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* Corresponding author.
E-mail addresses: pugal.smile@gmail.com, arivalagan.pugazhendhi@tdtu.edu.vn (A. Pugazhendhi).
https://doi.org/10.1016/j.ijhydene.2021.06.034
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article as: Karuppiah T et al., Processing of electroplating industry wastewater through dual chambered microbial fuel
cells (MFC) for simultaneous treatment of wastewater and green fuel production, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2021.06.034
2 international journal of hydrogen energy xxx (xxxx) xxx
Article history: Microbial fuel cells (MFC) provide a breakthrough development for wastewater treatment
Received 19 April 2021 combined with electricity production. Though, MFC applications are restricted in labora-
Received in revised form tory scale level. Present study an effort has been made to employ the electroplating in-
26 May 2021 dustrial wastewater as feedstock in dual chambered anaerobic microbial fuel cell for
Accepted 6 June 2021 organic content removal as well as energy production. The ultimate goal of this research is
Available online xxx to analyze the effect of organic load (OL) on removal of organic matter and power pro-
duction. The maximum removal efficiency of total, soluble oxygen demands (TCOD, SCOD)
Keywords: and total suspended solids (TSS) of about 87%, 79% and 72% respectively was obtained at
Microbial fuel cells the OL of 1.5 gCOD/L. The maximum power and current density of about 260 mW/m2
Fed-batch mode dual-chamber (6.2 W/m3) and 364 mA/m2 was also recorded at a same OL of 1.5 gCOD/L. From the above
Wastewater treatment findings proposed that utilization of high strength organic wastewater in MFC could pave
Electroplating the way to handle the problem of electroplating industries as well as minimize a small
Energy demand portion of energy demand.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article as: Karuppiah T et al., Processing of electroplating industry wastewater through dual chambered microbial fuel
cells (MFC) for simultaneous treatment of wastewater and green fuel production, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2021.06.034
international journal of hydrogen energy xxx (xxxx) xxx 3
performance of MFC are migration of electron and proton, sludge) was continuously fed gradually into the anode cham-
proper reduction of electron acceptors, and catabolism of ber using peristaltic pump and maintained under anaerobic
microbe. Practical application of MFC is carried out in dairy condition. The performance of MFC was analyzed over a period
industry wastewater [7], alcohol distillery wastewater [8], sur- of 110 days at room temperature (27 ± 3 C). The anode
gical cotton industry wastewater [9] and seafood processing chamber was further filled with 250 mL of sludge and waste-
wastewater [10]. Also, studies have reported the treatment of water was added up to the brim. In this study, the period of the
dye industry wastewater with MFC containing carbon as an acclimatization phase is 15 days (Fig. 1). Concerned with the
electrode [11]. acclimatization of the inoculum to the wastewater, normally it
This study was put forward to fill the research gap in pro- is able to utilize the substrate for current generation within
cessing electroplating wastewater treatment via interlinked 24e72 h. Though the inoculum was acclimatized with the
green energy production by microbial fuel cells. In this study, electroplating industry wastewater (pH adjusted to 7) for more
the electroplating industry wastewater was experimented than 1 week, it resulted in only 77 mV and in spite of employing
through a fed-batch mode dual-chamber MFC. Effect of carbon veil as electrode. Carbon veil is well known for its
organic load on maximum power generation by the fed-batch highly porous nature which favours biofilm formation.
mode dual-chamber MFC was experimented and reported. Therefore, the complex heavy metals in the electroplating
wastewater must have contributed for longer duration of
acclimatization of the microbial consortium to the wastewater.
Materials and methodology Before starting up the reaction a pinch of BES (BromoEthane-
Sulphonate) was added to eliminate the methane formation
Initial waste water characterization because the methane gas would affect the power generation
[9]. The reactor was operated in open circuit mode without any
The electroplating industry's wastewater was collected from external resistance. The substrate was added in the dual
PRT Enterprises at Athipet, Ambattur Industrial Estate, chambered MFC during this acclimatization stage. The reactor
Chennai, Tamil Nadu, India. Thus obtained wastewater was was changed into closed-circuit mode when the open-circuit
stored at 4 C and was characterized for its physico-chemical voltage reached 180 mV. The phosphate buffer solution
characteristics such as pH, total solids (mg/L), total dissolved [NaH2PO4$H2O 2.45 g/L, Na2HPO4 -58 g/L, KCl 0.13 g/L and
solids (mg/L), total suspended solids (mg/L), chemical oxygen NH4Cl 0.31 g/L] was used to fill the cathode. The effectiveness
demand (mg/L), biological oxygen demand (mg/L), chloride of the phosphate diffusion is ten times that of the proton free
(mg/L), sulfates (mg/L), and total alkalinity (mg/L) using diffusion. At the top of the cathode chamber, one part is pre-
standard methods as mentioned in APHA [12]. The charac- sent for aeration and a wire point is present for circuit
teristics of the electroplating industry wastewater are connection. Before filling up the cathode chamber with phos-
depicted in Table 1. phate buffer, the phosphate buffer was maintained at a con-
stant pH of 7. The electrode used in booth the anode and
Microbial fuel cell setup and operations cathode chamber in the MFC is the carbon veil electrode of
dimension 15 cm by 9.5 cm one of the key components in
In the present study, continuous mode MFC has been used deciding the performance of the MFC is the electrodes.
with an anode compartment of volume 500 mL and a cathode Henceforth, these electrodes are placed in the anode and
compartment of volume 600 mL. The corresponding diameter, cathode chamber in tubular form. The carbon veil electrodes
breadth, and length of the compartments are 6 cm, 7 cm, and used in the MFC are having several advantageous properties
112 cm respectively. The anode chamber consists of a circuit such as good chemical stability, conductivity, low cost, high
connection, inlet, and outlet. The electrode is positioned inside
the chamber. The electroplating industrywastewater obtained
from Ambattur Industrial Estate was filled at the bottom of the
anode chamber. Initially, the mixed liquor suspended solids
concentration was reduced to 6000 mg//L. The electroplating
industry wastewater along with the inoculum (waste activated
Please cite this article as: Karuppiah T et al., Processing of electroplating industry wastewater through dual chambered microbial fuel
cells (MFC) for simultaneous treatment of wastewater and green fuel production, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2021.06.034
4 international journal of hydrogen energy xxx (xxxx) xxx
mechanical strength, higher adsorption capacity, and surface and 360 mg/L, respectively. In this study, we varied the OL in
area over other type of electrode such as activated carbon fibre the range between 0.5 and 2.5 gCOD/L to evaluate the removal
felt (ACFF), carbon cloth (CC) and carbon paper (CP) [10]. A efficiency of TCOD and SCOD by the dual chamber MFC. The
gasket holding the proton exchange membrane is used for removal efficiency of TCOD by the dual chamber MFC at
connecting the two chambers. varying OL is depicted in the figure. It can be observed from
the figure (Fig. 2) that with the increase in the organic load, the
Operational conditions removal efficiency of TCOD increases steadily and reaches a
maximum removal efficiency of about 87% at an organic load
The reactor was operated at OL 0, 0.5, 1, 1.5, 2, and 2.5 g COD/L. of 1.5 gCOD/L. From this data, we can say that the operation
the different OL. At each OL, the removal efficiency of COD and time and organic load required by the microorganism are the
solids were determined along with the total power generated. two important factors to be considered for efficiently utilizing
The wastewater in the MFC was periodically checked for its pH the substrate. From the figure, it can be seen that with the
and the pH was maintained at 7.0. increase of organic load above 1.5 gCOD/L, the removal effi-
ciency of TCOD starts to decline gradually. At an organic load
Experimental analysis of 2.0 and 2.5 gCOD/L, the removal efficiency of TCOD got
reduced to 79% and 68% respectively. The reason for the
At definite time intervals, a digital multimeter was used to reduction in the removal efficiency of COD with an increase in
measure the voltage across the external circuit which con- organic load is the presence of methanogenic organisms.
tains a resister. The equation described by Jayashree et al. [10] Recent research state that whenever the organic substrate
was utilized for deriving the power (mW). loading rate is higher than that of the maximum electron
transfer rate of the dual-chamber MFC, we must consider that
P¼I*V the excess substrate provides a favorable condition for
methanogens and methanogenesis [13].
The power (mW) was calculated for wash OL, where P, I, A similar trend was observed for the removal efficiency of
and V represents power, current, and voltage respectively. SCOD by the dual chamber MFC at varying OL. It can be
Anode surface area was used for the calculation of current observed from the figure (Fig. 3) that the maximum SCOD
denoting (Co) and power density (Po). removal efficiency is about 79% at an organic load of 1.5 gCOD/
L. Like in the case of TCOD, the removal efficiency of SCOD
Coulombic efficiency (CE) gradually decreased with an increase in organic load above 1.5
gCOD/L. The removal efficiency of SCOD decreased and
The formula described by Tamilarasan et al. [9] was used for reached 72% and 61% at an organic load of 2.0 and 2.5 gCOD/L
the calculation of CE. respectively. The reason for the removal of maximum TCOD
and SCOD is due to the presence of electrogenic bacteria and
CE ¼ 8*I/F*q*D COD non-electrogenic bacteria (including methanogens) in the
anode chamber [14]. Since BES was added to the anode
Where 8 is a constant, CE represents coulombic efficiency, I chamber along with the substrate there might be predomi-
represents current (A), F represents Faraday constant nant role of electrogenic microorganism in the COD removal.
(96,500C/mol), D COD represents the removal of COD (g/L), and The above statement is supported by Arulazhagan et al. [15],
q represents the effluent of wastewater (m3/s). The possibility who in his study reported that excess of substrate provides a
for the presence of methanogenic bacteria in this study is niche for methanogens and methanogenesis must be antici-
represented by the coulombic efficiency. Once the MFC pated whenever substrate loading rate is higher than the
reached a steady stage, the polarization curve was obtained maximum electron transfer rate of the MFC [9]. Recent
for every OL by changing the external resistance of the circuit.
Analytical method
Please cite this article as: Karuppiah T et al., Processing of electroplating industry wastewater through dual chambered microbial fuel
cells (MFC) for simultaneous treatment of wastewater and green fuel production, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2021.06.034
international journal of hydrogen energy xxx (xxxx) xxx 5
Fig. 3 e SCOD removal efficiency at various OL. Fig. 4 e Effect of TSS removal on different OL.
research state that whenever the organic substrate loading removal efficiency of TSS decreases with the increase in the
rate is higher than that of the maximum electron transfer rate organic load and reaches a minimum of 56% at 2.2 gCOD/L.
of the dual-chamber MFC, we must consider that the excess This reduction in the removal efficiency of TSS with an in-
substrate provides a favorable condition for methanogens and crease in organic load is due to the longitudinal section of the
methanogenesis [13]. dual-chamber MFC. At higher organic load, the fermentable
The wastewaters nature and flow rate in MFC, the source of organic matters present in the wastewater get fermented and
inoculum, surface area and characteristics of the electrode forms an intermediate product. This intermediate product
used, configuration of the MFC, and membrane between the gets accumulated in the MFC and reduces the removal effi-
chambers are the differing aspects that make the MFC studies ciency by intoxicating the microorganisms [16]. Owing to this,
difficult to compare. The maximum COD removal efficiency of the biomass gets reduced resulting in increased TSS concen-
MFC utilizing various types of wastewater is depicted in Table tration in the effluent. In our study, the TSS concentration was
2. When compared to the maximum COD removal efficiency minimum at 1.5 gCOD/L and maximum removal efficiency
of dual chambered MFC utilizing various types of wastewater resulted as there was no loss of biomass. Table 3.
such as swine wastewater (77.1%), paper recycling wastewater
(76%), fish market wastewater (80%), Domestic wastewater Effect of OL on power production
(54.2%), and slaughterhouse wastewater (72%), our work
which utilizes dye industry wastewater (85%) has the highest After keeping the anaerobic dual-chamber MFC (treating
COD removal efficiency. electroplating industry wastewater) in an open circuit for 15
Please cite this article as: Karuppiah T et al., Processing of electroplating industry wastewater through dual chambered microbial fuel
cells (MFC) for simultaneous treatment of wastewater and green fuel production, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2021.06.034
6 international journal of hydrogen energy xxx (xxxx) xxx
days in the acclimatization phase, an open circuit voltage of of the MFC declined sharply in the initial stages at lower
100 mV was obtained. As the microorganisms require more resistance disregarding the organic load. Due to the decrease
time in the inoculum for stabilizing, the open circuit mode in voltage, the current density of the MFC increased sharply.
was maintained for 30 days. Following this, the electroplating This is caused by the ohmic losses occurring due to the ionic
industry wastewater was supplied to the dual-chamber MFC resistance of all circuit elements [18]. Research states that the
at various organic load after closing the open circuit. The po- power produced by the MFC is dependent on the loading rate
larization curve obtained at various organic load while treat- of the wastewater [9]. At an organic load of 0.5 gCOD/L, the
ing the electroplating industry wastewater using dual- voltage, current density, and power density obtained by the
chamber MFC is depicted in Fig. 5. The polarization curve MFC is 650 mV, 180 mA/m2, and 120 mW/m2 (2.9 W/m3)
was drawn by based on the study of Min and Logan [17] and respectively. With further increase in the organic load to 1.0
Arulazhagan et al [15], the external resistance varies in the gCOD/L, the voltage, current density, and power density
range of in the range of 16,000 Ue100 U was chosen and increased to about 750 mV, 280 mA/m2, and 180 mW/m2
incorporated in polarization curves. In our study, the MFC (4.3 W/m3) respectively, and reached a maximum value of
behaved similarly to a typical fuel cell. When the external load 80 mV, 370 mA/m2, and 260 mW/m2 (6.2 W/m3) at an organic
was removed, the MFC stabilized rapidly at higher resistance load of 1.5 g COD/L. One of the reasons for the increase in
and the MFC stabilized slowly at lower resistance. At lower power density after increasing the organic load could be due
and higher resistance, a maximum power density of about 49 to the inoculum utilizing the wastewater effectively. It can be
and 55 mW/m2 (1.2 and 1.3 W/m3) was obtained respectively. noted that we obtained maximum voltage, power density, and
Owing to the anode surfaces slow redox condition, the voltage current density at an organic load in which we obtained
Please cite this article as: Karuppiah T et al., Processing of electroplating industry wastewater through dual chambered microbial fuel
cells (MFC) for simultaneous treatment of wastewater and green fuel production, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2021.06.034
international journal of hydrogen energy xxx (xxxx) xxx 7
maximum COD removal efficiency. From the figure, we can industry wastewater (52 ± 2.4%) [25], cattle wastewater (54.9%)
observe that by increasing the organic load from 1.5 gCOD/L to [26] and domestic wastewater (7%) [27] are less when
2.0 g COD/L, the voltage, current density, and power density of compared to that of our work (56%).
the MFC decreases to 670 mV, 310 mA/m2, and 200 mW/m2
(4.8 W/m3) respectively. The reason for the reduction in
voltage, current density, and power density at higher organic Conclusion
load is due to the saturation of the activity of the microor-
ganisms at higher organic load. To utilize MFC for treating For the production of sustainable energy, complex industrial
wastewater efficiently and obtain maximum voltage, power wastewater is being identified as a potential substrate. De-
density, a current density, we must eliminate this internal mand for eco-friendly technology to the removal of organic
resistance. Some of the various factors that determine the pollutants from the industrial wastewater and the MFC is only
internal resistance of the MFC are the electrode material, the best suitable method in future generation. The dual
reactor configuration, loading rate of the wastewater, and chambered anaerobic MFC performed under batch mode for
distance between the electrodes [19]. We achieved a the treatment of electroplating industrial wastewater accom-
maximum power density of 260 mW/m2 (6.2 W/m3) at an plished power production simultaneously organic removal.
organic load of 1.5 gCOD/L and the internal resistance of the The important key parameters for the predictions of MFC
MFC at this condition was 300U. Hence to increase the power performance such as TCOD, SCOD and TSS removal effi-
production efficiency of the dual-chamber MFC, the reactor ciencies were achieved 87%, 79% and 72% respectively at a OL
must be designed and configured in such a way to reduce the of 1.5 gCOD/L. the maximum power and current density were
ohmic losses [20]. found to be 260 mW/m2 (6.2 W/m3) and 364 mA/m2 respectively
was achieved at the same optimum OL of 1.5gCOD/L. From the
Coulombic efficiency research outcomes, it can be a promising economical feasible
technique for an industrial wastewater treatment.
In our study, maximum coulombic efficiency was obtained at
lower organic load, and with an increase in organic load, the
Coulombic efficiency gradually decreases. We obtained a Declaration of competing interest
maximum coulombic efficiency of about 56% at an organic
load of 0.5 gCOD/L (Fig. 6). The reason for maximum The authors declare that they have no known competing
coulombic efficiency at lower organic load is that with less financial interests or personal relationships that could have
amount of substrate present for the methanogens to produce appeared to influence the work reported in this paper.
methane, coulombic efficiency increases [21]. Competition
between exo electrogenic micro-organisms and other types of
bacteria with respect to anode surface at high organic loading
can pave the way to decrease in coulombic efficiency [9]. At Acknowledgement
the organic load corresponding to the highest power density,
the coulombic efficiency decreased to about 35%. Owing to the R. S is thankful to the Graduate School and Faculty of Science,
anode surface's high saturation condition, the electrogenic Chulalongkorn University (U), for senior post-doctoral fellow-
bacteria and other bacteria are made to compete with each ship from CU Ratchadaphiseksomphot Endowment Fund. The
other. This is the reason for the decrease in the coulombic authors would like to thank IGPRED (www.igpred.com) for
efficiency of the dual-chamber MFC [22e24]. The minimum providing insight and expertise on the research topic and for
coulombic efficiency of 15% was obtained at an organic load of the assistance that greatly improved the manuscript.
2.5 gCOD/L. The coulombic efficiency of the dual chambered
MFC utilizing various types of wastewater such as seafood references
Please cite this article as: Karuppiah T et al., Processing of electroplating industry wastewater through dual chambered microbial fuel
cells (MFC) for simultaneous treatment of wastewater and green fuel production, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2021.06.034
8 international journal of hydrogen energy xxx (xxxx) xxx
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Please cite this article as: Karuppiah T et al., Processing of electroplating industry wastewater through dual chambered microbial fuel
cells (MFC) for simultaneous treatment of wastewater and green fuel production, International Journal of Hydrogen Energy, https://
doi.org/10.1016/j.ijhydene.2021.06.034