Production & Supply Chain
Hydrogen Generation from Wood Chip and Biochar by Combined Continuous Pyrolysis and Hydrothermal Gasification
Jun 2021
Publication
Hydrothermal gasification (HTG) experiments were carried out to extract hydrogen from biomass. Although extensive research has been conducted on hydrogen production with HTG limited research exists on the use of biochar as a raw material. In this study woodland residues (wood chip) and biochar from wood-chip pyrolysis were used in HTG treatment to generate hydrogen. This research investigated the effect of temperature (300–425 °C) and biomass/water (0.5–10) ratio on gas composition. A higher temperature promoted hydrogen production because the water–gas shift reaction and steam-reforming reaction were promoted with an increase in temperature. The methane concentration was related positively to temperature because of the methanation and hydrogenation reactions. A lower biomass/water ratio promoted hydrogen production but suppressed carbon-monoxide production. Most reactions that produce hydrogen consume water but water also affects the water–gas shift reaction balance which decreases the carbon-monoxide concentration. By focusing on the practical application of HTG we attempted biochar treatment by pyrolysis (temperature of heating part: 700 °C) and syngas was obtained from hydrothermal treatment above 425 °C.
Synthetic Natural Gas Production from CO2 and Renewable H2: Towards Large-scale Production of Ni–Fe Alloy Catalysts for Commercialization
Apr 2020
Publication
Synthetic natural gas (SNG) is one of the promising energy carriers for the excessive electricity generated from variable renewable energy sources. SNG production from renewable H2 and CO2 via catalytic CO2 methanation has gained much attention since CO2 emissions could be simultaneously reduced. In this study Ni–Fe/(MgAl)Ox alloy catalysts for CO2 methanation were prepared via hydrotalcite precursors using a rapid coprecipitation method. The effect of total metal concentration on the physicochemical properties and catalytic behavior was investigated. Upon calcination the catalysts showed high specific surface area of above 230 m2 g−1. Small particle sizes of about 5 nm were obtained for all catalysts even though the produced catalyst amount was increased by 10 times. The catalysts exhibited excellent space-time yield under very high gas space velocity (34000 h−1) irrespective of the metal concentration. The CO2 conversions reached 73–79% at 300 °C and CH4 selectivities were at 93–95%. Therefore we demonstrated the potential of large-scale production of earth-abundant Ni–Fe based catalysts for CO2 methanation and the Power-to-Gas technology.
Power-to-gas for Injection into the Gas Grid: What Can We Learn from Real-life Projects, Economic Assessments and Systems Modelling
Sep 2018
Publication
Power-to-gas is a key area of interest for decarbonisation and increasing flexibility in energy systems as it has the potential both to absorb renewable electricity at times of excess supply and to provide backup energy at times of excess demand. By integrating power-to-gas with the natural gas grid it is possible to exploit the inherent linepack flexibility of the grid and shift some electricity variability onto the gas grid. Furthermore provided the gas injected into the gas grid is low-carbon such as hydrogen from renewable power-to-gas then overall greenhouse gas emissions from the gas grid can be reduced.<br/>This work presents the first review of power-to-gas to consider real-life projects economic assessments and systems modelling studies and to compare them based on scope assumptions and outcomes. The review focuses on power-to-gas for injection into the gas grid as this application has specific economic technical and modelling opportunities and challenges.<br/>The review identified significant interest in and potential for power-to-gas in combination with the gas grid however there are still challenges to overcome to find profitable business cases and manage local and system-wide technical issues. Whilst significant modelling of power-to-gas has been undertaken more is needed to fully understand the impacts of power-to-gas and gas grid injection on the operational behaviour of the gas grid taking into account dynamic and spatial effects.
EU Hydrogen Strategy: A Case for Urgent Action Towards Implementation
Jul 2020
Publication
Interest in hydrogen as one route to the decarbonisation of energy systems has risen rapidly over the past few years with the publication of a number of hydrogen strategies from countries across the global energy economy. The momentum in Europe has increased sharply this month with the publication of an EU strategy to incorporate hydrogen into its plans for a net zero emission future. This Comment reviews the key elements of this strategy and provides an initial commentary on the main goals. We highlight the challenges that will be faced in meeting hydrogen production targets in particular via the “green hydrogen” route and analyse the plans for expanding the consumption of hydrogen in Europe. We also assess the infrastructure questions that will need to be answered if and when hydrogen takes on a greater role in the region and note the extensive state support that will be needed in the early years of the implementation of the strategy. Despite this though we applaud the ambition laid out by the EU and look forward to the provision of more detailed plans over the coming months and years.
Link to document on OIES website
Link to document on OIES website
Hollow Cobalt Sulfide Nanocapsules for Electrocatalytic Selective Transfer Hydrogenation of Cinnamaldehyde with Water
Feb 2021
Publication
Designing nanostructured electrocatalysts for selective transfer hydrogenation of α β-unsaturated aldehydes with water as the hydrogen source is highly desirable. Here a facile self-templating strategy is designed for the synthesis of CoS2 and CoS2-x nanocapsules (NCs) as efficient cathodes for selective transfer hydrogenation of cinnamaldehyde a model α β-unsaturated aldehyde. The hollow porous structures of NCs are rich in active sites and improve mass transfer resulting in high turnover frequency. The specific adsorption of the styryl block on pristine CoS2 NCs is conducive to the selective formation of half-hydrogenated hydrocinnamaldehyde with 91.7% selectivity and the preferential adsorption of the C = O group induced by sulfur vacancies on defective CoS2-x NCs leads to the full-hydrogenated hydrocinnamyl alcohol with 92.1% selectivity. A cross-coupling of carbon and hydrogen radicals may be involved in this electrochemical hydrogenation reaction. Furthermore this selective hydrogenation method is also effective for other α β-unsaturated aldehydes illustrating the universality of the method.
Power-to-fuels Via Solid-oxide Electrolyzer: Operating Window and Techno-economics
May 2019
Publication
Power-to-fuel systems via solid-oxide electrolysis are promising for storing excess renewable electricity by efficient electrolysis of steam (or co-electrolysis of steam and CO2) into hydrogen (or syngas) which can be further converted into synthetic fuels with plant-wise thermal integration. Electrolysis stack performance and durability determine the system design performance and long-term operating strategy; thus solid-oxide electrolyzer based power-to-fuels were investigated from the stack to system levels. At the stack level the data from a 6000-h stack testing under laboratory isothermal conditions were used to calibrate a quasi-2D model which enables to predict practical isothermal stack performance with reasonable accuracy. Feasible stack operating windows meeting various design specifications (e.g. specific syngas composition) were further generated to support the selection of operating points. At the system level with the chosen similar stack operating points various power-to-fuel systems including power-to-hydrogen power-to-methane power-to-methanol (dimethyl ether) and power-to-gasoline were compared techno-economically considering system-level heat integration. Several operating strategies of the stack were compared to address the increase in stack temperature due to degradation. The modeling results show that the system efficiency for producing H2 methane methanol/dimethyl ether and gasoline decreases sequentially from 94% (power-to-H2) to 64% (power-to-gasoline) based on a higher heating value. Co-electrolysis which allows better heat integration can improve the efficiency of the systems with less exothermic fuel-synthesis processes (e.g. methanol/dimethyl ether) but offers limited advantages for power-to-methane and power-to-gasoline systems. In a likely future scenario where the growing amount of electricity from renewable sources results in increasing periods of a negative electricity price solid oxide electrolyser based power-to-fuel systems are highly suitable for levelling the price fluctuations in an economic way.
Recent Advances in Seawater Electrolysis
Jan 2022
Publication
Hydrogen energy as a clean and renewable energy has attracted much attention in recent years. Water electrolysis via the hydrogen evolution reaction at the cathode coupled with the oxygen evolution reaction at the anode is a promising method to produce hydrogen. Given the shortage of freshwater resources on the planet the direct use of seawater as an electrolyte for hydrogen production has become a hot research topic. Direct use of seawater as the electrolyte for water electrolysis can reduce the cost of hydrogen production due to the great abundance and wide availability. In recent years various high-efficiency electrocatalysts have made great progress in seawater splitting and have shown great potential. This review introduces the mechanisms and challenges of seawater splitting and summarizes the recent progress of various electrocatalysts used for hydrogen and oxygen evolution reaction in seawater electrolysis in recent years. Finally the challenges and future opportunities of seawater electrolysis for hydrogen and oxygen production are presented.
Laser Induced Hydrogen Emission from Ethanol with Dispersed Graphene Particles
Apr 2021
Publication
Efficient hydrogen emission from ethanol with disperse graphene foam particles by using a continuous wave infrared laser diode is reported. The products of ethanol dissociation - hydrogen methane and carbon oxide were measured using mass spectrometry. It was found that the most efficient generation of hydrogen was observed when graphene particles were irradiated by a focused laser beam proceeded at the surface of ethanol solution. The process was assisted by intense white light emission resulting from the laser induced multiphoton ionization of graphene combined with the simultaneous emission of hot electrons. The hot electron emission enables the efficient dissociation of ethanol molecules located close to the solution surface with graphene foam particles.
Comprehensive Study on Hydrogen Production via Propane Steam Reforming Inside a Reactor
Feb 2021
Publication
In the proton exchange membrane fuel cells the required hydrogen must be produced in some way. The power generators in the path of these fuel cells generally include a steam reactor that through other fuels provides the needed energy to produce hydrogen. This study investigates a steam reactor powered by propane fuel consisting of a shell and tube heat exchanger. The shell contains a catalyst that receives the mixture of propane and steam and the tubes embedded inside the reformer contain hot gases that provide a suitable substrate for the reaction. Velocity and temperature fields inside the reformer species concentration control and reaction rate are studied. The conversion of reactants and yield of products are investigated according to the reaction rate. The results show that the hydrogen production yield can vary from 77.5 % to 92.2 %. The reaction rate can be controlled by the velocity and temperatures of the hot gases. However for the T=900 K full propane consumption is achieved at the reformer outlet.
A Review of the CFD Modeling of Hydrogen Production in Catalytic Steam Reforming Reactors
Dec 2022
Publication
Global demand for alternative renewable energy sources is increasing due to the consumption of fossil fuels and the increase in greenhouse gas emissions. Hydrogen (H2 ) from biomass gasification is a green energy segment among the alternative options as it is environmentally friendly renewable and sustainable. Accordingly researchers focus on conducting experiments and modeling the reforming reactions in conventional and membrane reactors. The construction of computational fluid dynamics (CFD) models is an essential tool used by researchers to study the performance of reforming and membrane reactors for hydrogen production and the effect of operating parameters on the methane stream improving processes for reforming untreated biogas in a catalyst-fixed bed and membrane reactors. This review article aims to provide a good CFD model overview of recent progress in catalyzing hydrogen production through various reactors sustainable steam reforming systems and carbon dioxide utilization. This article discusses some of the issues challenges and conceivable arrangements to aid the efficient generation of hydrogen from steam reforming catalytic reactions and membrane reactors of bioproducts and fossil fuels.
Modulating Electronic Structure of Metal-organic Frameworks by Introducing Atomically Dispersed Ru for Efficient Hydrogen Evolution
Mar 2021
Publication
Developing high-performance electrocatalysts toward hydrogen evolution reaction is important for clean and sustainable hydrogen energy yet still challenging. Herein we report a single-atom strategy to construct excellent metal-organic frameworks (MOFs) hydrogen evolution reaction electrocatalyst (NiRu0.13-BDC) by introducing atomically dispersed Ru. Significantly the obtained NiRu0.13-BDC exhibits outstanding hydrogen evolution activity in all pH especially with a low overpotential of 36 mV at a current density of 10 mA cm−2 in 1 M phosphate buffered saline solution which is comparable to commercial Pt/C. X-ray absorption fine structures and the density functional theory calculations reveal that introducing Ru single-atom can modulate electronic structure of metal center in the MOF leading to the optimization of binding strength for H2O and H* and the enhancement of HER performance. This work establishes single-atom strategy as an efficient approach to modulate electronic structure of MOFs for catalyst design.
Boosting Photocatalytic Hydrogen Production from Water by Photothermally Induced Biphase Systems
Feb 2021
Publication
Solar-driven hydrogen production from water using particulate photocatalysts is considered the most economical and effective approach to produce hydrogen fuel with little environmental concern. However the efficiency of hydrogen production from water in particulate photocatalysis systems is still low. Here we propose an efficient biphase photocatalytic system composed of integrated photothermal–photocatalytic materials that use charred wood substrates to convert liquid water to water steam simultaneously splitting hydrogen under light illumination without additional energy. The photothermal–photocatalytic system exhibits biphase interfaces of photothermally-generated steam/photocatalyst/hydrogen which significantly reduce the interface barrier and drastically lower the transport resistance of the hydrogen gas by nearly two orders of magnitude. In this work an impressive hydrogen production rate up to 220.74 μmol h−1 cm−2 in the particulate photocatalytic systems has been achieved based on the wood/CoO system demonstrating that the photothermal–photocatalytic biphase system is cost-effective and greatly advantageous for practical applications.
Membrane-Based Electrolysis for Hydrogen Production: A Review
Oct 2021
Publication
Hydrogen is a zero-carbon footprint energy source with high energy density that could be the basis of future energy systems. Membrane-based water electrolysis is one means by which to produce high-purity and sustainable hydrogen. It is important that the scientific community focus on developing electrolytic hydrogen systems which match available energy sources. In this review various types of water splitting technologies and membrane selection for electrolyzers are discussed. We highlight the basic principles recent studies and achievements in membrane-based electrolysis for hydrogen production. Previously the NafionTM membrane was the gold standard for PEM electrolyzers but today cheaper and more effective membranes are favored. In this paper CuCl–HCl electrolysis and its operating parameters are summarized. Additionally a summary is presented of hydrogen production by water splitting including a discussion of the advantages disadvantages and efficiencies of the relevant technologies. Nonetheless the development of cost-effective and efficient hydrogen production technologies requires a significant amount of study especially in terms of optimizing the operation parameters affecting the hydrogen output. Therefore herein we address the challenges prospects and future trends in this field of research and make critical suggestions regarding the implementation of comprehensive membrane-based electrolytic systems.
Experimental Challenges in Studying Hydrogen Absorption in Ultrasmall Metal Nanoparticles
Jun 2016
Publication
Recent advances on synthesis characterization and hydrogen absorption properties of ultrasmall metal nanoparticles (defined here as objects with average size ≤3 nm) are briefly reviewed in the first part of this work. The experimental challenges encountered in performing accurate measurements of hydrogen absorption in Mg- and noble metal-based ultrasmall nanoparticles are addressed. The second part of this work reports original results obtained for ultrasmall bulk-immiscible Pd–Rh nanoparticles. Carbon-supported Pd–Rh nanoalloys in the whole binary chemical composition range have been successfully prepared by liquid impregnation method followed by reduction at 300°C. EXAFS investigations suggested that the local structure of these nanoalloys is partially segregated into Rh-rich core and Pd-rich surface coexisting within the same nanoparticles. Downsizing to ultrasmall dimensions completely suppresses the hydride formation in Pd-rich nanoalloys at ambient conditions contrary to bulk and larger nanosized (5–6 nm) counterparts. The ultrasmall Pd90Rh10 nanoalloy can absorb hydrogen-forming solid solutions under these conditions as suggested by in situ X-ray diffraction (XRD). Apart from this composition common laboratory techniques such as in situ XRD DSC and PCI failed to clarify the hydrogen interaction mechanism: either adsorption on developed surfaces or both adsorption and absorption with formation of solid solutions. Concluding insights were brought by in situ EXAFS experiments at synchrotron: ultrasmall Pd75Rh25 and Pd50Rh50 nanoalloys absorb hydrogen-forming solid solutions at ambient conditions. Moreover the hydrogen solubility in these solid solutions is higher with increasing Pd content and this trend can be understood in terms of hydrogen preferential occupation in the Pd-rich regions as suggested by in situ EXAFS. The Rh-rich nanoalloys (Pd25Rh75 and Pd10Rh90) only adsorb hydrogen on the developed surface of ultrasmall nanoparticles. In summary in situ characterization techniques carried out at large-scale facilities are unique and powerful tools for in-depth investigation of hydrogen interaction with ultrasmall nanoparticles at local level.
How Do Dissolved Gases Affect the Sonochemical Process of Hydrogen Production: An Overview of Thermodynamic and Mechanistic Effects – On the “Hot Spot Theory”
Dec 2020
Publication
Although most of researchers agree on the elementary reactions behind the sonolytic formation of molecular hydrogen (H2) from water namely the radical attack of H2O and H2O2 and the free radicals recombination several recent papers ignore the intervention of the dissolved gas molecules in the kinetic pathways of free radicals and hence may wrongly assess the effect of dissolved gases on the sonochemical production of hydrogen. One may fairly ask to which extent is it acceptable to ignore the role of the dissolved gas and its eventual decomposition inside the acoustic cavitation bubble? The present opinion paper discusses numerically the ways in which the nature of dissolved gas i.e. N2 O2 Ar and air may influence the kinetics of sonochemical hydrogen formation. The model evaluates the extent of direct physical effects i.e. dynamics of bubble oscillation and collapse events if any against indirect chemical effects i.e. the chemical reactions of free radicals formation and consequently hydrogen emergence it demonstrates the improvement in the sonochemical hydrogen production under argon and sheds light on several misinterpretations reported in earlier works due to wrong assumptions mainly related to initial conditions. The paper also highlights the role of dissolved gases in the nature of created cavitation and hence the eventual bubble population phenomena that may prevent the achievement of the sonochemical activity. This is particularly demonstrated experimentally using a 20 kHz Sinaptec transducer and a Photron SA 5 high speed camera in the case of CO2-saturated water where degassing bubbles are formed instead of transient cavitation.
Enhanced Hydrogen Generation from Hydrolysis of MgLi Doped with Expanded Graphite
Apr 2021
Publication
Hydrolysis of Mg-based materials is considered as a potential means of safe and convenient real-time control of H2 release enabling efficient loading discharge and utilization of hydrogen in portable electronic devices. At present work the hydrogen generation properties of MgLi-graphite composites were evaluated for the first time. The MgLi-graphite composites with different doping amounts of expanded graphite (abbreviated as EG hereinafter) were synthesized through ball milling and the hydrogen behaviors of the composites were investigated in chloride solutions. Among the above doping systems the 10 wt% EG-doped MgLi exhibited the best hydrogen performance in MgCl2 solutions. In particular the 22 h-milled MgLi-10 wt% EG composites possessed both desirable hydrogen conversion and rapid reaction kinetics delivering a hydrogen yield of 966 mL H2 g−1 within merely 2 min and a maximum hydrogen generation rate of 1147 mL H2 min−1 g−1 as opposed to the sluggish kinetics in the EG-free composites. Moreover the EG-doped MgLi showed superior air-stable ability even under a 75 RH% ambient atmosphere. For example the 22 h-milled MgLi-10 wt% EG composites held a fuel conversion of 89% after air exposure for 72 h rendering it an advantage for Mg-based materials to safely store and transfer in practical applications. The similar favorable hydrogen performance of MgLi-EG composites in (simulate) seawater may shed light on future development of hydrogen generation technologies.
Hydrogen-Rich Gas Production from Two-Stage Catalytic Pyrolysis of Pine Sawdust with Nano-NiO/Al2O3 Catalyst
Feb 2022
Publication
Hydrogen production from biomass pyrolysis is economically and technologically attractive from the perspectives of energy and the environment. The two-stage catalytic pyrolysis of pine sawdust for hydrogen-rich gas production is investigated using nano-NiO/Al2O3 as the catalyst at high temperatures. The influences of residence time (0–30 s) and catalytic temperature (500–800 ◦C) on pyrolysis performance are examined in the distribution of pyrolysis products gas composition and gas properties. The results show that increasing the residence time decreased the solid and liquid products but increased gas products. Longer residence times could promote tar cracking and gas-phase conversion reactions and improve the syngas yield H2/CO ratio and carbon conversion. The nano-NiO/A12O3 exhibits excellent catalytic activity for tar removal with a tar conversion rate of 93% at 800 ◦C. The high catalytic temperature could significantly improve H2 and CO yields by enhancing the decomposition of tar and gas-phase reactions between CO2 and CH4 . The increasing catalytic temperature increases the dry gas yield and carbon conversion but decreases the H2/CO ratio and low heating value.
Hydrous Hydrazine Decomposition for Hydrogen Production Using of Ir/CeO2: Effect of Reaction Parameters on the Activity
May 2021
Publication
In the present work an Ir/CeO2 catalyst was prepared by the deposition–precipitation method and tested in the decomposition of hydrazine hydrate to hydrogen which is very important in the development of hydrogen storage materials for fuel cells. The catalyst was characterised using different techniques i.e. X-ray photoelectron spectroscopy (XPS) transmission electron microscopy (TEM) scanning electron microscopy (SEM) equipped with X-ray detector (EDX) and inductively coupled plasma—mass spectroscopy (ICP-MS). The effect of reaction conditions on the activity and selectivity of the material was evaluated in this study modifying parameters such as temperature the mass of the catalyst stirring speed and concentration of base in order to find the optimal conditions of reaction which allow performing the test in a kinetically limited regime.
Electronic Structure and d-Band Center Control Engineering over Ni-Doped CoP3 Nanowall Arrays for Boosting Hydrogen Production
Jun 2021
Publication
To address the challenge of highly efficient water splitting into H2 successful fabrication of novel porous three-dimensional Ni-doped CoP3 nanowall arrays on carbon cloth was realized resulting in an effective self-supported electrode for the electrocatalytic hydrogen-evolution reaction. The synthesized samples exhibit rough curly and porous structures which are beneficial for gaseous transfer and diffusion during the electrocatalytic process. As expected the obtained Ni-doped CoP3 nanowall arrays with a doping concentration of 7% exhibit the promoted electrocatalytic activity. The achieved overpotentials of 176 mV for the hydrogen-evolution reaction afford a current density of 100 mA cm−2 which indicates that electrocatalytic performance can be dramatically enhanced via Ni doping. The Ni-doped CoP3 electrocatalysts with increasing catalytic activity should have significant potential in the field of water splitting into H2. This study also opens an avenue for further enhancement of electrocatalytic performance through tuning of electronic structure and d-band center by doping.
A Tale of Two Phase Diagrams Interplay of Ordering and Hydrogen Uptake in Pd–Au–H
Apr 2021
Publication
Due to their ability to reversibly absorb/desorb hydrogen without hysteresis Pd–Au nanoalloys have been proposed as materials for hydrogen sensing. For sensing it is important that absorption/desorption isotherms are reproducible and stable over time. A few studies have pointed to the influence of short and long range chemical order on these isotherms but many aspects of the impact of chemical order have remained unexplored. Here we use alloy cluster expansions to describe the thermodynamics of hydrogen in Pd–Au in a wide concentration range. We investigate how different chemical orderings corresponding to annealing at different temperatures as well as different external pressures of hydrogen impact the behavior of the material with focus on its hydrogen absorption/desorption isotherms. In particular we find that a long-range ordered L12 phase is expected to form if the H2 pressure is sufficiently high. Furthermore we construct the phase diagram at temperatures from 250 K to 500 K showing that if full equilibrium is reached in the presence of hydrogen phase separation can often be expected to occur in stark contrast to the phase diagram in para-equilibrium. Our results explain the experimental observation that absorption/desorption isotherms in Pd–Au are often stable over time but also reveal pitfalls for when this may not be the case.
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