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.     

A new side-looking at the dark fermentation of sugarcane vinasse: Improving the carboxylates production in mesophilic EGSB by selection of the hydraulic retention time and substrate concentration

In recent years, a lot of scientific effort has been put into reusing the energy potential of sugarcane vinasse by dark fermentation. However, the findings so far indicate that new pathways need to be followed. In this context, this study assessed the effect of hydraulic retention time (HRT, from 24 to 1 h) on vinasse fermentation (10, 20, and 30 g COD L^?1) in three mesophilic expanded granular sludge bed reactors (EGSB). The carbohydrate conversion remained above 60% at all organic loading rates applied. The maximum hydrogen production rate (8.77 L day^?1 L^?1) was obtained for 720 kg COD m^?3 day^?1 and associated to the lactate-acetate pathway. The highest productivities of propionic, acetic, and butyric acids were 3.11, 1.68, and 2.45 g L^?1 h^?1, respectively, at a HRT of 1 h. At this HRT, the degrees of acidification remained between 54% and 76% in all EGSB reactors. This research provides insights for carboxylate production from sugarcane vinasse and suggests applying the EGSB setup in the acidogenic stage of two-stage processes.     

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.     

Impact of operational conditions on development of the hydrogen-producing microbial consortium in an AnSBBR from cassava wastewater rich in lactic acid

Biohydrogen production from cassava starch wastewater was evaluated in anaerobic sequencing batch biofilm reactor (AnSBBR) using different inoculum (mixed cultures from naturally fermented wastewater and anaerobic sludge thermally treated) and feeding strategies (batch and fed-batch). The highest hydrogen productivity (2.4 LH₂ L⁻¹ d⁻¹) and yield (11.7 molH₂ kg⁻¹Carbohydrates) were verified in low and intermediate organic load rates (12 and 14 g L⁻¹ d⁻¹) and longer cycle time (4 h), respectively. The productivity was favored by fed-batch strategy, and yield by batch. The hydrogen production was verified in both inoculum sources. However, in the assays inoculated from naturally fermented wastewater, with higher organic load rate (18 g L⁻¹ d⁻¹) and intermediate cycle time (3 h) no hydrogen was observed, regardless the feeding strategy, indicating that the inhibitory effects of the indigenous microorganisms present in cassava starch wastewater were more expressive in these conditions. The operational conditions applied to hydrogen production in AnSBBR from cassava starch wastewater may influence the microflora development in the reactor. In this study three possible scenarios were verified: hydrogen-producing bacteria (HPB) growth; hydrogen-producing bacteria inhibition or coexistence between ones and lactic acid bacteria (LAB), which are autochthones of this wastewater.     

Enhancement of bio-hydrogen generation by spirulina via an electrochemical photo-bioreactor (EPBR)

The biological production of hydrogen by microalgae is considered as an advantageous process. However, its yields are sometimes limited. To go beyond this limit, the improvement of the H₂ generation rate by Spirulina was studied via an electrochemical photo-bioreactor (EPBR). This EPBR led to hydrogen evolution rates of up to 27.49 and 13.37 mol of H₂.d⁻¹.m⁻³ for the anode and cathode chambers, respectively, under 0.3 V voltage and ~2.5 mA current. These results represent about a 4-fold increase compared to the H₂ production rate recorded without the application of a voltage. This increase in bio-hydrogen production is correlated with a drop in the concentration of NADPH. The Electrochemical Sequential Batch Reactor (ESRB) provided a more interesting total production rate which was 2.65 m³ m⁻³ d⁻¹, compared to the batch mode, which gave 1.2 m³ m⁻³.d⁻¹. The results show, for the first time, the boosting effect of the voltage on the metabolism of H₂ production by the Spirulina strain.     

Screening and optimisation of hydrogen production by newly isolated nitrogen-fixing cyanobacterial strains

Recently, there has been a propensity to postpone dealing with the world's climate concerns until later, resulting in a 1.5 °C rise in temperature over the last century. Therefore, interest in biologically derived, inexhaustible energy sources based on solar energy is growing. Cyanobacteria have the potential to produce clean, renewable fuels in the form of hydrogen (H₂) gas, derived from solar energy and water. The current study reports the screening 11 cyanobacterial strains isolated from rice paddies and hotsprings for efficient H₂ producers. According to our findings, H₂ concentrations in the species ranged from 3.6 to 48.9 μmol mg⁻¹ Chl a h⁻¹. H₂ production by isolated species was shown to have a 2% positive influence on oxygen (O₂) and carbon dioxide (CO₂) concentrations and a 2% negative effect on all nitrogen gas (N₂) concentrations. It was discovered that at high CO₂ concentrations, photosynthesis is enhanced but H₂ production is suppressed. Anabaena variabilis BTA-1047 was found to be the most active H₂-producing species, with an H₂ production activity of 21.3 μmol mg⁻¹ Chl a h⁻¹. Moreover, a 1% O₂: 2% CO₂ gas mixture doubled the strain activity of H₂ production. The findings of the study called into the question the notion that only an anaerobic environment is required for H₂ production by N₂-fixing cyanobacterial species and explored whether H₂ productivity can be increased by stimulating the micro-anaerobic environment with a carbon source.     

Polyaniline sensitized Pt@TiO2 for visible-light-driven H2 generation

Polyaniline is a typical conducting polymer with high migration electron rate, good stability, eco-friendly properties, and high absorption coefficients for visible light. In the present study, polyaniline decorated Pt@TiO₂ for visible light-driven H₂ generation is reported for the first time. The above-mentioned nanocomposite is prepared through a simple oxidative-polymerization and characterized by infrared spectroscopy, transmission electron microscopy, X–ray diffraction, thermogravimetric analysis, and ultraviolet–visible diffuse reflectance spectra. Polyaniline modification improves the absorption of the nanocomposite in visible light region via a photosensitization effect similar to dye–sensitization but does not influence the crystal structure and size of Pt@TiO₂. The polyaniline modified Pt@TiO₂ exhibits a remarkable visible light activity (61.8 μmol h⁻¹ g⁻¹) and good stability for H₂ generation (with an average apparent quantum yield of 10.1%) with thioglycolic acid as an electron donor. This work provides new insights into using conducting polymers, including polyaniline, as a sensitizer to modify Pt@TiO₂ for visible-light hydrogen generation.     

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.     

Wind-powered 250 kW electrolyzer for dynamic hydrogen production: A pilot study

Alkaline water electrolysis is the most promising approach for the industrial production of green hydrogen. This study investigates the dynamic operational characteristics of an industrial-scale alkaline electrolyzer with a rated hydrogen production of 50 m³/h. Strategies for system control and equipment improvement in dynamic-mode alkaline electrolytic hydrogen production are discussed. The electrolyzer can operate over a 30%–100% rated power load, thereby facilitating high-purity (>99.5%) H₂ production, competitive DC energy efficiency (4.01–4.51 kW h/Nm³ H₂, i.e., 73.1%–65.0% LHV), and good gas–liquid fluid balance. A safe H₂ content of 2% in O₂ (50% LFL) can be guaranteed by adjusting the system pressure. In transient operation, the electrolyzer can realize minute-level power and pressure modulation with high accuracy. The results confirm that the proposed alkaline electrolyzer can absorb highly fluctuating energy output from renewables because of its capability to operate in a dynamic mode.     

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.     

High-efficiency of novel hierarchical 3D macroporous g-C3N4 material on solar-driven photocatalytic water-splitting for hydrogen evolution

The use of multi-pore nanostructured g-C₃N₄ photocatalysts is an efficient approach to separate photogenerated charge carriers and increase visible light photocatalytic performance. Recent progress has yielded nanostructured material through hard templating, which limits potential applications. Integrating the 2D building block into multidimensional porous structures remains a significant challenge in scalable production. Herein, a novel technique based on P407 bubble clusters templating and fixation by freezing is described for the first time to fabricate a 3D opened-up macroporous g-C₃N₄ nanostructures for photocatalytic H₂ evolution. Three-dimensional hierarchical nanostructures provide more contact active sites and synergistically promote the creation of heterogeneous catalytic interfaces. This feature is very useful for understanding the transfer path of photoinduced charges as well as the origins of the high charge separation efficiency in photocatalytic reactions, thus yielding a remarkable visible light-induced H₂ evolution rate of 4213.6 μmol h⁻¹ g⁻¹, which is nearly 5.6 times (716 μmol h⁻¹ g⁻¹) higher than that of lamellar bulk g-C₃N₄. This newly developed approach offers a promising alternative to synthesize broad-spectral response 3D hierarchal g-C₃N₄ nanostructures and can be extended to assemble other functional nanomaterials as building blocks into macroscopic configurations coupled with electronic modulation strategy simultaneously.     

Turning glycerol surplus into renewable syngas through glycerol steam reforming over a sol-gel Ni–Mo2C-Al2O3 catalyst

In this work, a sol-gel Ni–Mo₂C–Al₂O₃ catalyst is employed for the first time in the glycerol steam reforming for syngas production. Catalyst stability and activity are investigated in the temperature range of 550 °C–700 °C and time on stream up to 30 h. As reaction temperature increases, from 550 °C to 700 °C, H₂ yield boosts from 22% to 60%. The stability test, carried out at milder conditions (600 °C and Gas-Hourly Space-Velocity (GHSV) of 50,000 mL h⁻¹.g_cat⁻¹), shows high catalyst stability, up to 30 h, with final conversion, H₂ yield, and H₂/CO ratio of 95%, 53% and 1.95, respectively. Both virgin and spent catalysts have been characterized by a multitude of techniques, e.g., Atomic-Absorption spectroscopy, Raman spectroscopy, N₂-adsorption-desorption, and Transmission Electron Microscopy (TEM), among others. Regarding the spent catalysts, carbon deposits’ morphology becomes more graphitic as the reaction temperature increases, and the total coke formation is mitigated by increasing reaction temperature and lowering GHSV.     

New cyanobacterial strains for biohydrogen production

Under certain conditions, cyanobacteria can switch from photosynthesis to hydrogen production, which is a good energy carrier. However, the biological diversity of hydrogen-releasing cyanobacteria has a great unexplored potential. This study is aimed to investigate the ability of new strains of cyanobacteria Cyanobacterium sp. IPPAS B-1200, Dolichospermum sp. IPPAS B-1213, and Sodalinema gerasimenkoae IPPAS B-353 to release H₂ and to evaluate the effects of photosystem II inhibitor 3-(3,4-dichlorphenyl)-1,1-dimethylurea (DCMU) on H₂ production under light and dark conditions. The results showed that cultures treated with DCMU produced several times more H₂ than untreated cells. The highest rate of H₂ photoproduction of 4.24 μmol H₂ (mg Chl a h)^?1 was found in a Dolichospermum sp. IPPAS B-1213 culture treated with 20 μM DCMU.     

Titanate quantum dots-sensitized Cu2S nanocomposites for superficial H2 production via photocatalytic water splitting

TiO₂ quantum dots-sensitized Cu₂S (Cu₂S/TiO₂) nanocomposites with varying concentration of TiO₂ QDs are synthesized via a facile two-stage hydrothermal-wet impregnation method. X-ray diffraction analysis confirms the formation of Cu₂S and TiO₂with chalcocite and anatase phases, respectively. The observed shoulder-like absorption peaks indicate the UV–visible light-driven properties of the composite. Morphological analysis reveals that the fabricated Cu₂S/TiO₂ composite consists of Cu₂S with a nano rod-like shape (average length and width of ～856 and ～213 nm, respectively) and nanosheets-like structures (average length and width of ～283 and ～289 nm, respectively), whereas the TiO₂ is formed as quantum dots with a size range of 8.2 ± 0.4 nm. Chemical state analysis shows the presence of Cu⁺, S^2?, Ni²⁺, and O^2? in the nanocomposite. The H₂ evolution rate over the optimized photocatalyst is found to be ～45.6 mmol h^?1g^?1_cat under simulated solar irradiation, which is around 5 and 2.4-fold higher than that of the pristine TiO₂ and Cu₂S, respectively. Continuous H₂ production for 30 h is achieved during time-on-stream experiments, demonstrating the excellent stability and durability of the Cu₂S/TiO₂ photocatalyst for large-scale applications.     

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.     

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.     

The dual capacity of the NiSn alloy/MWCNT nanocomposite for sodium and hydrogen ions storage using porous Cu foam as a current collector

A nanostructured NiSn alloy/multi-walled carbon nanotube (MWCNT) composite was successfully synthesized for highly reversible sodium and hydrogen ions storage by using an electrochemical deposition process on porous Cu foam. The surface morphology of the resulting NiSn alloy/MWCNT nanocomposite was characterized using a field-emission scanning electron microscope, indicating the formation of sphere-like NiSn alloy nanoparticles with an average size of 190 nm. On the other hand, X-ray diffraction analysis, energy dispersive and Fourier transform infrared spectroscopies were employed to determine the crystalline structure, elemental surface and chemical composition of the nanocomposite electrode. The initial sodium discharge capacity of the electrode was maximized at ∼550 mAh g⁻¹ under the current density of 1000 mA g⁻¹, and a high hydrogen discharge capacity of 5200 mAh g⁻¹ was obtained at 1100 mA g⁻¹ after 20 cycles. A comprehensive comparison between the sodium and hydrogen ions capacities in this study and those of the literature for different materials and structures was also performed. Accordingly, the resulting nanocomposite electrode with dual capacity may offer promising applications in both sodium-ion battery and hydrogen storage.     

System optimization for effective hydrogen production via anaerobic digestion and biogas steam reforming

To construct a system for the effective hydrogen production from food waste, the conditions of anaerobic digestion and biogas reforming have been investigated and optimized. The type of agitator and reactor shape affect the performance of anaerobic digestion reactors. Reactors with a cubical shape and hydrofoil agitator exhibit high performance due to the enhanced axial flow and turbulence as confirmed by simulation of computational fluid dynamics. The stability of an optimized anaerobic digestion reactor has been tested for 60 days. As a result, 84 L of biogas is produced from 1 kg of food waste. Reaction conditions, such as reaction temperature and steam/methane ratio, affect the biogas steam reforming reaction. The reactant conversions, product yields, and hydrogen production are influenced by reaction conditions. The optimized reaction conditions include a reaction temperature of 700 °C and H₂O/CH₄ ratio of 1.0. Under these conditions, hydrogen can be produced via steam reforming of biogas generated from a two-stage anaerobic digestion reactor for 25 h without significant deactivation and fluctuation.     

Hydrogen production from additive-free formic acid over highly active metal organic frameworks-supported palladium-based catalysts

The metal organic frameworks (MOFs) supported Pd catalysts for H₂ generation from formic acid (FA) were synthesized in this work, via a facile excessive impregnation-low temperature reduction approach. Among the synthetic catalysts, 10% Pd/MOF-Cr (18) displayed a remarkable performance for catalyzing FA dehydrogenation in additive-free aqueous solution, and the corresponding TOF_mid achieved 537.8 h^?1 at 323 K. Furthermore, the bimetallic Ni–Pd alloy catalysts were prepared by the introduction of Ni in the subsequent work. Fortunately, 10% Ni_0.4Pd_0.6/MOF-Cr was found to be a highly active and fairly durable catalyst, exhibiting a TOF_mid as high as 737.9 h^?1 at 323 K with almost 100% X_FA (final) and S_H2, and remained 94% of its original activity in the third cyclic catalysis. Meanwhile, Ni was discovered to be indispensable in increasing the electron density of Pd, downsizing the immobilized metal particles and inhibiting the agglomeration of the loaded nanoparticles.