06 May 2011

Wastewater treatment and production of electricity using MFC
S.H.J.A. Jameel (E/07/143), A.M. Rishath (E/07/299)
Department of Chemical and Process Engineering, University of Peradeniya

Keywords: Rice mill wastewater treatment Ceramic plate MFC Earthen plate MFC Power density Power per unit volume COD

Abstract The efficiency of wastewater treatment of a rice mill wastewater was evaluated in terms of electricity harvesting, and chemical oxygen demand (COD) removal using Ceramic Plate Microbial Fuel Cell (MFC-1) and Earthen plate Membrane Microbial Fuel Cell (MFC-2). Maximum chemical oxygen demand (COD) removal efficiencies of 57.5% and 48.75% were obtained in MFC-1 and MFC-2, respectively. Power density of 287.02 W/m2 and volumetric power of 15 mW/m3 was generated by MFC-1 with 100Ω external resistance at the influent COD concentration of 890 mg/L. The MFC-2 generated a maximum power density and volumetric power of 146 W/m2 and 7.7 mW/m3 respectively with 100Ω external resistance, when the influent COD was 960 mg/L. MFCs will be able to economically treat the rice mill wastewater simultaneously generating electricity. 1. Introduction Microbial Fuel Cell (MFC) has deserved the attention of the modern world due to the direct generation of electricity from organic matter in wastewater, while simultaneously treating wastewater. Microbial Fuel Cell functions as a reactor, which catalyzes the conversion of organic matter into electricity using microorganisms. This catalytic activity of microorganisms used to oxidize organic substrate in an anaerobic anode chamber to generate electrons and protons. Electrons are transferred from the anode to the cathode through an external circuit at the same time the protons are transferred towards the cathode through the membrane, which separates anodic and cathodic chambers. In the cathode chamber, electrons combine with protons and oxygen to form water.

Several studies have been carried out on MFCs earlier. Most of them have been conducted using pure compounds, such as acetate [1], glucose [2], sucrose [3], an amino acid [4], a protein [5], cysteine [6] and lignocelluloses [7]. Power Densities obtained are generally higher with pure compounds than with actual wastewaters. For an example, 354 mW/m2 using bovine serum albumin compared to 80 mW/m2 using a meat packing wastewater [8] in single chamber, air-cathode MFCs. Complex organic matter sources like, domestic wastewater [9],swine wastewater [10], meat packing wastewater[11], food processing wastewater [12], hydrogen fermentation reactor effluent [13], and corn Stover hydrolysates [14] were used in MFC studies. There were some studies has been carried out earlier in the treatment of rice mill wastewater using MFCs. few studies have been reported for its anaerobic treatment using up flow anaerobic sludge blanket (UASB) reactor [15]. Behera et al. [16] has reported better COD removal efficiency and electricity harvesting using rice mill wastewater in earthen plate membrane MFC. The power production in the MFC mainly depends on the reactor configuration and electrode material; performance of proton exchange membrane (PEM); specific source of substrate; and operating conditions such as temperature and pH [16]. In the present study, efficiency of electricity generation with simultaneously treating the rice mill wastewater has been investigated. The study was carried out in ceramic plate MFC and earthen plate MFC. Normally the rice mill wastewater is acidic therefore; neutralizing the pH of the wastewater is a need for biological treatment. The performance of the MFC for was evaluated in terms of maximum power densities (normalized to the anode surface area) and power per unit volume (normalized to the working volume of anode chamber) for reactors operated with two different membranes (ceramic plate and earthen plate).The effectiveness of treatment measured in terms of COD removal. 2. Materials and Methods 2.1 Rice mill wastewater sample 1kg of paddy was collected from a rice mill, which was soaked and stored for 6 days with 500ml water in ambient condition before feeding to the Microbial fuel cell. Then it was used as the influent of MFCs. The pH value of wastewater sample measured using analog pH meter (TOA pH meter model HM-5ES). COD of wastewater was measured at the beginning of the experiment and end of the experiment. COD measurements were conducted using standard methods. 2.2 Construction of the microbial fuel cell The MFC-1 was made up of Perspex sheet with anode chamber having working volume of 500 ml and cathode chamber having working volume of 420ml. Both anode and cathode chambers were separated by a ceramic plate with the thickness of 4mm (having dimensions 9cm×10cm). The electrode arrangements consisting of carbon rod with the

affective area of 191cm2 as cathode and stainless steel mesh with the surface area of 262.5cm2 was used as anode. Distilled water was used as cathodic electrolyte. Distilled water was aerated by an air pump but towards the end of the experiment air pump was removed and potassium permanganate was added as cathodic electron acceptor. MFC-2 is identical to the MFC-1 except the ceramic plate. In MFC-2, the earthen plate (thickness 7mm) was used to replace ceramic plate. Electrodes were connected using copper wire through an external resistance of 100 Ω. Microbial fuel cell was operated under batch mode. Reaction cycle time was 15 days for MFC-1 and 13 days for MFC-2. 2.3 Monitoring electricity produced Voltage, Internal resistance and current on MFCs were measured using a Digital Multimeter (fluke 73 series). Continuous measurements were taken according to the deviation of the voltage value with 100Ω external load. Internal resistance was observed using the direct reading of the Multimeter. All experiments were carried out at ambient temperature. 3. Calculations Current (I) was calculated as I (mA) = V (mV)/R (Ω), where V is the voltage and R is the external resistance. Power was evaluated according to P=IV, where P=power (W), I=current (A), and V=voltage (V). Power density was calculated by dividing power generated with the anode surface area. Power per Unit volume was obtained using the equation of power generated over net liquid volume of anode compartment. COD was measured by Closed Reflux, Titrimetric Method [17] and verified using stranded solution vials (range 0 – 15,000 COD). COD removal efficiency was evaluated by dividing the difference of influent and effluent COD with influent COD. 4. Results and Discussion The pH values of the wastewater samples were 4.5 and 4, before fed into the MFC-1 and MFC-2 respectively. When the experiment was initiated, the pH value of the anodic electrolyte was brought to 7.5 in MFC-1 and MFC-2. Usually rice mill wastewater is acidic. Higher acidity or alkalinity of wastewater affects both wastewater treatment efficiency and the environment inside the reactor [16]. Therefore, the pH of value of wastewater was brought to nearly neutral. The higher acidic or alkali environment is harmful for microorganisms in the wastewater. For acidic or alkaline industrial wastewaters, the pH is corrected to nearly neutral by suitable alkali or acid addition before biological treatment. In earlier studies, it was observed that low pH (pH 5 and 6) resulted in lower electricity generation [16]. The possible reason for higher current generation at pH 7.5 is the microorganisms’ growth was favored at this condition.

The influent wastewater having COD concentration of 890mg/l was fed to MFC-1 and 960mg/l was fed to MFC-2. After 15 days of reaction cycle, COD removal efficiency of MFC-1 was 57.5% and after 13 days of reaction cycle, COD removal efficiency of MFC-2 was 48.75%. Power density of 287.02 mW/m2 and volumetric power of 15.7 W/m3 were generated by MFC-1 with 100Ω external resistance at the influent COD concentration of 890 mg/L. The MFC-2 generated a maximum power density and volumetric power of 146.4 mW/m2 and 7.7 W/m3 respectively with 100Ω external resistance, when the influent COD was 960 mg/L. The ceramic plate MFC (MFC-1) generated higher power than the earthen plate MFC (MFC-2) through the experiment (figure 01&02). This was may be because of the wall material of the ceramic used may be effective for proton transfer than earthen pot because of its porosity and thickness of ceramic membrane was 4 mm, while thickness of earthen pot was 7mm.

Figure 01

Figure 02

Maximum voltages generation in MFC-1 and MFC-2 were 0.848 V and 0.620 V. The voltage readings gradually increased to a peak value and then it started to fall (fig. 03)

Figure 03 When the experiment was started, the amount of microorganisms that causes the electron production reaction in anode chamber was at some value. While the experiment was carried out the growth rate of microorganisms increased gradually. If the amount of microorganisms increased the electron production rate also increased, thus the voltage increased gradually. Thereafter the substrate-utilizing rate increased to certain value, so that the amount of food for the microorganisms reduced, due to that the voltage curve started to fall. The internal resistance also acted like voltage curve (fig. 04). As mentioned above when the voltage increased the electron exchange through the external circuit is increased. At the same time because of the voltage increased the following reactions’ rate increased in the cathode chamber. 4H+ + 4e + O2 2H2O H2O is a good non-conductor, which was formed on the surfaces of the carbon rod. The resistance of H2O is very high. Due to the internal resistance, reading was increased gradually. When internal resistance reached the peak value, it was started to fall down due the fall of the voltage. Internal resistance reading was not stable while the air pump was turned on. Internal resistance means the sum of carbons’ resistance, distilled water, membrane resistance, wastewater resistance, stainless steel resistance and copper wire resistance. When the distilled water was aerated with air pump, air bubbles also become a considerable value to add with internal resistance, therefore the internal resistance increased but air bubbles were not stable so the internal resistance also constable.

Figure-04 Potassium permanganate was used as cathodic electron acceptor towards the end of the experiment to evaluate the maximum power production capacity of these MFCs by overcoming the cathodic limitations [16].Therefore, 0.2 g/L of potassium permanganate was added as cathodic electrolyte. The addition of permanganate increased power output. 5. Conclusion The study demonstrated effective treatment of rice mill wastewater in microbial fuel cell, simultaneously generating bioelectricity. The ceramic plate MFC demonstrated a better performance in terms of electricity harvesting and COD removal for treatment of industrial wastewaters. The ceramic plate proved to be a good alternative to earthen plate, offering a better proton transfer. However, the power generated in ceramic plate MFC and the earthen plate MFC is not enough for practical application in rice mill; but there were effective treatment of the rice mill wastewater in both MFCs. There should be many MFCs need to be installed in rice mills to treat wastewater in a rice mill. It can be used in several stages. Therefore, it could be able to generate some more power. Eventually MFCs will be able to economically treat the rice mill wastewater simultaneously generating electricity.

Acknowledgments The authors wish to thank Prof. R. Shanthini (Project supervisor) for her excellent guidance, encouragement, and valuable suggestions during present study. The authors also wish to thank Ms. AMW. Menike (Co-supervisor), Mr. MMK. Sirisena (Workshop Engineer), Ms. T. Ariyaratne, The staff of Department of Chemical & Process Engineering and The staff of Environmental Engineering Laboratory of University of Perdeniya to their valuable contribution to carry out this study.

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The authors
Jameel SHJA, the author of this research paper is a Chemical and Process Engineering undergraduate of Faculty of Engineering, University of Peradeniya. He was born in Sainthamaruthu on 29 January 1988. He has completed his secondary education at Zahira College Kalmunai in 2007. He is interested in Energy Sustainable Engineering. E-mail: ameenullah@live.com Phone: 0776589523

Rishath AM, the author of this research paper is an engineering undergraduate in University of Peradeniya, have completed 3 years of academic in Chemical & Process Engineering. He was born in Akkaraipattu in August 1987. He has completed his secondary education at Akkaraipattu Muslim Central College in 2007. His interests include Water and Wastewater Treatment, Environmental Management and Petroleum industries. E-mail: rishadh1987@yahoo.com Phone: 0714451287 and 0672277683

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