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.     

Sustainable biohydrogen production by Chlorella sp. microalgae: A review

The use of fossil fuels is causing a huge environmental impact due to the emission of air pollutants, greenhouse gases, and other ground and water contaminants; also, these fuels are depleting; the world is facing an energy crisis in the years to come if no preventive actions are done. Renewable energies are arising as promising technologies that will complement and even replace conventional fuels shifting the global energy matrix to a cleaner and eco-friendly future. Microalgal biohydrogen is one of those emerging technologies that is showing positive results. This work provides an overview of the key parameters to produce hydrogen from microalgae especially from the genus Chlorella. Current status of chemical and biological hydrogen producing technologies is presented, along with the main metabolic processes for this purpose in microalgae, their characteristic enzymes, several strategies to induce hydrogen production, the key operation parameters and finally providing some remarks about scaling-up and industrial-scale applications.     

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.     

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.     

Simultaneous biohydrogen (H2) and bioplastic (poly-β-hydroxybutyrate-PHB) productions under dark,photo, and subsequent dark and photo fermentation utilizing various wastes

The present study is focused on bio hydrogen (H₂) and bioplastic (i.e., poly-β-hydroxybutyrate; PHB) productions utilizing various wastes under dark fermentation, photo fermentation and subsequent dark-photo fermentation. Potential bio H₂ and PHB producing microbes were enriched and isolated. The effects of substrate (rice husk hydrolysate, rice straw hydrolysate, dairy industry wastewater, and rice mill wastewater) concentration (10–100%) and pH (5.5–8.0) were examined in the batch mode under the dark and photo fermentation conditions. Using 100% rice straw hydrolysate at pH 7, the maximum bio H₂ (1.53 ± 0.04 mol H₂/mol glucose) and PHB (9.8 ± 0.14 g/L) were produced under dark fermentation condition by Bacillus cereus. In the subsequent dark-photo fermentation, the highest amounts of bio H₂ and PHB were recorded utilizing 100% rice straw hydrolysate (1.82 ± 0.01 mol H₂/mol glucose and 19.15 ± 0.25 g/L PHB) at a pH of 7.0 using Bacillus cereus (KR809374) and Rhodopseudomonas rutila. The subsequent dark-photo fermentative bio H₂ and PHB productions obtained using renewable biomass (i.e., rice husk hydrolysate and rice straw hydrolysate) can be considered with respect to the sustainable management of global energy sources and environmental issues.     

A review on pretreatment methods,photobioreactor design and metabolic engineering approaches of algal biomass for enhanced biohydrogen production

The development of alternative fuels has been promoted by the extreme fossil fuel consumption brought on by urbanisation and deteriorating pollution. Due to its high energy and combustible qualities, biohydrogen has been perceived as a potential fuel substitute in dealing with issues related to the rising emission of greenhouse gases and global warming. As a source of carbon sequestration and sustainable renewable energy, biohydrogen synthesis by algae species has been prevalent in research scale. This review focuses on the novel and recent metabolic approaches for enhanced algal based biohydrogen production. Pretreatment methods available and scaling techniques used for enhancing the biohydrogen productivity using algal species have been elaborated in the review. Algal characteristics that make them suitable alternative for biohydrogen production are discussed briefly. Various pretreatment methods such as physical, chemical, biological and thermal are elaborated. In addition, the factors involved in influencing the biohydrogen productivity and the metabolic engineering approaches for modifying the pathway in algae are highlighted. Scaling up of process using different types of photobioreactors such as tubular, flat panel, airlift and stirred tank are reported that briefs about merits and demerits of each photobioreactor.     

Integrated process to produce biohydrogen from wheat straw by enzymatic saccharification and dark fermentation

In this study, different pretreatment methods, including lyophilization, hydrothermal pretreatment, and ultrasound combined with dilute alkali post-cooking, were investigated to enhance the efficiency of enzymatic saccharification and biohydrogen production of the wheat straw. All pretreatment methods could effectively remove lignin and hemicellulose while retaining cellulose, further enhancing the biomass accessibility for subsequently enzymatic saccharification and biohydrogen production. A reducing sugar concentration of 13.18 g/L was acquired when wheat straw was treated with ultrasound and dilute alkali cooking (R_U). The sequential fermentative hydrogen yield of the substrate R_U was 133.6 mL/g total solids (TS), which was 5.6-fold larger than that of the raw material (23.9 mL/g TS). The study confirmed that ultrasound combined with dilute alkali cooking was an effective method, which not only provided significant guideline for improving biohydrogen production but also presented helpful direction for the efficient pretreatment of other lignocellulosic biomass.     

Leachate valorization in anaerobic biosystems: Towards the realization of waste-to-energy concept via biohydrogen,biogas and bioelectrochemical processes

Leachate generated in landfills is considered as a hazardous waste stream due to its composition and needs adequate treatment for environmental protection purposes. Nonetheless, a contemporary technology should not only be able to deal with its degradation, but at the same time, recover energy in various forms. Such valorization approaches with priority on these dual-aims are potentially those that rely on anaerobic biosystems. In the literature, processes considered on that matter include fermentative, digestive and bioelectrochemical set-ups to deliver energy-carriers such as biohydrogen (DF), biogas (AD) and electricity (BES), respectively. Moreover, to enhance the global efficiency of leachate utilization, it has been recently trending to develop integrated options by combining these systems (DF, AD, BES) into a cascade scheme. In this review, it is intended to give an insight to the research activities realized in these fields and show possible directions towards the better exploitation of leachate feedstock under anaerobic conditions.     

Hydrogen-rich syngas production by gasification of Urea-formaldehyde plastics in supercritical water

Supercritical water is a promising medium to convert plastics into hydrogen and other recyclable products efficiently. In previous research, supercritical water gasification characteristics investigations focus on thermoplastics instead of thermoset plastics due to its chemical, thermal and mechanical stability. Urea-formaldehyde (UF) plastics were selected as a typical kind of thermoset plastics for investigation in this paper and quartz tubes were used as the reactor in order to avoid the potential catalytic effect of metal reactor wall. Conversion characteristic were studied and the influence of different operating parameters such as temperature, reaction time, feedstock mass fraction and pressure were investigated respectively. The molar fraction of hydrogen could reach about 70% in 700 °C. Products in gas phase and solid phase were analyzed, and properties, chemical structures and inhibition mechanism of thermoset plastics was analyzed after comparing with polystyrene (PS) plastics. The result showed that increase of high temperature and long reaction time could promote gasification process, meanwhile the increase in the feedstock mass fraction would result in suppression of the gasification process. Finally, kinetic study of UF was carried out and the activation energy and pre-exponential factor of the Arrhenius equation were calculated as 30.09 ± 1.62 kJ/mol and 0.1199 ± 0.0049 min⁻¹, respectively.     

Synergistic enhancement of biohydrogen production by supplementing with green synthesized magnetic iron nanoparticles using thermophilic mixed bacteria culture

The production of biohydrogen can be improved by focusing on the nutrients needed by fermentative bacteria like iron. Iron reacts with the [Fe-Fe]-hydrogenase enzyme within the mixed bacteria culture for optimum hydrogen release. Iron nanoparticles (NPs) are attractive due to its unique properties and high reactivity. It can be produced through green synthesis, a more eco-friendly and relatively lower cost process, by using iron salt as precursor and green coconut shell extracted by deep eutectic solvent (DES) as reducing agent. The coconut shell extract consists of phytochemicals that help in producing polydisperse magnetic iron oxide nanoparticles at ～75 nm in size. The addition of optimum concentration of 200 mg Fe/L magnetic iron NPs resulted in the maximum cumulative hydrogen production, glucose utilization and hydrogen yield of 101.33 mL, 9.12 g/L and 0.79 mol H₂/mol glucose respectively. Furthermore, the kinetic analysis on Gompertz model using the optimum magnetic iron NPs concentration showed that the hydrogen production potential (P) and hydrogen production rate (R_m) increased to 50.69 mL and 3.30 mL/h respectively and the lag phase time reduced about 7.12 h as compared with the control experiment (0 mg Fe/L). These results indicated the positive effects of magnetic iron NPs supplementation on fermentative biohydrogen production of mixed bacteria culture and proved the feasibility of adding the magnetic iron NPs as the micronutrient for enhancement of such hydrogen production system.     

Reducing stranded asset risk in off-grid renewable mine sites by including hydrogen production

Mine sites are an ideal candidate to be decarbonised through the installation of variable renewables and storage. However, the operation of mine sites is dependent on many factors, including mineral price, which can vary significantly, leading to periods of inactivity. Therefore, for sites that have invested in renewable generation and storage, there exists a potential of stranded assets, which negatively impact their business case, potentially reducing investment in such equipment and, therefore, decarbonisation potential. The current study therefore has investigated the potential of using variable renewable energy coupled with thermal energy storage and biodiesel to supply heat to a mine site. With the base case established, the economic impact of lower or no mine operations on the net present value were evaluated. To reduce the impact of mine turndown, the potential of installing a hydrogen production facility in an effort to utilise the stranded assets was also undertaken. Preliminary results show the base case to be very economical with a net present cost of $151.4 M after 30 operational years. This value was reduced to $45.7 M and -$81.1 M if the mine only operated at half capacity or did not operate at all, respectively. The addition of hydrogen production powered by the installed variable renewable generation resulted in a slightly better net present value of $174.7 M if the mine operated as normal for 30 years. For the two other cases, the installation of an electrolyser resulted in significantly better results than if it had not been installed for the half capacity and no operation cases with net present costs of $90.9 M and -$7.1 M, respectively. A sensitivity analysis on these results show that while the hydrogen production only plays a minor role in site savings, a price of between $1.1/kg to $2.0/kg is necessary for the system to be economically justifiable. Therefore, the current study shows that the addition of an electrolyser can significantly reduce the risk of stranded assets in fully renewable mine sites by providing an additional revenue stream during mine turndown events.     

Improving inter-plant integration of syngas production technologies by the recycling of CO2 and by-product of the Fischer-Tropsch process

This paper deals with the emission reduction in synthesis-gas production by better integration and increasing the energy efficiency of a high-temperature co-electrolysis unit combined with the Fischer-Tropsch process. The investigated process utilises the by-product of Fischer-Tropsch, as an energy source and carbon dioxide as a feedstock for synthesis gas production. The proposed approach is based on adjusting process streams temperatures with the further synthesis of a new heat exchangers network and optimisation of the utility system. The potential of secondary energy resources was determined using plus/minus principles and simulation of a high-temperature co-electrolysis unit. The proposed technique maximises the economic and environmental benefits of inter-unit integration. Two scenarios were considered for sharing the high-temperature co-electrolysis and the Fischer-Tropsch process. In the first scenario, by-products from the Fischer-Tropsch process were used as fuel for a high-temperature co-electrolysis. Optimisation of secondary energy sources and the synthesis of a new heat exchanger network reduce fuel consumption by 47% and electricity by 11%. An additional environmental benefit is reflected in emission reduction by 25,145 tCO₂/y. The second scenario uses fossil fuel as a primary energy source. The new exchanger network for the high-temperature co-electrolysis was built for different energy sources. The use of natural gas resulted in total annual costs of the heat exchanger network to 1,388,034 USD/y, which is 1%, 14%, 116% less than for coal, fuel oil and LPG, respectively. The use of natural gas as a fuel has the lowest carbon footprint of 7288 tCO₂/y. On the other hand, coal as an energy source has commensurable economic indicators that produce 2 times more CO₂, which can be used as a feedstock for a high-temperature co-electrolysis. This work shows how in-depth preliminary analysis can optimise the use of primary and secondary energy resources during inter-plant integration.     

Hydrogen production using chemical looping technology: A review with emphasis on H2 yield of various oxygen carriers

Natural H₂ in useful quantities is negligible, which makes hydrogen unsuitable as an energy resource compared to other fuels. H₂ production by solar, biological, or electrical sources needs more energy than obtained by combusting it. Lower generation of pollutants and better energy efficiency makes hydrogen a potential energy carrier. Hydrogen finds potential applications in automobile and energy production. However, the cost of producing hydrogen is extremely high. Chemical-looping technology for H₂ generation has caught widespread attention in recent years. This work, presents some recent findings and provides a comprehensive overview of different chemical looping techniques such as chemical looping reforming, syngas chemical looping, coal direct chemical looping, and chemical looping hydrogen generation method for H₂ generation. The above processes are discussed in terms of the relevant chemical reactions and the associated heat of reactions to ascertain the overall endothermicity or exothermicity of the H₂ production. We have compared the H₂ yield data of different Fe/Ni, spinel and perovskites-based oxygen carriers (OC) reported in previous literature. This review is the first comprehensive study to compare the H₂ yield data of all the previously reported oxygen carriers as a function of temperature and redox cycles. In addition, the article summarizes the characteristics and reaction mechanisms of various oxygen carrier materials used for H₂ generation. Lastly, we have reviewed the application of Density Function Theory (DFT) to study the effect of various dopant addition on the efficiency of H₂ production of the oxygen carriers and discussed ASPEN simulations of different chemical looping techniques.     

Analysis and recompilation of kinetic data about the hydrogen production by the catalytic decomposition of hydrous hydrazine

The kinetics of the catalytic decomposition of hydrous hydrazine was determined for the experimental data published in 23 articles. The acquired database contains 139 data sets having 2038 data points. The collected data were analyzed by the integral method, which revealed that hydrazine decomposition follows power-law kinetics. The calculated values of apparent activation energies ranges between 22 and 64 kJ/mol - average value 50.3 kJ/mol, while the reaction orders concerning hydrazine concentration range between 0 and 0.64 - average value 0.33. Analysis showed that the catalyst support significantly impacts the reaction mechanism and activation energy. On average, the catalyst durability was tested by 7.1 cycles, and catalysts retained 69% of their initial activity. The average value of turnover number (TON) is 142, while the estimated value of TON for automotive applications ranges from 10⁵–10⁶, far above the value evaluated on the basis of the reported durability tests.     

Biomass gasification coupled with producer gas cleaning,bottling and HTS catalyst treatment for H2-rich gas production

The aim of the present study is to demonstrate the production of hydrogen-rich fuel gas from J. curcas residue cake. A comprehensive experimental study for the production of hydrogen rich fuel gas from J. curcas residue cake via downdraft gasification followed by high temperature water gas shift catalytic treatment has been carried out. The gasification experiments are performed at different equivalence ratios and performance of the process is reported in terms of producer gas composition & its calorific value, gas production rate and cold gas efficiency. The producer gas is cleaned of tar and particulate matters by passing it through venturi scrubber followed by sand bed filter. The clean producer gas is then compressed at 0.6 MPa and bottled into a gas cylinder. The bottled producer gas and a simulated mixture of producer gas are then subjected to high temperature shift (HTS) catalytic treatment for hydrogen enriched gas production. The effect of three different operating parameters GHSV, steam to CO ratio and reactor temperature on the product gas composition and CO conversion is reported. From the experimental study it is found that, the presence of oxygen in the bottled producer gas has affected the catalyst activity. Moreover, higher concentration of oxygen concentration in the bottled producer gas leads to the instantaneous deactivation of the HTS catalyst.     

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.     

Hydrogen production from phototrophic microorganisms: Reality and perspectives

Hydrogen is a promising alternative to fossil fuel for a source of clean energy due to its high energy content. Some strains of phototrophic microorganisms are known as important object of scientific research and they are being explored to raise biohydrogen (BioH₂) yield. BioH₂ is still not commonly used in industrial area because of the low biomass yield and valuable down streaming process. This article deals with the methods of the hydrogen production with the help of two large groups of phototrophic microorganisms – microalgae and cyanobacteria. Microalgal hydrogen is environmentally friendly alternative to conventional fossil fuels. Algal biomass has been considered as an attractive raw source for hydrogen production. Genetic modified strains of cyanobacteria are used as a perspective object for obtaining hydrogen. The modern photobioreactors and outdoor air systems have been used to obtain the biomass used for hydrogen production. At present time a variety of immobilization matrices and methods are being examined for their suitability to make immobilized H₂ producers.     

Economic viability assessment of sustainable hydrogen production,storage, and utilisation technologies integrated into on- and off-grid micro-grids: A performance comparison of different meta-heuristics

In recent years, there has been considerable interest in the development of zero-emissions, sustainable energy systems utilising the potential of hydrogen energy technologies. However, the improper long-term economic assessment of costs and consequences of such hydrogen-based renewable energy systems has hindered the transition to the so-called hydrogen economy in many cases. One of the main reasons for this is the inefficiency of the optimization techniques employed to estimate the whole-life costs of such systems. Owing to the highly nonlinear and non-convex nature of the life-cycle cost optimization problems of sustainable energy systems using hydrogen as an energy carrier, meta-heuristic optimization techniques must be utilised to solve them. To this end, using a specifically developed artificial intelligence-based micro-grid capacity planning method, this paper examines the performances of twenty meta-heuristics in solving the optimal design problems of three conceptualised hydrogen-based micro-grids, as test-case systems. Accordingly, the obtained numeric simulation results using MATLAB indicate that some of the newly introduced meta-heuristics can play a key role in facilitating the successful, cost-effective development and implementation of hydrogen supply chain models. Notably, the moth-flame optimization algorithm is found capable of reducing the life-cycle costs of micro-grids by up to 6.5% as compared to the dragonfly algorithm.     

MOFs in photoelectrochemical water splitting: New horizons and challenges

Growing energy consumption with the augmentation in universal population to more than nine billion by 2050 and exhausting fossil fuel reserves necessitates a harsh revolution from non-renewable energy reservoirs to renewable energy reservoirs with zero carbon emission. In the present scenario, solar energy prompted photoelectrochemical (PEC) water splitting or “Artificial Photosynthesis” via light gripping semiconductor material, originates out as the most promising methodology in accomplishing the global energy crisis. Recent studies have amply demonstrated the potential of metal-organic frameworks (MOF) towards PEC applications. They are porous crystalline coordination polymers assembled through an appropriate choice of metal ions and multidentate organic ligands. Owing to their structural regularity and synthetic tunability, MOFs integration with PEC is considered in terms of enhancing and broadening light absorption, providing active sites and directing charge transfer dynamics. Here, we have explored MOFs role in PEC and classified them into different categories such as photosensitizers, co-catalysts, counter electrode, template and also for imparting additional stability to the electrode system. MOFs mediated PEC water splitting is promising but is still rare and in its infancy. Therefore, it is pertinent and timely to take stock of the advancements made and develop insight on the use of MOFs, as an emerging solution for the problems encountered in PEC. This review covers the basics of MOF & mainly describes various case studies done during last 10 years and providing adequate impetus to researchers for critically assessing the recent advances and challenges that are faced by scientists and researchers at large.