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Environmental Technology
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Decolourization of melanoidins by a electrocoagulation process using aluminium electrodes


M. Kobya & E. Gengec
a a b

Gebze Institute of Technology, Department of Environmental Engineering, Cayrova, Gebze, Kocaeli, Turkey
b

Kocaeli University, Department of Environmental Protection, Arslanbey, Kartepe, Kocaeli, Turkey Available online: 01 Mar 2012

To cite this article: M. Kobya & E. Gengec (2012): Decolourization of melanoidins by a electrocoagulation process using aluminium electrodes, Environmental Technology, DOI:10.1080/09593330.2012.671371 To link to this article: http://dx.doi.org/10.1080/09593330.2012.671371

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Environmental Technology iFirst, 2012, 110

Decolourization of melanoidins by a electrocoagulation process using aluminium electrodes


M. Kobyaa and E. Gengecb
a Gebze

Institute of Technology, Department of Environmental Engineering, Cayrova, Gebze, Kocaeli, Turkey; b Kocaeli University, Department of Environmental Protection, Arslanbey, Kartepe, Kocaeli, Turkey (Received 29 November 2012; nal version received 24 February 2012 )

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The decolourization of melanoidins was studied with a batch electrocoagulation (EC) process using aluminium electrodes. The eects of conductivity ( = 5003000 S/cm), initial pHi (4.28.2), current density (j = 2.57.5 A/m2 ), initial melanoidin concentration (C0 = 100800 mg/L) and operating time (tEC = 060 min) were investigated on the decolourization eciency. The results obtained from the EC process were extremely ecient and able to achieve a decolourization eciency of >98% at pHi = 4.2, j = 5 A/m2 , = 2500 S/cm, C0 = 100 mg/L and tEC = 10 min. The decolourization performance was dependent on pHi value since the lower pH values led to faster reactions and higher decolourization eciency. Melanoidins in the EC process were removed by precipitation and charge neutralization at pH < 6.5, and both adsorption and sweep coagulation by amorphous Al(OH)3(s) occurred at pH > 6.5. The operating cost was calculated as 0.0096 /m3 . Keywords: melanoidins; decolourization; electrocoagulation; operating cost

1. Introduction Melanoidins are found in some wastewaters such as distilleries and fermentation plants that use molasses [1]. Information on the structural composition of melanoidins can be found in the literature [2]. Melanoidins are high molecular weight nitrogenous brown polymers and are formed during the non-enzymatic browning reaction (Millard reaction) between amino compounds and carbohydrates [3]. The existence of melanoidins in water causes a dark brown colour. When untreated, melanoidins prevent the penetration of sunlight when discharged into a water resource, thus aecting the dissolved oxygen concentration and photosynthetic activity of marine plants, and creating anaerobic conditions that kill most of the aerobic marine plants and animals. Hence, melanoidins in wastewater require treatment before its safe disposal into the environment [4]. Removal of wastewaters containing melanoidins has been studied by several treatment methods such as oxidation of ozonation, ultraviolet (UV)/H2 O2 and electrochemical process [511], adsorption [12] and coagulationocculation [3,1316]. Conventional biological processes are eective in removing the biochemical oxygen demand from wastewaters containing melanoidins. However, the brown colour remains or even darkens in the biologically treated euent due to repolymerization of pigments [14,15]. Moreover, the biological processes have drawbacks such as longer treatment time, requirements of additional nutrients and pure cultures. Some of the above methods are
Corresponding

not successful due to lower eciencies of colour removal. These methods also require high reagent dosages, high operating costs and generate a large amount of sludge [3]. Therefore, the electrochemical treatment methods such as electrocoagulation (EC) may be used eectively for the removal of organic pollutants in terms of lower operating time and costs. Recently, the EC process has been widely and successfully used to treat numerous wastewaters including those from tannery [16], textile and dying [1719], distillery and fermentation [7,8,10,11], metal plating [20,21], pulp and paper mill [22], poultry slaughterhouse [23] and olive mill [24] processes and so on. Recently, the EC process has also been used for the removal of residual colour and chemical oxygen demand (COD) from wastewaters containing natural melanoidins such as molasses, alcohol distillery and yeast processes [8,10,11] but no studies have focused on the removal mechanism associated with EC from synthetic melanoidins. The purpose of this study was to conduct experimental investigations into the decolourization of synthetic melanoidins in the EC process. The eects of several operating parameters such as initial pH (pHi ), current density, conductivity, initial melanoidin concentration and operating time on the decolourization eciency were investigated, and removal mechanisms were discussed based on experimental results. The operating costs in the EC process were also calculated.

author. Email: kobya@gyte.edu.tr

ISSN 0959-3330 print/ISSN 1479-487X online 2012 Taylor & Francis http://dx.doi.org/10.1080/09593330.2012.671371 http://www.tandfonline.com

M. Kobya and E. Gengec Na2 CO3 (99% purity, Merck) were dissolved in a litre of distilled water. Then the solution was autoclaved at 121 C for 3 h and following this the resulting brown solution was dialyzed against distilled and deionized water for 2 weeks by a membrane (Cellu Sep H1, Membrane Filtration Products, Inc, USA) having 10 kDa molecular weight cut-o. The nondialysable fraction was dried at 60 C for 24 h. The synthesis of melanoidins was performed and the yield was around 10%. Low molecular substances from the powder product were removed by a Soxhlet extractor with ether. Solutions of known concentrations were prepared by dissolving the powdered melanoidins in distilled water.

2. Description of the EC process The EC process is based on the in situ formation of the coagulant as the sacricial anode corrodes due to applied current, while the simultaneous evolution of hydrogen at the cathode allows for pollutant removal by otation. Three main processes occur during the EC: (i) electrolytic reactions at the electrode surfaces, (ii) formation of coagulants in the aqueous phase and (iii) adsorption of soluble or colloidal pollutants on coagulants, and removal by sedimentation or otation. Therefore, the mechanisms of the EC are highly dependent on the chemistry of the aqueous medium [25,26]. When aluminium is used as an electrode material, the reactions are as follows. At the anode: Al Al3+ + 3e (1)

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Al3+ and hydroxyl ions are generated by the electrode reactions in Equations (1) and (3) to form various monomeric species such as Al(OH)2+ , Al(OH)+ 2 , Al(OH)4 at low + pH values, and polymeric species such as Al2 (OH)4 2 , 3+ 4+ 4+ 7+ Al6 (OH)15 , Al7 (OH)17 , Al8 (OH)20 , Al13 O4 (OH)24 and + Al13 (OH)5 34 are transformed initially into Al(OH)3(s) and nally polymerized to Aln (OH)3n (Equations (2) and 93)) in the solution [18,27]: nAl(OH)3 Aln (OH)3n Al
3+

3.2. Experimental set-up and procedure The EC set-up and experimental procedure can be found in our previous study [8]. The synthetic melanoidin solutions were prepared using distilled water. The pH and conductivity were adjusted to desired values. In each run, a 0.85 L melanoidin solution was placed into the EC reactor and the current density was adjusted to the desired value by a digital DC power supply (TDK-Lambda Genesys model; 50 V 30 A) operated in galvanostatic mode and the experimental operation was started.

(2)
+

+ 3H2 O Al(OH)3(s) + 3H

(3)

At the cathode: 3H2 O + 3e 3/2H2 + 3OH (4)

On the other hand, the cathode may be chemically attacked by hydroxyl ions generated during H2(g) evolution at high pH values [17,28]: 2Al + 6H2 O + 2OH 2Al(OH) 4 + 3H2 (5)

The formation rates of the dierent species in the EC process also play an important role in the decolourization process. Several interaction mechanisms are possible between organic molecules such as humic substances or melanoidins and hydrolysis by-products and the rates of these depend on the pH of the aqueous medium and types of ions present. There are four removal mechanisms of humic substances in the literature which are precipitation, charge neutralization of negatively charged colloids by cationic polymeric hydrolysis products, adsorption on amorphous Al(OH)3(s) and sweep coagulation [3,8,1315]. 3. Materials and methods 3.1. Preparation of synthetic melanoidins Synthetic melanoidins were prepared following the report given in the literature [29]. 1 M glucose (99% purity, Merck), 1 M glycine (99% purity, Merck) and 0.5 M

3.3. Instruments and analysis procedures Decolourization of melanoidins was measured using a UVVisible spectrophotometer (PerkinElmer 550 SE) at 475 nm [6]. The samples were analysed for COD and total organic carbon (TOC) according to Standard Methods [30]. COD was measured by the closed reux titrimetric method and TOC levels were determined through combustion of the samples at 680 C using a non-dispersive infrared (IR) source (Tekmar Dohrmann Apollo 9000). The CHN elemental composition of nondialysable melanoidins was determined using a model Thermo Finnigan Flash EA 1112 Series. The compositions of synthetic melanoidins were: 42.7 1.6% C, 5.6 0.3% H, 6.6 0.3% N and 6.47 0.2% C/N. The IR spectra of the samples were recorded in the range 4000650 cm1 on a PerkinElmer Spectro 100 T spectrophotometer using a pellet technique. Fifty scans were collected for each sample at a resolution of 3 cm1 . A Malvern zeta potential and size analyser (Malvern Instruments, Zetasizer Nano Series, UK) was used to determine the zeta potential of the solution during the EC process. The conductivity measurement was carried out using a conductivity meter (Elmetron CX-401 model). The conductivity of the solutions was adjusted by adding NaCl (99.5%, Merck). The pH of the solutions was measured by using a pH meter (WTW inolab pH 720 model) and adjusted by either 0.1 M NaOH or 0.1 M H2 SO4 (Merck).

Environmental Technology 4. Results and discussion The eects of the parameters on the decolourization eciency of melanoidins by the EC process were studied to determine the optimum operating conditions. The decolourization mechanism was discussed with the experimental results.

4.1.

Eect of initial pH on decolourization

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The pH is an important parameter inuencing the removal of melanoidins in the EC process. The water solubility of melanoidins can be increased by altering the pH of the solution and the colour intensity of melanoidin changes. In general, the brown colour intensies at a high pH, and the bleaching of melanoidins can be observed at low pH values [3]. Thus, melanoidin solutions with pHi 2.0 12.0 without the EC process were adjusted to examine colour (absorbance) changes at 475 nm. The polymerization degree of the melanoidin solution changed with pHi . The decolourization eciency at pH 2.04.2 decreased from 72.0% to 5.0% (Figure 1) due to the precipitation of the melanoidins (depolymerization or decolourization). The studies in the literature revealed that the isoelectric point of melanoidins was 2.5. At pHi 2.5, melanoidins have a net zero charge [3]. However, as the pH was increased, the net electrical charge of melanoidins became more negative. At such pHi , melanoidins may acquire a net zero charge consequently leading to their precipitation from the solution. These results may be attributed to be the predominance of an undissociated form of melanoidin at a pHi < pKa of the melanoidins, which is 3.5 [3]. The pKa generally serves as the starting point of the melanoidin precipitation from the solution. The decolourization eciency at pHi 812 decreased from 0.0 to 5.0% (polymerization or colourization). Increasing the solution pHi enhanced the degree

Figure 2. (a) Eect of pHi on decolourization and (b) change of nal pHf during the EC process (conditions: j = 5A/m2 , C0 = 100 mg/L, = 2500 S/cm).

Figure 1. The absorbance and colour removal of melanoidin solutions with pHi 2.012.0.

of polymerization. There was a stable region between pHi 4.2 and 8.0 for the decolourization. The EC experiments were performed in the pHi range of 4.28.2 at j = 5 A/m2 , = 2500 S/cm and C0 = 100 mg/L. As seen in Figure 2(a), the decolourization eciency depended on both the operating time and pHi . The pHi values aected the removal of melanoidins. For example, over 98% of the decolourization eciency was realized at 10, 21, 25 and 30 minutes with pHi 4.2, 5.2, 6.2 and 8.2, respectively. The results indicated that the decolourization performance was dependent on pHi values, because the lower pH values led to faster reactions and higher decolourization eciency. Almost complete removal of melanoidins was observed after 10 min of the operating time. The nal pH (pHf ) of the solution was around 6.5, close enough to neutral for discharge to the environment. The decolourization eciency at pHi 4.2 was faster than that of the rest of pHi values (Figure 2(a)). When pHi was xed at 4.2, 5.2, 6.2 and 8.2 for the decolourization of melanoidins, euent pHf was observed to be 6.5 at 10 min, 7.9 at 21 min, 8.3 at

M. Kobya and E. Gengec Charge neutralization and precipitation: MMs + Monomeric Al (MMs Monomeric Al)(s) MMs + Polymeric Al (MMs Polymeric Al)(s) (pH56.5) (7) (pH45) (6)

25 min and 8.9 at 30 min, respectively (Figure 2(b)). On the other hand, the amounts of aluminium ions generated within the EC reactor according to Faradays law at these optimum operating times were 3.95 103 kg/m3 for initial pHi 4.2, 8.29 103 kg/m3 for pHi 5.2, 9.87 103 kg/m3 for pHi 6.2 and 11.84 103 kg/m3 for pHi 8.2, respectively. As seen in Figure 2(b) for pHi 4.2, the pHf of the decolourized solution varied between 4.2 and 7.5. As an example, pHf was 6.4 at 10 min. 4.1.1. Decolourization mechanism of melanoidin molecules Melanoidin molecules (MMs) resemble humic substances, being acidic, polymeric and highly dispersed colloids, which are negatively charged due to the dissociation of carboxylic, hydroxyl and phenolic groups. Melanoidins consist of both hydrophobic (neutral and acidic) and hydrophilic components such as OH, NH2 , > C=O, COOH and NHCH=O [3133]. MMs are connected with hydrogen bonds between functional groups. The most active functional groups are carboxyl and phenolic hydroxyl groups, and dissociation of H+ relates to the pH of the solution. When pH is acidic, carboxyl and hydroxyl ions exist in COOH and OH forms, respectively. When the pH is alkaline, they can exist in COO and O forms [12,33]. At this pH MMs take more negative charge and they consequently need more positive charge to neutralize the negative charge. Melanoidins are soluble in dilute alkaline solution but precipitate from an acidied solution (pHi < 2.5). The acidic nature of melanoidins is usually attributed to the ionization behaviour of the COOH and phenolic OH groups. Hydrophobic groups of MMs were primarily adsorbed on Al-hydroxides ocs in the EC process. Thus, it was anticipated that formation of less polar and more hydrophobic molecules would lead to enhanced adsorption on Al-hydroxides. Adsorption at interfaces, depending on the adsorbate and the interface, was inuenced by hydrophilic, electrostatic, hydration and hydrophobic interactions [7,14]. On the other hand, formation rates of the dierent species played an important role in the decolourization process of melanoidins in the EC process. Several interaction mechanisms, which are discussed in detail by Migo et al. [3], were possible between MMs and the hydrolysis product as the rates of these depend on the pH of the medium and the types of ions present. Monomeric/polymeric Alspecies and Al(OH)3(s) between pH 4 and 9 and Al(OH) 4 in pH > 9 were formed during the EC process. The amorphous Al(OH)3(s) ocs (sweep ocs) having a large specic surface area can absorb some soluble organic compounds such as MMs onto their surface [13,15,34]. Amorphous Al(OH)3(s) has a minimum solubility within the pH range of 6.57.8 [26]. The monomeric and polymeric Al-species are explained in Equations (6)(10) with respect to change in pH values:

Adsorption and sweep coagulation (pH > 6.5): MMs + Al(OH)3(s) (MMs Al(OH)3(s) ) + Al(OH)3(s) MMs + Al(OH)3(s) (MMs Polymeric Al)(s) + Al(OH)3(s) MMs + Al(OH)3(s) MMs Polymeric Al Al(OH)3(s) + Al(OH)3(s) (10) (9) (8)

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The decolourization of MMs and the pHf of the solution within 10 min of operating time rose to 98.4% and 6.4 when pHi was 4.2. The decolourization results in Figure 2 showed that the MMs with the species were eectively removed by mechanisms of precipitation and charge neutralization between pHi of 4.2 and 6.5. Charge neutralization was achieved when the net negative charge of MMs was neutralized by the positively charged Al3+ ions, thus allowing their agglomeration and settling to take eect. The removal mechanism was controlled by adsorption and sweep coagulation due to the amorphous Al(OH)3(s) ocs that formed after the euent pH = 6.4 and >10 min of operating time (Figure 2). The decolourization eciencies were lower at pHi values (5.28.2) until the 15 min of operating time since functional groups in MMs became more negative and there were not enough positive polymeric species present for charge neutralization and precipitation. Therefore no precipitation was observed at these pH ranges. After 20 min of operating time, the decolourization eciencies increased to >98% which enhanced oc formations and the euent pH increased to over 7.7. The removal mechanism was controlled at these pH ranges by adsorption and sweep coagulation. 4.1.2. Zeta potential measurements Colloids are maintained in suspension by electrostatic repulsion between particles. The zeta potential provides an eective measurement of the charge on a particle. The addition of aluminium coagulant can suppress the electric double layer around the colloidal particle, thus encouraging the pollutant [15,35]. As seen in Figure 3(a), the values of the zeta potential rstly decreased sharply until 4 min of operating time. The polymeric Al-species and amorphous Al(OH)3(s) (the theoretical amount of electrochemically dissolved aluminium at the anode is 4.74 mg/L at 12 min) were formed by

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Figure 4. (a) Fourier transform IR analysis of sludge and (b) ratios of absorbance before and after the EC process.

Figure 3. Zeta potential measurements: (a) melanoidin solutions during the EC process and (b) melanoidin solutions at dierent pH values after the EC process (conditions: C0 = 100 mg/L, pHi 4.2, = 2500 S/cm, j = 2.5 A/m2 ).

OH ions after 4 min of operating time. This was probably due to an increase in negatively charged ions formed at the cathode. For this reason the zeta potential started to increase, so that the MMs were governed by precipitation and charge neutralization from polymeric Al-species and nally were adsorbed on Al(OH)3(s) . Moreover, carboxyl or amino groups of the MMs interacted with the hydroxyl ions generated at the cathode during the EC process and negatively charged COO was formed, causing the lowering of the zeta potential, especially in the rst stage of the EC process. When a high enough amount of coagulant was produced at the anode, the coagulant interacted with the negatively charged fragments of the MMs which led to an increase in the zeta potential. After the EC, the zeta potential of the treated wastewater decreased with an increase in the pHf (Figure 3(b)). This pH dependent phenomenon was probably due to the deprotonation (COO ) of acidic organic functional groups such as carboxylic acid (COOH) in MMs and the formation of Al(OH) 4 . The results of zeta potential measurements also supported the proposed mechanisms.

4.1.3. Fourier transform IR spectrum analysis The infrared spectra of sludge from the melanoidins were recorded in the 4000650 cm1 range (Figure 4(a)). The changed and shifted functional groups were extremely important to the understanding of the changing of the melanoidin structure before and after the EC process. For the structural characterization, the samples were analysed. The stretching frequencies at 3426, 2940, 1721, 1658, 1641, 1566 and 1408 cm1 were corresponding to the presence of an alcoholic (OH), CH stretching, ketonic (=C=O), aldehydic (COH), carboxylic (COOH), carboncarbon double bound (C=C) and asymmetric NO2 group, respectively (Table 1). Figure 4(b) showed the ratios of absorbances before and after the EC process versus the wavenumber. The peak at 1739 cm1 was attributed to the conjugated CC double bonds corresponding to the deep brown colour. 4.2. Eect of current density Current density and operating time are important operational parameters for the decolourization and cost of the removal processes [11]. The decolourization eciency as a function of the operating time was studied at current density values in the range of 2.57.5 A/m2 (Figure 5). As seen in Figure 5, a steep increase in melanoidin removal at only >2.5 A/m2 was observed and then became gradual. The

M. Kobya and E. Gengec the EC process as in all other electrolytic processes. ENC s (kWh/m3 ) were calculated using the following equation: ENC = UitEC v (12)

Table 1. Fourier transform IR analysis of melanoidin and sludge produced during the EC process. Wavenumber (cm1 ) 34003200 28003100 1739 1641 1595 1375, 1301 1217 1063 972 1870 Functional group OH stretch form COOH and COH CH stretch from CH, CH2 , and CH3 C=C stretching HOH C=O stretching OH stretching CN stretching AlO AlOHO COC asymmetric stretching

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where U is the cell voltage (V). Values of ENC and ELC, charge loading (Q), current eciency and removal eciency (Rm ) with respect to different current densities and operating times are illustrated in Table 2. 97% or more of the decolourization eciencies were obtained at 2.5, 5.0 and 7.5 A/m2 for 10, 5 and 4 min, respectively (Table 2). The values of ELC and ENC increased as the current density was increased (Table 2). In the EC process, the number of aluminium ions produced was proportional to the charge loading. The increase in the decolourization eciency of melanoidins was expected as the charge loading (F/m3 ) increased since it aected the decolourization eciency: Q= itEC Fv (13)

Figure 5. Eect of current density on decolourization eciency of melanoidin (conditions: C0 = 100 mg/L, pHi 4.2, 100 mg/L, = 2500 S/cm).

maximum decolourization eciencies at 14 min of operating time and current densities of 2.5, 5.0 and 7.5 A/m2 were 96.9%, 99.1% and 99.2% respectively. However, as the current density was increased from 2.5 to 7.5 A/m2 , the optimum operating time was decreased from 10 to 4 min. This can be attributed to high current densities; the extent of anodic dissolution (Faradays law, Equation (12)) increased positively charged polymeric Al-species resulting in increased melanoidin removal: ELC = itEC Mw zF v (11)

where ELC is the electrode consumption (kg/m3 ), tEC (s) is the operating time, z is the number of electrons involved in the oxidation/reduction reaction for Al, z = 3. Mw is the atomic weight of the anode material (Mw = 26.98 g/mol), F is Faradays constant (96485 C/mol) and v is the volume (m3 ) of the solution in the EC reactor. According to Faradays law, the charge passed to the solution was directly proportional to the amount of electrode dissolved. The energy consumptions (ENC ) given in Equation (12) are also an extremely important parameter in

Experiments in the EC process may provide information on the optimal conditions to generate the amounts of Al3+ ions and Al hydroxides needed for the decolourization of melanoidins. Table 2 showed the eect of charge loading on the decolourization eciency and on the loss of aluminium mass via dissolution in the EC process. The increase of charge loading increased the amount of Al electrode dissolved in the EC process and improved the decolourization eciency. Greater than 98% of decolourization eciency at 2.5, 5.0 and 7.5 A/m2 was achieved at the 10, 5 and 4 min operating times. Charge loading at the optimum operating conditions was found to be 0.439 F/m3 . The decolourization eciency and loss of Al electrode mass were 98% and 0.0044 kg/m3 . The Faradic yield or current eciency (CE ) is dened as the ratio of the actual electrode consumption to the theoretical value. The CE calculation was based on the comparison of experimental weight loss of the aluminium electrodes (Ce ) and the theoretical amounts of aluminium dissolution (Ct ) according to Equation (11) through the electrode consumption dierence before and after the EC process. CE at dierent current densities was calculated using the following equation: CE (%) = Ce 100 Ct (14)

CE at dierent current densities and operating times was changed in the range of 103115% (Table 2). The dierence in mass may be explained by the corrosion pitting phenomenon which caused holes and practically led to a metallic Al loss on the electrode surface [36].

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Table 2. j (A/m2 ) 2.5 5.0 7.5 2.5 5.0 7.5 2.5 5.0 7.5
Optimum

Decolourization eciency of melanoidin with dierent current densities. i (A) 0.06 0.12 0.18 0.06 0.12 0.18 0.06 0.12 0.18 U (V) 1.44 2.26 2.95 1.40 2.30 2.95 1.40 2.30 2.95 tEC (min) 10 10 10 5 5 5 4 4 4 ENC (kWh/m3 ) 0.0169 0.0532 0.1041 0.0082 0.0271 0.0521 0.0066 0.0216 0.0416 ELC (kg/m3 ) 0.0043 0.0086 0.0124 0.0021 0.0046 0.0062 0.0017 0.0033 0.0051 Q (F/m3 ) 0.439 0.878 1.317 0.219 0.439 0.658 0.176 0.351 0.527 CE (%) 108 109 104 106 115 103 106 103 106 Rm (%) 96.5 98.6 98.8 6.5 96.8 97.9 5.8 74.4 97.5

decolourization conditions

4.3. Eect of conductivity The conductivity of melanoidin solutions aects the voltage between the electrodes, the energy and the electrode consumptions. The solution resistance is reduced by the decreasing distance between the electrodes which leads to decrease in the electrode potential [17,25,26]. NaCl was used to obtain the desired conductivity in the EC process. Increasing solution conductivity using NaCl could signicantly reduce the adverse eects of bicarbonate and sulphate anions. Figure 6 shows the eect of conductivity on the decolourization eciency of melanoidins between 500 and 3000 S/cm. From Figure 6(a), it can be seen that the decolourization eciency increased from 95.4% to 98.2% with an increase in conductivity of melanoidins after 5 min. In addition, the energy consumption decreased from 0.0377 to 0.0261 kWh/m3 with increasing conductivity (Figure 6(b)). Voltages decreased from 3.2 to 2.9, 2.5, 2.3 and 2.2 with increasing conductivity. Energy consumption considerably reduced to almost a third with changes in the conductivity. The electrode consumption varied from 0.0127 to 0.0038 kg/m3 in the conductivity range of 500 3000 S/cm. The higher decolourization eciency with lower energy and electrode consumptions was obtained for melanoidin solutions at about = 2500 S/cm. Our results showed a good agreement with literature studies [8,17,25]. 2500 S/cm was selected as the optimum conductivity value and this value was used in the experiments.
Figure 6. Eect of conductivity on decolourization eciency (conditions: C0 = 100 mg/L, pHi 4.2, 5 min; j = 5A/m2 ).

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4.4. Eect of initial melanoidin concentration The melanoidin solutions with dierent initial melanoidin concentrations (100800 mg/L) were treated in the EC process. The decolourization eciency was decreased from 98.9% to 94.8% with an increase in concentration of melanoidins from 100 to 800 mg/L at 55 min. When initial melanoidin concentrations were 100, 400 and 800 mg/L, values of COD for melanoidins were 128, 464 and 924 mg/L which had some relation with the value of C0 as CCOD is equal to approximately 1.20 C0 (Figure 7). The removal eciencies of colour and COD for dierent initial concentrations and minimum operating times were

98.4% and 97% for 100 mg/L at 10 min, 98.1% and 91% for 400 mg/L at 40 min and 94.8% and 90% for 800 mg/L at 60 min, respectively. Moreover, the electrode consumptions increased from 0.0096 to 0.0742 kg/m3 in the concentration range of 100800 mg/L at optimum operating times. It is quite clear that under the optimum experimental conditions, lower melanoidin concentrations and lower operating times resulted in a higher percentage of the decolourization eciency. This was likely due to the formation of insucient polymeric Al-species produced by the electrode to coagulate the greater number of MMs

M. Kobya and E. Gengec energy, electrode material and chemicals costs for decolourization of the melanoidins were taken into account as major cost items in the calculation of the OC in /m3 [23]: OC = aENC + bELC + cCC (15)

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Figure 7. Eect of initial melanoidin concentration on decolourization and COD eciencies (conditions: = 2500 S/cm, pHi 4.2, j = 5A/m2 ).

at higher concentrations, which led to a decrease in the decolourization and COD eciencies. In addition, at higher initial melanoidin concentrations, Al(OH)3(s) formed near the surface, fouling the electrodes, and intermediate products formed in the solution, which blocked the electrode active sites. Both of these factors gave rise to a decrease in the decolourization and COD eciencies. Briey, increasing concentration of melanoidins resulted in the increase of anionic charges and coagulant demand in the EC process to maintain eective removal of MMs.

Costs for ELC (kg/m3 ) in Equation (11) and ENC (kWh/m3 ) in Equation (12) were calculated. a, b and c given for the Turkish market in June 2011 were electrical energy price (0.072/kWh), electrode material price (1.65/kg Al) and chemical costs (CC, 0.73/kg for NaOH, 0.29/kg for H2 SO4 and 0.15/kg for NaCl), respectively. Table 3 shows the OC value under optimum operating conditions for the decolourization eciency of melanoidins In the EC process, total OC increased with increasing current density and operating time since energy and electrode consumptions were related to these parameters. OC s at 2.5 7.5 A/m2 changed from 0.0084 to 0.0115 /m3 . OCs at 5003000 S/cm decreased from 0.0238 to 0.0083 /m3 since energy and electrode consumptions decreased at constant current density. OC s also increased from 0.0096 to 0.0742 /m3 with increasing initial concentration (100 800 mg/L) due to increase of the operating time for higher decolourization eciency and electrode dissolution in the EC process. As a result, the OC for the decolourization eciency of melanoidins under the optimum conditions was 0.0096 /m3 . 5. Conclusions The optimum operating conditions for the decolourization of melanoidins were pHi = 4.2, j = 5 A/m2 , = 2500 S/cm, C0 = 100 mg/L and tEC = 10 min. The decolourization eciencies were lower at initial pH values until 10 min of operating time since functional groups in MMs became more negative and there were not enough positive polymeric Al-species present for charge neutralization and precipitation. After 20 min of operating time, the values of the decolourization eciency were increased

4.5. Operating cost of melanoidin decolourization Operating cost (OC ) is an important economical parameter in the EC process. The OC includes material cost (mainly electrodes), utility cost (mainly electrical energy), as well as labour, maintenance and other xed costs. In this study,
Table 3.

Operating cost values for decolourization eciency of melanoidin at optimum conditions. Results pHi (-) 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2 4.2 j (A/m2 ) 2.5 5.0 7.5 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 tEC (min) 10 5 4 5 5 5 5 5 5 30 55 Rm (%) 96.5 96.8 97.5 95.2 95.8 96.2 96.8 96.8 96.8 95.6 94.2 ENC (kWh/m3 ) 0.0169 0.0266 0.0417 0.0377 0.0341 0.0283 0.0266 0.0261 0.0266 0.0268 0.0271 ELC (kg/m3 ) 0.0043 0.0046 0.0051 0.0127 0.0114 0.0078 0.0046 0.0038 0.0046 0.0239 0.0437 OC (/m3 ) 0.0084 0.0096 0.0115 0.0238 0.0214 0.0150 0.0096 0.0083 0.0096 0.0415 0.0742

Operating parameters C0 (mg/L) 100 100 100 100 100 100 100 100 100 400 800 Conductivity (S/cm) 2500 2500 2500 500 1000 1500 2500 3000 2500 2500 2500

Environmental Technology to >98% which enhanced oc formations and the removal mechanism was controlled at these pH ranges by adsorption and sweep coagulation. OC at the optimum conditions was 0.0096 /m3 .

References
[1] P. Kumar and R. Chandra, Decolourisation and detoxication of synthetic molasses melanoidins by individual and mixed cultures of Bacillus spp., Bioresource Technol. 97 (2006), pp. 20962102. [2] B. Cammerer, V. Jalyschkov, and L.W. Kroh, Carbohydrate structures as part of the melanoidin skeleton, Int. Congress Series 1245 (2002), pp. 269273. [3] V.P. Migo, E.J. Del Rosario, and M. Matsumura, Flocculation of melanoidins induced by inorganic ions, J. Ferment. Bioeng. 83 (1997), pp. 287291. [4] S. Mohana, C. Desai, and D. Madamwar, Biodegrading and decolourization of anaerobically treated distillery spent wash by a novel bacterial consortium, Biores. Technol. 98 (2007), pp. 333339. [5] M. Coca, M. Pena, and G. Gonzalez, Variables aecting eciency of molasses fermentation wastewater ozonation, Chemosphere 60 (2005), pp. 14081415. [6] J. Dwyer, L. Kavanagh, and P. Lant, The degradation of dissolved organic nitrogen associated with melanoidin using a UV /H2 O2 AO. Chemosphere, 71 (2008), pp. 17451753. [7] Y. Satyawali, W. Verstraete, and M. Balakrishnan, Integrated electrolytic treatment and adsorption for the removal of melanoidins, Clean 38 (2010), pp. 409412. [8] E. Gengec, M. Kobya, E. Demirbas, A. Akyol, and K. Oktor, Optimization of bakers yeast wastewater using response surface methodology by electrocoagulation, Desalination 286 (2012), pp. 200209. [9] P. Canizares, M. Hernndez-Ortega, M.A. Rodrigo, C.E. Barrera-Diaz, G. Roa-Morales, and C. Sez, A comparison between conductive-diamond electrochemical oxidation and other advanced oxidation processes for the treatment of synthetic melanoidins, J. Hazard. Mater. 164 (2009), pp. 120125. [10] Y. Yavuz, EC and EF processes for the treatment of alcohol distillery wastewater, Sep. Purif. Technol. 53 (2007), pp. 135140. [11] M. Kobya and S. Delipinar, Treatment of the bakers yeast wastewater by electrocoagulation, J. Hazard. Mater. 154 (2008), pp. 11331140. [12] A. Simaratanamongkol and P. Thiravetyan, Decolorization of melanoidin by activated carbon obtained from bagasse bottom ash, J. Food Eng. 96 (2010), pp. 1417. [13] Z. Liang, Y. Wang, Y. Zhou, H. Liu, and Z. Wu, Stoichiometric relationship in the coagulation of melanoidins-dominated molasses wastewater, Desalination 250 (2010), pp. 4248. [14] Z. Liang, Y. Wang, Y. Zhou, H. Liu, and Z. Wu, Variables aecting melanoidins removal from molasses wastewater by coagulation/occulation, Sep. Purif. Technol. 68 (2009), pp. 382389. [15] Y. Zhou, Z. Liang, and Y. Wang, Decolorization and COD removal of secondary yeast wastewater euents by coagulation using aluminum sulfat, Desalination 225 (2008), pp. 301312. [16] G.B. Raju, S. Prabhakar, S.S. Rao, and K. Gopalakrishna, Pilot-scale studies on the treatment of tannery euents by electrootation, Int. J. Environ. Pollut. 30 (2007), pp. 332344.

[17] M. Kobya, E. Demirbas, O.T. Can, and M. Bayramoglu, Treatment of levax orange textile dye solution by electrocoagulation, J. Hazard. Mater. 132 (2006), pp. 183188. [18] M. Kobya, O.T. Can, and M. Bayramoglu, Treatment of textile wastewaters by electrocoagulation using iron and aluminum electrodes, J. Hazard. Mater. 100 (2003), pp. 163178. [19] I. Arslan-Alaton, I. Kabdasli, V. Burcu, and O. Tunay, Electrocoagulation of simulated reactive dyebath euent with aluminum and stainless steel electrodes, J. Hazard. Mater. 164 (2009), pp. 15861594. [20] I. Kabdasli, T. Arslan, I. Arslan-Alaton, T. Olmez-Hanci, and O. Tunay, Organic matter and heavy metal removals from complexed metal plating euent by the combined electrocoagulation/Fenton process, Water Sci. Technol. 61 (2010), pp. 26172624. [21] M. Kobya, E. Demirbas, N.U. Parlak, and S. Yigit, Treatment of cadmium and nickel electroplating rinse water by electrocoagulation, Environ. Technol. 31 (2010), pp. 14711481. [22] M. Vepsalainen, J. Selin, P. Rantala, M. Pulliainen, H. Sarkka, K. Kuhmonen, A. Bhatnagar, and M. Sillanpaa, Precipitation of dissolved sulphide in pulp and paper mill wastewater by electrocoagulation, Environ. Technol. 32 (2011), pp. 13931400. [23] M. Kobya, E. Senturk, and M. Bayramoglu, Treatment of poultry slaughterhouse wastewaters by electrocoagulation, J. Hazard. Mater. 133 (2006), pp. 172176. [24] T. Coskun, F. lhan, N.U. Demir, E. Debik, and U. Kurt, Optimization of energy costs in the pretreatment of olive mill wastewaters by electrocoagulation, Environ. Technol. 33 (2012), pp. 801807. [25] O.T. Can, M. Bayramoglu, and M. Kobya, Decolorization of reactive dye solutions by electrocoagulation using aluminum electrodes, Ind. Eng. Chem. Res. 42 (2003), pp. 33913396. [26] M.Y.A. Mollah, R. Schennach, J.R. Parga, and D.L. Cocke, Electrocoagulation (EC)-science and applications, J. Hazard. Mater. 84 (2001), pp. 2941. [27] A.S. Koparal, Y.S. Yildiz, B. Keskinler, and N. Demircioglu, Eect of initial pH on the removal of humic substances from wastewater by electrocoagulation, Sep. Purif. Technol. 59 (2008), pp. 175182. [28] H. Liu, C. Hu, H. Zhao, and J. Qu, Coagulation of humic acid by PACl with high content of Al13 : The role of aluminum speciation, Sep. Purif. Technol. 70 (2009), pp. 225230. [29] J. Dahiya, D. Singh, and P. Nigam, Decolorization of synthetic and spentwash melanoidins using the white-rot fungus Phanerochaete chrysosporium JAG40, Biores. Technol. 78 (2001), pp. 9598. [30] APHA/AWWA/WPCF, Standard Methods for the Examination of Water and Wastewater, Washington, DC, USA, 1998. [31] Y. Shi, H. Liu, X. Zhou, A. Xie, and C.Y. Hu, Mechanism on impact of internal electrolysis pretreatment on biodegradability of yeast wastewater, Chinese Sci. Bull. 54 (2009), pp. 21242130. [32] X. Zhou, H. Liu, Y. Q. Liang, and M. Zuo, The main components of color and dissolved organic matter from yeast industry euent, 2nd Conference on Environmental Science and Information Application Technology, 1718 July 2010, China, Vol. 1, pp. 833836. [33] D. Ghernaout, B. Ghernaout, A. Saiba, A. Boucherit, and A. Kellil, Removal of humic acids by continuous electromagnetic treatment followed by electrocoagulation in batch using aluminium electrodes, Desalination 239 (2009), pp. 295308.

Downloaded by [Kocaeli Universitesi] at 12:15 23 April 2012

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M. Kobya and E. Gengec


coagulation and occulation, Environ. Technol. 31 (2010), pp. 423432. [36] X. Chen, G. Chen, and P.L. Yue, Separation of pollutants from restaurant wastewater by electrocoagulation, Sep. Purif. Technol. 19 (2000), pp. 6576.

[34] M. Rebhun and M. Lurie, Control of organic matter by coagulation and oc separation, Water Sci. Technol. 27 (1993), pp. 120. [35] M. Jang, H. Lee, and Y. Shim, Rapid removal of ne particles from mine water using sequential processes of

Downloaded by [Kocaeli Universitesi] at 12:15 23 April 2012