Biohydrogen production: Current perspectives and the way forward

Global research is moving forward in developing biological production of hydrogen (biohydrogen) as a renewable energy source to alleviate stresses due to carbon dioxide emissions and depleting fossil fuels resource. Biohydrogen has the potential to replace current hydrogen production technologies relying heavily on fossil fuels through electricity generation. While biohydrogen research is still immature, extensive work on laboratory- and pilot-scale systems with promising prospects has been reported. This work presents a review of advances in biohydrogen production focusing on production pathways, microbiology, as well as bioreactor configuration and operation. Challenges and prospects of biohydrogen production are also outlined.     

Biohydrogen yield efficiency and the benefits of dark,photo and dark-photo fermentative production technology in circular Asian economies

Twenty-six new data envelopment analysis (DEA) models with 55 biohydrogen production experiments categorized into three groups including dark fermentation (DF), photo fermentation (PF), and dark-photo sequential fermentation (DF-PF) technologies, are used to evaluate their biohydrogen yield efficiency. The results reveal the average yield efficiencies of DF, PF and DF-PF are 0.2844, 0.3460 and 0.7040, respectively. The most efficient overall combination of biohydrogen inputs is PhBR1/Rhodobacter capsulatus B10/Rhodobacter capsulatus in DF-PF. Statistical tests demonstrate DF-PF has statistically double the efficiency of PF and DF, and the efficiency of PF significantly exceeds that of DF, supporting some of the literature findings. A flexible DEA model must be carefully chosen when evaluating biohydrogen production. All inputs and outputs of biohydrogen statistically influenced yield efficiency to a significant level. India and Japan are the top two economies benefitting from improved biohydrogen yield efficiency. Improving biohydrogen yield efficiency can improve macroeconomic growth and develop the renewable hydrogen and biohydrogen industry.     

Enhancement of biohydrogen production from palm oil mill effluent (POME): A review

Palm oil mill effluent (POME), a wastewater from the most significant agricultural industry in Southeast Asia is produced in tremendous amounts that requires proper management to mitigate its negative environmental effects. The feasibility of treating POME in a closed dark fermentation (DF) system to replace the existing inefficient open ponding treatment has been thoroughly investigated. Theoretically, the maximum H₂ yield obtained by DF process is 4 mol_H2/mol_glucose, however, it is not achievable due to the nature of POME. In this study, several enhancement methods for increasing H₂ yield and DF process stability were discussed. An apprehension into the different pre-treatment methods on POME including physicochemical, chemical and biological and their effects on the characteristics of POME including pH, temperature, sugar content, solid content, viscosity, nutrients and by-product toxicity on the biohydrogen production and effluent quality were reviewed. Various bioreactor designs were used for biohydrogen from POME, the modifications applied on the system design to increase the stability and productivity of POME treatment have been examined. Moreover, higher biohydrogen productivity could be obtained with the addition of nanoparticle nutrients and introducing genetically modified H₂-producing bacteria. Finally, further investigation in the future shall focus on the development of a more inclusive and efficient POME treatment via DF process that favours biohydrogen production, environmental benign and economically viable.     

Approbation of an innovative method of pretreatment of dark fermentation feedstocks

According to the International Energy Agency, only a small part of the full potential of biomass energy is currently used in the world. The annual amount of agricultural waste in the Russian Federation is estimated at about 152 million tons, and the energy potential of animal waste is 201 PJ/year. Anaerobic digestion is an efficient method of converting organic waste into renewable energy sources. Previously, the positive effect of pretreatment of various organic feedstocks in vortex layer apparatus (VLA) on the characteristics of anaerobic digestion and energy efficiency was shown. Currently, there is a significant interest in the world in obtaining biohydrogen from organic waste using the dark fermentation (DF) process. During pretreatment in the VLA, the iron working bodies are abraded and iron particles are introduced into the feedstock of the DF reactor. This may have a positive effect on the production rate and yield of hydrogen, which has not been previously studied. This work is aimed at evaluating the possibility of using the VLA as a method for pretreatment of a dark fermentation feedstock for the intensification of biohydrogen production. To achieve this goal, an experimental setup was constructed. It consisted of a 45 L DF reactor, a VLA and a process control system to collect data on the DF process parameters every 5 min. At a hydraulic retention time in the DF reactor of 24 h and in the VLA of 30 s, the hydrogen content in the biogas increased from 51.1% to 52.2%. At the same time, the pH increased from 3.85 to 4.8–4.9, and the hydrogen production rate increased by 16% to 1.941 L/(L day). The hydrogen yield was 80.9 ml/g VS. Thus, pretreatment of the feedstock in VLA can be an effective way to intensify the DF process; however, further study of the VLA operating modes is required in order to optimize the concentrations of iron particles introduced into the feedstock for the most efficient continuous production of dark fermentative biohydrogen.     

Renewable biohydrogen production from straw biomass – Recent advances in pretreatment/hydrolysis technologies and future development

Straw is an abundant natural bioresource, especially in developing and agricultural countries. Bio-hydrogen production from this renewable biomass through biological methods is an active research area. Because of its distinctive characteristic of being rich in cellulose, straw has been extensively considered as a promising raw material for clean energy production. In this paper, the recent progress of bio-hydrogen production from straw was reviewed with the emphasis on the advances in pretreatment and hydrolysis technologies. The future development of straw-based biohydrogen production was also analyzed. Based on the physicochemical properties of straw biomass and mechanisms of bio-hydrogen fermentation, various pretreatment procedures have been developed to make the straw substrate more available for hydrogen-producing bacteria to realize large-scale bio-hydrogen production from straw. This review summarized the recent technologies of straw pretreatment and hydrolysis as well as elaborated on the bottlenecks in the field of straw biotransformation in great detail. Furthermore, based on the current technology status and potential, the challenges, prospects and future directions of the production methods were further proposed.     

Dark fermentative biohydrogen production from confectionery wastewater in continuous-flow reactors

The production of biohydrogen from industrial wastewater through the dark fermentation (DF) process has attracted increased interest in recent years. To implement a DF process on a large scale, a thorough knowledge of laboratory scale process control is required. The operating parameters and design features of the reactors have a great influence on the efficiency of the process. In this work, the possibility of continuous production of biohydrogen from confectionery wastewater was evaluated. The DF process was carried out at 37 ± 1 °C in two different reactors: an upflow anaerobic filter (AF) and a fluidized bed reactor (AFB). Polyurethane foam (PU) was used to immobilize the biomass. The DF process was studied at four hydraulic retention times (HRT) (1.5, 2.5, 7.5 and 15 days) and the corresponding organic loading rates (OLR) (9.21, 6.12, 2.04 and 1.02 g COD_init/(L day)). The highest hydrogen yield (HY) (44.73 ml/g COD_init) and hydrogen production rate (HPR) (92.5 ml/(L day)) was observed in AFB at HRT of 7.5 days and 2.5 days, respectively. The highest concentration of hydrogen in biogas was 34% in AF and 36% in AFB at HRT of 7.5 days. In contrast to AF, the COD removal efficiency in AFB increased with increasing HRT. The pH of the effluent was low (3.95–4.38). However, due to the use of PU for biomass immobilization, it is possible that there were local zones in the reactor that were optimal for the functioning of not only acidogens, but also methanogens. This was evidenced by a rather high content of methane in biogas (2.5% in AF and 9.6% in AFB at HRT of 15 days). These results provide valuable data for optimizing the continuous DF of wastewater from confectionery and other food industries to produce biohydrogen or biohythane.     

Multiscale mixing analysis and modeling of biohydrogen production by dark fermentation

Hydrogen production by dark fermentation (DF) from wastewater, food waste, and agro-industrial waste combines the advantages to be renewable, sustainable and environmentally friendly. But this attractive process involves a three-phase gas-liquid-solid system highly sensitive to mixing conditions. However, mixing is usually disregarded in the conventional strategies for enhancing biohydrogen productivity, even though H₂ production can be doubled, e.g. versus of reactor design (0.6–1.5 mol H₂/mol hexose). The objective of this review paper is, therefore, to highlight the key effects of mixing on biohydrogen production among the abiotic parameters of DF. First, the pros and cons of the different modes of mixing in anaerobic digesters are described. Then, the influence of mixing on DF is discussed using recent data from the literature and theoretical analysis, focusing on the multiphase and multiscale aspects of DF. The methods and tools available to quantify experimentally the role of mixing both at the local and global scales are summarized. The 0-D to 3-D strategies able to implement mixing in fermentation modeling and scale-up procedures are examined. Finally, the perspectives in terms of process intensification and scale-up tools using mixing optimization are discussed with the issues that are still to be solved.     

Biohydrogen purification by membranes: An overview on the operational conditions affecting the performance of non-porous,polymeric and ionic liquid based gas separation membranes

Many types of membranes are available to enrich hydrogen. Nevertheless, there are some with special potential for biohydrogen purification such as the non-porous, polymeric and ionic liquid based membranes. The attractiveness of these membranes comes from the fact that they can be employed nearly under the conditions where biohydrogen formation taking place. Therefore, they appear as promising candidates to be coupled with hydrogen producing bioreactors and hence giving the chance for in situ biohydrogen concentration. It is known that the feasibility and efficiency of membrane technology – beside material selection and module design – significantly depend on the separation circumstances. Thus, the operation of membranes is a key issue and the most important factors to be considered for gas purification are the composition of gas to be separated, the pressure and temperature applied. The scope of this study is to give a comprehensive overview on the recent applications of non-porous, polymeric and ionic liquid supported membranes for biohydrogen recovery, placing emphasis on the operational conditions affecting membrane's behavior and performance. Furthermore, a novel concept for integrated biohydrogen production and purification using gas separation membranes is demonstrated and discussed.     

Strategies for improvement of biohydrogen production from organic-rich wastewater: A review

Biohydrogen can be produced from organic wastewater but the process is limited by low production yields. The aim of this review is to summarize the production strategies which are recently researched for enhancing biohydrogen yield and productivity from organic wastewater. The survey of published work indicates that the dark hydrogen fermentation is the most promising production mode. Current strategies geared towards improving biohydrogen production include: microbial culture immobilization, bioreactor modifications, the optimization of process conditions (temperature, pH, OLR and HRT), culture selection and enrichments, substrate choice, and the metabolic engineering of biohydrogen specialists. Comparative analysis of energy recovery from anaerobic digestion using vinasse-related substrates indicates that the production of methane has a higher energy yield than production of hydrogen. A sequential combination of biohydrogen and biomethanation production phases has the potential for even higher bioenergy recovery from organic wastewater.     

Mathematical model of biohydrogen production in microbial electrolysis cell: A review

Microbial electrolysis cell (MEC) is a promising reactor. However, currently, the reactor cannot be adapted for industrial-scale biohydrogen production. Nevertheless, this drawback can be overcome by modeling studies based on mathematical equations. The limitation of analytical instrumentation to record the non-linearity of the dynamic behavior for biohydrogen processes in an MEC has led to the introduction of computational approach that has the potential to reduce time constraints and optimize experimental costs. Reviews of comparative studies on bioelectrochemical models are widely reported, but there is less emphasis on the MEC model. Therefore, in this paper, a comprehensive review of the MEC mathematical model will be further discussed. The classification of the model with respect to the assumptions, model improvement, and extensive studies based on the model application will be critically analyzed to establish a methodology algorithm flow chart as a guideline for future implementation.     

Assessment via the modified gompertz-model reveals new insights concerning the effects of ionic liquids on biohydrogen production

Lignocellulosic biofuel, in particular hydrogen gas production is governed by successful feedstock pretreatment, hydrolysis and fermentation. In these days, remarkable attention is paid to the use of ionic liquids to make the fermentable regions of lignocellulose biomass more accessible to the biocatalysts. Although these compounds have great potential for this purpose, their presence during the consecutive fermentation stage may pose a threat on process stability due to certain toxic effects. This, however, has not been specifically elaborated for dark fermentative biohydrogen generation. Hence, in this work, two common imidazolium-type ionic liquids (1-butyl-3-methylimidazolium acetate, ([bmim][Ac]) and 1-butyl-3-methylimidazolium chloride, ([bmim][Cl])) were employed in mixed culture biohydrogen fermentation to investigate the possible impacts related to their presence and concentrations. The batch assays were evaluated comparatively via the modified Gompertz-model based on the important parameters characterizing the process, namely the biohydrogen production potential, maximum biohydrogen production rate and lag-phase time.     

Cladophora sp. as a sustainable feedstock for dark fermentative biohydrogen production

Macroalgae are rich in carbohydrates which can be used as a promising substrate for fermentative biohydrogen production. In this study, Cladophora sp. biomass was fermented for biohydrogen production at various inoculum/substrate (I/S) ratios against a control of inoculum without substrate in laboratory-scale batch reactors. The biohydrogen production yield ranged from 40.8 to 54.7 ml H₂/g-VS, with the I/S ratio ranging from 0.0625 to 4. The results indicated that low I/S ratios caused the overloaded accumulation of metabolic products and a significant pH decrease, which negatively affected hydrogen production bacteria's metabolic activity, thus leading to the decrease of hydrogen fermentation efficiency. The overall results demonstrated that Cladophora sp. biomass is an efficient fermentation feedstock for biohydrogen production.     

Study on the environment-resource-economy comprehensive efficiency evaluation of the biohydrogen production technology

Focusing on the incompatible measurement of the environment property, resources property and economy property, the article aims to make a generalized environment-resource-economy analysis of the processes and to present an overview of different biohydrogen production technologies from the standpoint of the mass production and the whole commercialization chain. One part of the model is the emergy comprehensive efficiency index calculation model, the other is the ternary diagram of structure coefficient for emergy input. The model is used to the organic wastewater of the biohydrogen industrialization demonstration project, and then compared with other biohydrogen and typical renewable energy production technologies. The outputs indicate that the industrialization efficiency of biohydrogen production is available. After the application case of demonstration project, the exploratory work enlightens the similar literature from several aspects. Firstly, the efficiency evaluation model supplies a scientific judgment foundation stone for future laboratory research. Secondly, it provides an alternative theoretical logic to optimize the operation and decision-making of the industrialization and commercialization of the new technologies. Thirdly, it provides a new perspective and quantitative calculation method to effectively integrate that the components comprehensive efficiency of biohydrogen technology change with the different technology processes.     

Biohydrogen production from wastewater-based microalgae: Progresses and challenges

Microalgae originating from wastewater has been exhibiting particularly promising results in terms of biohydrogen production and wastewater treatment. This paper aims to review the factors affecting production, pretreatment techniques to improve synthesis, advanced technologies utilized for enhancing biohydrogen production, and techno-economic feasibility evaluation of the processes at a commercial scale. Microalgae possess metabolic components to synthesize biohydrogen using photobiological and fermentative processes but must undergo pretreatment for efficient biohydrogen production. The efficiency of these processes is influenced by factors such as the microalgae species, light intensity, cell density, pH, temperature, substrates, and the type of bioreactors. Moreover, many limitations, such as oxygen sensitivity, altered thylakoid constitution, low photon conversion efficiency, light capture disruption, and the evolution of harmful by-products hinder the sustainability of biohydrogen production processes. High operational and maintenance costs serve as the major bottleneck in the scaling up of the process as an industrial technology. Therefore, future research needs to be directed towards increasing optimization of the processes by reducing energy and resource demand, recycling metabolic wastes and process components, genetically engineered microalgae to adopt more efficient routes, and conducting pilot studies for commercialization.     

Modeling and simulation of net energy gain by dark fermentation

For dark fermentation (DF) to be accepted as a sustainable process for biohydrogen production, the net energy gain should be positive and as high as possible. A theoretical approach is proposed in this study to evaluate the net energy gain possible from hydrogen generated by the DF process as well as from the end products of DF via anaerobic digestion (AD) and microbial fuel cells (MFC). Experimental data on hydrogen evolution and aqueous end products formation from sucrose and from sucrose/dairy manure blends were used to validate the proposed approach for estimating net energy gain via DF, DF + AD, DF + MFC. Good agreement was found between the experimental and predicted net energy gain values, with overall correlation coefficient of 0.998. Based on the results of this study, DF + MFC is recommended as the best combination to maximize net energy gain.     

Modeling microbial growth of dynamic membrane in a biohydrogen production bioreactor

Biohydrogen is renewable and has a huge potential to replace fossil fuels. Understanding mechanisms of controlling microbial processes of the dynamic membrane is critical for effective dark fermentative biohydrogen production in a dynamic membrane bioreactor (DMBR). This paper aims to develop a sophisticated model of biofilm growth, dynamic membrane formation, and dark fermentative hydrogen production within a platform of coupled lattice Boltzmann and cellular automata. The model was validated against the experimental data available and then was applied for the investigation of biohydrogen production in bioreactors under different membrane structures and inlet velocities. The results showed that porous twisted channels in the dynamic membrane could significantly affect biohydrogen extraction and biofilm patterns. In all cases, the dynamic membrane formation has three phases: the initial bacteria deposit, stable biofilm growth, and stable maximum biofilm biomass. The biohydrogen production could increase by 16.4% by optimizing the porous structure and increase 30%–40% of the hydrogen extraction. Inlet velocity also affects biohydrogen extraction in a range of ?28.3%–71.2%. Both porous structure and inlet velocity would be critical operational parameters for continuous biohydrogen production. The present model demonstrated its capability to investigate dark fermentative hydrogen production and its potential applications to porous bioreactors.     

Efficiency and economic benefit of dark-fermentative biohydrogen production in Asian circular economies: Evaluation using soft-link methodology with data envelopment analysis (DEA) and computable general equilibrium model (CGE)

This study combines a data envelopment analysis, a dynamic computable general equilibrium model with estimated secondary material flows for circular economy, based on economist Joseph Schumpeter's macroeconomic theory, to develop a novel soft-link model to determine the efficiency of forty-three dark-fermentative technology of biohydrogen, and technology improvement impacts on biohydrogen output and supply price for six major emerging Asian countries. The integrated model is found to be feasible.This study finds that efficiency of continuous technology significantly exceeds that of batch technology. Biomass substrate concentration is the most important input in the generation of biohydrogen statistically; pH influences the efficiency of the batch technology, and the efficiency of continuous production technologies significantly exceeds that of batch technologies, but still have a gap to improve to full production efficiency for most of continuous technologies. India and China generate highest output growth of biohydrogen in baseline scenario. Japan and India can most benefit from improvements in batch and continuous biohydrogen production technology. The models and results of this study provides guidelines and references for decision-makers in industry and government who are responsible for reforming future energy policy.     

Application of nanotechnology in dark fermentation for enhanced biohydrogen production using inorganic nanoparticles

Fermentation is an important innovation by mankind and this process is used for converting organic substrate into useful products. Using natural conditions, specifically, light and dark conditions, photo-fermentation and dark fermentation techniques can be developed and operated under controlled conditions. Generally, products such as biofuels, bioactive compounds and enzymes have been produced using the dark fermentation method. However, the major requirement for today's industralized world is biofuels in its clean and pure forms. Biohydrogen is the most efficient and cleanest form of energy produced using dark fermentation of organic substrates. Nevertheless, the quantity of biohydrogen produced via dark fermentation is low. In order to increase the product quantity and quality, several internal and external stress or alterations are made to conventional fermentation conditions. In recent times, nanotechnology has been introduced to enhance the rate of dark fermentation. Nanoparticles (NPs), specifically, inorganic NPs such as silver, iron, titanium oxide and nickel have increased the production rate of biohydrogen. Therefore, the present review focuses on exploring the potential of nanotechnology in the dark fermentation of biohydrogen production, the mechanisms involved, substrates used and changes to be made to increase the production efficiency of dark fermentation.     

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.     

Screening of biohydrogen production based on dark fermentation in the presence of nano-sized Fe2O3 doped metal oxide additives

Increasing the biohydrogen production efficiency through the dark fermentation process has become the biggest challenge in recent years. We aim to enhance biohydrogen production yield by adding nano-sized iron oxide doped metal oxides prepared by the wet impregnation method. Biohydrogen production in the presence of additives was evaluated by the screening of (i) type (Fe₂O₃@Al₂O₃, Fe₂O₃@ZrO₂, and Fe₂O₃@TiO₂) and (ii) concentration (0–200 mg/L) of additives. During the screening of additive type, approximately 14 wt% nano-sized (6 nm) hematite (Fe₂O₃) doped Al₂O₃ showed the highest improvement for biohydrogen production yield among all additives. Batch experiments conducted through dark fermentation demonstrated that 50 mg/L Fe₂O₃@Al₂O₃ addition caused an acceleration in biohydrogen production by 34% and an increment in yield by 15%, despite even low concentrations Al₂O₃ addition inhibited the process.