Biomass-derived Hydrogen Research Articles

A thermodynamic view on the in-situ carbon dioxide reduction by biomass-derived hydrogen during calcium carbonate decomposition

In the carbonate industry, deep decarbonization strategies are necessary to effectively remediate CO2. These strategies mainly include both sustainable energy supplies and the conversion of CO2 in downstream processes. This study developed a coupled process of biomass chemical looping H2 production and reductive calcination of CaCO3. Firstly, a mass and energy balance of the coupled process was established in Aspen Plus. Following this, process optimization and energy integration were implemented to provide optimized operation conditions. Lastly, a life cycle assessment was carried out to assess the carbon footprint of the coupled process. Results reveal that the decomposition temperature of CaCO3 in an H2 atmosphere can be reduced to 780 oC (generally around 900 oC), and the conversion of CO2 from CaCO3 decomposition reached 81.33% with an H2:CO ratio of 2.49 in gaseous products. By optimizing systemic energy through heat integration, an energy efficiency of 86.30% was achieved. Additionally, the carbon footprint analysis revealed that the process with energy integration had a low GWP of -2.624 kgCO2-eq·kg-CaO-1. Conclusively, this work performed a systematic analysis of introducing biomass-derived H2 into CaCO3 calcination and demonstrated the positive role of reductive calcination using green H2 in mitigating CO2 emissions within the carbonate industry.

Exploring Hydrogen Sources in Catalytic Transfer Hydrogenation: A Review of Unsaturated Compound Reduction.

Catalytic transfer hydrogenation has emerged as a pivotal chemical process with transformative potential in various industries. This review highlights the significance of catalytic transfer hydrogenation, a reaction that facilitates the transfer of hydrogen from one molecule to another, using a distinct molecule as the hydrogen source in the presence of a catalyst. Unlike conventional direct hydrogenation, catalytic transfer hydrogenation offers numerous advantages, such as enhanced safety, cost-effective hydrogen donors, byproduct recyclability, catalyst accessibility, and the potential for catalytic asymmetric transfer hydrogenation, particularly with chiral ligands. Moreover, the diverse range of hydrogen donor molecules utilized in this reaction have been explored, shedding light on their unique properties and their impact on catalytic systems and the mechanism elucidation of some reactions. Alcohols such as methanol and isopropanol are prominent hydrogen donors, demonstrating remarkable efficacy in various reductions. Formic acid offers irreversible hydrogenation, preventing the occurrence of reverse reactions, and is extensively utilized in chiral compound synthesis. Unconventional donors such as 1,4-cyclohexadiene and glycerol have shown a good efficiency in reducing unsaturated compounds, with glycerol additionally serving as a green solvent in some transformations. The compatibility of these donors with various catalysts, substrates, and reaction conditions were all discussed. Furthermore, this paper outlines future trends which include the utilization of biomass-derived hydrogen donors, the exploration of hydrogen storage materials such as metal-organic frameworks (MOFs), catalyst development for enhanced activity and recyclability, and the utilization of eco-friendly solvents such as glycerol and ionic liquids. Innovative heating methods, diverse base materials, and continued research into catalyst-hydrogen donor interactions are aimed to shape the future of catalytic transfer hydrogenation, enhancing its selectivity and efficiency across various industries and applications.

Cutting-edge technological advancements in biomass-derived hydrogen production

Cutting-edge technological advancements in biomass-derived hydrogen production

Performance evaluation of desulfurization and environmental impact of using waste from mines as adsorbent

This study aims to reduce the environmental impact of impurity adsorption systems on hydrogen production. Biomass is a carbon-neutral hydrogen fuel with a low environmental impact. However, during the production of biomass-derived hydrogen (biohydrogen), the hydrogen sulfide contained in the gasified biomass reduces the performance of fuel cells when hydrogen is used. Generally, hydrogen sulfide (H 2 S) is removed via impurity adsorption. However, common adsorbents such as metal oxides have a significant environmental impact. Therefore, adsorbents with lower environmental impacts are required. Thus, to improve metal depletion from the circular economy perspective, this study proposes using neutralized sediment, a waste product from the mining wastewater treatment, as an H 2 S adsorbent. In this study, we discuss the environmental impact of H 2 S adsorption systems that use neutralized sediments as adsorbents. Although the use of waste materials has a small environmental impact, it is necessary to consider the environmental impact of the inputs and outputs related to waste material generation based on life cycle assessment (LCA). Because fossil fuel-generated electricity and chemical neutralizers are input in mine wastewater treatment, the use of neutralized sediment may have a large environmental impact than the use of metal oxides from the viewpoint of LCA. Therefore, we quantitatively evaluated the environmental impact of neutralized sediment using LCA and investigated whether the environmental impact of using neutralized sediment is less than that of using metal oxides. In addition, it is not appropriate to include the production stage in the system boundary to meet the LCA standards because mineral water treatment, which is the production stage of neutralized sediment, is conducted whether neutralized sediment is utilized or not as an H 2 S adsorbent. Therefore, an LCA that does not include the production stage was also conducted to indicate the environmental benefit of waste utilization according to the actual situation. The amount of neutralized sediment used, which is calculated by the sulfur capture capacity, is necessary for the LCA calculation. However, the sulfur capture capacity of neutralized sediment has never been investigated. Hence, dynamic adsorption tests were conducted during gasification at low (40–120 °C) and high (200–300 °C) temperatures to investigate the sulfur capture capacity of the neutralized sediment in each temperature range. The results showed that the sulfur capture capacity of the neutralized precipitates was 2.28 (at 40 °C) and 5.73 (at 300 °C) g S/100 g sorbent. The results of the LCA, with and without including the neutralized sediment production process, based on the sulfur capture capacity, demonstrated that the use of neutralized sediment as an adsorbent improved the global warming potential (GWP) by 75.1% and 98.9%, respectively, compared with the use of metal oxides. In other words, this study quantitatively indicated that the use of neutralized sediment as H 2 S adsorbents has a smaller environmental impact than existing adsorbents and shows the importance of considering the actual situation in LCA for waste utilization.

Energy and environmental assessment of hydrogen from biomass sources: Challenges and perspectives

Hydrogen is considered as one of the pillars of the European decarbonisation strategy, boosting a novel concept of the energy system in line with the EU's commitment to achieve clean energy transition and reach the European Green Deal carbon neutrality goals by 2050. Hydrogen from biomass sources can significantly contribute to integrate the renewable hydrogen supply through electrolysis at large-scale production. Specifically, it can cover the non-continuous production of green hydrogen coming from solar and wind energy, to offer an alternative solution to such industrial sectors necessitating of stable supply. Biomass-derived hydrogen can be produced either from thermochemical pathways (i.e., pyrolysis, liquefaction, and gasification) or from biological routes (i.e., direct or indirect-biophotolysis, biological water–gas shift reaction, photo- and dark-fermentation). The paper reviews several production pathways to produce hydrogen from biomass or biomass-derived sources (biogas, liquid bio-intermediates, sugars) and provides an exhaustive review of the most promising technologies towards commercialisation. While some pathways are still at low technology readiness level, others such as the steam bio-methane reforming and biomass gasification are ready for an immediate market uptake. The various production pathways are evaluated in terms of energy and environmental performances, highlighting the limits and barriers of the available LCA studies. The paper shows that hydrogen production technologies from biomass appears today to be an interesting option, almost ready to constitute a complementing option to electrolysis.

LCA analysis and quantification of adsorption performance of Kanuma clay by simultaneous adsorption of H2S and NH3

In recent years, fuel cell (FC) applications have shown promise in contributing to the abatement of greenhouse gas (GHG) emissions, thereby expanding the demand for hydrogen fuel. Currently, non-renewable sources such as fossil fuels are the primary source of hydrogen. Therefore, for mitigating the GHG emissions during the hydrogen production phase, the focus has been directed toward biomass-derived hydrogen (Bio-H2) production processes. In this study, the environmental impact of Bio-H2 production from sewage sludge has been discussed. The bio-syngas contain various impurities, such as H2S, HCl, and NH3. These impurities could damage the performance of the FC operation. Our previous experimental studies have proposed the use of hydroxyl aluminum silicate clay (HAS-Clay) as an adsorbent in the impurity removal process. HAS-Clay can adsorb a significant amount of H2S by physisorption and is an environment-friendly adsorbent. However, it was found that NH3 decreased the adsorption performance of HAS-Clay. The life cycle assessment revealed that any reduction of eco-burden would be less obtained. Therefore, in this study, Kanuma clay (Kc), which is a natural resource, was used to first adsorb NH3 and aim for maintaining the adsorption performance of HAS-Clay. Kc adsorption capacities of H2S and NH3 have been obtained. However, the adsorption capacity in the simultaneous adsorption of H2S and NH3 has never been investigated. Thus, in this study, the simultaneous adsorption of H2S and NH3 was conducted using an adsorption column with the adsorbents as Kc and HAS-Clay. Finally, the environmental burden of the system was assessed.

Non-stationary and LCA analysis of impurity adsorption using Kanuma clay and HAS-Clay in a Bio-H production system

In recent years, fuel cell (FC) applications have shown potential in the reduction of greenhouse gas (GHG) emissions, leading to an increase in demand for hydrogen fuel. The current source of hydrogen is generally fossil fuel origin. Therefore, for mitigating GHG emissions in the hydrogen production stage, we focused on the biomass-derived hydrogen (Bio-H2) production process. In this study, we discuss the environmental impacts of Bio-H2 through the biomass pyrolysis process of Blue Tower (BT) biomass gasification. The bio-syngas contains H2S, HCl, and NH3 as impurities, which can reduce the performance of FCs. In our previous experimental studies, we used hydroxyl aluminum silicate clay (HAS-Clay) as an adsorbent for removing impurities. However, based on the life cycle assessment methodology, it was found that the impact of HAS-Clay was higher, indicating that the environmental contribution of the one through operation using HAS-Clay would be lower. Thus, in this study, using Kanuma clay, which is a natural resource and lower impact adsorbent, we used the desulfurization test and designed an optimal process to mitigate its eco-burden and maintain removal performance. Finally, using the dynamic process simulator of ANSYS fluent (2020 R1), we compared the proposed process to the conventional process in terms of plant performance and evaluated the environmental impacts. The results showed that there was a 12.3% reduction in GWP due to the replacement of Kanuma clay and HAS-Clay as compared to ZnO, a chemical adsorbent.

Delivering carbon negative electricity, heat and hydrogen with BECCS – Comparing the options

Biomass can be converted into a range of different end-products; and when combined with carbon capture and storage (CCS), these processes can provide negative CO2 emissions. Biomass conversion technologies differ in terms of costs, system efficiency and system value, e.g. services provided, market demand and product price. The aim of this study is to comparatively assess a combination of BECCS pathways to identify the applications which offer the most valuable outcome, i.e. maximum CO2 removal at minimum cost, ensuring that resources of sustainable biomass are utilised efficiently. Three bioenergy conversion pathways are evaluated in this study: (i) pulverised biomass-fired power plants which generate electricity (BECCS), (ii) biomass-fuelled combined heat and power plants (BE-CHP-CCS) which provide both heat and electricity, and (iii) biomass-derived hydrogen production with CCS (BHCCS). The design and optimisation of the BECCS supply chain network is evaluated using the Modelling and Optimisation of Negative Emissions Technology framework for the UK (MONET-UK), which integrates biogeophysical constraints and a wide range of biomass feedstocks. The results show that indigenous sources of biomass in the UK can remove up to 56 MtCO2/yr from the atmosphere without the need to import biomass. Regardless of the pathway, Bio-CCS deployment could materially contribute towards meeting a national CO2 removal target and provide a substantial contribution to a national-scale energy system. Finally, it was more cost-effective to deploy all three technologies (BECCS, BE-CHP-CCS and BHCCS) in combination rather than individually.

Enhanced hydrogen production from catalytic biomass gasification with in-situ CO2 capture

In order to cope with the global energy crisis and environmental pollution problems, there are urgent needs for clean energy such as biomass-derived hydrogen. CaO is effective to promote hydrogen production from biomass gasification due to its high capacity of in-situ CO2 capture. In this work, a two-stage fixed bed reactor was used to produce hydrogen by catalytic conversion of biomass with and without in-situ CO2 capture. In addition, three Ni loadings (5 wt%, 10 wt%, and 20 wt%) supported by Al2O3 and sol-gel CaO have been prepared and tested. The BET analysis shows the surface area of the catalysts increases first and then decreases with the increase of Ni loading. Results from high-resolution transmission electron microscopy (HRTEM) images reveals that NiO particles are well distributed over the porous CaO. The X-ray diffraction (XRD) analysis indicates the NiO nanocrystalline size is increased with increasing Ni loading on Ni/Al2O3, and the most homogeneous dispersion was shown by 10 wt% Ni/CaO. Around 666 mgCO2/gCaO of CO2 adsorption capacity and 850 min stability were obtained using the sol-gel CaO sorbent. Compared to the reference Ni/Al2O3 catalysts, the resistance of carbon deposition on the Ni/CaO results in a lower coke deposition, which is attributed to the basicity of the catalysts. In addition, the increase of loading promotes the decomposition of biomass-derived oxygenated compounds. Much more hydrogen is obtained using the Ni/CaO catalysts compared with Ni/Al2O3 due to in-situ CO2 capture. However, the sintering and particle agglomeration using the 20 wt% Ni-catalyst might be responsible for the reduction of hydrogen production. The highest H2 concentration of 19.32 vol% at 424 °C was obtained when the 10 wt% Ni/CaO catalyst was used.

Effect of hydrogen donor on glycerol hydrodeoxygenation to 1,2-propanediol

Abstract The effect of various biomass-derived hydrogen donors in liquid phase hydrodeoxygenation of glycerol to 1,2-propanediol over Cu:Zn:Al catalyst is investigated. The effectiveness of each H2 donor (methanol, formic acid, ethanol, ethylene glycol, 2-propanol, 1-propanol, 2-butanol, 1-butanol and tert-butanol) is compared with that of glycerol and water in the feed. When glycerol serves as H2 source, mostly via aqueous phase reforming, it is converted by 68.1%, showing moderate selectivity to 1,2-propanediol (40.9%). Improved catalytic results are obtained with the addition of a H2 donor molecule in the feed. Except for ethylene glycol and formic acid, H2 donors’ presence in the feed and especially at increased concentration, enhances the activity and the target product yield, without affecting the distribution of hydrodeoxygenation products. In terms of hydrogen production and 1,2-propanediol formation, methanol is the best H2 donor (74% 1,2-propanediol yield), followed by 2-propanol (59.6% 1,2-propanediol yield). Formic acid has also potential as H2 donor, as its activity in the catalytic hydrogen transfer is favored at low H₂ donor/ glycerol molar ratios.

Hydrogen production via steam reforming of acetic acid over biochar-supported nickel catalysts

Development of high-performance and low-cost catalysts will make the biomass-derived hydrogen production technology, steam reforming of bio-oil, becomes to be more and more economical and promising. Biochar, which was produced via fast pyrolysis of rice husk, was activated by different methods, and then it was used as a support for the nickel catalyst, and tested in the steam reforming of acetic acid. The physicochemical properties of the Ni/biochar (BCx) catalysts were characterized by BET, XRD, SEM, TEM and H2-TPR. The development of pore structure and improvement of surface properties were achieved by the activation. Subsequently, the activity of several catalysts on hydrogen production was investigated. It was found that the Ni/BC4 catalyst (biochar activated by KOH alkalization coupled with HNO3 reflux) exhibited the best catalytic performance. Under the conditions of T = 700 °C, S/C = 2.5 and LHSV = 10 h−1, the carbon conversion and hydrogen yield reached to 91.2% and 71.2%, respectively.

Transient Impurity Concentration of Absorption and Desorption in Metal Hydride

Biomass-derived hydrogen (Bio-H2) has been attracting much attention as a low environmental load type of hydrogen. Among the potential applications of Bio-H2, use as a fuel for polymer electrolyte membrane fuel cells (PEMFCs) would require the removal of contaminants. Therefore, we propose the use of metal hydride for the purification and storage of Bio-H2. Metal hydride can store a larger volumetric amount of hydrogen than that other hydrogen storage, and the hydrogenate is processed at near atmospheric pressure and room temperature. In addition, by exploiting the selective hydrogen absorption properties of metal hydride, we have successfully reduced the concentration of methane in the hydrogen using metal hydride, the storage performance of which was evaluated in our previous study. Pressure swing adsorption was used to reduce the contaminant concentration, which was measured as 3% of methane. For practical application, the hydrogen recovery rate over the hydrogen absorption and desorption processes is evaluated.

A Review on the Production and Purification of Biomass-Derived Hydrogen Using Emerging Membrane Technologies

Hydrogen energy systems are recognized as a promising solution for the energy shortage and environmental pollution crises. To meet the increasing demand for hydrogen, various possible systems have been investigated for the production of hydrogen by efficient and economical processes. Because of its advantages of being renewable and environmentally friendly, biomass processing has the potential to become the major hydrogen production route in the future. Membrane technology provides an efficient and cost-effective solution for hydrogen separation and greenhouse gas capture in biomass processing. In this review, the future prospects of using gas separation membranes for hydrogen production in biomass processing are extensively addressed from two perspectives: (1) the current development status of hydrogen separation membranes made of different materials and (2) the feasibility of using these membranes for practical applications in biomass-derived hydrogen production. Different types of hydrogen separation membranes, including polymeric membranes, dense metal membranes, microporous membranes (zeolite, metal-organic frameworks (MOFs), silica, etc.) are systematically discussed in terms of their fabrication methods, gas permeation performance, structure stability properties, etc. In addition, the application feasibility of these membranes in biomass processing is assessed from both practical and economic perspectives. The benefits and possibilities of using membrane reactors for hydrogen production in biomass processing are also discussed. Lastly, we summarize the limitations of the currently available hydrogen membranes as well as the gaps between research achievements and industrial application. We also propose expected research directions for the future development of hydrogen gas membrane technology.

An Overview of Biomass-fuelled Proton Exchange Membrane Fuel Cell (PEMFC) Systems

Abstract PEMFC fuelled by biomass-derived hydrogen is an efficient and sustainable energy system for small-scale residential applications. Gasification and anaerobic digestion combined with steam reforming are seen as the most suitable conversion processes for hydrogen production. Since the biomass-derived hydrogen contains many kinds of contaminants including CO, CO2, H2S, NH3 and N2, extensive work has been done on the mechanism and mitigation methods for their poisoning the PEMFC. Although the biomass-fuelled PEMFC systems have been tested in several experiments and checked through simulation work for different perspectives, further research and demonstration work are required to improve the system efficiency and reliability.

F221005 マイクロ燃料電池 : バイオ水素の可能性(【F22100】高付加価値エネルギー変換の最前線,マイクロ・ナノ工学部門企画,先端技術フォーラム)

F221005 マイクロ燃料電池 : バイオ水素の可能性(【F22100】高付加価値エネルギー変換の最前線,マイクロ・ナノ工学部門企画,先端技術フォーラム)

Enhancement of hydrogen production by secondary metal oxide dopants on NiO/CaO material for catalytic gasification of empty palm fruit bunches

The increase of fossil fuel burning to meet massive energy demands has resulted in major environmental problems. Extensive green house gas emissions and the depletion of non-renewable resources have promoted the use of hydrogen as an alternative energy source. Empty palm fruit bunches (EFB) are a type of agricultural waste that have a high potential for use as a sustainable biomass feedstock for hydrogen production. This study is focused on generation of biomass-derived hydrogen through catalytic biomass gasification using a modified CaO-based catalyst. The catalyst was prepared by adding 5% Ni as a primary dopant, followed by the addition of secondary dopants (La, K, Co, Fe) through a wet impregnation method, and characterised by X-ray diffractometer (XRD), N2 adsorption (BET) and Thermogravimetric Analysis (TGA). The synthesised catalysts were used as the primary catalysts in the reaction and were tested in temperature programmed gasification (TPG). The reaction was carried out in a partial oxygen environment by incorporating the biomass with the catalyst in a ratio of 1:2 from 50 to 900 °C and the product gases were detected by an online mass spectrometer. Interestingly, the addition of secondary dopants significantly increased the hydrogen production with notable changes in the CO2 absorption capacity of the catalyst. Moreover, K, Co and Fe dopants showed tar reforming properties and the highest hydrogen yield was observed with K as the added catalyst.

A strategy for introducing modern bioenergy into developing Asia to avoid dangerous climate change

This paper explores the cost-effective strategy for introducing modern bioenergy into developing Asia through the 21st century under a 400 ppmv CO 2 stabilization constraint using a global energy model that treats the bioenergy sector in detail. The major conclusions are the following. First, under the 400 ppmv CO 2 stabilization constraint, it is cost-effective to use modern bioenergy largely to generate heat and replace direct coal use in developing Asia in the first half of the century, because direct heat generation from modern biomass is efficient and expected to achieve large CO 2 reduction. As second-generation bioenergy conversion technologies (mainly gasification-based technologies) become mature in the second half of the century, it becomes cost-effective to introduce biomass-derived hydrogen, electricity, and Fischer–Tropsch synfuels and bioethanol produced using these technologies into developing Asia instead of modern biomass-derived heat. All biomass gasification-based conversion technologies are combined with CO 2 capture and storage from 2060, which enables negative CO 2 emissions and makes a substantial contribution to achieving the stringent climate stabilization target. Second, due to its small availability of biomass resources, large-scale import of biofuels and wood pellets is inevitable in developing Asia except southeastern Asia under the CO 2 constraint used here. It is shown that this contributes to diversifying liquid fuel import sources and improving energy security in developing Asia. Third, sensitivity analysis shows that these findings are robust to bioenergy-related cost parameters.

Biomass-derived hydrogen from an air-blown gasifier

The goal of this research is to produce high concentrations of hydrogen from gasification of biomass. Air-blown gasification of biomass in fluidized bed reactors produces relatively low concentrations of hydrogen (about 8 vol.%). Steam reforming of tars and light hydrocarbons and reacting steam with carbon monoxide via the water–gas shift reaction can increase hydrogen content in the producer gas to almost 30 vol.%. In these experiments, the temperature, space velocity, and steam/gas ratio were varied to determine the effect of these variables on hydrogen production. Characterization of the catalysts by X-ray photoelectron spectroscopy (XPS) and BET analysis was also performed. These analyses showed that coke and small quantities of sulfur and chlorine deposited on the catalysts, although catalytic deactivation was not evident during the tests.