Co-generation of hydrogen and electricity from biodiesel process effluents

In this study, we apply a short-term voltage (0.2–0.8 V) to both crude glycerol (CG) and an anaerobic digestion (AD) effluent in a single-chamber microbial fuel cell (MFC) for power production. This improves the bioelectrogenesis in both CG (in MFC-1) and the AD effluent (in MFC-2), but higher power generation is attained in MFC-2. The use of domestic and synthetic wastewaters in the AD process leads to the generation of 195 and 350 mL H₂/L-medium, respectively. MFC-2 performs better than MFC-1 in terms of both voltage generation and chemical oxygen demand (COD) reduction. The application of 0.8 V yields a power density of 311 mW/m² (1.94 times higher than that of the control (160 mW/m²)). In addition, MFC-2 exhibits a 70% COD removal at 0.8 V, which decreases to 56% at 0.2 V. Thus, the application of a short-term voltage in MFC can stimulate both bioelectrogenesis and COD removal.     

A novel quaternized poly(ether sulfone) membrane for alkaline fuel cell application

A new type of poly(ether sulfone)‐based self‐aggregated anion exchange membrane (AEM) was successfully synthesized and used in H₂/O₂ fuel cell applications. The self‐aggregated structural design improves the effective mobility of OH^? ion and increases the ionic conductivity of AEM. Proton nuclear magnetic resonance and Fourier transform infrared spectroscopy spectra confirm successful chloromethylation and quaternization in the poly(ether sulfone). Thermogravimetric analysis curves show the self‐aggregated membrane was thermally stable up to 180 °C. The AEM also has excellent mechanical properties, with tensile strength 53.5 MPa and elongation at break 47.6% under wet condition at room temperature. The performance of H₂/O₂ single fuel cell at 30 °C showed the maximum power density of 162 mW cm^?2. These results show that the self‐aggregated quaternized poly(ether sulfone) membrane is a potential candidate for alkaline fuel cell applications. Copyright © 2014 John Wiley & Sons, Ltd.     

Amelioration in physicochemical properties and single cell performance of sulfonated poly(ether ether ketone) block copolymer composite membrane using sulfonated carbon nanotubes for intermediate humidity fuel cells

A composite membrane composed of a sulfonated diblock copolymer (SDBC) based on poly(ether ether ketone) blocks copolymerized with partially fluorinated poly(arylene ether sulfone) and sulfonated carbon nanotubes (SCNTs) was fabricated by simple solution casting. Addition of the SCNT filler enhanced the water absorption and proton conductivity of membranes because of the increased per‐cluster volume of sulfonic acid groups, at the same time reinforced the membranes' thermal and mechanical properties. The SDBC/SCNT‐1.5 membrane exhibited the most improved physicochemical properties among all materials. It obtained a proton conductivity of 10.1 mS/cm at 120°C under 20% relative humidity (RH) which was 2.6 times more improved than the pristine membrane (3.9 mS/cm). Moreover, the single cell performance of the SDBC/SCNT‐1.5 membrane at 60°C and 60% RH at ambient pressure exhibited a peak power density of 171 mW/cm² at a load current density of 378 mA/cm², while the pristine membrane exhibited 119 mW/cm² at a load current density of 294 mA/cm². Overall, the composite membrane exhibited very promising characteristics to be used as polymer electrolyte membrane in fuel cells operated at intermediate RH.     

Assessment of two ionic exchange membranes in a bioelectrochemical system for wastewater treatment and hydrogen production

Bioelectrochemical systems are devices where organic matter (e.g. wastewater) is oxidized through exoelectrogenic bacteria; this process is a new alternative to energy crisis and to mitigate climate change. If the products of such oxidation are electrons they are called microbial fuel cell (MFC), otherwise if the product is hydrogen these devices are called microbial electrolysis cells (MEC) Mostly, MEC's studies have reported double chamber designs, where the anode and cathode are separated by an ion exchange membrane. Nafion is a proton exchange membrane widely used to study bioelectrochemical devices; however, to our knowledge there are no reports of bipolar membranes (BPM) in these systems. In this study, a double-chambered MEC was constructed to evaluate the performance of the system using Nafion^® 117, and FUMASEP^®FBM bipolar membrane, separately. Biofilm formation was monitored by cyclic voltammetry and open circuit potential (OCP); maximum power for MFC-Nafion and MFC-BPM were 105.1 and 3.6 mW/m², respectively. Hydrogen yield and COD removal were significantly different for both MEC systems. Whereas COD removal for MEC-BPM was 44.8%; MEC-Nafion exhibited a COD removal of 87.4%. Solely the latter system produced hydrogen, with a yield of 7.6%.     

Innovative multi‐processed N‐doped carbon and Fe3O4 cathode for enhanced bioelectro‐Fenton microbial fuel cell performance

A novel bioelectro‐Fenton microbial fuel cell (BEF‐MFC) cathode has been fabricated by modification of electrode using multi‐processing of nitrogen‐doped carbon (NDC)/nano‐Fe₃O₄ method with the aims of cost‐effectiveness, high oxygen reduction reaction (ORR) efficiency, and power performance enhancement. In this study, BEF‐MFC with carbon cloth (CC) cathode pyrolyzed with NDC‐M100/Fe₃O₄ at 700°C achieved higher ORR activity compared with the commercial Pt/C under same operational conditions. It also exhibited excellent crystalline structure according to high‐resolution transmission electron microscope (HRTEM) analysis. Moreover, using NDCN/Fe₃O₄ can facilitate further Fenton‐like reaction for the treatment of wastewater. Chemical oxygen demand (COD) removal efficiency of the reactor was 78% with maximum power density of 1.57 W/m³ in 216 hours. Thus, an innovative multi‐processing method with feasibility for enhanced wastewater treatment and improved power performance of the MFC was investigated. This can be effectively applied in related alternative energy production techniques and bio‐electrochemical systems in the future.     

Enhanced properties of SPEEK with incorporating of PFSA and barium strontium titanate nanoparticles for application in DMFCs

Novel blend nanocomposite proton‐exchange membranes were prepared using sulfonated poly (ether ether ketone) (SPEEK), perfluorosulfonic acid (PFSA), and Ba_0.9Sr_0.1TiO₃ (BST) doped‐perovskite nanoparticles. The membranes were evaluated by attenuated total reflection, X‐ray diffraction spectroscopy, water uptake, proton conductivity, methanol permeability, and direct methanol fuel cell test. The effect of two additives, PFSA and BST, were investigated. Results indicated that both proton conductivity and methanol barrier of the blend nanocomposite membranes improved compared with pristine SPEEK and the as‐prepared blend membranes. The methanol permeability and the proton conductivity of the blend membrane containing 6 wt% BST obtained 3.56 × 10^?7 cm² s^?1 (at 25 °C) and 0.110 S cm^?1 (at 80 °C), respectively. The power density value for the optimum blend nanocomposite membrane (15 wt% PFSA and 6 wt% BST) (54.89 mW cm^‐2) was higher than that of pristine SPEEK (31.34 mW cm^‐2) and SPF15 blend membrane (36.12 mW cm^‐2).     

Determination of optimal operating conditions for a polymer electrolyte membrane fuel cell stack: optimal operating condition based on multiple criteria

A methodology for optimal control of the polymer electrolyte membrane fuel cell (PEMFC) with multiple criteria is presented here. In this regard, thermoelectric objectives and thermoeconomic objective are considered, simultaneously. The proposed fuel cell is a 1200 W Ballard PEMFC namely Nexa? power module. The net power density and exergetic efficiency of the PEMFC are maximized, and the unit cost of the generated power is minimized in a multi‐objective optimization procedure using the NSGA‐II (non‐dominated sorting genetic algorithm). Operating temperature and pressure, air stoichiometric coefficient at the cathode and the current density are considered as controlling parameters in order to acquire optimal performance of the PEMFC. A set of optimal solution namely the Pareto frontier is obtained, and a final optimal solution is selected from available solutions located on the Pareto frontier using the fuzzy decision‐making process based on the Bellman–Zadeh approach. Results are compared with corresponding results obtained previously in single objective optimization scenarios. It has been shown that the optimal operating condition obtained based on the multiple criteria approach has least deviation from the ideal features of the fuel cell in comparison to the corresponding optimal solution obtained in conventional single‐objective optimization approaches. Copyright © 2013 John Wiley & Sons, Ltd.     

The optimization performance of cross‐linked sodium alginate polymer electrolyte bio‐membranes in passive direct methanol/ethanol fuel cells

Consumption of methanol and ethanol as a fuel in the passive direct fuel cells technologies is suitable and more useful for the portable application compared with hydrogen as a preliminary fuel due to the ease of management, including design of cell, transportation, and storage. However, the cost production of commercial membrane is still far from the acceptable commercialization stage. Based to our previous works, the low cost of cross‐linked sodium alginate (SA) polymer electrolyte bio‐membrane shown the virtuous chemical, mechanical, and thermal characterization as polymer electrolyte membrane in the direct methanol fuel cells (DMFCs). This study will further the investigation of cross‐linked SA polymer electrolyte bio‐membrane performance in the passive DMFCs and the passive direct ethanol fuel cells (DEFCs). The experimental study investigates the influence of the membrane thickness, loading of catalysts, temperature, type of fuel, and fuel concentration in order to achieve the optimal working operation performances. The passive DMFCs is improved from 1.45 up to 13.5 mW cm^?2 for the maximum peak of power density, which is obtained by using 0.16 mm as an optimum thick of SA bio‐membrane that shown the highest selectivity 6.31 10⁴ S s cm^?3, 4 mg cm^?2 of Pt‐Ru as an optimum of anode catalyst loading, 2 mg cm^?2 of Pt at the cathode, 2M of methanol as an optimum fuel concentration, and an optimum temperature at 90°C. Under the same conditions of cells, the passive DEFCs are shown to be 10.2 mW cm^?2 in the maximum peak of power density with 2M ethanol. Based on our knowledge, this is the first work that reports the optimization works of performance SA‐based membrane in the passive DMFCs via experimental studies of single cells and the primary performance of passive DEFCs using the SA‐based membrane as polymer electrolyte membrane.     

Innovation of vapor-feed microfluidic fuel cell with novel geometric configuration and operation parameters optimization

The harmless reaction process makes the fuel cells possess the environment-friendly characteristic, but the application of fuel cells is limited by their low fuel utilization. To improve this, a model of vapor-feed microfluidic fuel cell with a novel geometric configuration is established in present study, and the effects of various parameters on cell performance are investigated in detail. Simulation results show that structural parameters contribute significantly to the improvement in cell performance. After a series of optimizations, the maximum power density of 47.43 mW/cm² is achieved, the fuel utilization and exergy efficiency are increased to 46.03% and 5.24%, respectively. This indicates that the structural optimization measures such as tower-type gas chamber and embedded electrode are significant for improving the performance of the vapor-feed microfluidic fuel cell.     

Electricity generation and COD removal of microbial fuel cells (MFCs) operated with alkaline substrates

The characteristics of electricity generation and COD removal of dual-chamber microbial fuel cells (MFCs) operated with alkaline substrates were studied. Substrates with constant pH of either 7 or 9 as well as varying pH in a cycle of 7-8-9-8-7 were used. MFCs operated with these substrates were denoted as MFC-pH7, MFC-pH9 and MFC-pHV, respectively. The experimental results indicate that the MFC-pHV can generate the highest performance of 2554 ± 159 mW/m². Cyclic voltammetry (CV), active biomass and electrochemical impedance spectroscopy (EIS) measurements were conducted and these results suggested that the MFC-pHV had the highest electrochemical activity per unit biomass and the lowest internal resistance, which together contributed to the improved power output of the MFC-pHV. In addition, compared with the other two MFCs operated at fixed pH values, the COD removal efficiency of the MFC-pHV was improved due to the stronger adaptation to the varying pH-environment.     

Process engineering for stable power recovery from dairy wastewater using microbial fuel cell

Microbial fuel cells (MFCs) are one of the sustainable technologies that can effectively treat wastewater with concomitant generation of electricity. The present study investigated the treatment of real dairy wastewater (RDW) using Shewanella algae (MTCC-10608) within a single chamber microbial fuel cell (SCMFC). The study was conducted in both batch and fed-batch modes with initial chemical oxygen demand (COD) of 4000 mg/L and 2000 mg/L, respectively, in 0.2 L working volume of RDW for 15 days. However, the fed-batch strategy involved subsequent feeding of dairy wastewater with 6000 mg/L and 8000 mg/L COD on the 5th and 10th day, respectively. This two-step feeding strategy resulted in a maximum open-circuit voltage of 666 mV at 286 h of incubation with a COD removal efficiency of 92.21% and a columbic efficiency of 27.45%. The kinetic studies predicted the saturation constant of 55.83 mg COD/L and current density of 143.3 mA/m², which are similar to the findings from the experiments and polarization curve obtained. The maximum current density and power density from experiments were found to be 141 mA/m² and 50 mW/m² respectively. Thus, this study successfully indicates the utilization of dairy wastewater as a potential substrate for the sustainable power generation using Shewanella algae as a biocatalyst in the microbial fuel cell.     

The influence of anode diffusion layer on the performance of direct dimethyl ether fuel cell

The effects of the parameters of the anode gas diffusion layer (GDL), including the PTFE content in the backing layer (BL), the PTFE content in the microporous layer (MPL), and the carbon black loading on the performance of a liquid‐feed direct dimethyl ether fuel cell (DDFC), were experimentally investigated. The results indicated that increase in the PTFE content can produce more cracks across the whole surface of the MPL. These cracks were benefit to the anode two‐phase mass transport. The optimal PTFE content in anode BL and MPL was 18 and 40 wt%, respectively. The performances of the DDFCs tended to decline with the increase in the carbon black loading in the anode GDLs due to the difficult long path of mass transport. The maximum power density was obtained with 18 wt% PTFE in BL and 0 mg cm^?2 carbon black loading, the optimal result, was 76.6 mW cm^?2 at ambient pressure. Copyright © 2011 John Wiley & Sons, Ltd.     

Optimizing energy harvest in wastewater treatment by combining anaerobic hydrogen producing biofermentor (HPB) and microbial fuel cell (MFC)

This study focused on the optimization of energy harvest from wastewater treatment by integrating two novel biotechnologies: anaerobic hydrogen production and microbial fuel cell (MFC). The simultaneous production of hydrogen and electricity from wastewater was examined at continuous flow at different organic loading rates (OLR) by changing chemical oxygen demand (COD) and hydraulic retention time (HRT). The experimental results showed that the specific hydrogen yield (SHY, mole H₂/mole glucose) increased with the decrease in OLR, and reached at the maximum value of 2.72 mol H₂/mole glucose at the lowest OLR of 4 g/L.d. The effluent from hydrogen producing biofermentor (HPB) was fed to a single chamber MFC (SCMFC), obtaining the highest power density and coulombic efficiency (CE) of 4200 mW/m³ and 5.3%, respectively. The energy conversion efficiency (ECE) increased with OLR and reached the peak value of 4.24% at the OLR of 2.35 g/L.d, but decreased with higher OLR. It was demonstrated that the combination of HPB and MFC improved the ECE and COD removal with the maximum total ECE of 29% and COD removal of 71%. The kinetic analysis was conducted for the HPB-MFC hybrid system. The maximum hydrogen production was projected to be 2.85 mol H₂/mole glucose. The maximum energy recovery and COD removal efficiency from MFC were projected to be 559 J/L and 97%, respectively.     

Power recovery with multi-anode/cathode microbial fuel cells suitable for future large-scale applications

Multi-anode/cathode microbial fuel cells (MFCs) incorporate multiple MFCs into a single unit, which maintain high power generation at a low cost and small space occupation for the scale-up MFC systems. The power production of multi-anode/cathode MFCs was similar to the total power production of multiple single-anode/cathode MFCs. The power density of a 4-anode/cathode MFC was 1184 mW/m³, which was 3.2 times as that of a single-anode/cathode MFC (350 mW/m³). The effect of chemical oxygen demand (COD) was studied as the preliminary factor affecting the MFC performance. The power density of MFCs increased with COD concentrations. Multi-anode/cathode MFCs exhibited higher power generation efficiencies than single-anode/cathode MFCs at high CODs. The power output of the 4-anode/cathode MFCs kept increasing from 200 mW/m³ to 1200 mW/m³ as COD increased from 500 mg/L to 3000 mg/L, while the single-anode/cathode MFC showed no increase in the power output at CODs above 1000 mg/L. In addition, the internal resistance (R_in) exhibited strong dependence on COD and electrode distance. The R_in decreased at high CODs and short electrode distances. The tests indicated that the multi-anode/cathode configuration efficiently enhanced the power generation.     

A spiral shaped regenerative microfluidic fuel cell with Ni‐C based porous electrodes

Microchannel geometry, electrode surface area, and better fuel utilization are important aspects of the performance of a microfluidic fuel cell (MFC). In this communication, a membraneless spiral‐shaped MFC fabricated with Ni as anode and C as a cathode supported over a porous filter paper substrate is presented. Vanadium oxychloride and dilute sulfuric acid solutions are used as fuel and electrolyte, respectively, in this fuel cell system. The device generates a maximum open‐circuit voltage of ~1.2 V, while the maximum energy density and current density generated from the fuel cell are ~10 mW cm^?2 and ~51 mA cm^?2, respectively. The cumulative energy density generated from the device after five cycles are measured as ~200 mW after regeneration of the fuel by applying external voltage. The spiral design of the fuel cell enables improved fuel utilization, rapid diffusive transport of ions, and in‐situ regeneration of the fuel. The present self‐standing spiral‐shaped MFC will eliminate the challenges associated with two inlet membrane‐less fuel cells and has the potential to scale up for commercial application in portable energy generation.     

Performance characteristics of a passive direct formate fuel cell

A passive direct formate fuel cell using ambient air is designed, fabricated, and tested. This fuel cell does not use any auxiliary devices such as pumps, gas compressors, and gas blowers. The simple and compact structure well fits the need of portable applications. In this fuel cell, a solution having formate and alkali is anode fuel, while ambient oxygen is used as cathode oxidant, and a cation exchange membrane serves as an ionic conductor between two electrodes. Our performance tests have shown that a peak power density of 16.6 mW cm^?2 as well as an open‐circuit voltage of 0.97 V are achieved by the present fuel cell at 60 °C, when running on anode fuel containing 5.0 M sodium formate and 3.0 M sodium hydroxide. This performance is even 31.7% higher than that achieved by an active direct formate fuel cell reported in the open literature (12.6 mW cm^?2), which also uses a cation exchange membrane. The effects of the operating parameters are also investigated, including the concentrations of fuel and alkali as well as the operating temperature. The fuel solution at low concentrations results in an inadequate local concentration of reactants, so that the anodic kinetics becomes sluggish. Although increasing the sodium hydroxide concentration enhances the anodic formate oxidation kinetics, too high concentration of sodium hydroxide leads to too many active sites being covered by hydroxide ions and thus adsorption and reaction of formate ions being limited. Moreover, too high concentration of sodium hydroxide or sodium formate also leads to the fuel solution being highly viscous, hindering the motion of various ions, as well as thus increasing both concentration loss and the ohmic loss. The compromise between benefits and the drawbacks of using high‐concentration reactants results in an optimal composition of the fuel solution, which contains 5.0 M sodium formate and 3.0 M sodium hydroxide. Furthermore, the present fuel cell delivers a voltage around 0.6 V for 20 hours at 4.0 mA cm^?2.     

Three-dimensional numerical simulation and experimental validation on ammonia and hydrogen fueled micro tubular solid oxide fuel cell performance

The main aim of this research is to investigate the performance of ammonia-powered microtubular solid oxide fuel cells in order to use ammonia as a possible candidate for eco-friendly and sustainable power generation systems. The performance of a direct ammonia-powered cell has been elucidated and validated with the experimental results of pure hydrogen gas at Ni?de Ömer Halisdemir University Prof. T. Nejat Veziro?lu Clean Energy Research Center. For both studies, the cathode electrode is supplied with atmospheric air. The performance of anode, electrolyte, and cathode-supported microtubular solid oxide fuel cells has been compared numerically. The findings confirmed that the peak possible power densities obtained numerically using direct ammonia, hydrogen and experimentally using pure hydrogen gas are is 628.92 mW/cm², 622.29 mW/cm^2, and, 589.28 mW/cm² respectively at the same geometrical dimensions, component materials, and operating parameters. Thus, the results of this study demonstrate that simultaneous experimental and numerical studies make a great contribution to minimizing biases due to literature data during model validation. The numerical simulation also indicates that the performance of cathode supported is superior to that of anode supported cells run with hydrogen and ammonia fuel. Likewise, parametric sweep analysis asserts that the working temperature has a greater effect than operating pressure on tubular cell performance. Therefore, the results of this study advise that ammonia will become a carbon-free alternative fuel for solid oxide fuel cells in the coming years.     

Optimization of block structure parameters of PEMFC novel block channels using artificial neural network

Flow channel design is critically important to the performance of proton exchange membrane fuel cell (PEMFC) due to its great influence on liquid water removal and mass and heat transfer. Block flow channel shows good prospect to improve liquid water removal and mass transport, benefiting the PEMFC performance. In this study, the block structures, namely the length, width and height of the block, are optimized for a novel block channel using data-driven surrogate model based on the artificial neural network (ANN). The training/test datasets are obtained from a three-dimensional multi-phase model based on the volume of fluid (VOF) method, with the water removal time (T) and the maximum channel pressure drop (ΔP) taken as the output and optimization objectives. The results show that the ANN prediction agrees well with the physical model results, with the coefficient of determination (R²) of T and ΔP are 0.99598 and 0.99677, respectively. The block parameters are further optimized using the comprehensive scoring method considering both T and ΔP. The block parameters with the length of 0.8 mm, width of 0.375 mm and height of 0.75 mm are found to be the optimum in terms of the highest score. The optimum parameters obtained from the data-driven surrogate model are verified by the physical model, indicating that the ANN model is an effective and fast method to optimize block structure of block flow channel from the perspective of liquid water removal and channel pressure drop.     

Enhancing operating capacity of microbial fuel cells by using low-cost electrodes and multi anode-cathode connections in a membrane-less configuration

Air-cathode microbial fuel cells (MFCs) are common configurations for real scales, especially wastewater treatment due to direct access to oxygen and scaling up capability. Herein, a single-chamber MFC (SCMFC) was used. The fabrication of graphite paint/stainless steel mesh (GP/SSM) anodes in sinusoidal geometry increased the electrode surface area per unit volume of the SCMFC and made it possible to utilize the maximum reactor capacity. Under batch mode, the SCMFC produced 1597 mW/m³ using six anodes and eight air-cathodes, and the maximum COD removal was obtained 93.22% and 93.54% in the second and fourth batches, respectively. Moreover, the effect of electrode surface area on power output was investigated; the power density became 2-fold when the air-cathodes’ surface area increased eight times, and increasing the anode surface area improved the power production per unit volume. The COD removal of 82.14% with 20.46% columbic efficiency was achieved after 72 h of continuous operation.     

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.