Utilizing acid-rich effluents of fermentative hydrogen production process as substrate for harnessing bioelectricity: An integrative approach

Lower substrate degradation is one of the limiting factors associated with fermentative hydrogen production process. To overcome this, an attempt was made to integrate microbial fuel cell (MFC) as a secondary energy generating process with the fermentative hydrogen (H₂) production. The acid-rich effluents generated from the acidogenic sequential batch biofilm reactor (AcSBBR) producing H₂ by fermenting vegetable waste was subsequently used as substrate for bioelectricity generation in single chambered MFC (air cathode; non-catalyzed electrodes). AcSBBR was operated at 70.4 kg COD/m³-day and the outlet was fed to the MFC at three variable organic loading rates. The final outlet from AcSBBR was composed of fermentative soluble acid intermediates along with residual carbon source. Experimental data illustrated the feasibility of utilizing acid-rich effluents by MFC for both additional energy generation and wastewater treatment. Higher power output (111.76 mW/m²) was observed at lower substrate loading condition. MFC also illustrated its function as wastewater treatment unit by removing COD (80%), volatile fatty acids (79%), carbohydrates (78%) and turbidity (65.38%) effectively. Fermented form of vegetable wastewater exhibited higher improvement (94%) in power compared to unfermented wastewater. The performance of MFC was characterized with respect to polarization behavior, cell potentials, cyclic voltammetry and sustainable power. This integration approach enhanced wastewater treatment efficiency (COD removal, 84.6%) along with additional energy generation demonstrating both environmental and economic sustainability of the process.     

Microbial community dynamics and electricity generation in MFCs inoculated with POME sludges and pure electrogenic culture

Palm Oil Mill Effluent (POME) requires treatment before disposal due to its high organic matter content. In this study, the electrical performance and wastewater treatment efficiency were evaluated for Microbial Fuel Cells (MFC) treating unsterile POME with chemical oxygen demand (COD) from 200 to 10 000 mg/L. Since the inoculum type is a key factor in MFC performance, three types of sludge (methanogenic sludge (MS), facultative sludge (FS), and dry sludge (DS), obtained from the current POME treatment ponds were evaluated as inoculum. Dry sludge (DS) developed a maximum power output of 3.30 W/m³ by oxidizing 71% out of the COD provided by POME (1000 mg/L). Also, raw POME microbiota contributed to an enrichment of the community in DS inoculum along with the operation, in which Geobacter was the predominant genus reaching a current generation of 247 mA/m² and a power density of 2.36 W/m³. Conversely, pure electrogenic (Shewanella sp.) inoculation led to a diversification process, resulting in a lower current generation of 52 mA/m² and a power density of 0.10 W/m³. Consequently, microbial community dynamics revealed that MFC inoculation tends to a microbial equilibrium wherein generation of high current density was achieved by gradual microbial enrichment rather than external electrogenic invasion.     

A graphite-granule membrane-less tubular air-cathode microbial fuel cell for power generation under continuously operational conditions

An air-cathode microbial fuel cell (MFC) is an efficient and sustainable MFC configuration for recovering electrical energy from organic substances. In this paper, we developed a graphite-granule anode, tubular air-cathode MFC (GTMFC) capable of continuous electricity generation from glucose-based substrates. This GTMFC produced a maximum volumetric power of 50.2 W m⁻³ at current density of 216 A m⁻³ (R_EX = 22 Ω). Electrochemistry impedance spectroscopy (EIS) measurements demonstrated an overall internal resistance of 27 Ω, consisting of ohmic resistance of R_ohm = 13.8 Ω (51.1%), a charge-transfer resistance of R_c = 6.1 Ω (22.6%) and a diffusion resistance of R_d = 7.2 Ω (26.3%). Power generation with respect to initial chemical oxygen demand (COD) concentration was described well by an exponential saturation model. Recirculation was to found to have a significant effect on electrochemical performance at low COD concentrations, while such effect was absent at high COD concentrations. This study suggests a feasible and simple method to reduce internal resistance and improve power generation of sustainable air-cathode MFCs.     

Effect of hydraulic retention time on biohydrogen production from palm oil mill effluent in anaerobic sequencing batch reactor

The feasibility of hydrogen generation from palm oil mill effluent (POME), a high strength wastewater with high solid content, was evaluated in an anaerobic sequencing batch reactor (ASBR) using enriched mixed microflora, under mesophilic digestion process at 37 °C. Four different hydraulic retention times (HRT), ranging from 96 h to 36 h at constant cycle length of 24 h and various organic loading rate (OLR) concentrations were tested to evaluate hydrogen productivity and operational stability of ASBR. The results showed higher system efficiency was achieved at HRT of 72 h with maximum hydrogen production rate of 6.7 LH₂/L/d and hydrogen yield of 0.34 LH₂/g COD_feeding, while in longer and shorter HRTs, hydrogen productivity decreased. Organic matter removal efficiency was affected by HRT; accordingly, total and soluble COD removal reached more than 37% and 50%, respectively. Solid retention time (SRT) of 4-19 days was achieved at these wide ranges of HRTs. Butyrate was found to be the dominant metabolite in all HRTs. Low concentration of volatile fatty acid (VFA) confirmed the state of stability and efficiency of sequential batch mode operation was achieved in ASBR. Results also suggest that ASBR has the potential to offer high digestion rate and good stability of operation for POME treatment.     

Improved performance of air-cathode single-chamber microbial fuel cell for wastewater treatment using microfiltration membranes and multiple sludge inoculation

Substantial optimization and cost reduction are required before microbial fuel cells (MFCs) can be practically applied. We show here the performance improvement of an air-cathode single-chamber MFC by using a microfiltration membrane (MFM) on the water-facing side of the cathode and using multiple aerobic sludge (AES), anaerobic sludge (ANS), and wetland sediment (WLS) as anodic inoculums. Batch test results show that the MFC with an MFM resulted in an approximately two-fold increase in maximum power density compared to the MFC with a proton exchange membrane (PEM). The Coulombic efficiency increased from 4.17% to 5.16% in comparison with the membrane-less MFC, without a significant negative effect on power generation and internal resistance. Overall performance of the MFC was also improved by using multiple sludge inoculums in the anode. The MFC inoculated with ANS + WLS produced the greatest maximal power density of 373 mW m⁻² with a substantially low internal resistance of 38 Ω. Higher power density with a decreased internal resistance was also achieved in MFC inoculated with ANS + AES and ANS + AES + WLS in comparison with those inoculated with only one sludge. The MFCs inoculated with AES + ANS achieved the highest Coulombic efficiency. Over 92% COD was removed from confectionery wastewater in all tested MFCs, regardless of the membrane or inoculum used.     

Effect of recirculation on bioelectricity generation using microbial fuel cell with food waste leachate as substrate

Recirculation is one of the effective techniques used to upsurge the output of anaerobic reactors. The present study investigates the effect of recirculation of anolyte on bioelectricity generation using food waste leachate in two chamber Microbial Fuel Cell (MFC) with carbon electrodes and Ultrex as proton exchange membrane (PEM). The MFCs are operated in fed-batch mode at varying COD concentrations of 500–1250 mg/L with the hydraulic retention time of 17 h for recirculation. Maximum current density, power density and columbic efficiencies of 100.34 mA/m², 14.42 mW/m² and 10.25% respectively for MFC without recirculation and 150.30 mA/m², 29.23 mW/m² and 14.22% respectively for MFC provided with recirculation are obtained at COD of 1250 mg/L. Comparative performance analysis of the cells indicates that recirculation enhances the bioelectricity production in MFC. Scanning Electron Microscope (SEM) and Fourier Transform Infrared Spectroscopy (FTIR) analyses are also done to find the changes in PEM.     

Start-up study of biohydrogen production from palm oil mill effluent in a lab-scale up-flow anaerobic sludge blanket fixed-film reactor

A start-up study of lab-scale up-flow anaerobic sludge blanket fixed-film reactor (UASFF) was conducted to produce biohydrogen from palm oil mill effluent (POME). The reactor was fed with POME at different hydraulic retention time (HRT) and organic loading rate (OLR) to obtain the optimum fermentation time for maximum hydrogen yield (HY). The results showed the HY, volumetric hydrogen production rate (VHPR), and COD removal of 0.5–1.1 L H₂/g COD_consumed, 1.98–4.1 L H₂ L^?1 day^?1, and 33.4–38.5%, respectively. The characteristic study on POME particles was analyzed by particle size distribution (PSD), Scanning electron microscopy (SEM), and Energy-dispersive X-ray spectroscopy (EDX). The microbial Shannon and Simpson diversity indices and Principal Component Analysis assessed the alpha and beta diversity, respectively. The results indicated the change of bacterial community diversity over the operation, in which Clostridium sensu stricto 1 and Lactobacillus species were contributed to hydrogen fermentation.     

Effects of process,operational and environmental variables on biohydrogen production using palm oil mill effluent (POME)

A batch study for biohydrogen production was conducted using raw palm oil mill effluent (POME) and POME sludge as a feed and inoculum respectively. Response Surface Methodology (RSM) was used to design the experiments. Experiments were conducted at different reaction temperatures (30–50 °C), inoculum size to substrate ratios (I:S) and reaction times (8–24 h). An optimum condition of biohydrogen production was achieved with COD removal efficiency of 21.95% with hydrogen yield of 28.47 ml H₂ g^?1 COD removed. The I:S ratio was 40:60, with reaction temperature of 50 °C at 8 h of reaction time. The study showed that a lower substrate concentration (less than 20 g L^?1) for biohydrogen production using pre-settled POME was achievable, with optimum HRT of 8 h under thermophilic condition (50 °C). This study also found that pre-settled POME is feasible to be used as a substrate for biohydrogen production under thermophilic condition.     

Production of electricity from the treatment of urban waste water using a microbial fuel cell

In this work, is studied the oxidation of the pollutants contained in an actual urban wastewater using a two-chamber microbial fuel cell (MFC). By using an anaerobic pre-treatment of the activated sludge of an urban wastewater treatment plant, the electricity generation in a MFC was obtained after a short acclimatization period of less than 10 days. The power density generated was found to depend mainly on the organic matter contain (COD) but not on the wastewater flow-rate. Maximum power densities of 25 mW m⁻² (at a cell potential of 0.23 V) were obtained. The rate of consumption of oxygen in the cathodic chamber was very low. As the oxygen reduction is coupled with the COD oxidation in the anodic chamber, the COD removed by the electricity-generating process is very small. Thus, taking into account the oxygen consumption, it was concluded that only 0.25% of the removed COD was used for the electricity-generation processes. The remaining COD should be removed by anaerobic processes. The presence of oxygen in the anodic chamber leads to a deterioration of the MFC performance. This deterioration of the MFC process occurs rapidly after the appearance of non-negligible concentrations of oxygen. Hence, to assure a good performance of this type of MFC, the growth of algae should be avoided.     

Enhanced sludge stabilization coupled with microbial fuel cells (MFCs)

This study presents research results on electricity production from waste activated sludge using MFCs during stabilization process. Different MFC configurations equipped with various electrodes were used. Voltage measurements were continuously done during 35 days of MFC operation. Experimental results showed that bioelectricity generation was linked to volatile solids (VS) and protein reductions as a fraction of extracellular polymeric substances (EPS). Double chamber MFC reactor equipped with graphite electrodes had better power and current densities as 312.98 mW/m² and 39.07 μA/cm² while single chamber MFC equipped with titanium electrodes revealed better power and current densities as 97.60 mW/m² and 17.63 μA/cm², respectively. Molecular results indicated that power outputs of MFCs effected by diverse microbial communities in anode biofilms. Although organic matter degradation is reported as 35%–55% VS reduction for digesters, this research provided a promising approach for sludge stabilization with enhanced degrading of organic matters up to 75% by using MFCs.     

Thermophilic biohydrogen recovery from palm oil mill effluent

Enhancement of biological H₂ production efficiency with pre-ozonation process of palm oil mill effluent (POME) prior to thermophilic dark fermentation (55 °C) was investigated. H₂ fermentation experiments were conducted using varying concentrations of raw and ozonated POME. Results revealed that H₂ can be produced from both raw and ozonated POME under thermophilic fermentation. Maximum H₂ production yield of 77 mL.g⁻¹COD_removed was obtained from ozonated POME, which was higher than that of 51 mL·g⁻¹ COD_removed obtained from raw POME at the highest concentration of 35,000 mg COD.L⁻¹. Meanwhile, the specific H₂ production rate (R'_max) of 1.9 and 1.5 mL·h⁻¹·g⁻¹ TVS were observed in raw and ozonated POME at the concentration of 25,000 mg COD.L⁻¹, respectively. The main metabolic products during POME fermentation were acetic and butyric acids and trace amount of valeric acid. Propionic acid and ethanol have contributed, which could be reduced H₂ production in all batch experiments for both POME. The highest efficiency of total and soluble COD removal of 24 and 25% was obtained from the raw POME, and those of 19 and 25% was obtained from the ozonated POME. The present study demonstrates that the POME loading was greatly influenced on the H₂ production yields and rates. The comparative results showed that the ozonated POME gave higher H₂ yields than the raw POME. Thus, demonstrating that the ozonation process significantly improved the POME biodegradability, which is able to enhance H₂ production yields. However, the ozone pre-treatment was not improved in the specific H₂ production rates.     

Biohydrogen production by Clostridium butyricum EB6 from palm oil mill effluent

A hydrogen producer was successfully isolated from anaerobic digested palm oil mill effluent (POME) sludge. The strain, designated as Clostridium butyricum EB6, efficiently produced hydrogen concurrently with cell growth. A controlled study was done on a synthetic medium at an initial pH value of 6.0 with 10 g/L glucose with the maximum hydrogen production at 948 mL H₂/L-medium and the volumetric hydrogen production rate at 172 mL H₂/L-medium/h. The supplementation of yeast extract was shown to have a significant effect with a maximum hydrogen production of 992 mL H₂/L-medium at 4 g/L of yeast extract added. The effect of pH on hydrogen production from POME was investigated. Experimental results showed that the optimum hydrogen production ability occurred at pH 5.5. The maximum hydrogen production and maximum volumetric hydrogen production rate were at 3195 mL H₂/L-medium and 1034 mL H₂/L-medium/h, respectively. The hydrogen content in the biogas produced was in the range of 60–70%.     

Improved performance of microbial fuel cell using combination biocathode of graphite fiber brush and graphite granules

The efficiency and sustainability of microbial fuel cell (MFC) are heavily dependent on the cathode performance. We show here that the use of graphite fiber brush (GBF) together with graphite granules (GGs) as a basal material for biocathode (MFC reactor type R1) significantly improve the performance of a MFC compared with MFCs using GGs (MFC reactor type R2) or GFB (MFC reactor type R3) individually. Compared with R3, the use of the combination biocathode (R1) can shorten the start-up time by 53.75%, improve coulombic efficiencies (CEs) by 21.0 ± 2.7% at external resistance (R_EX) of 500 Ω, and increase maximum power densities by 38.2 ± 12.6%. Though the start-up time and open circuit voltage (OCV) of the reactor R2 are similar to R1, the CE (R_EX = 500 Ω) and maximum power density of R2 are 21.4 ± 1.7% and 38.2 ± 15.6% lower than that of R1. Fluorescence in situ hybridization (FISH) analyses indicate the bacteria on cathodes of R1 and R2 are richer than that of R3. Molecular taxonomic analyses reveal that the biofilm formed on the biocathode surface is dominated by strains belonging to Nitrobacter, Achromobacter, Acinetobacter, and Bacteroidetes. Combination of GFB and GGs as biocathode material in MFC is more efficient and can achieve sustainable electricity recovery from organic substances, which substantially increases the viability and sustainability of MFCs.     

Optimization of biohydrogen production of palm oil mill effluent by ozone pretreatment

The biohydrogen (H₂) production in batch experiments under varying concentrations of raw and ozonated palm oil mill effluent (POME) of 5000–30,000 mg COD.L⁻¹, at initial pH 6, under mesophilic (37 °C), thermophilic (55 °C) and extreme-thermophilic (70 °C) conditions. Effects of ozone pretreatment, substrate concentration and fermentation temperature on H₂ production using mesophilic seed sludge was undertaken. The results demonstrated that H₂ can be produced from both raw and ozonated POME, and the amounts of H₂ production were directly increased as the POME concentrations were increased. H₂ was successfully produced under the mesophilic fermentation of ozonated POME, with maximum H₂ yield, and specific H₂ production rate of 182 mL.g⁻¹ COD_removed (30,000 mg COD.L⁻¹) and 6.2 mL.h⁻¹.g⁻¹ TVS (25,000 mg COD.L⁻¹), respectively. Thus, indicating that the ozone pretreatment could elevate on the biodegradability of major constituents of the POME, which significantly enhanced yields and rates of the H₂ production. H₂ production was not achieved under the thermophilic and extreme-thermophilic fermentation. In both fermentation temperatures with ozonated POME, the maximum H₂ yield was 62 mL.g⁻¹ COD_removed (30,000 mg COD.L⁻¹) and 63 mL.g⁻¹ COD_removed (30,000 mg COD.L⁻¹), respectively. The highest efficiency of total and soluble COD removal was obtained at 44 and 37%, respectively following the mesophilic fermentation, of 24 and 25%, respectively under the thermophilic fermentation, of 32 and 20%, respectively under the extreme-thermophilic fermentation. The production of volatile fatty acids increased with an increased fermentation time and temperature in both raw and ozonated POME under all three fermentation temperatures. The accumulation of volatile fatty acids in the reactor content were mostly acetic and butyric acids. H₂ fermentation under the mesophilic condition of 37 °C was the better selection than that of the thermophilic and extreme-thermophilic fermentation.     

Simultaneous thermophilic hydrogen production and phenol removal from palm oil mill effluent by Thermoanaerobacterium-rich sludge

Thermoanaerobacterium-rich sludge was used for hydrogen production and phenol removal from palm oil mill effluent (POME) in the presence of phenol concentration of 100–1000 mg/L. Thermoanaerobacterium-rich sludge yielded the most hydrogen of 4.2 L H₂/L-POME with 65% phenol removal efficiency at 400 mg/L phenol. Butyric acid and acetic acid were the main metabolites. The effects of oil palm ash, NH₄NO₃ and iron concentration (Fe²⁺) on hydrogen production and phenol removal efficiency from POME by Thermoanaerobacterium-rich sludge was investigated using response surface methodology (RSM). The RSM results indicated that the presence of 0.2 g Fe²⁺/L, 0.3 g/L NH₄NO₃ and 20 g/L oil palm ash in POME could improved phenol removal efficiency, with predicted hydrogen production and phenol removal efficiency of 3.45 L H₂/L-POME and 93%, respectively. In a confirmation experiment under optimized conditions highly reproducible results were obtained, with hydrogen production and phenol removal efficiency of 3.43 ± 0.12 L H₂/L-POME and 92 ± 1.5%, respectively. Simultaneous hydrogen production and phenol removal efficiency in continuous stirred tank reactor at hydraulic retention time (HRT) of 1 and 2 days were 4.0 L H₂/L-POME with 85% and 4.2 L H₂/L-POME with 92%, respectively. Phenol degrading Thermoanaerobacterium-rich sludge comprised of Thermoanaerobacterium thermosaccharolyticum, Thermoanaerobacterium aciditolerans, Desulfotomaculum sp., Bacillus coagulans and Clostridium uzonii. Phenol degrading Thermoanaerobacterium-rich sludge has great potential to harvest hydrogen from phenol-containing wastewater.     

Performance comparison of up-flow microbial fuel cells fabricated using proton exchange membrane and earthen cylinder

Continuous bioelectricity generation was studied in a novel up-flow bio-cathode microbial fuel cell (MFC). The performance of MFC-1, employing commercially available proton exchange membrane (PEM), was evaluated under different organic loading rates (OLRs). Maximum volumetric power density of 10.04 W m⁻³ was obtained in MFC-1 at the OLR of 0.923 kg COD m⁻³ d⁻¹. Overall chemical oxygen demand (COD) removal efficiency more than 90% was achieved under all the OLRs. The performance of MFC-1 was compared with MFC-2, in which the inner anode chamber was made up of earthen cylinder, without employing polymer membrane. MFC-2 generated maximum volumetric power density of 14.59 W m⁻³ at OLR of 0.923 kg COD m⁻³ d⁻¹, which was 46% higher than that produced in MFC-1. The internal resistance of MFC-1 (96 Ω) was higher than MFC-2 (69 Ω). The earthen cylinder MFC demonstrated better COD removal and power generation than the MFC employing PEM.     

Microbial fuel cell performance of multiwall carbon nanotubes on carbon cloth as electrodes

Microbial fuel cell (MFC), which can produce electricity during treatment of wastewater, has become one of the emerging technologies in the field of environmental protection and energy recovery. Of all parts of MFC, the electrode materials play a crucial role in the electricity generation. In this study, we investigate the performance of carbon nanotube (CNT) modified carbon cloth electrodes in single-chamber MFC. The MFC is first inoculated with bacteria in wastewater and then its capability of using acetate sodium as fuel is examined. The results show that the MFC with CNT coated onto carbon cloth electrode improves the power density. In this study, the obtained maximum power density is 65 mW m⁻², the highest chemical oxygen demand (COD) removal efficiency is 95%, and the maximum Coulombic efficiency is 67%. Compared with other reported studies, the CNT/carbon cloth composite electrode has demonstrated high potential for the use of MFC.     

Effects of biomass,COD and bicarbonate concentrations on fermentative hydrogen production from POME by granulated sludge in a batch culture

Effects of three selected variables viz. biomass concentration, initial chemical oxygen demand (COD) concentration and initial bicarbonate alkalinity (BA) on biological hydrogen production from palm oil mill effluent (POME) using the granulated sludge in batch culture were investigated. The experimental results were analyzed and modeled using a central composite design (CCD) of response surface methodology (RSM). In order to carry out a comprehensive analysis of the biohydrogen production process, indicative parameters namely hydrogen yield (Y_H), specific hydrogen production rate (SHPR), and COD removal efficiency were studied as the process responses. Maximum hydrogen yield (124.5 mmol H₂/g COD_removed) and specific hydrogen production rate (55.42 mmol H₂/g VSS.d) were achieved at COD_in 3000 and 6500 mg/l, MLVSS 4000 and 2000 mg/l, and initial BA 1100 mg CaCO₃/l, respectively.     

A novel pico-hydro power (PHP)-Microbial electrolysis cell (MEC) coupled system for sustainable hydrogen production during palm oil mill effluent (POME) wastewater treatment

Due to accelerating global efforts toward decarbonization, a clean hydrogen (H₂) producing technology, Microbial Electrolysis Cell (MEC), has garnered considerable attention. However, MEC's external energy requirement has raised concerns about its sustainability, scalability and application costs. The objective of this research was to build a renewable energy generating system for MECs' performance enhancement during the treatment of Palm oil mill effluent (POME). A novel integration of a pico-hydro-power generator (PHP) with single-chambered MECs exceptionally improved its performance. The performance boost was observed as 1.16 m³-H₂/m³d H₂ and 113 A/m³current production in concomitant with 73% organics removal from Palm Oil Mill Effluent (POME) wastewater, which is higher than the previous single-chambered MECs studies. 78% H₂ recovery r_cat (H₂) along with 57% coulombic efficiency (CE) corroborated the removal of a high percentage of electrons from POME organic materials to generate >96% pure H₂. The MEC nourished POME wastewater degrading communities while stimulating growth of electroactive Geobacter in the anodic biofilm which produced H₂. The overall H₂ recovery, COD removal rate and energy efficiency of PHP-MEC are superior than other MECs powered by other external renewable energy sources reported to date. The PHP-MEC prototype paves the path of scale up studies to build a renewable energy dependent future.     

UASFF start-up for biohydrogen and biomethane production from treatment of Palm Oil Mill Effluent

A start-up study was conducted to produce biohydrogen and biomethane from Palm Oil Mill Effluent (POME) using a two-stage up-flow anaerobic sludge fixed-film (UASFF) bioreactor. 100% molasses was used to start the system, and POME was added at 10% increments until it reached 100% after 59 days. During this period of continuous operation, the HRT and temperature were adjusted in order to optimize the condition for biogas production. Hydrogen and methane gas production fluctuated between 53–70% and 90–95%, respectively, in the last four days of operation (days 56–59), with POME percentage being increased from 70% to 100% (30%–0% molasses). Using 100% raw POME led to a total COD removal of 83.70%, average gas production rates of 5.29 L H₂ d⁻¹ (57.11% H₂) and 9.60 L CH₄ d⁻¹ (94.08% CH₄), in their respective units. This output is comparable to, if not better than using 100% molasses as substrate. This work concludes that based on the relative consistency of biogas production on days 56–59, the two-stage UASFF bioreactor operating at a final HRT of 4 h and temperature of 43 °C has taken a period of two months for start-up.