Process Biochemistry 40 (2005) 11891198

Substrate removal kinetics in an upow anaerobic sludge blanket reactor decolorising simulated textile wastewater
Mustafa Iik, Delia Teresa Sponza s
Environmental Engineering Department, Engineering Faculty, Dokuz Eylul University, Kaynaklar Campus, 35160 Buca-Izmir, Turkey Received 26 December 2003; received in revised form 31 March 2004; accepted 10 April 2004

Abstract A simulated wastewater containing sizing agents, azo dyes, salts and other additives was treated using a lab-scale upow anaerobic sludge blanket (UASB) reactor at different hydraulic retention times (HRT) in order to obtain the substrate removal kinetic of the reactor through decolorization of dyes. COD removal efciencies decreased from 80 to 29.5% when the HRT decreased from 100 to 6 h. The colour removal efciencies were between 90 and 95% for HRTs of 100 and 6. Monod, Contois, Grau second order, modied Stover-Kincannon, and rst order kinetic models were applied to determine the substrate removal kinetic of UASB reactor. The experimental data obtained from the steady-state conditions showed that Grau second order, modied Stover-Kincannon and Contois substrate removal kinetic models were suitable than the other applied models for predicting the performance of lab-scale UASB reactor treating the azo dyes. 2004 Elsevier Ltd. All rights reserved.
Keywords: Simulated textile wastewater; UASB; Grau; Stover-Kincannon; Contois

1. Introduction Textile industries produce high quantities of wastewater with varying composition depending on the wet processes employed [1]. Textile efuents are complex waste products containing dyes, sizing agents and dyeing auxiliaries. They are characterized by their deep blue colour and high concentration of environmental pollutants. Various physicochemical, advanced oxidation processes, biological processes and usually a combination of processes are applied to treat them to meet regulatory discharge limits [2]. In the past, mainly chemical coagulation followed by extended activated sludge processes were used to treat textile wastewaters because colour discharge limits were not applied in studies of wastewater treatment. It is important to note that the aforementioned treatment processes met the discharge limits based on the COD of efuent. Currently, through new regulations, pressure is being placed on companies to reduce the amount of colour in industrial wastewater in developed and developing countries. Azo dyes are characterized by their typical nitrogen to nitrogen (N=N) bonds. They conCorresponding author. Tel.: +90 232 4531008/1144; fax: +90 232 4531153. E-mail address: delya.sponza@deu.edu.tr (D.T. Sponza). 0032-9592/$ see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.procbio.2004.04.014

stitute about 6070% of dyes produced. Dyes are synthetic organics and generally have a complex chemical structure. They are xenobiotic in biotic environments and hence show persistence to biodegradation in nature. Apart from the aesthetic deterioration of the natural water bodies, dyes also cause harm to the ora and fauna in the natural environment [3]. Due to the electron withdrawing nature of the azo dyes, they are not susceptible to aerobic oxidative catabolism [4] and hence are not removed in aerobic processes. However, under anaerobic conditions, in the presence of co-substrate, decolorization of azo dyes is achieved with cleavage of the azo bond, thus rendering the azo dye colourless, with formation of corresponding aromatic amines [5]. Anaerobic treatment is widely employed for treatment of most of the industrial wastewater containing high concentrations of soluble organic mater. Studies concerning the anaerobic treatability of textile wastewaters have been limited [6]. The upow anaerobic sludge blanket (UASB) reactor system developed by Lettinga et al. [7] in the 1970s has received widespread acceptance and has been successfully used to treat a variety of biodegradable industrial wastewaters. Although several researchers have investigated the anaerobic treatability of real textile wastewaters [6,8,9], the anaerobic decolorization of simulated textile wastewaters [1012] and the colour removal efciencies in synthetic wastewaters containing pure

1190

M. Iik, D.T. Sponza / Process Biochemistry 40 (2005) 11891198 s

dyes [1316], none determined the kinetics of simulated textile wastewater in an UASB reactor. Therefore, the aims of this paper were to determine the process kinetics of anaerobic digestion and to compare kinetics among the models applied for describing the substrate removal kinetics of UASB reactor treating/decolorizing a simulated textile wastewater.

Monod and Contois Eqs. (4) and (5) as follows: = = max S KS + S max S X+S (4) (5)

2. Kinetic approaches Mathematical models are used in fundamental research of anaerobic processes to examine the hypotheses, to determine the importance of relationships between variables to guide the experimental design and to evaluate the experimental results. These models also used to control and predict the treatment plant operation performance and to optimize the plant design and the results of scale-up pilot studies. At present, simplied models, involving only few variables, are easier to monitor and are needed for industrial applications in order to determine the kinetic constants [17]. Monod type kinetic models have been widely used to describe the process kinetics of anaerobic digesters [18]. Although there has been some success in applying Monod type kinetics to the anaerobic process, some research workers found that it is difcult to apply this kinetic. For instance, Grady et al. [19] have shown that the efuent substrate concentration, expressed as COD, was not dependent on the inuent substrate concentration entering the reactor when pure or heterogeneous cultures were used. In the equation proposed by Contois and co-workers [20,21], the specic growth rate was considered as a function of growth limiting nutrient in both inuent and efuent substrate concentrations using an empirical constant, which was related to biomass levels. 2.1. Application of Monod and Contois kinetic For an UASB reactor without biomass recycle, the rate of change of biomass and substrate in the system can be expressed as Eq. (1): dX Q Q = X0 XE + X K d X dt V V Q Q X dS = S0 S dt V V Y (1) (2)

If it is assumed that the concentration of biomass in the inuent can be neglected at steady-state conditions (dX/dt = 0 and dS/dt = 0) and the HRT( H ) is dened as the volume of the reactor divided by the ow rate of the inuent, following equations can be obtained by substituting and rearranging Eqs. (3)(5) into Eqs. (1) and (2); = 1 + Kd C (6) (7)

1 max S + Kd = KS + S C

The kinetic parameters Y, Kd for Monod and Contois model can be obtained by rearranging equations as shown below: (S0 S) 1 = H X Y 1 C + 1 Kd Y (8)

The value of max and KS could be determined by plotting Eq. (9), which was derived by rearranging Eq. (7). C KS 1 1 = + 1 + C Kd max S max (9)

By substituting Eq. (5) instead of the Monod equation into Eq. (1), Eq. (10) can be obtained: max S 1 = + Kd X+S C (10)

Similarly, the values of max , and can be obtained by plotting Eq. (11), which is obtained by rearranging Eq. (10). The value of max can be calculated from the intercept of the straight line and nally, could be obtained from the slope of the line. C X 1 = + 1 + C Kd max S max (11)

2.2. Grau second-order multicomponent substrate removal model The general equation of a second-order kinetic model is illustrated in Eq. (12) [22,23]. dS = kS X dt S S0
2

The ratio of the total biomass in the reactor to biomass wasted per given time represent the average time called as mean cell-residence time ( C ) and calculated from the Eq. (3) for UASB reactor. C = V X Q XE (3)

(12)

If Eq. (12) is integrated and then linearilized, Eq. (13) will be obtained: S0 H S0 = H S0 S kS X (13)

The relationship between the specic growth rate and the rate limiting substrate concentration can be expressed by the

M. Iik, D.T. Sponza / Process Biochemistry 40 (2005) 11891198 s

1191

If the second term of the right part of Eq. (13) is accepted as a constant, the Eq. (14) will be obtained, S0 H = b H + a S0 S (14)

(S0 S)/S0 expresses the substrate removal efciency and is symbolized as E. Therefore, the last equation can be written as follows: H (15) = a + b H E 2.3. Modied Stover-Kicannon model In this model the substrate utilization rate is expressed as function of the organic loading rate by monomolecular kinetic for biolm reactors such as rotating biological contactors and biological lters. Equation of the modied Stover/Kincannon model are as follows [24]: dS Rmax (Q S0 /V ) = dt KB + (Q S0 /V ) where dS/dt is dened in Eq. (17): dS Q = (S0 S) dt V V KB V 1 = + Q (S0 S) Rmax Q S0 Rmax 2.4. First order substrate removal model The rate of change in substrate concentration in the system with assuming the rst order model for substrate removal could be expressed as follows: dS Q Q = S0 S k1 S dt V V (19) (17) (16)

and was taken from the methanogenic reactor treating the wastewater of Pakmaya Yeast Baker Factory in Izmir. The UASB reactor was operated at 37 C using an electronic heater in the medium part of the system. The suspended solids (SS) and volatile suspended solids (VSS) in the UASB reactor were 31.7 g l1 and 22.4 gVSS l1 , respectively. 3.2. Simulation of cotton textile wastewater A simulated textile wastewater was prepared to give the reproducibility for continuous studies. The processes, generating wastewater in a cotton textile mill are desizing, scouring, bleaching, dyeing, and printing. The simulated wastewater used in this study exhibited similar composition to the synthetic wastewater used by ONeill and co-workers [25,26]. The composition and characteristics of simulated wastewater used in this study are given in Table 1. The mixture of azo dyes included 50 mg l1 of Reactive Black 5, Direct Red 28, Direct Black 38, Direct Brown 2 and Direct Yellow 12 as 250 mg l1 of total dye concentration in simulated wastewater. Azo dyes were hydrolyzed with NaOH at 80 C for 2 h. The size, CMC and starch, were hydrolyzed by mixing with 40 g l1 of NaOH and leaving it at room temperature overnight. The UASB reactor was initially started to operate after one month of adaptation period with simulated wastewater since the aforementioned reactor had been previously used to treat the azo dyes and real textile wastewater at an organic loading rate as high as 25 kg COD m3 per day. Once steady-state conditions achieved at each run at different feed ow-rates and loading conditions, the daily methane production, COD, pH, total volatile fatty acids of the efuents were monitored. Steady state was dened by the constant daily, efuent COD concentrations, efuent volatile fatty acid (VFA) concentrations and pH values within 10% variation for consecutive 24 days in each reactor. 3.3. Operating conditions A laboratory scale UASB reactor was operated with simulated textile wastewater during 46 days in order to investigate the process kinetics at different hydraulic retention times (HRT) (6100 h). HRT decreased from 100 to 6 h by increasing the organic loading rates (OLR) from 1.0 to 15.8 kg m3 per day in UASB reactor through 46 days of operation period. The F/M ratios were between 0.1141.718 kg COD kg VSS1 per day through operation of UASB reactor These F/M ratios, in this study, exhibited similar operating conditions to those studied by Zhu et al. [28] (0.75 kg COD kg VSS1 per day), An et al. [29] (0.269 kg COD kg VSS1 per day), and ONeill et al. [25] (0.15 kg COD kg VSS1 per day) treating the dye manufacturing, dye wastes and simulated textile wastewaters, respectively in UASB reactors.

Eq. (18) obtained from linearization of Eq. (17) as follows: (18)

Under steady-state conditions, the rate of change in substrate concentration (dS/dt) is negligible and the equation given above can be reduced to the Eq. (20): S0 S = k1 S H (20)

The value of k1 can be obtained by plotting (S0 S/ H ) versus S in Eq. (20), which is obtained by rearranging Eq. (19). The value of k1 can be obtained from the slope of the line.

3. Material and methods 3.1. Experimental lab-scale reactor and seed The anaerobic UASB reactor used for treatment of simulated wastewater was 6 cm in diameter, 100 cm in length and had an effective volume of 2.5 l. Partially granulated anaerobic sludge was used as seed in the UASB reactor

1192 Table 1 Characteristics of simulated wastewater Materials used Carboxymethyl cellulose (CMC) Starch Acetic acid Azo dyes Reactive black 5 Direct red 28 Direct black 38 Direct brown 2 Direct yellow 12 NaOH H2 SO4 NaCl Na2 CO3 NaHCO3 Glucose Vanderbilt mineral medium [27] Parameters COD Total alkalinity as mg CaCO3 l1 pH

M. Iik, D.T. Sponza / Process Biochemistry 40 (2005) 11891198 s

Concentration (mg l1 ) 150 1500 500 250 50 50 50 50 50 660 357 500 1000 2000 2062.5

The functions of material Sizing Sizing Suitable pH Dyeing

Hydrolysis pH neutralization For xing For xing pH buffer in UASB reactor Substrate for bacterial growth For bacterial growth

4214 241 (n = 6) 3090 260 (n = 9) 8.83 0.11 (n = 9)

3.4. Analytical procedures Gas production was measured by a liquid displacement method [30]. The methane percentage in biogas was determined by Drger Pac Ex methane gas analyzer. Colour in the inuent and efuent samples of the anaerobic reactor was measured at maximum wavelengths.The soluble COD was measured colorimetrically using closed reux methods [31]. Total alkalinity of samples was determined by titrating a sample with 0.1N of standard sulphuric acid solution to a pH of 4.3. Bicarbonate alkalinity (B.Alk.) and total volatile fatty acid (VFA) concentrations were measured simultaneously by Anderson and Yang [32] titrimetric method. Biomass were measured as suspended solids and volatile suspended solids in UASB reactor following Standard Methods [31].

4. Results and discussion 4.1. Reactor performance In order to obtain kinetics coefcients for different kinetic models the UASB reactor was operated with simulated wastewater containing desizing agents, dye, salts etc. at six different HRTs through 46 days of the operation period. The results obtained for steady state conditions during reactor operation at six different HRTs are summarized in Table 2. As the HRT was decreased from 100 to 6 h, the pH and B. Alk. levels decreased from 7.25 and 3425 mg CaCO3 l1 to 6.71 and 2273 mg l1 while the VFA concentration increased from 709 to 2073 mg l1 . The sensitivity of the methanogens to pH, coupled with the VFAs, which are the intermediates

of the anaerobic stabilization of organic matter, result in a negative response by the anaerobic system [33]. Although the pH remained in the optimal working range for anaerobic conditions (6.57.5) the VFA concentrations were increased to 2073 mg CH3 COOH l1 through the operation at an HRT of 6 h. The optimal pH could be explained by the neutralization of hydrogen ions released from the volatile fatty acid together with the carbonates dissociated from the carbonic acid with the bicarbonate alkalinity inside the UASB reactor [27]. The VFA/B.Alk. ratio was greater than 0.4 at an organic loading rate of 7.16 kg m3 per day, indicating the moderate instability of the UASB reactor [34]. Total gas production, methane gas production, methane percentage and methane gas yield were 1176 and 647 ml per day, 54.8% and 0.318 l methane g COD1 at the beginning of operation at an HRT of 100 h. When the HRT was decreased to 6 h, the aforementioned parameters were found to be 6480 and 1209 ml per day, 18.7% and 0.104 l methane g COD1 , respectively. The optimum organic loading rate and HRT for optimum pH, VFA/B.Alk. ratio, and methane fraction was about 3.2 kg m3 per day and 32 h in the UASB reactor, respectively. When the rate of acid formation exceeds the rate of break down to methane, a process unbalance results with decreases in pH and CH4 content of the biogas [35]. Eighty percent COD removal efciency was obtained at an HRT of 100 h while the COD removal efciencies decreased to 29.4 at an HRT of 6 h. Ninety one percent and 90% colour removal efciencies were obtained at HRTs of 100 and 6 h while the decolorization efciency was 95% at an HRT of 14 h (see Table 2). This shows that colour removal efciencies were not affected directly by these HRTs in the UASB reactor.

M. Iik, D.T. Sponza / Process Biochemistry 40 (2005) 11891198 s Table 2 Experimental data obtained under steady state conditions at six different HRTs Parameter HRT (h) 100 Operation period (days) Sludge retention time (days) pH VFA(mg CH3 COOH l1 ) B.Alk. (mg CaCO3 l1 ) VFA/B.Alk. Eluent COD (mg l1 ) COD removal efciencies (%) Colour removal efciencies (%) Total gas production rate (ml per day) Methane gas production rate (ml per day) Methane percentage (%) Methane yield (l methane g COD1 added) 09 736 7.25 0.04 709 106 3425 30 0.21 0.02 835 93 79.9 2.4 90.6 12 1176 154 647 107 54.8 1.8 0.318 0.060 46 1017 339 7.20 0.13 840 5 2993 135 0.28 0.01 1118 63 73.5 1.5 91.1 9 2000 211 997 78 50.3 2.2 0.248 0.015 32 1827 232 7.20 0.02 797 64 2969 136 0.27 0.03 1108 54 73.7 1.3 94.2 5 5130 1275 2390 692 48.7 1.2 0.404 0.114 14 2832 104 6.95 0.06 1314 30 2348 4.9 0.56 0.01 2233 256 47 6.1 94.3 3 5680 277 1973 175 35.8 3.18 0.238 0.052 9 3338 63 6.82 0.06 1837 190 2291 100 0.80 0.05 2785 230 33.9 5.4 93.8 3 6223 1616 1756 475 28.2 1.6 0.182 0.070 6 3946 47

1193

6.71 0.06 2073 157 2273 90 0.91 0.10 2975 61 29.4 1.5 90.3 3 6480 635 1209 164 18.7 2.08 0.104 0.013

4.2. Monod kinetic model Six steady state sets of data were used to determine the kinetic parameters required for applying all the kinetic models. Fig. 1 was plotted from Eq. (8) for determining the values of Y and Kd for Monod model. Y and Kd values calculated from the intercept and the slope of the straight line as illustrated in Fig. 1 as 0.125 g VSS g COD1 and 0.0065 per day, respectively. The value of max and KS were determined from Fig. 2 using Eq. (9) as 0.105 per day and >4000 mg l1 , respectively. 4.3. Contois kinetic model For the Contois model the values of specic growth rate (max ) and were determined from Fig. 3 by plotting Eq. (11) and the kinetic parameters, max and were calculated from the intercept and the slope of the straight line
0.250 (S0-S)/(HRT*X) 0.200 0.150 0.100 0.050 0.000 0.0000 0.0050 0.0100 y = 7.9974x + 0.0523 R = 0.9193 0.0150 0.0200 0.0250
2

140.0 SRT/(1+SRT*Kd) 120.0 100.0 80.0 60.0 40.0 20.0 0.0 0 0.0004 0.0008 1/S
Fig. 2. Determination of maximum specic growth rate (max ) and half saturation constant (KS ) for Monod kinetic model.

y = 98895x + 9.5641 2 R = 0.9671

0.0012

0.0016

150 SRT/(1+SRT*Kd) 125 100 75 50 25 0 0 5 10 15 X/S 20 25 30 y = 4.4461x + 9.5641 2 R = 0.9671

1/SRT (1/day)
Fig. 1. Determination of yield coefcient (Y) and death rate constant (Kd ).

Fig. 3. Determination of maximum specic growth rate (max ) and kinetic constant () in Contois model.

1194

M. Iik, D.T. Sponza / Process Biochemistry 40 (2005) 11891198 s

6.0 5.0

3500 3000 (S0-S)/HRT 2500 2000 1500 1000 500 0 S

Fig. 6. The model plot of rst order substrate removal.

y = 0.6152x + 116.41 R = 0.932

2

(S0*HRT)/(S0-S)

4.0 3.0 2.0 1.0 0.0 0.0 1.0 2.0 3.0 HRT (day) 4.0 5.0 y = 1.0946x + 0.562 R = 0.9948
2

Fig. 4. Determination of kinetic constants (a, b and ks ) for Grau second order multicomponent substrate removal model.

as 0.105 per day and 0.465 mg COD mg VSS1 , respectively. 4.4. Grau second-order multicomponent substrate removal model In order to determine the kinetic coefcients (a, b and ks ) Eq. (15) was plotted in Fig. 4. The values of a, and b calculated from the intercept and slope of the straight line on the graph. The values of a, and b were found to be 0.562 and 1.095 with high correlation coefcients of (R2 ) 0.995. The multicomponent substrate removal rate constant (ks ) was then calculated from the equation a = S0 /(ks. X) as 0.337 per day indicating substrate removal for each unit of microorganism depending on second order substrate removal rate constant (ks ). 4.5. Modied Stover-Kicannon model Fig. 5 shows the graph plotted between reciprocal of total organic loading removal rate, [V/(Q(S0 S)], against to the reciprocal of total organic loading rate, V/(QS0 ). Since the plot of [V/(Q(S0 S)] versus V/(QS0 ) was linear, linear regressions (least squares method) were used to determine the intercept and the slope. A straight line portion of intercept,
1.4 1.2 V/Q*(S0-S) 1.0 0.8 0.6 0.4 0.2 0.0 0.0 0.2 0.4 0.6 V/(Q*S0) 0.8 1.0 1.2 y = 1.0947x + 0.1333 2 R = 0.9948

1/Rmax and a slope of KB /Rmax results on graph. Saturation value constant (KB ) and maximum utilization rate (Rmax ) were calculated from the line plotted on graph in Fig. 5 as 8.2 g (l per day) and 7.5 g (l per day), indicating the substrate removed by microorganisms during time and the maximum substrate removed by the anaerobic organisms versus time, respectively. 4.6. First order substrate removal model The value of k1 was obtained from the slope of the line by plotting (S0 S)/HRT versus S in Eq. (20). Fig. 6 shows the plot between (S0 S0 )/HRT and S k1 was calculated as 0.615 per day with correlation coefcient of 0.932. 4.7. Evaluation of the kinetic models All kinetic coefcients calculated from models are summarized in Table 3 with correlation coefcients. The kinetic data showed that Stover-Kincannon, Grau second order multicompenant and Contois substrate removal kinetics were more appropriate than the other models for predicting the performance of the lab scale UASB reactor when the regression coefcients and kinetic coefcients were compared. Table 4 summarizes the constants determined from the applicable models in previous studies. In this study, the determined Contois kinetic coefcient (0.465 mg COD mg VSS1 ) is very similar to the kinetic coefcient (0.482 mg COD mg VSS1 ) obtained by Hu et. al. [37]. However, the max value (0.105 per day) obtained in this study was lower than the max value (0.923 per day) found by Hu et. al. [37]. The most likely reason for the differences in max values is the signicant variations in reactor congurations, wastewater characteristics and microorganisms used in the studies. According to the Contois equation (Eq. (5)), low max values decreases the substrate removal rate, therefore the substrate removal rates calculated in this study was lower than the study mentioned above. Similarly the saturation constant (KB ) and maximum utilization rate (Rmax ) values obtained in this study are smaller than those obtained by Yu et al. [24] and Bykkamac and Filibeli [36] in a modied Stover-Kicannon model. According to

Fig. 5. Stover-Kincannon model plot.

M. Iik, D.T. Sponza / Process Biochemistry 40 (2005) 11891198 s Table 3 Kinetic parameters of UASB reactor treating simulated cotton textile wastewater Kinetic models Monod Kinetic parameters Y (mg VSS mg COD1 ) Kd (per day) kmax (max Y1 ) (per day) max (per day) KS (mg l1 ) Y (mg VSS mg COD1 ) Kd (per day) max (per day) (mg COD mg VSS1 ) a (per day) b (dimensionless) ks (per day) KB (g (l per day)) Rmax (g COD (l per day)) k1 (per day) Values 0.125 0.0065 0.84 0.105 >4000 0.125 0.0065 0.105 0.465 0.562 1.095 0.337 8.211 7.501 0.615

1195

Regression coefcients (R2 ) 0.912 0.912 0.967 0.967 0.967 0.912 0.912 0.967 0.967 0.995 0.995 0.995 0.995 0.995 0.932

Contois

Grau second order

Modied Stover-Kincannon First order

Grau second order kinetic models, the multicomponent substrate removal rate constant (ks ) value obtained in this study was higher than the ks values determined in other studies. The ks value will be increased as the substrate removal rate increased depending to initial substrate (So ) and microorganism concentrations (X) in the reactor. The modied Stover-Kincannon model suggests that the substrate removal rate is affected by the organic loading rate entering to the reactor as described in Eq. (16). Kinetic coefcients of this model (Rmax , KB ) were lower than the data obtained in other studies as seen in Table 4. For anaerobic systems a review of common substrate utilization kinetic models was recently carried out by Kuroda

et al., [38], and also by Mata-Alvarez and Cecchi [39]. The Monod model is most widely used for UASB reactors and for industrial efuents [40]. In this study, however, it was found that the Monod model was not appropriate for interpreting the kinetic data of the UASB reactor treating simulated textile wastewater. Although KS values estimated from the Monod model are very large, kmax and Y values were acceptable as 0.125 mg VSS mg COD1 0.84 per day, respectively. kmax , Y, and KS values were 0.776.67 mg COD (mg VSS1 per day), 0.040.11 mg VSS mg COD1 , and 1053180 mg COD l1 , respectively, for anaerobic oxidation of long-chain fatty acids [41].

Table 4 Comparison of kinetic constants in the Grau second order, modied Stover Kincannon, and Contois models Models Substrate Reactor type UASB UASB AHR UASB Inuent COD (mg l1 ) 230445 900025000 200015000 4214 HRT (day) Kinetic parameters ks 0.251.0 1.72.8 0.52 0.254.16 0.217 38.5 10.81 0.337 Rmax Modied-Stover Kincannon Modied-Stover Kincannon Modied-Stover Kincannon Molasses Soybean wastewater Simulated wastewater AHR AF UASB 200015000 752011450 4214 0.52 11.45 0.254.16 83.3 83.3 7.5 max Contois Contois Ice-cream wastewater Simulated wastewater CSTR UASB 5500 4214 2.997.45 0.254.16 0.930 0.105 a 0.002 0.013 0.033 0.562 KB 186.23 85.5 8.2 0.482 0.465 Y 0.212 0.125 Bykkamac and Filibeli [36] Yu et al. [24] This study Kd 0.0131 0.0065 Hu et al. [37] This study b 1.346 1.066 1.192 1.095 Ubay [42] ztrk et al. [23] Bykkamac and Filibeli [36] This study References

Grau second order Grau second order Grau second order Grau second order

Municipal wastewater Landll leachate Molasses Simulated wastewater

AF: anaerobic lter AHR: anaerobic hybrid reactor AFBR: anaerobic uidized-bed reactor; ACR: anaerobic contact reactor UASB: upow anaerobic sludge reactor CSTR: continuous stirred tank reactor.

1196

M. Iik, D.T. Sponza / Process Biochemistry 40 (2005) 11891198 s

4000 Monod 3500 Predicted COD conc. (mg l )

-1

y = 1.165x - 239.8 y = 1.0872x - 167.87 y = 0.9924x - 126.28

R2 = 0.9153 R = 0.9701 R2 = 0.9681

2

5 1 2 3 4 6

Contois Grau

3000 2500 2000 1500 1000 500 0 0

Stover-Kincannon y = 0.891x + 208.41 First Order 500 1000 1500 y = 0.9716x + 811.16 2500 3000
-1

R2 = 0.9698 R2 = 0.9105 3500 4000

2000

Measured COD values of effluent (mg l ) Monod (1) Stover-Kincannon (4) Contois (2) First order (5) Grau (3) Actual (6)

Fig. 7. Comparison of the predicted and the actual COD values from the lab-scale UASB reactor.

The models applied in this study were also evaluated by comparing the predicted COD values with the tentative values obtained from this continuous operation of lab-scale UASB reactor. The COD values predicted with the Stover-Kincannon, Grau, second order and Contois models gave a high correlation (97%) with actual COD concentrations measured from the UASB reactor as shown in Fig. 7. A rst order substrate removal model was not suitable for predicting the COD values compared to the other investigated models. In conclusion, based on the kinetic studies, it appears that the kinetic coefcients obtained from the anaerobic treatment of simulated cotton textile wastewater, agree with the Stover-Kincannon, second order multicomponent and Contois substrate kinetic models. Although several studies relevant to anaerobic treatment of some industrial wastewaters were reported in literature none of the studies contained a kinetic study relevant to anaerobic reactors treating a simulated cotton textile wastewater. As seen in Table 3, a Grau second order kinetic model gives the same correlation as the modied Stover-Kincannon substrate kinetic model. This result is not surprising because two models are very similar as mentioned below: Second order linearized equation (Eq. (13)) could be transformed to the modied Stover-Kincannon model (Eq. (18)) by dividing So each part the equation. V V 1 = + Q (S0 S) Q S0 kS X (21)

equations given above. As a results of this similarity, the two models have the same sensitivity in order to obtain the kinetic coefcients from the plots when the regression coefcient of the graphs are compared. Similar results were observed between Eqs. (4) and (5) in Monod and Contois kinetic models, respectively, where X is equal to Ks .

5. Conclusions The result of this study showed that simulated wastewater containing sizing agents, azo dyes, salts and other additives could be treated effectively by UASB reactor at different HRTs varying between 6 and 100 h. COD removal efciencies decreased from 80.2 to 29.4% with decreasing HRT. Colour removals were between 90 and 95% at HRTs. The concentration of VFAs and VFA/B.Alk. ratio increased when the HRT decreased from 100 to 6 h. This show that there was instability between acidogenesis and methanogenesis into UASB reactor at low HRTs. In this study the kinetics of UASB reactors treating simulated textile wastewater was investigated using different models such as Monod, Contois, Grau second order, modied Stover-Kincannon, and rst order kinetic. Grau second order and modied Stover-Kincannon kinetic models with correlation coefcients of 0.995 were found to be more suitable than the other applied models for predicting the performance of lab-scale UASB reactor together with signicant kinetic coefcients. A Contois type kinetic model with a correlation coefcient of 0.967 was also found to be suitable for expressing the microbial kinetics of the UASB reactor. The results of kinetic studies obtained from the lab scale UASB reactor can be used to predict the treatment performance of full-scale UASB reactors if the textile wastewa-

If Eq. (21) is simulated to the modied Stover-Kincannon model, the following equation can be obtained: KB = Rmax (22)

The calculated kinetic parameters from the plots of both models are appropriate to the values calculated from the

M. Iik, D.T. Sponza / Process Biochemistry 40 (2005) 11891198 s

1197

ter was treated at similar loading conditions and wastewater composition.

Acknowledgements This study was supported by the Turkish Scientic and Technical Research Council (TBITAK) for the project numbered 199 Y 110, and fund of Ni de University with a g project numbered 2002/03, Turkey. The authors gratefully acknowledge the nancial support from these organizations.

Appendix A. Nomenclature a b k1 KB Kd kmax KS ks Q Rmax S0 , S X0 , X, XE V Y C (SRT) Cmin H (HRT) , max S0 (ks X)1 (per day) constant for Grau second-order model (dimensionless) rst order kinetic constant (per day) saturation value constant (g (l per day)) death rate constant (per day) maximum specic substrate utilization rate (mg COD (mg VSS per day)) half saturation concentration (mg l1 ) Grau second-order substrate removal rate constant (per day) inow rate (l per day) maximum substrate removal rate (mg COD (l per day)) substrate concentration in the feed and efuent (g COD l1 or mg COD l1 ) concentrations of biomass in the feed, reactor and reactor efuent (g VSS l1 ) reactor volume (l) yield coefcient (g VSS g COD1 ) kinetic parameter (g COD g VSS1 for Contois model) mean cell-residence time (day) minumum mean cell-residence time (day) hydraulic retention time (day) specic growth rate and, maximum specic growth rate, respectively (per day)

References
[1] Delee W, ONeill FH, Pinhero HM. Anaerobic treatment of textile efuents: a review. J Chem Technol Biotechnol 1998;73:32335. [2] Banat IM, Nigam P, Marchant R. Singh, Di, Microbial Decolorization of textile-dye containing efuents: a review. Bioresour Technol 1996;58:21727. [3] Manu B, Chaudhari S. Decolorization of indigo and azo dyes in semicontinuous reactors with long hydraulic retention times. Process Biochem 2003;38:121321. [4] Knackmuss HJ. Basic knowledge and perspectives of bioelimination of xenobiotic compounds. J Biotechnol 1996;51(4):28795.

[5] Carliell CM, Barclay SJ, Naidoo N, Buckley CA, Mulholland DA, Senior E. Microbial decolourasition of a reactive azo dye under anaerobic conditions. Water SA 1995;21(1):619. [6] Kuai L, De Vreese I, Vandevivere P. GAC-amended UASB reactor for the stable treatment of toxic textile wastewater. Environ Technol 1998;19:11117. [7] Lettinga G, Vanvelsen AFM, Hobina SM, Zee W, Klapswik A. Use of the upow sludge blanket (USB) reactor concept for biological wastewater treatment. Biotechnol Bioeng 1980;22(4):699734. [8] Zaoyan YKS, Guangliang S, Fan Y, Jinshan D, Huanian M. Anaerobic-aerobic treatment of a dye wastewater by combination of RBC with activated sludge. Water Sci Technol 1992;26(9-11):2093 6. [9] Carliell CM, Barclay SJ, Buckley CA. Treatment of exhausted reactived dyebath efuent using anaerobic digestion: Laboratory and full-scale trials. Water SA 1996;22:22533. [10] Basibuyuk M, Forster F. The use of sequential anaerobic/aerobic processes for the biotreatment of a simulated dyeing wastewater. Environ Technol 1997;18:8438. [11] ONeill C, Hawkes FR, Esteves SRR, Hawkes DL, Wilcox SJ. Anaerobic and aerobic treatment of a simulated textile efuent. J Chem Technol Biotechnol 1999;74:9939. [12] Manu B, Chaudhari S. Anaerobic decolorization of simulated textile wastewater containing azo dyes. Bioresour Technol 2002;82:22531. [13] Tan NCG, Prenafeta-Boldu FX, Opsteeg JL, Lettinga G, Field JA. Biodegradation of azo dyes in cocultures of anaerobic granular sludge with aerobic aramatic amine degrading enrichment cultures. Appl Microbiol Biotechnol 1999;51:86571. [14] Kalyuzhnyi S, Sklyar V. Biomineralisation of azo dyes and their breakdown products in anaerobicaerobic hybrid and UASB reactors. Water Sci Technol 2000;41(12):2330. [15] Sponza DT, Ik M. Decolorization and azo dye degradation by anaers obic/aerobic sequential process. Enzyme Microb Technol 2002;31(1 2):10210. [16] Ik M, Sponza DT. Aromatic amine degradation in an UASB/CSTR s sequential system treating Congo Red dye. J Environ Sci Health Part A 2003;A38(10):230115. [17] Iza J, Colleran E, Paris JM, Wu WM. International workshop on anaerobic treatment technology for municipal and industrial wastewaters: summary paper. Water Sci Technol 1991;24(8):116. [18] Anderson GK, Kasapgil B, Ince O. Microbial kinetics of a membrane anaerobic reactor system. Environ Technol 1996;17:44964. [19] Grady CPL, Harlow LJ, Riesing RR. Effects of growth rate and inuent substrate concentration on efuent quality from chemostats containing bacteria in pure and mixed culture. Biotechnol Bioeng 1972;14:391410. [20] Contois DE. Kinetics of bacterial growth: relationship between population density and space growth rate of continuous cultures. J Gen Microbiol 1959;21:4050. [21] Chen YR, Hashimoto AG. Substrate utilisation kinetic model for biological treatment processes. Biotechnol Bioeng 1980;22:208195. [22] Grau P, Dohanyas M, Chudoba J. Kinetic of multicomponent substrate removal by activated sludge. Water Res 1975;9:33742. [23] ztrk I, Altinbas M, Arikan O, Demir A. Anaerobic UASBR treatment of young landll leachate. In: Proceedings of the First International Workshop on Environmental Quality and Environmental Engineering in the Middle East Region. Konya, Turkey; 1998. [24] Yu H, Wilson F, Tay J. Kinetic analysis of an anaerobic lter treating soybean wastewater. Water Res 1998;32(11):334152. [25] ONeill C, Hawkes FR, Hawkes DL, Esteves SRR, Wilcox SJ. Anaerobicaerobic biotreatment of simulated textile efuent containing varied ratios of starch and azo dye. Water Res 2000;34(8):2355 61. [26] Shaw CB, Carliell CM, Wheatley AD. Anaerobic/aerobic treatment of coloured textile wastewater using sequencing batch reactor. Water Res 2002;36:19932002.

1198

M. Iik, D.T. Sponza / Process Biochemistry 40 (2005) 11891198 s [35] Eckenfelder Jr WW. Industrial water pollution control. 2nd ed. Signapore: McGraw-Hill; 1989. [36] Bykkamac N, Filibeli A. Determination of kinetic constants of an anaerobic hybrid reactor. Process Biochem 2002;38:739. [37] Hu WC, Thayanith K, Forster CF. A kinetic study of the anaerobic digestion of ice-cream wastewater. Process Biochem 2002;37:965 71. [38] Kuroda M, Sakakibara Y, Jin W, Erjie Y, Baozhen W, Quanda Y. A therotical consideration of the kinetics of multiple substrate utilization in anaerobic digestion. Water Sci Technol 1993;28(7):77 80. [39] Malta-Alvarez J, Cechi F. Kinetic models applied to anaerobic biodegradation of complex organic matter. In: Kamely D, Chakrabardy A, Omenn GS, editors. Biotecnology and biodegradation advances in applied biotechnology, vol. 4 (Chapter 17). The Woodlands, TX: Portfolio Pub; 1990. p. 31744. [40] Castillo A, Llabres P, Mata-Alvarez J. Kinetic study of a combined anerobicaerobic system for treatment of domestic sewage. Water Res 1999;33(7):17427. [41] Pavlostathis SG, Giraldo-Gomez E. Kinetics of anaerobic treatment. Water Sci and Technol 1991;24(8):3559. [42] Ubay, G. Anaerobic treatment of municipal wastwaters, Ph.D. Thesis, Istanbul Technical University, Turkey, 1994.

[27] Speece RE. Anaerobic biotechnology for industrial wastewaters. Nashville, TN: Archae Press; 1996. p.35. [28] Zhu J, Yang Y, An H, Qian Y. A study of dye waste treatment using anerobicaerobic processes. In: Proceedings of 17th International Symposium on Anaerobic Digestion. Cape Town, South Africa; 1994. p. 36063. [29] An H, Qian Y, Gu X, Tang WZ. Biological treatment of dye wastewater using anaerobic-oxic system. Chemosphere 1996;33(12):2533 42. [30] Beydilli MI, Pavlosathis SG, Tincher WC. Decolorization and toxicity screening of selected reactive azo dyes under methanogenic conditions. Water Sci Technol 1998;38(45):22532. [31] APHAAWWA. Standard methods for water and wastewater. 17th ed. American Public Health Assoc/American Water Works Assoc. Washington DC, USA; 1992. [32] Anderson GK, Yang G. Determination of bicarbonate and total volatile acid concentration in anaerobic digesters using a simple titration. Water Environ Res 1992;64:539. [33] Grady CPL, Daigger GT, Lim HC. Biological wastewater treatment. 2nd ed. New York: Marcelll Dekker; 1999. p. 261,632. [34] Behling E, Diaz A, Colina G, Herrera M, Gutierrez E, Chacin E, et al. Domestic wastewater treatment using a UASB reactor. Bioresour Technol 1997;61:23945.