. Ozone Sci. Engng 9, 153. into three types, i.e. low, medium and high strength Green J. M. and Sokol C. (1985) Using ozone to decolorize dyeing plant wustewater. Am. Dyes. Reptr. 74, 67. wastes. The COD content and color o f the waste effluent were observed to increase greatly in intensity Groves G. R. and Buckley C. A. (1980) Treatment of textile effluents by membrane separation processes. In Proc. 7th accordingly. Treatments of those waste effluents have Int. Syrup. on Fresh Water from the Sea. Vol. 2, p. 249. become increasingly more difficult. Results of the Gurnham C. F. (Ed.) (1956) Industrial Waste Control. present experiments have revealed that ozonation is Academic Press, New York. highly effective in removing the color of these waste Hamza A. and Hamoda M. F. (1980) Multiprocess treatment of textile wastewater. In Proc. 35th Purdue Ind. effluents. For low strength dye waste effluents, ozonaWaste Conf., West Lafayette, Ind. tion alone is sufficient to totally eliminate the color McKay G. (1980) Color removal by adsorption. Am. Dyes. and reduce the turbidity. However, for the medium Reptr. 69, 38. McKay G. (1984) The adsorption of dyestuffs from aqueous and high strength waste effluents, ozonation is found solutions using the activated carbon adsorption model to to be sufficient to reduce the color, but not enough determine breakthrough curves. Chem. Engng J. 28, 95. to reduce the turbidity. Hence, coagulation using Paprowicz J. and Slodczyk S. (1988) Application of biologialuminum sulfate or polymer/PAC will be necessary. cally activated sorptive columns for textile wastewater Ozonation is observed to be relatively ineffective in treatment. Envir. Technol. Lett. 9, 271. reducing the COD concentration, especially that in Rice R. G. (1981) Ozone for the treatment of hazardous materials. AIChE Symp. 709, 79. the medium and high strength waste effluents. HowSnider E. H. and Porter J. J. (1974) Ozone treatment of ever, in conjunction with chemical coagulation, the textile wastes. J. War. Pollut. Control Fed. 46, 886. C O D reduction can be as high as 70%. The residual Souther R. H. and Alspaugh T. A. (1957) Textile waste treatment studies. J. {Vat. Pollut. Control Fed. 29, 804. C O D is attributable to the small organic molecules