Desalination 240 (2009) 143 150

Treatment of a denim producing textile industry wastewater using pilot-scale membrane bioreactor
N.O. Yigita, N. Uzalb, H. Koseoglua, I. Harmana, H. Yukselerb, U. Yetisb, G. Civelekoglua, M. Kitisa*
Department of Environmental Engineering, Suleyman Demirel University, Isparta, 32260 Turkey Tel. +90 246 211 1855; Fax +90 246 237 0859; email: mkitis@mmf.sdu.edu.tr b Department of Environmental Engineering, Middle East Technical University, Ankara, 06531 Turkey
Received 31 July 2007; revised 29 October 2007; accepted 5 November 2007
a

Abstract The objective of this study was to investigate the performance of a pilot-scale membrane bioreactor (MBR) system for the treatment of a highly concentrated mixed wastewater from wet processes (dyeing, finishing, and sizing) of a denim producing textile industry. The MBR system, containing a submerged hollow fiber membrane module in the aeration tank, was operated aerobically for about 3 months on-site at a continuous flow mode. The system was operated at two different operation stages: (1) no sludge wastage with a typical permeate flux of 20 L/m2 h and (2) a solids retention time of 25 days with the same flux. During the whole operation period, despite the high dissolved solids content in the influent, very high treatment efficiencies were achieved. The performance of the MBR system was not adversely affected by the variations in the influent characteristics, food/ microorganism ratio, organic loading rate, and specific substrate utilization rate. The average values of some effluent quality parameters found in the entire operation period were color, 53 Pt Co; turbidity, 0.31 NTU; TSS, 0.6 mg/L; BOD5, 15 mg/L; COD, 37 mg/L; NH3 N, 1.0 mg/L; NO3 N, 9.6 mg/L; and TN, 10.5 mg/L. Reduction in permeate flux due to membrane fouling was observed only once during all operation and such fouling was removed by applying chemical backwashing and chemical cleaning procedures. The results indicated that complex and highly polluted denim textile wastewaters could be treated very effectively by MBR systems. Color values from as high as 8100 Pt Co levels were significantly reduced to about 50 Pt Co levels, indicating that MBR effluent could be reused in the production processes. Keywords: Color; Dyeing; Membrane bioreactor; Textile wastewater; Treatment

*Corresponding author.

Presented at the Third Membrane Science and Technology Conference of Visegrad Countries (PERMEA), Siofok, Hungary, 26 September 2007.
0011-9164/09/$ See front matter # 2009 Elsevier B.V. All rights reserved. doi: 10.1016/j.desal.0000.00.000

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1. Introduction The textile industry is characterized not only by the vast quantity of process water used, but also by the variety of chemicals used. The primary source of wastewater in textile dyeing operations is spent dye bath and rinsing waters [1,2]. For the treatment of textile wastewaters, biological treatment, chemical precipitation, adsorption, and membrane technology are the common processes applied [35]. However, because of low biodegradability, toxicity, and color issues, advanced treatment options are generally required for textile wastewaters [3]. More stringent discharge limits and increases in process water costs are the main drivers to reuse treated wastewaters in textile industry. Membrane bioreactor (MBR) process is the combination of conventional activated sludge process and membranes for solids separation. Complete solids removal, a significant physical disinfection capability, very high degree of carbon and nitrogen compounds, and color removal are the main advantages of MBR processes, which result in very high quality of treated water for further reuse [6,7]. Therefore, MBR technology has been an attractive option for the treatment and reuse of municipal and industrial wastewaters from various industries including food processing, slaughterhouse, pulp and paper, chemical production, pharmaceuticals, mining and metal production, textile, etc. [3,6,8,9]. The main objective of this study was to investigate the performance of a pilot-scale aerobic MBR system for the treatment of a highly concentrated mixed wastewater from wet processes of a denim producing textile industry. Furthermore, the impacts of MBR operation parameters on treatment performances were investigated. 2. Materials and methods ZW-10 unit (GE Water & Process Technologies, Zenon Membrane Solutions) was used as

the pilot-scale MBR system, which contained a submerged hollow fiber membrane module in the bioreactor. The membrane module had a nominal pore size of 0.04 mm. The treatment capacity of the unit was 3801500 L/day. The bioreactor was a high-density polyethylene (HDPE) tank with 230-L solution volume. The system was operated aerobically for about 3 months on-site at a continuous flow mode. A routine backwashing (15 s after each 10 min of permeate production) was employed at a flowrate of 600 mL/min, which was about two times the normal permeation flowrate. The system was operated at two different operation stages: (1) no sludge wastage with a typical permeate flux of 20 L/m2 h and (2) a solids retention time (SRT) of 25 days with the same flux. The target hydraulic retention time (HRT) in both the stages was 14 h. The wastewater was pumped from the neutralization tank of the on-site full-scale treatment plant of the textile industry into the feed tank of the MBR system. The wastewater was then pumped from the feed tank to the bioreactor via a peristaltic pump. A coarse filter cartridge (25 mm) was located in the connection between feed tank and bioreactor to remove fibers and coarse particles. Prior to start-up of the pilot-scale MBR, concentrated biomass (via settling) was obtained from the on-site full-scale treatment plant treating the same wastewater, which provided an MLSS concentration of 13,900 mg/L directly in the start-up, enabling a faster adaptation and acclimation of biomass in the MBR. The MBR operational parameters including trans-membrane pressure (TMP), influent (to MBR) and permeate flowrates, dissolved oxygen (DO) concentration, mixed liquor suspended solids (MLSS) concentration, temperature, flowrate and frequency of backwashing, periods and types of chemical cleaning, and air flowrates were continuously monitored and controlled, if necessary. The range of MLSS concentrations

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for both the operation stages was between 13,900 and 17,000 mg/L. The treatment performance of the system was determined through measurements of color, biochemical oxygen demand (BOD5), chemical oxygen demand (COD), ammonia nitrogen (NH3 N), nitrate nitrogen (NO3 N), nitrite nitrogen (NO2 N), total Kjeldahl nitrogen (TKN), total nitrogen (TN), total phosphorus (TP), turbidity, total solids (TS), total dissolved solids (TDS), conductivity, alkalinity, and pH according to Standard Methods [10]. During the operation of MBR system, the measured parameters, sampling points, and sampling frequency are presented in Table 1. Furthermore, the values of food/microorganism ratio (F/M) and organic loading rate (OLR) were measured and/or calculated for at least 3 days in a week. The studied textile plant produces denim textile starting from raw cotton. Textile production starts with fiber manufacturing, continues with sizing, dyeing, weaving, and ends up with finishing. Among these sizing, dyeing, and finishing are the wet processes. In the plant, more than 50% of the water is consumed in the dyeing and finishing processes and they are responsible for 80% of the total wastewater generated. 3. Results and discussion During the entire MBR operation, the characteristics of influent wastewater was quite variable mainly due to the variations in the textile production program and break offs during weekends for cleanings, etc. A total of about 400 different dyeing recipes were employed in the plant which included the use of hundreds of different chemicals and dyes. Thus, the variations in influent wastewater characteristics are inherent. The values of measured parameters in the influent and permeate are summarized in Table 2. Despite the high and variable

Table 1 The measured parameters, sampling points, and sampling frequency during MBR operation Parameter Temperature pH DO Conductivity TMP Color COD BOD5 TSS Turbidity TS MLSS NO3 N NO2 N NH3 N TKN TN TP Influent and permeate Once a day, 7 days/week Once a day, 7 days/week Once a day, 6 days/week Once a day, 6 days/week Once a day, 3 days/week Once a day, 6 days/week Once a day, 6 days/week Once a day, 3 days/week Once a day, 5 days/week Once a day, 5 days/week Once a day, 5 days/week Once a day, 3 days/week Once a day, 3 days/week Once a day, 3 days/week MBR Once a day, 7 days/week Once a day, 7 days/week Once a day, 7 days/week Once a day, 7 days/week Once a day, 7 days/week Once a day, 3 days/week

TDS/conductivity, BOD5, and COD concentrations in the influent, very high organic (BOD5 and COD) removals were obtained for both stages of the operation (Fig. 1). Although COD and BOD5 removals in the MBR were slightly

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Table 2 The performance of the MBR system during the entire operation period Parameter BOD5 (mg/L) COD (mg/L) NH3 N (mg/L) NO3 N (mg/L) NO2 N (mg/L) TKN (mg/L) TN (mg/L) TP (mg/L) TSS (mg/L) TDS (mg/L) Turbidity (NTU) Conductivity (mS/cm) Color (Pt Co Unit) Influent average (min. max.) 455 (290 610) 1411 (686 2278) 11.2 (4.8 28.0) 42.6 (16.3 76.5) 0.35 (0.14 1.13) 4.2 (2.3 7.9) 49.2 (19.5 81.0) 6.3 (1.2 19.8) 137 (60 212) 2563 (789 4720) 294 (194 419) 5125 (1578 9440) 2447 (286 8100) Permeate average (min. max.) 15 (8 20) 37 (13 60) 1.0 (0.2 4.8) 9.6 (1.3 20.0) 0.13 (0.01 0.60) 0.9 (0.3 2.0) 10.5 (2.1 21.0) 2.6 (0.2 8.1) 0.6 (0.4 0.8) 2455 (1410 4075) 0.31 (0.18 0.65) 4910 (2820 8150) 53 (32 105)

lower in no sludge wastage conditions, such removals were always over 95% in both of the SRT conditions. Similarly, Badani et al. reported high COD removals at about 97% for the treatment of textile wastewaters by a MBR [3]. The average BOD5/COD ratio in the influent was about 0.32 in our work, suggesting the dominance of slowly-biodegradable and/or biorecalcitrant organics in the textile wastewater. Despite all these negative aspects, the sustainable and
Concentration (mg/L) 10000 1000 100 10 1 26.7

successful performance of the biological activity demonstrated the presence of a robust and specialized biomass mixture in the MBR that could respond to sudden variations in the influent and degrade synthetic chemicals such as dyes. This can be attributed to the fact that all biomass is retained in MBRs by micro- or ultrafiltration, resulting in high MLSS concentrations and a community structure with a wide spectrum of degradation capability. In addition to the advantages of membrane filtration, this is another advantage of MBRs over conventional activated sludge processes from a microbiology perspective [11,12]. F/M and OLR values were in the range of 0.030.07 kg BOD5/kg MLSS day and 0.37 1.01 kg BOD5/m3 day, respectively, for both of the MBR operation stages. Irrespective of the high variations in F/M and OLR values, almost complete and continuous oxidation of organic compounds was achieved in both of the operation stages (Figs. 2 and 3). The influent and permeate ammonia concentrations during the whole operation period of the MBR system are shown in Fig. 4. The average permeate NH3 N concentration was about 1 mg/L. Although sudden peaks in influent TDS concentrations were experienced, nitrification was not inhibited. Nitrification was negatively affected only once, in the first stage of the operation, in which HRT was suddenly
100
BOD5 Removal (%) F/M (kg BOD5 /kg MLSS-day)

0.30 0.25 0.20

80 60 40 20 0 26.7 2.8 9.8 16.8 23.8 30.8 6.9

0.15 0.10 0.05 0.00 SRT = 25 days No sludge wastage Date (2006) BOD5 Removal F/M

2.8

9.8

16.8

23.8

30.8

6.9

No sludge wastage SRT = 25 days Date (2006) Feed COD Feed BOD5 Permeate COD Permeate BOD5

Fig. 1. BOD5 and COD concentrations throughout MBR operation.

Fig. 2. The relationship between the F/M ratio and BOD5 removals throughout the MBR operation.

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3 OLR (kg BOD5/m -day)

147
30 28 26 24 22 20 18 16 14 12

BOD5 Removal (%)

80 60 40 20 0 26.7 2.8 9.8 16.8 23.8 30.8 6.9

0.8 0.6 0.4 0.2 0.0 No sludge wastage SRT = 25 days Date (2006) BOD5 Removal OLR

NH3N Removal (%)

100

1.0

100 80 60 40 20 0 26.7 2.8 9.8 16.8 23.8 30.8 6.9

Decrease in NH3 removal due to reduced HRT

SRT = 25 days No sludge wastage Date (2006) NH3 Removal HRT

Fig. 3. The relationship between the OLR and BOD5 removals throughout the MBR operation.

Fig. 5. The relationship between the HRT and NH3 N removals throughout the MBR operation.

reduced from 23 to 14 h after cleaning of the fouled membrane (increased permeate flux) (Fig. 5). However, nitrifiers immediately recovered within a week and NH3 N concentrations less than 1 mg/L were achieved. Nitrification was also not negatively influenced by the variations in operational parameters including SRT, F/M ratio, OLR, DO concentrations, temperature, and conductivity. Similarly, Lubello and Gori reported very high ammonia removals in a MBR treating textile wastewaters [13]. Although denitrification was not targeted in the study, TN removals as high as 78% were achieved. This may be due to high MLSS concentrations (13,90017,000 mg/L) which may result in anoxic regions among flocs or at the bottom of the reactor. Fig. 6 shows TSS removals throughout MBR operation. During the whole operation period
100.0 NH3N (mg/L) Increase in NH3 conc. due to reduced HRT

very high TSS removal efficiencies were achieved and permeate TSS values were lower than B1 mg/L, indicating membrane integrity throughout operation. Moreover, the removal performance of TSS was not affected by the variations in the influent TSS concentrations. Similar to the TSS removal, very high turbidity removals were achieved in the permeate independent of the variations in the influent (Fig. 7). Maximum and minimum turbidity values achieved in permeate were 0.65 and 0.18 NTU, respectively. These results indicate that in addition to high performance of organic carbon removal and nitrification excellent removal of particulate matter was also achieved by the MBR independent of operational conditions, which is a major advantage over conventional activated sludge processes. Very high color removals (97%) were obtained throughout the entire operation
/ /

10.0
TSS (mg/L)

1000 100 10 1 0.1 267

1.0

0.1 26.7

2.8

9.8

16.8

23.8

30.8

6.9
28 98 168 238 308 69

No sludge wastage SRT = 25 days Date (2006) Feed Permeate

No sludge wastage SRT = 25 days Date (2006) Feed Permeate

Fig. 4. NH3 N operation.

concentrations

throughout

MBR Fig. 6. TSS concentrations throughout MBR operation.

HRT (h)

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1000 Turbidity (NTU) 100 10 1 0.1 267

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28

98

168

238

308

69

No sludge wastage SRT = 25 days Date (2006) Feed Permeate

Fig. 7. Turbidity values throughout MBR operation.

although color removals were slightly higher in SRT: 25 d condition (Fig. 8). Such high color removals obtained in this work are consistent with those reported in the literature [3,7,1416]. The maximum color values in the influent and permeate samples were 8100 and 105 Pt Co, respectively. Color values as low as 32 Pt Co were found in permeate samples. Since ultrafiltration is employed in the MBR process the color in permeate samples is mainly caused by nonbiodegradable dissolved organics. The mechanisms of color removal in the MBR are mainly biodegradation and sorption onto solids. Such high color removal performances in textile wastewaters indicate another advantage of MBR processes over conventional activated sludge systems. For the two operation stages of the study, the target instantaneous permeate flux was 20 L/m2 h. The ranges of measured instantaneous
10000 Color (Pt Co) 1000 100 10 1 26.7

permeate flux were 1119 and 1618 L/m2 h in stage 1 and 2, respectively (Fig. 9). Similarly, the ranges of measured TMP values were 0.14 0.56 bar (28 psi) and 0.270.34 bar (45 psi) in stages 1 and 2, respectively. The maximum permissible TMP as indicated by the membrane manufacturer is about 0.62 bar (9 psi). As indicated previously, a routine backwashing with produced permeate was employed during the entire operation. A chemical cleaning was necessary after 35 days of operation when TMP values reached about 8 psi (Fig. 9). First, chemical backpulse cleaning was employed (backpulsing membranes with permeate containing sodium hypochlorite concentration of 250 mg/L as chlorine for 5 min). However, such cleaning was not successful in removing the irreversible foulants. Therefore, an ex situ chemical cleaning procedure was applied, which included soaking the membrane module in sodium hypochlorite solution of 250 mg/L (as chlorine) for 3 h, then in HCl solution (pH 2) for 5 h, washing the module with tap water, and assembling the module back into the reactor. After this chemical cleaning, the fouling was removed and permeate flux was increased to 19 L/m2 h and TMP was decreased to 2.5 psi. In the second stage of the operation (SRT: 25 d), no chemical cleaning was necessary based on the measured flux and TMP values.
30 25 Flux (L/m2 . h) 20 15 10 5 0 26.6 Increase in flux, decrease in TMP due to chemical cleaning 3.7 10.7 17.7 24.7 31.7 7.8 14.8 21.8 28.8 4.9 11.9 Chemical backpulse Chemical cleaning 10 9 8 7 6 5 4 3 2 1 0

2.8

9.8

16.8

23.8

30.8

6.9

No sludge wastage Date (2006) Instantaneous flux TMP

SRT = 25 days

No sludge wastage SRT = 25 days Date (2006) Feed Permeate

Fig. 8. Color values throughout MBR operation.

Fig. 9. Instantaneous ux, TMP, and applied chemical cleanings throughout MBR operation.

TMP (psi)

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4. Conclusions During the entire MBR operation, despite the high TDS levels in the influent, very high removal efficiencies were obtained for various parameters. The performance of the MBR system was not adversely affected by the variations in the influent characteristics, F/M ratio, OLR, specific substrate utilization rate, and DO levels. Except for a duration of 1 week after a sudden reduction in HRT, continuous and consistent nitrification was achieved. At SRT: 25 day condition, effluent quality was slightly better than at infinite SRT (i.e. no sludge wastage) condition. Although not targeted, a significant degree of denitrification (TN removals as high as 78%) was achieved due to high MLSS concentrations and thus anoxic regions formed among flocs or at the bottom of the reactor. The average values of some effluent quality parameters found in the entire operation period were color, 53 Pt Co; turbidity, 0.31 NTU; TSS, 0.6 mg/L; BOD5, 15 mg/L; COD, 37 mg/L; NH3 N, 1.0 mg/L; NO3 N, 9.6 mg/L; and TN, 10.5 mg/L. During the 3 months of operation, membrane fouling indicated by an increase in the TMP up to 8 psi (0.56 bar) levels was observed only once in no sludge wastage conditions (after 35 days of operation). Such fouling was eliminated by applying chemical backwashing and chemical cleaning procedures. In the second stage of operation, no chemical cleaning was required and regular backwashing was sufficient to maintain the operation. One chemical cleaning in a 3-month operation period may be regarded as seldom compared to typical MBR applications for industrial wastewaters. Influent color values from as high as 8100 Pt Co levels were significantly reduced to about 50 Pt Co levels, indicating that the MBR effluent could be reused in the textile sizing, dyeing, and/or finishing processes. However, since the dissolved solids could not be removed by ultrafiltration as employed in MBR processes further treatment

(i.e. nanofiltration or reverse osmosis) to remove dissolved solids is required prior to reuse of MBR effluent, especially in dyeing and finishing processes. The degree of required salt removal is dependent on the production process in which the water is to be reused. For example, low dissolved solid concentrations (B100 mg/L) are required for dyeing processes. On the other hand, MBR effluents could be directly reused for washing and rinsing of the tanks in the production line, on-site irrigation, and for other minor usages. Furthermore, the MBR effluent could be mixed with other process waters to decrease fresh water consumption. The results overall indicated that complex and highly polluted textile wastewaters can be treated much more effectively by MBR processes than conventional activated sludge systems, and the treated wastewaters by MBRs have high potential for reuse in the textile industry.
/

Acknowledgements This work was funded by the Scientific and Technical Research Council of Turkey (TUBITAK) via Grant No. 105Y088. We thank the technical and administrative staff of the textile plant for their cooperation and assistance. We also thank Zenon Environmental Inc. (now GE Water & Process Technologies) for providing the ZW-10 unit. References
[1] U.S. Environmental Protection Agency, EPA Ofce of Compliance Sector Notebook Project: Prole of the Textile Industry, EPA/310-R-97-009, 1997. [2] A.H. Gemeay, I.A. Masour, R.G. El-Sharkawy and A.B. Zaki, J. Mol. Catal., 193 (2003) 109 120. [3] Z. Badani, H. Ait-Amar, A. Si-Salah, M. Brik and W. Fuchs, Desalination, 185 (2005) 411 417. [4] C.T.M.J. Frijters, R.H. Vos, G. Scheffer and R. Mulder, Wat. Res., 40 (2006) 1249 1257. [5] P.K. Malik, J. Hazard. Mater., B113 (2004) 81 88.

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M. Kitis, Regional EMWater Project Conference on Efcient Management of Wastewater Treatment and Reuse in the Mediterranean Countries, October 30 November 1, Amman, Jordan, 2006. C. Lubello and R. Gori, Wat. Sci. Tech., 50(2) (2004) 133 119. A. Rozzi, F. Malpei, L. Bonomo and R. Bianchi, Wat. Sci. Tech., 39(5) (1999) 121 128. X.Z. Li and Y.G. Zhao, Wat. Sci. Tech., 39 (10 11) (1999) 245255. D.R. Van Veldhuisen, Technical and Economical Aspects of Measures to Reduce Water Pollution from the Textile Finishing Industry, Comission des Communautes Europeennes, Direction Generale, Environment Securite Nucleaire et Protection Civile, 1991.

[6] T. Stephenson, S. Judd, K. Brindle, Membrane Bioreactors for Wastewater Treatment, IWA Publishing, London, 2000. [7] M. Brik, P. Schoeberl, B. Chamam, R. Braun and W. Fuchs, Process. Biochem., 41 (2006) 1751 1757. [8] W. Yang, N. Cicek and J. Ilg, J. Membr. Sci., 270 (2006) 201 211. [9] P. Le-Clech, V. Chen and T.A.G. Fane, J. Membr. Sci., 284 (2006) 17 53. [10] APHA, Standard Methods for the Examination of Water and Wastewater, twentieth ed., Washington DC, 1998. [11] F. Malpei, L. Bonomo and A. Rozzi, Wat. Sci. Tech., 47(10) (2003) 33 39. [12] N.O. Yigit, I. Harman, G. Civelekoglu, H. Koseoglu, N. Cicek, L. Yilmaz, R. Arviv,

[13] [14] [15] [16]