Desalination 190 (2006) 277286

Dyeing and printing wastewater treatment using a membrane bioreactor with a gravity drain
Xiang Zheng, Junxin Liu*
Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, PR China Tel./Fax: +86 (10) 6284 9133; email: jxliu@mail.rcees.ac.cn Received 1 June 2005; accepted 8 September 2005

Abstract A laboratory-scale membrane bioreactor (MBR) with a gravity drain was tested for dyeing and printing wastewater treatment from a wool mill. The MBR was operated with continuous permeate by gravity and without chemical cleaning for 135 days. Results showed that excellent effluent quality could meet the reuse water standard in China. The average concentrations of COD, BOD5, turbidity and color in the effluent were 36.9 mg l!1, 3.7 mg l!1, 0.2 NTU and 21 dilution times (DT), respectively. The average removal rates of COD, BOD5, turbidity and color were 80.3%, 95.0%, 99.3% and 58.7%, respectively. The membrane flux increased with increasing of aeration intensity, and its increasing rate was related to pressure-heads. The higher the pressure-head, the greater the impact of aeration intensity on membrane flux. Statistical analysis also showed that both the pressure-head and aeration intensity significantly affected membrane flux. Due to its compact design, simple operation and easy maintenance, MBR with a gravitational filtration system hs low energy consumption and is cost-effective to build and operate. If the life expectancy of the membrane is set for 34 years and the membrane flux is set at 15 l/m2.h, such a MBR would be very competitive. Keywords: Gravitational filtration; Membrane bioreactor (MBR); Dyeing and printing wastewater

1. Introduction The textile industry is one of the most important industries in China. Many textile factories consume considerable amounts of water in the manufacturing process. In 2003, the total discharge of Chinese industrial wastewater was about 21.2 billion m3/y, of which 1.6 billion m3/y was textile industry wastewater [1]. More than 80% textile wastewater was discharged by dye*Corresponding author.
doi:10.1016/j.desal.2005.09.008

ing and printing manufacturing facilities. Since 1996, China has tightened controls on the effluent from textile facilities, and about 10,000 enterprises in the textile industry were closed down because they could not meet national wastewater discharge standards. In addition, since the introduction of ISO 14,000 in China, the concept of environmental protection has become more and more important for industry to meet the needs of the market and consumers. All of these factors contribute to textile companies paying more

0011-9164/06/$ See front matter 2006 Elsevier B.V. All rights reserved

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attention to wastewater treatment in order to meet national environmental standards. Generally, effluent from textile manufacturing facilities is highly colored, even though it is considered to be fairly non-toxic. However, due to the stability of modern dyes that are most often used in the textile industry, dyeing and printing wastewater has a low ratio of BOD5/COD and heavy color, and becomes one of the most difficult wastewaters to be treated in China. Conventional processes treating dyeing and printing wastewater include biological, physical and chemical methods such as oxidation, adsorption, or coagulation by aluminum or iron salts [25]. However, these processes are increasingly facing a challenge with variability of the dye composition in the wastewater to meet the more and more strict Chinese wastewater discharge standards. Therefore, it is important to develop more efficient technologies for dyeing and printing wastewater treatment. Recently, more attention has been paid to the membrane bioreactor (MBR) for wastewater treatment because of its higher efficiency of pollutant removal and excellent effluent quality [6]. Now, two types of anaerobic/oxic pilot-scale (10 t/d) MBRs have been tested and used for textile industry wastewater treatment in China [7,8]. One is the side-stream MBR, and the other is the submerged MBR with a suction pump. Results showed the quality of treated water was excellent and met the gray water reuse standards [9]. However, high capital and operating costs are associated with the use of MBRs in these applications. The application of the side-stream MBR system is limited in China due to high energy consumption (5 kWh/m3). Although high power requirements of the side-stream MBR can be partially overcome by immersing the membrane module directly into the aerobic tank, the benefits using the submerged suction MBR are partially offset by more membrane area required to produce the same flux. The most significant factors influencing the

capital cost for submerged suction MBR are the costs of the membrane and control unit, which account for about 50% and 15% of the total capital costs, respectively [10]. In China, most membrane modules used in submerged suction MBR in practice are made by Mitsubishi Rayon (Japan). Their price is about 34 times that of membrane modules made in China. A new membrane bioreactor was thus developed to decrease capital and operating costs of submerged suction MBR for dyeing and printing wastewater treatment. In this MBR system, a membrane module made in China is submerged into an airlift bioreactor, and the permeate of the MBR is continuously obtained by gravity. As a result, no suction pump and control unit are needed. Therefore, this MBR is cost-effective, with simple operation and easy maintenance in comparison with conventional submerged suction MBRs. The MBR with a gravity drain runs according to the constant pressure-head. Hence, it is very important to initiate the membrane at a proper pressure-head at which the flux remains stable or decreases slowly. In addition, aeration intensity is one of the key factors affecting membrane fouling and energy consumption [11,12]. Therefore, the objective of this paper was to test this new MBR for the treatment of dyeing and printing wastewater and to investigate the impact of operation parameters (pressure-head, aeration intensity and MLSS) on membrane flux. Meanwhile, a cost analysis was also made for MBR applications in dyeing and printing wastewater treatment in order to provide useful information for potential customers. 2. Materials and methods 2.1. Test system The MBR with a gravity drain is showed in Fig. 1. The aerobic reactor is an airlift reactor with 16 L of maximum working volume, that can

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Fig. 1. Flow sheet of the experimental apparatus.

be adjusted in accordance to experimental demands. An anaerobic tank was added to improve efficiencies of COD removal and decolorization for dyeing and printing wastewater treatment. The working volume of the anaerobic tank was 12 L. The membrane module was set in the downside of the aerobic reactor. The membrane flux was driven by the pressure-head between the liquid level in the bioreactor and the effluent pipe. Compressed air is supplied from the bottom of the module, and the membrane surface can be cleaned by air turbulence. The tested membrane module was made of polyvinylidene fluoride hollow fibers, and its effective surface area and pore size were 0.18 m2 and 0.22 m, respectively. The length of the membrane module was 270 mm. Compared to a conventional submerged MBR with a suction pump, this MBR with gravity has no suction pump or control unit, but is operated by continuous permeation with gravity at a given pressure-head. Therefore, the new MBR is easier to operate and maintain, and can save energy consumption during wastewater treatment.

2.2. Operating conditions The MBR was operated at a HRT of 612 h. The average F/M ratio and volume loading rates in the MBR throughout the experimental operation period were 0.24 kg COD kgSS!1 d!1 and 0.43 kg COD m-3 d!1, respectively. Temperature of the mixed liquor varied between 14 and 29EC. In order to eliminate the influence of temperature on the membrane flux, all fluxes J(T) measured at temperature T were corrected to values J(25) at a temperature of 25EC by the following equation: J(25) = J(T) * 1.02525!T Neither chemical cleaning of the membrane nor sludge discharging in this MBR was carried out throughout the operation period of 135 days. The characteristics of the raw wastewater are summarized in Table 1. 2.3. Analytical methods Color, suspended solids (SS), mix liquid

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Table 1 Operating parameters of the membrane bioreactor Range Pressure-head, kPa Aeration intensity, m3m!2h!1 Temp., EC DO, mg l!1 HRT, h MLSS, g l!1 F:M, kg COD kgSS d!1 4.420.3 40240 1428 3.09.3 5.9234 0.43.8 0.080.80 Avg. SD 15.0 2.7 128 40 22 5 3.8 2.3 10.0 4.3 2.2 1.0 0.30 0.15

suspended solids (MLSS) and volatile suspended solids (VSS) were determined according to the Standard Methods [13]. The pH was measured with a pH meter (pHS-3C, China). COD was analyzed with a CTL-12 COD meter (Huatong, China). BOD5 was determined with a BOD TrakTM (Hach, USA). Turbidity was measured by a turbidity meter (Model 8391-37 Turbidity, USA). Dissolved oxygen (DO) and temperature were measured with a portable DO meter combined with a temperature probe (JBP-607 DO, China). Statistical analysis including Pearson and Spearmans rank correlation analysis was carried out using the statistical software SPSS 11.0. 3. Results and discussion 3.1. Removal of pollutants The characteristics of the pollutants in influent and effluent of the MBR are shown in Table 2 and Fig. 2. Results clearly showed that the effluent quality of the MBR was excellent, and could meet with the reuse water standard of China [9]. Although the influent COD concentration varied from 128 to 321 mg l!1, the average effluent COD concentration was stable at 36.9 mg l!1. The average COD and BOD5 removal efficiencies were 80.3% and 95.0%, respectively. This implies that the biodegradable pollutants in the wastewater were almost removed by the system.

The average color in the effluent was decreased to 30 DT compared with that in the influent changing between 30 DT and 70 DT. The effluent turbidity was lower than 0.4 NTU, and its average was 0.24 NTU when the turbidity of influent varied from 15 to 84 NTU. The ratio of MLVSS and MLSS was stable at 0.740.81, which means few inert solids accumulated in the biomass, though no sludge was discharged throughout the operation period except samples taken for analysis. In order to investigate the effect of the membrane on COD removal and the influence of organic matter in mixed liquor on membrane fouling, COD concentration in the supernatant of the MBR was measured. The supernatant was collected after the mixed liquid samples from the MBR settled for about 30 min. Compared with low COD values of the membrane effluent, the changes of COD values in the supernatant were higher than those in effluent (Fig. 3). A possible explanation is that the accumulated recalcitrant organic matter due to its poor biodegradation and the released organic matter from dead biomass or the microbial metabolic products may contribute to a rise in COD in the supernatant. In addition, this phenomenon showed that the membrane cutoff played a very important role in the COD removal in this MBR for dyeing and printing wastewater treatment. 3.2. Impact of operating parameters on membrane flux Unlike most membrane process operations, fouling was rapid at the initial stages of filtration. Many researchers reported that the clogging of pores inside the membrane matrix contributes significantly to an increase of membrane resistance [1416]. The higher the initial flux, the faster the clogging inside the membrane matrix. The initial membrane flux in this study was therefore set at a low value of 6 2.5 l m!2 h!1 at 12.7 kPa in the first 35 days. The membrane flux

X. Zheng, J. Liu / Desalination 190 (2006) 277286 Table 2 Characteristics of influent and effluent in the experimental MBR system COD, mg@l!1 Influent: Average SD Range Effluent: Average SD Range Removal rate: Average SD Range Reuse water standarda: Flush water Car washing Irrigation
a

281

BOD5, mg@l!1 74.8 21.8 3695 3.7 5.3 0.014 95.0 8.9 80.6100 15 10 20

Turbidity, NTU 74.8 17.5 1584 0.2 0.1 0.10.3 99.3 0.4 98.299.7 10 5 10

Color, DT 51 10 3070 21 5 1530 58.7 8.5 42.975.0 30 30 30

SS, mg@l!1 n.d. n.d. 100 100

195.9 45.1 128321 36.911.1 1559 80.3 7.9 54.390.7

Water reuse standards in China [9].

Fig. 2. Pollutant removal in the MBR system.

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Fig. 3. Variation of the supernatant COD concentration.

Fig. 4. Performance of flux and pressure-head..

Fig. 5. Influence of aeration intensity on the membrane flux.

Fig. 6. Relationship between membrane resistance and aeration intensity.

was stepped in increments to about 12 l m!2 h!1 from a low value at the same pressure before the 64th day. Along with a pressure-head increase, the membrane flux increased to 15 2.5 l m!2 h!1 at 17.4 kPa from the 65th to the 114th day. However, membrane flux did not increase correspondingly with increasing the pressure-head from 17.4 kPa to 20.3 kPa after 114 days (Fig. 4). The influence of aeration intensity on membrane flux at different pressures was investigated (Fig. 5). Results clearly showed that the membrane flux increased with increasing aeration intensity. The increasing rate of membrane flux was also related to the pressure-heads. The higher the pressure, the more the influence of aeration intensity on membrane flux. At optimal aeration intensity, it is effective to limit sludge deposition

on the membrane surface, thus maintaining stable membrane flux. Equations from the results of Fig. 6 are summarized in Table 3. When aeration intensity increased from 40 m3 m!2 h!1 to 200 m3 m!2 h!1, membrane resistance decreased from 6.98E+12 to 4.24E+12 at 12.7 kPa and from 6.58E+12 to 3.29E+12 at 17.4 kPa, respectively (Fig. 6). These results showed that the aeration intensity played an important role in removing external deposits on the membrane surface and preventing the compaction of a cake layer, and thus had a great impact on membrane flux. Statistical analysis confirmed that both the pressurehead and the aeration intensity significantly affected membrane flux, but MLSS had no impact on membrane flux (Table 4). Hence, it is possible to maintain high and stable long-term

X. Zheng, J. Liu / Desalination 190 (2006) 277286 Table 3 Relativity between aeration intensity and flux Pressure (kPa) 4.4 12.7 17.2 20.3 Aeration intensity (x) and flux (Y) Y = 0.0104x + 5.9933 Y = 0.0260x + 5.8475 Y = 0.0461x + 5.4353 Y = 0.0365x + 8.1850 R2 0.9624 0.9797 0.9979 0.9820 Operating parameters Range

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Table 4 Correlations between operation parameters and membrane flux Pearson Spearman correlations rank correlations .713a .631a .173b

membrane flux through controlling different operation parameters. 3.3. Economic assessment In this study the MBR (240 m3/d) treating dyeing and printing wastewater was set for cost analysis, and its operating parameters were chosen from this study and other studies about large-scale MBRs [1719]. The designed membrane flux affects not only capital costs but also the membrane replacement costs, which is an important component of operating costs. Therefore, according to previous studies, 8 L/m2.h and 10 L/m2.h were set as the lower and upper limits of membrane flux, respectively [20,21]. The selected membrane module for submerged MBR was from Motian Membrane Technology (China). Two types of costs in this cost analysis were considered: capital and operating. Capital costs include membrane units and non-membrane unit costs (fixed costs); non-membrane units costs include all mechanical and electrical items, control equipment and associated civil engineering costs. The cost of land acquisition was not included in the capital costs of MBR. Operating costs comprise depreciation of fixed costs, membrane replacement, labor costs, chemical requirement and energy consumption. In the operating cost analysis, depreciation of fixed costs was based on values of 15 years of operation. Depreciation of membrane unit costs was based on a membrane life expectancy of 2 years with which manufac-

Pressure-head, 4.420.3 .709a kPa Aeration intensity, 40240 .703a m3m!2h!1 MLSS, g l!1 1.03.8 .169b
a

Correlation is significant at the 0.01 level (two-tailed). Correlation is significant at the 0.05 level (two-tailed).

turers usually provide a warranty for membranes. A unit energy consumption of 0.8kWh/m3 was chosen from previously reported pilot studies [20,21]. Due to its compact design and degree of automation, it was assumed that the MBR system only requires one person for maintenance and repair. The annual salary of a worker is assumed to be RMB 12,000 in 2004. The annual consumption of chemicals (NaOH) used in membrane cleaning was 50 kg/y (4 RMB/kg), and its cost could be ignored compared with labor costs. Capital requirements and operating costs for a MBR system of 240 m3/d are shown in Table 5. The total capital costs of the MBR are 400,000 430,000 RMB, including RMB 280,000 of nonmembrane units costs and 120,800150,000 RMB of membrane units costs. The costs of the membrane unit accounted for 27.934.9% of the total capital costs. The unit operating costs of the MBR are 1.45 1.62 RMB per m3 of wastewater. An analysis of MBR operating costs indicates that the membrane replacement cost is the dominant factor for the submerged MBR, 47.653.1% of total operating costs. A sensitivity analysis on membrane replacement cost also suggests that it is sensitive to the set membrane flux, membrane life expectancy and the membrane price [22,23]. In the declining

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Table 5 Costs of MBR facilities with different membrane fluxes (240 m3/d) Gravitational filtration Design and operating parameters: Membrane module Operation mode Control unit Designed membrane flux, Lm!2h!1) Designed membrane area, m2 Unit membrane module price, RMB/m2 Unit energy consumption, kWh/m3 Unit energy cost, RMB/kWh Membrane life expectancy, y Non-membrane life expectancy, y Capital costs: Non-membrane costs, RMB10,000 Membrane costs, RMB10,000 Total capital costs, RMB10,000 Unit capital costs, RMB/m3 Operating costs: Depreciation of assets, RMB/m3 Membrane replacement, RMB/m3 Energy cost, RMB/m3 Other, RMB/m3 Total operating costs, RMB/m3 Motian (China) Continuous flux Auto-control 8 1250 120 0.8 0.5 2 15 28 15 43 1792 0.21 0.86 0.40 0.15 1.62 Gravitational filtration Motian (China) Continuous flux Auto-control 10 1000 120 0.8 0.5 2 15 28 12 40 1667 0.21 0.69 0.40 0.136 1.45

Notes: Energy price is estimated as 0.5 RMB/kWh (1 US$ = 8.27 RMB).

Areamembrane, designed membrane area (m2); CapacityMBR treatment, MBR treatment capacity (m3/d); CostMembrane, Membrane costs (RMB); CostNon-membrane, Non-membrane costs (RMB); CostTotal, Total capital costs; CostOperating, Total operating costs (RMB/m3); DepreciationAssets, Depreciation of assets (RMB/m3); DepreciationMembrane replacement, Membrane replacement cost (RMB/m3); EnergyMBR, Unit energy consumption of MBR (kWh/m3); Flux, designed membrane flux (Lm!2h!1); LifeNonmembrane, nonmembrane life expectancy (y); LifeMembrane, membrane life expectancy (y); PriceMembrane module, unit membrane module price (RMB/m2); PriceEnergy, Energy price (RMB/kWh).

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trend of membrane module price, it dropped from RMB 150 m!2 in the year 2000 to about RMB 120 m!2 at present, and could be reduced as low as approximately RMB 100 m!2 in the year 2006. In contrast with the declining price of membrane modules, water prices are being gradually raised in many cities in China because of both the aggravation of water pollution and shortages of water. For example, the water price in Beijing has been increased from 0.12 RMB/m3 (US $0.015) in 1990 to 2.9 RMB m3 (US $0.35) in 2003, with an annual growth of 25.6%. It is expected to be about 5 RMB/m3 (US $0.60) in 1 or 2 years. Therefore, there is an increasing economic driving force for using the new MBR for wastewater treatment and reuse. If the membrane life expectancy reaches 34 years and stable membrane flux is maintained at 15 L/m2.h, MBRs with gravitational filtration will be more competitive in the near future.

Acknowledgenents The research was funded by the National Natural Science Foundation of China and Chinese Saving Energy and Investment Company (No. 50238050), and the National Hi-Tech Development Plan (863) (2002AA601310). References
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4. Conclusions 1. The new MBR with a gravity drain was feasible and effective for dyeing and printing wastewater treatment. The quality of treated water was excellent, i.e., 36.9 mg COD/l, 3.7 mg BOD5/l, 0.2 NTU of turbidity, and 21 DT of color, respectively, and meets the reuse water standard [9]. 2. Statistical analysis showed that both the pressure-head and aeration intensity significantly affected membrane flux. Membrane flux increased accordingly with increasing both the pressure-head and aeration intensity. The increase rate of membrane flux also related to pressureheads. 3. A cost analysis of the MBR shows that it is increasingly considered as a competitive method to dyeing and printing wastewater treatment since membrane prices have gradually declined and water prices are being raised in China.

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