Biohydrogen and biomethane production from cassava wastewater in a two-stage anaerobic sequencing batch biofilm reactor

The objective of the present study was to determine the energetic potential from cassava starch wastewater in a two-stage system (BioH₂ + BioCH₄) composed by anaerobic sequencing batch biofilm reactors (AnSBBR). Included in this general objective, the behavior of the methanogenic AnSBBR regarding organic matter removal and biomethane production will be investigated. The acidogenic AnSBBR was operated with organic loading rate (OLR) of 14 gCarb.L⁻¹.d⁻¹, influent concentration of 5 gCarb.L⁻¹ and cycle time of 4 h. The methanogenic AnSBBR was submitted to OLR increase (3.7–12 gCOD.L⁻¹.d⁻¹), provided by arrangements between influent concentration (2.8; 4.0 and 6.0 gCOD.L⁻¹) and cycle time (6; 8 and 12 h). For the evaluated condition, the acidogenic reactor presented productivity of 0.7 LH₂.L⁻¹.d⁻¹ and yield of 1.1 molH₂.kg⁻¹Carb. The methanogenic reactor presented stable methane production (%CH₄ > 78) during the 260-days operating period. The maximum methane productivity (2.71 LCH₄.L⁻¹.d⁻¹) and yield (0.263 LCH₄.g⁻¹COD) were obtained at OLR of 12 gCOD.L⁻¹.d⁻¹ and cycle time of 6 h. The estimated energy production rate in the two-stage system (BioH₂ + BioCH₄) was 105.2 kJ.L⁻¹.d⁻¹.     

Avenues to the financial viability of microbial electrolysis cells [MEC] for domestic wastewater treatment and hydrogen production

We propose targets, based on real world data, necessary to design a financially viable microbial electrolysis cell (MEC) for the treatment of domestic wastewater. By reducing the cost of the anode and current collecting materials by 90%, a viable organic loading rate would be between 800 and 1,400g-COD/m³/d (2–3A/m²). The anode and current collector materials account for 94% of the total material costs; consequently, cost savings in any other material are moot. If the bioanode can be reused after 20 years, further, significant savings could be achieved. To develop targets we used real world data, for the first time, to evaluate the financial viability of MECs against the current predominant method of wastewater treatment: activated sludge. We modelled net present values for eight potential scenarios and the performances required for MECs to break-even.     

Improvement of biohydrogen production from brewery wastewater: Evaluation of inocula,support and reactor

This work explores the production of biohydrogen from brewery wastewater using as inoculum a culture produced by natural fermentation of synthetic wastewater and Klebsiella pneumoniae isolated from the environment. Klebsiella pneumoniae showed good performance as inoculum, as evaluated using assays of between 9 and 16 cycles, with durations of 12 and 24 h, carbohydrate concentrations from 2.79 to 7.22 g L⁻¹, and applied volumetric organic loads from 2.6 to 12.6 g carbohydrate L⁻¹ day⁻¹. The best results were achieved with applied volumetric organic loads of 12.6 g carbohydrate L⁻¹ day⁻¹ and cycle length of 12 h, resulting in mean volumetric productivity of 0.88 L H₂ L⁻¹ day⁻¹, maximum molar flow of 10.80 mmol H₂ h⁻¹, and mean yield of 0.70 mol H₂ mol⁻¹ glucose consumed. The biogas H₂ content was between 18 and 42%, while the mean organic compounds removal and carbohydrate conversion efficiencies were 23 and 81%, respectively. The inoculum produced by natural fermentation was not viable.     

Biogas from lignocellulosic feedstock: A review on the main pretreatments,inocula and operational variables involved in anaerobic reactor efficiency

Research focused on reusing lignocellulosic waste has been gaining ground, both for the purpose of obtaining energy from renewable sources, as well as for reducing feedstock costs and preventing environmental pollution. Despite being currently evaluated as a promising feedstock, large-scale application of lignocellulosic waste to obtain bioenergy is still scarce. One of the obstacles in terms of reusing it is its recalcitrant composition, often requiring pretreatment applications to break its fibers, increasing its bioavailability. In addition to the type of substrate, there are many operational parameters that may affect the process efficiency, including the type of reactor, temperature, pH, inoculum source, among others. Considering this, it is interesting to consider using statistical tools instead of “one-factor-at-a-time” methods for simultaneous optimization of these variables to increase the production of value-added compounds, such as Plackett-Burman screening design and Central Composite Rotational Design. In this context, this review aimed at compiling data regarding obtaining value-added compounds, focusing on bio-H₂ and bio-CH₄, from different lignocellulosic waste, such as sugarcane bagasse, citrus peel waste, coffee and cereal husks, brewer's spent grain, cocoa processing waste, sawdust, among others, considering the main operational parameters involved (temperature, pH, inoculum) and the type of pretreatment applied (physical, chemical and/or biological). The results described here may support future research on reusing residual lignocellulosic waste, in addition to elucidating the importance of different operational parameters to convert this waste into H₂ and/or CH₄.     

A comprehensive review on the proton conductivity of proton exchange membranes (PEMs) under anhydrous conditions: Proton conductivity upper bound

The present study aims to assess the proton conductivities of the most investigated proton exchange membranes (PEMs) used in PEM fuel cells (PEMFCs). Specifically, PEMs are analyzed for their use in anhydrous fuel cells and proton conductivity upper bounds were provided for them. Considering the direct relationship between proton conductivity and temperature, an upper bound is presented. Based on the obtained upper bounds, suitable membranes for high-temperature performance are determined, and the average range of proton conductivity for each polymer group is discussed. By comparing the available proton conductivity data with upper bound, it was demonstrated that some of poly (ionic liquid)s have provided the highest proton conductivities, however aromatic polymers such as polybenzimidazole (PBI) are found more suitable choices for application at anhydrous conditions and high temperatures. The proton conductivity upper bound for anhydrous PEMs demonstrates the availability of promising polymer options for the deployment of anhydrous fuel cells.     

HRT control as a strategy to enhance continuous hydrogen production from sugarcane juice under mesophilic and thermophilic conditions in AFBRs

The objective of this study was to evaluate the effects of hydraulic retention time (HRT) (8–1 h) on H₂ production from sugarcane juice (5000 mg COD L⁻¹) in mesophilic (30 °C, AFBR-30) and thermophilic (55 °C, AFBR-55) anaerobic fluidized bed reactors (AFBRs). At HRTs of 8 and 1 h in AFBR-30, the H₂ production rates were 60 and 116 mL H₂ h⁻¹ L⁻¹, the hydrogen yields were 0.60 and 0.10 mol H₂ mol⁻¹ hexose, and the highest bacterial diversities were 2.47 and 2.34, respectively. In AFBR-55, the decrease in the HRT from 8 to 1 h increased the hydrogen production rate to 501 mL H₂ h⁻¹ L⁻¹ at the HRT of 1 h. The maximum hydrogen yield of 1.52 mol H₂ mol⁻¹ hexose was observed at the HRT of 2 h and was associated with the lowest bacterial diversity (0.92) and highest bacterial dominance (0.52).     

Graphite nanopowder functionalized 3-D acrylamide polymeric anode for enhanced performance of microbial fuel cell

3-D highly conductive polyvinyl formaldehyde sponges functionalized with acrylamide are fabricated using polyvinyl alcohol with varying concentrations of graphite nanopowder. The properties of the fabricated anodes are analyzed and its application in microbial fuel cells is evaluated. A comparative study with Graphite felt is also performed to evaluate its commercial viability. The presence of Hydroxyl and Amine functional groups enhanced the hydrophilic and biocompatible nature of the synthesized anodes. The phylogenetic analysis substantiated the biocompatible nature and mercury porosimetry showed macroporous nature of the fabricated anode. The highest power density of ~8 W/m² is recorded for C10 establishing solid biofilm formation. A ~94% COD removal revealed the versatility of the anode for MFC based wastewater treatment. The MFC performance was twice than that of control and was also highest among the most reported modified 3-D anodes. The durability study displayed the commercial opportunity of the anode for real-time MFC operation.     

Transient performances of the gas turbine recuperating waste heat through hydrogen rich fuels

Operational rules and control strategies of the chemically recuperated gas turbine (CRGT) in the marine propulsion are investigated in this paper. The Minimization of Gibbs free energy method is used to calculate the diesel-steam reforming reaction which products synthetic hydrogen rich fuels, and a universal model of the chemical regenerator which is easily applied to different application environments is created. The hydrogen production and hydrogen molar fraction are investigated to verify that the CRGT improve the combustion performances under low working conditions. Off-design calculations are performed to derive proper operational rules, and transient calculations are performed to investigate the best control strategies for the systems. The modelling approach of the chemical regenerator can be generally used in the chemically recuperated gas turbine. The elaborate operational rules can greatly improve the thermal efficiencies under every working condition. The system using synchronous control strategies have better regulation speed and operation stability than that using asynchronous control strategies.     

Harvest of electrical energy from fermented microalgal residue using a microbial fuel cell

The application of microalgal biomass for fermentation has been highlighted as a means of producing a range of value-added biofuels and chemicals. On the other hand, the microalgal residue from the fermentation process still contains as much as 50% organic contaminants, which can be a valuable substrate for further bioenergy recovery. In this study, a microbial fuel cell and automatic external load control by maximum power point tracking (MPPT) were implemented to harvest the electrical energy from waste fermented microalgal residue (FMR). The MFC with MPPT produced the highest amount of energy (1.82 kJ/L) compared to the other MFCs with fixed resistances: 0.98 (1000 Ω), 1.16 (500 Ω), and 1.17 kJ/L (300 Ω). The MFC with MPPT also showed the highest maximum power density (88.6 mW/m²) and COD removal efficiency (620.0 mg COD/L removal with 85% removal efficiency). The implementation of MPPT gained an approximate 12.9% energy yield compared to the previous fermentation stage. These results suggest that FMR can be an appropriate feedstock for electrical energy recovery using MFCs, and the combined fermentation and MFC system improves significantly the energy recovery and treatment efficiency from FMR.     

Transition metal/carbon nanoparticle composite catalysts as platinum substitutes for bioelectrochemical hydrogen production using microbial electrolysis cells

Various metal nanoparticle catalysts supported on Vulcan XC-72 and carbon-nanomaterial-based catalysts were fabricated and compared and assessed as substitutes of platinum in microbial electrolysis cells (MECs). The metal-nanoparticle-loaded cathodes exhibited relatively better hydrogen production and electrochemical properties than cathodes coated with carbon nanoparticles (CNPs) and carbon nanotubes (CNTs) did. Catalysts containing Pt (alone or mixed with other metals) most effectively produced hydrogen in terms of overall conversion efficiency, followed by Ni alone or combined with other metals in the order: Pt/C (80.6%) > PtNi/C (76.8%) > PtCu/C (72.6%) > Ni/C (73.0%) > Cu/C (65.8%) > CNPs (47.0%) > CNTs (38.9%) > plain carbon felt (38.7%). Further, in terms of long-term catalytic stability, Ni-based catalysts degraded to a lesser extent over time than did the Cu/C catalyst (which showed the maximum degradation). Overall, the hydrogen generation efficiency, catalyst stability, and current density of the Ni-based catalysts were almost comparable to those of Pt catalysts. Thus, Ni is an effective and inexpensive alternative to Pt catalysts for hydrogen production by MECs.     

Effect of organic fraction of municipal solid waste addition to high rate activated sludge system for hydrogen production from carbon rich waste sludge

Municipal solid waste has been used for bio-methane production for many years. However, both methane and carbon dioxide that is produced during bio-methanization increases the greenhouse gas emissions; therefore, hydrogen production can be one of the alternatives for energy production from waste. Hydrogen production from the organic substance was studied in this study with the waste activated sludge from the municipal wastewater treatment. High rated activated sludge (HRAS) process was applied for the treatment to reduce energy consumption and enhance the organic composition of WAS. The highest COD removal (76%) occurred with the 12 g/L organic fraction of municipal solid waste (OFMSW) addition at a retention time of 120 min. The maximum hydrogen and methane yields for the WAS was 18.9 mL/g VS and 410 mL/g VS respectively. Total carbon emission per g VS of the substrate (OFMSW + waste activated sludge) was found as 0.087 mmol CO₂ and 28.16 mmol CO₂ for dark fermentation and bio-methanization respectively. These kinds of treatment technologies required for the wastewater treatment plantcompensate it some of the energy needs in a renewable source. In this way, the HRAS process decreases the energy requirement of wastewater treatment plant, and carbon-rich waste sludge enables green energy production via lower carbon emissions.     

Enhanced methane production using pretreated sludge in MEC-AD system: Performance,microbial activity,and implications at different applied voltages

Although various pretreatment methods are employed to promote sludge hydrolysis and thereby promoting methane production in the subsequent microbial electrolysis cell assisted anaerobic digestion (MEC-AD) system, the questions arise are, “which pretreatment method on waste activated sludge (WAS) maximises the sludge hydrolysis and what is the optimal applied voltage on anaerobic digestion (AD) to stimulates the direct interspecies electron transfer (DIET) performance and thereby accelerating the methane production fed with pretreated WAS?” was still unanswered. Herein, firstly, a series of pretreatment methods to hydrolyse and mineralise the organic matter of WAS was performed to evaluate solubilization efficiency and thereafter, the influence of different applied voltages (0.3 V, 0.6 V, and 0.9 V) on coupled MEC-AD reactors fed with pretreated WAS was investigated to apprehend the DIET promotion for methane production. The results indicated that in MEC-AD reactors, the methane yield increased by 27.2%, 44.8%, and 37.3% when the applied voltages were 0.3 V, 0.6 V, and 0.9 V, respectively. Therefore, the alkaline-thermal pretreatment (ATP) enhanced the sludge hydrolysis in WAS, followed by an applied voltage of 0.6 V in the MEC-AD reactor fed with pretreated WAS, enhanced methane production under DIET stimulation induced by the increased abundance of electroactive microorganisms (EAM) and the advanced electron transfer. Besides, the energy balance estimation validates that with an applied voltage of 0.6 V in MEC-AD could achieve higher net energy input.     

Continuous H2 production during fermentation of the carbon components of lignocellulose hydrolysates: Insight into the influence of pH conditions on the conversion efficiency of individual sugars

Sugars released from lignocellulose biomass are a promising substrate for biohydrogen production. This study evaluates the effect of pH controlled between 4.0 and 7.5 on continuous dark-fermentative H₂ production from the mixture of cellobiose, xylose and arabinose. High hydrogen production rate was obtained for pH values between 6.0 and 7.0 with a maximum of 7.41 ± 0.16 L/L-d at pH 7.0. On the other hand, the highest H₂ yields of around 1.74 ± 0.02 mol/mol_consumed were obtained at pH 4.5, 5.0 and 6.0. Cellobiose was completely utilized in nearly the entire pH range, while the highest consumption of xylose and arabinose was obtained at pH 6.0 and 7.0, respectively. It shows the challenges in selecting optimum pH for fermentation of mixed sugars. Significant impact of pH conditions on the microbial structure was observed. Between pH 4.0 and 7.0 Clostridium genus dominated the consortium, while above pH 7.0 relative abundance of Bacillus genus increased significantly.     

Experimental investigations of fracturing fluid flowback and retention under forced imbibition in fossil hydrogen energy development of tight oil based on nuclear magnetic resonance

Experimental works have proved that imbibition under forced pressure (FP, the difference between hydraulic fluid pressure and original pore pressure) has a positive effect on fossil hydrogen energy development in tight oil reservoir. However, the knowledge of the influence of imbibition under forced pressure (forced imbibition, FI) on fracturing fluid flowback and water retention is still limited. In this paper, experiments were designed and conducted to reveal the mechanism of fracturing fluid flowback and water retention under imbibition effect in tight sandstones. As a comparison, unconsolidated sandstones were also investigated in this study. Core samples were divided into two categories: the imbibition ones (treated by imbibition) and the filtration ones (treated by displacement), in accordance with the real oil-water distribution after well shut-in. An imbibition core and a filtration core were stitched together to conduct a flowback experiment. During the experiment, fluid distribution in different pore sizes was monitored continuously by using a low-field nuclear magnetic resonance device. Results show that the flowback recovery in tight sandstones is much lower than that in unconsolidated sandstones due to the difference of pore structure. Meanwhile, forced imbibition leads to higher oil recovery than spontaneous imbibition (SI) in tight sandstones since forced pressure enhances water imbibition. The water imbibed into small-macro and macro pores contributes the major flowback recovery, but the imbibed water in micro pores is rather difficult to displace and finally retains in these pores during the flowback process. Overall, forced imbibition not only enhances oil recovery but also increases water retention, explaining the mechanism of well productivity increase by using the shut-in method in the field. This study can help to clarify the influence of forced imbibition on fracturing fluid flowback and enhancement of fossil hydrogen development, and further provide guidance for flowback designs.     

Producing hydrogen from the fermentation of cheese whey and glycerol as cosubstrates in an anaerobic fluidized bed reactor

This study aimed to evaluate the effect of the organic loading rate (OLR) (60, 90, and 120 g Chemical Oxygen Demand (COD). L^?1. d^?1) on hydrogen production from cheese whey and glycerol fermentation as cosubstrates (50% cheese whey and 50% glycerol on a COD basis) in a thermophilic fluidized bed reactor (55 °C). The increase in the OLR to 90 gCOD.L^?1. d^?1 favored the hydrogen production rate (HPR) (3.9 L H₂. L^?1. d^?1) and hydrogen yield (HY) (1.7 mmol H₂. gCOD^?1_app) concomitant with the production of butyric and acetic acids. Employing 16S rRNA gene sequencing, the highest hydrogen production was related to the detection of Thermoanaerobacterium (34.9%), Pseudomonas (14.5%), and Clostridium (4.7%). Conversely, at 120 gCOD.L^?1. d^?1, HPR and HY decreased to 2.5 L H₂. L^?1. d^?1 and 0.8 mmol H₂. gCOD^?1_app, respectively, due to lactic acid production that was related to the genera Thermoanaerobacterium (50.91%) and Tumebacillus (23.56%). Cofermentation favored hydrogen production at higher OLRs than cheese whey single fermentation.     

Analysis of air conditioning system impact on a fuel cell vehicle performance based on a realistic model under actual urban conditions

In this study, a practical fuel cell vehicle considering the Heating, Ventilation, and Air conditioning system is considered to analyze hydrogen consumption under different working conditions. As a prevalent hydrogen-fueled vehicle, Toyota Mirai has been meticulously modeled in Simecenter Amesim software. The simulated model covers all of the vehicle's components with a concentration on Heating, Ventilation, and Air conditioning system. Since the air temperature and ‘weather conditions can significantly impact the vehicle's overall performance, various environmental conditions, including temperature variations, humidity, and varied solar fluxes, are taken into account. Furthermore, New York City is chosen as a densely populated megacity to simulate the dynamic behavior of the fuel cell vehicle under actual driving circumstances. The results illustrate that the Heating, Ventilation, and Air conditioning system can notably alter hydrogen consumption under real driving conditions. In this regard, turning on the Heating, Ventilation, and Air Conditioning system results in a 19% increase in fuel consumption. Moreover, the degradation phenomenon, which is a typical result of using fuel cell vehicles under urban driving conditions, impacts the vehicle's mileage and hydrogen consumption. The simulation results indicate that a fresh fuel cell stack consumes 80 g of hydrogen, while for 2500 and 5500 working hours fuel cells, the stack consumes 89.6 and 107 g of hydrogen, respectively. Based on the obtained results, a 33.75% increase in fuel consumption occurs by implementing a degraded fuel cell stack under real driving conditions.     

Kinetics of formic acid decomposition in subcritical and supercritical water – a Raman spectroscopic study

The decomposition of formic acid is studied in a continuous sub- or supercritical water reactor at temperatures between 300 and 430 °C, a pressure of 25 MPa, residence times between 4 and 65 s, and a feedstock concentration of 3.6 wt%. In situ Raman spectroscopy is used to produce real-time data and accurately quantify decomposition product yields of H₂, CO₂, and CO. Collected spectra are used to determine global decomposition rates and kinetic rates for individual reaction pathways. First-order global Arrhenius parameters are determined as log A (s⁻¹) = 1.6 ± 0.20 and E_A = 9.5 ± 0.55 kcal/mol for subcritical decomposition, and log A (s⁻¹) = 12.56 ± 1.96 and E_A = 41.90 ± 6.08 kcal/mol for supercritical decomposition. Subcritical and supercritical Arrhenius parameters for individual pathways are proposed. The variance in rate parameters is likely due to changing thermophysical properties of water across the critical point. There is strong evidence for a surface catalyzed free-radical mechanism responsible for rapid decomposition above the critical point, facilitated by low density at supercritical conditions.     

Combustion characteristics and flame stability of linear esters of palmitic acid based on OH-PLIF technology

Experimental study on combustion characteristics and method for evaluating flame stability was carried out. Methyl palmitate, ethyl palmitate, propyl palmitate, butyl palmitate, and amyl palmitate were prepared using pyridine n-butyl bisulfate ionic liquid as catalyst in a self-designed reactor to catalyze esterification reaction of palmitic acid with methanol, ethanol, propanol, butanol, and pentanol, respectively. Combustion characteristics including the flame height, flame front area, and flame speed were analyzed; and OH-PLIF time-average total signal strength by the OH-PLIF technique and cold flow properties of linear-chain alkyl esters of palmitic acid were also studied. Image diagnosis was applied to the study of flame stability, and an image segmentation method using three color feature matrices of flame corresponding to the red, green, and blue components was proposed. A color was selected as the evaluation color and the iterative method was used to obtain the optimal threshold for the area where the flame was located. Each pixel in the matrix was compared with an optimal threshold, and the flame stability was evaluated by calculating the ratio variance under continuous conditions. The method is simple in operation, accurate in repeatability, less interfered, and provides some guidance for analysis and optimization of biodiesel combustion process.     

Dark fermentative biohydrogen production using pretreated Scenedesmus obliquus biomass under an integrated paradigm of biorefinery

In recent times, biohydrogen production from microalgal feedstock has garnered considerable research interests to sustainably replace the fossil fuels. The present work adapted an integrated approach of utilizing deoiled Scenedesmus obliquus biomass as feedstock for biohydrogen production and valorization of dark fermentation (DF) effluent via biomethanation. The microalgae was cultivated under different CO₂ concentration. CO₂-air sparging of 5% v/v supported maximum microalgal growth and carbohydrate production with CO₂ fixation ability of 727.7 mg L^?1 d^?1. Thereafter, lipid present in microalgae was extracted for biodiesel production and the deoiled microalgal biomass (DMB) was subjected to different pretreatment techniques to maximize the carbohydrate recovery and biohydrogen yield. Steam heating (121 °C) in coherence with H₂SO₄ (0.5 N) documented highest carbohydrate recovery of 87.5%. DF of acid-thermal pretreated DMB resulted in maximum H₂ yield of 97.6 mL g^?1 VS which was almost 10 times higher as compared to untreated DMB (9.8 mL g^?1 VS). Subsequent utilization of DF effluent in biomethanation process resulted in cumulative methane production of 1060 mL L^?1. The total substrate energy recovered from integrated biofuel production system was 30%. The present study envisages a microalgal biorefinery to produce biohydrogen via DF coupled with concomitant CO₂ sequestration.