Institution of Gas Engineers & Managers
Hydrogen Embrittlement in Advanced High Strength Steels and Ultra High Strength Steels: A New Investigation Approach
Dec 2018
Publication
In order to reduce CO2 emissions and fuel consumption and to respect current environmental norms the reduction of vehicles weight is a primary target of the automotive industry. Advanced High Strength Steels (AHSS) and Ultra High Strength Steel (UHSS) which present excellent mechanical properties are consequently increasingly used in vehicle manufacturing. The increased strength to mass ratio compensates the higher cost per kg and AHSS and UHSS are proving to be cost-effective solutions for the body-in-white of mass market products.
In particular aluminized boron steel can be formed in complex shapes with press hardening processes acquiring high strength without distortion and increasing protection from crashes. On the other hand its characteristic martensitic microstructure is sensitive to hydrogen delayed fracture phenomena and at the same time the dew point in the furnace can produce hydrogen consequently to the high temperature reaction between water and aluminum. The high temperature also promotes hydrogen diffusion through the metal lattice under the aluminum-silicon coating thus increasing the diffusible hydrogen content. However after cooling the coating acts as a strong barrier preventing the hydrogen from going out of the microstructure. This increases the probability of delayed fracture. As this failure brings to the rejection of the component during production or even worse to the failure in its operation diffusible hydrogen absorbed in the component needs to be monitored during the production process.
For fast and simple measurements of the response to diffusible hydrogen of aluminized boron steel one of the HELIOS innovative instruments was used HELIOS II. Unlike the Devanathan cell that is based on a double electrochemical cell HELIOS II is based on a single cell coupled with a solid-state sensor. The instrument is able to give an immediate measure of diffusible hydrogen content in sheet steels semi-products or products avoiding time-consuming specimen palladium coating with a guided procedure that requires virtually zero training.
Two examples of diffusible hydrogen analyses are given for Usibor®1500-AS one before hot stamping/ quenching and one after hot stamping suggesting that the increase in the number of dislocations during hot stamping could be the main responsible for the lower apparent diffusivity of hydrogen.
In particular aluminized boron steel can be formed in complex shapes with press hardening processes acquiring high strength without distortion and increasing protection from crashes. On the other hand its characteristic martensitic microstructure is sensitive to hydrogen delayed fracture phenomena and at the same time the dew point in the furnace can produce hydrogen consequently to the high temperature reaction between water and aluminum. The high temperature also promotes hydrogen diffusion through the metal lattice under the aluminum-silicon coating thus increasing the diffusible hydrogen content. However after cooling the coating acts as a strong barrier preventing the hydrogen from going out of the microstructure. This increases the probability of delayed fracture. As this failure brings to the rejection of the component during production or even worse to the failure in its operation diffusible hydrogen absorbed in the component needs to be monitored during the production process.
For fast and simple measurements of the response to diffusible hydrogen of aluminized boron steel one of the HELIOS innovative instruments was used HELIOS II. Unlike the Devanathan cell that is based on a double electrochemical cell HELIOS II is based on a single cell coupled with a solid-state sensor. The instrument is able to give an immediate measure of diffusible hydrogen content in sheet steels semi-products or products avoiding time-consuming specimen palladium coating with a guided procedure that requires virtually zero training.
Two examples of diffusible hydrogen analyses are given for Usibor®1500-AS one before hot stamping/ quenching and one after hot stamping suggesting that the increase in the number of dislocations during hot stamping could be the main responsible for the lower apparent diffusivity of hydrogen.
Direct Numerical Simulation of Hydrogen Combustion at Auto-ignitive Conditions Ignition, Stability and Turbulent Reaction-front Velocity
Mar 2021
Publication
Direct Numerical Simulations (DNS) are performed to investigate the process of spontaneous ignition of hydrogen flames at laminar turbulent adiabatic and non-adiabatic conditions. Mixtures of hydrogen and vitiated air at temperatures representing gas-turbine reheat combustion are considered. Adiabatic spontaneous ignition processes are investigated first providing a quantitative characterization of stable and unstable flames. Results indicate that in hydrogen reheat combustion compressibility effects play a key role in flame stability and that unstable ignition and combustion are consistently encountered for reactant temperatures close to the mixture’s characteristic crossover temperature. Furthermore it is also found that the characterization of the adiabatic processes is also valid in the presence of non-adiabaticity due to wall heat-loss. Finally a quantitative characterization of the instantaneous fuel consumption rate within the reaction front is obtained and of its ability at auto-ignitive conditions to advance against the approaching turbulent flow of the reactants for a range of different turbulence intensities temperatures and pressure levels.
Analyzing the Necessity of Hydrogen Imports for Net-zero Emission Scenarios in Japan
Jun 2021
Publication
With Japan’s current plans to reach a fully decarbonized society by 2050 and establish a hydrogen society substantial changes to its energy system need to be made. Due to the limited land availability in Japan significant amounts of hydrogen are planned to be imported to reach both targets. In this paper a novel stochastic version of the open-source multi-sectoral Global Energy System Model in conjunction with a power system dispatch model is used to analyze the impacts of both availability and price of hydrogen imports on the transformation of the Japanese energy system considering a net-zero emission target. This analysis highlights that hydrogen poses a valuable resource in specific sectors of the energy system. Therefore importing hydrogen can indeed positively impact energy system developments although up to 19mt of hydrogen will be imported in the case with the cheapest available hydrogen. In contrast without any hydrogen imports power demand nearly doubles in 2050 compared to 2019 due to extensive electrification in non-electricity sectors. However hydrogen imports are not necessarily required to reach net-zero emissions. In all cases however large-scale investments into renewable energy sources need to be made.
Enhanced Hydrogen Storage of Alanates: Recent Progress and Future Perspectives
Feb 2021
Publication
The global energy crisis and environmental pollution have caused great concern. Hydrogen is a renewable and environmentally friendly source of energy and has potential to be a major alternative energy carrier in the future. Due to its high capacity and relatively low cost of raw materials alanate has been considered as one of the most promising candidates for hydrogen storage. Among them LiAlH4 and NaAlH4 as two representative metal alanates have attracted extensive attention. Unfortunately the high desorption temperature and sluggish kinetics restrict its practical application. In this paper the basic physical and chemical properties as well as the hydrogenation/dehydrogenation reaction mechanism of LiAlH4 and NaAlH4 are briefly reviewed. The recent progress on strategic optimizations toward tuning the thermodynamics and kinetics of the alanate including nanoscaling doping catalysts and compositing modification are emphatically discussed. Finally the coming challenges and the development prospects are also proposed in this review.
Fuel Cell Power Systems for Maritime Applications: Progress and Perspectives
Jan 2021
Publication
Fuel cells as clean power sources are very attractive for the maritime sector which is committed to sustainability and reducing greenhouse gas and atmospheric pollutant emissions from ships. This paper presents a technological review on fuel cell power systems for maritime applications from the past two decades. The available fuels including hydrogen ammonia renewable methane and methanol for fuel cells under the context of sustainable maritime transportation and their pre-processing technologies are analyzed. Proton exchange membrane molten carbonate and solid oxide fuel cells are found to be the most promising options for maritime applications once energy efficiency power capacity and sensitivity to fuel impurities are considered. The types layouts and characteristics of fuel cell modules are summarized based on the existing applications in particular industrial or residential sectors. The various research and demonstration projects of fuel cell power systems in the maritime industry are reviewed and the challenges with regard to power capacity safety reliability durability operability and costs are analyzed. Currently power capacity costs and lifetime of the fuel cell stack are the primary barriers. Coupling with batteries modularization mass production and optimized operating and control strategies are all important pathways to improve the performance of fuel cell power systems.
Investigation of the Hydrogen Embrittlement Susceptibility of T24 Boiler Tubing in the Context of Stress Corrosion Cracking of its Welds
Dec 2018
Publication
For the membrane and spiral walls of the new USC boilers the advanced T24 material was developed. In 2010 however extensive T24 tube weld cracking during the commissioning phase of several newly built boilers was observed. As the dominant root cause Hydrogen Induced - Stress Corrosion Cracking was reported. An investigation into the interaction of the T24 material with hydrogen was launched in order to compare its hydrogen embrittlement susceptibility with that of the T12 steel commonly used for older boiler evaporators. Both base materials and simulated Heat Affected Zone (HAZ) microstructures were tested. Total and diffusible hydrogen in the materials after electrochemical charging were measured. Thermo Desorption Spectrometry was used to gain insights into the trapping behaviour and the apparent diffusion coefficient at room temperature was determined. Based on the hardness and the diffusible hydrogen pick-up capacity of the materials it was concluded that T12 is less susceptible to hydrogen embrittlement than T24 as base material as well as in the HAZ condition and that the HAZ of T24 is more susceptible to hydrogen embrittlement than the base material both in the as welded and in the Post Weld Heat Treated (PWHT) condition. However based on the results of this investigation it could not be determined if the T24 HAZ is less susceptible to hydrogen embrittlement after PWHT.
Accelerating to Net Zero with Hydrogen Blending Standards Development in the UK, Canada and the US - Part 2
Mar 2021
Publication
Hydrogen is expected to play a critical role in the move to a net-zero economy. However large-scale deployment is still in its infancy and there is still much to be done before we can blend hydrogen in large volumes into gas networks and ramp up the production that is required to meet demands of the energy transport and industry sectors. KTN Global Alliance will host two webinars to explore these challenges and opportunities in hydrogen blending on the 2nd and 3rd March 2021.
Exciting pilot projects are being conducted and explored in the UK Canada and US states such as California to determine the technical feasibility of blending hydrogen into existing natural gas systems. Whilst the deployment of hydrogen is in its early stages there is increasing interest around permitting significant percentage blends of hydrogen into gas networks which would enable the carbon intensity of gas supplies to be reduced creating a new demand for hydrogen and with the use of separation and purification technologies downstream support the transportation of pure hydrogen to markets.
Gaps in codes and standards need to be addressed to enable adoption and there may be opportunities for international collaboration and harmonisation to ensure that best practices are shared globally and to facilitate the growth of trade and export markets. There is an opportunity for the UK Canada and US three G7 countries to work together and show market making leadership in key enabling regulation for the new hydrogen economy.
Delivered by KTN Global Alliance on behalf of the British Consulate-General in Vancouver and the UK Science and Innovation Network in Canada and the US these two webinars will showcase hydrogen blending pilot projects in the UK Canada and California highlighting challenges and opportunities with regard to standards development for hydrogen blending and supporting further transatlantic collaboration in this area. The events also form part of the UK’s international engagement to build momentum towards a successful outcome at COP26 the UN climate summit that the UK will host in Glasgow in November 2021. The webinars will bring together experts from industry academia and policy from the UK Canada and California. Attendees will have an opportunity to ask questions and interact using Mentimeter.
Part 1 Highlights and Perspectives from the UK can be found here.
Exciting pilot projects are being conducted and explored in the UK Canada and US states such as California to determine the technical feasibility of blending hydrogen into existing natural gas systems. Whilst the deployment of hydrogen is in its early stages there is increasing interest around permitting significant percentage blends of hydrogen into gas networks which would enable the carbon intensity of gas supplies to be reduced creating a new demand for hydrogen and with the use of separation and purification technologies downstream support the transportation of pure hydrogen to markets.
Gaps in codes and standards need to be addressed to enable adoption and there may be opportunities for international collaboration and harmonisation to ensure that best practices are shared globally and to facilitate the growth of trade and export markets. There is an opportunity for the UK Canada and US three G7 countries to work together and show market making leadership in key enabling regulation for the new hydrogen economy.
Delivered by KTN Global Alliance on behalf of the British Consulate-General in Vancouver and the UK Science and Innovation Network in Canada and the US these two webinars will showcase hydrogen blending pilot projects in the UK Canada and California highlighting challenges and opportunities with regard to standards development for hydrogen blending and supporting further transatlantic collaboration in this area. The events also form part of the UK’s international engagement to build momentum towards a successful outcome at COP26 the UN climate summit that the UK will host in Glasgow in November 2021. The webinars will bring together experts from industry academia and policy from the UK Canada and California. Attendees will have an opportunity to ask questions and interact using Mentimeter.
Part 1 Highlights and Perspectives from the UK can be found here.
Ultrasonic-assisted Catalytic Transfer Hydrogenation for Upgrading Pyrolysis-oil
Feb 2021
Publication
Recent interest in biomass-based fuel blendstocks and chemical compounds has stimulated research efforts on conversion and upgrading pathways which are considered as critical commercialization drivers. Existing pre-/post-conversion pathways are energy intense (e.g. pyrolysis and hydrogenation) and economically unsustainable thus more efficient process solutions can result in supporting the renewable fuels and green chemicals industry. This study proposes a process including biomass conversion and bio-oil upgrading using mixed fast and slow pyrolysis conversion pathway as well as sono-catalytic transfer hydrogenation (SCTH) treatment process. The proposed SCTH treatment employs ammonium formate as a hydrogen transfer additive and palladium supported on carbon as the catalyst. Utilizing SCTH bio-oil molecular bonds were broken and restructured via the phenomena of cavitation rarefaction and hydrogenation with the resulting product composition investigated using ultimate analysis and spectroscopy. Additionally an in-line characterization approach is proposed using near-infrared spectroscopy calibrated by multivariate analysis and modelling. The results indicate the potentiality of ultrasonic cavitation catalytic transfer hydrogenation and SCTH for incorporating hydrogen into the organic phase of bio-oil. It is concluded that the integration of pyrolysis with SCTH can improve bio-oil for enabling the production of fuel blendstocks and chemical compounds from lignocellulosic biomass.
Detection, Characterization and Sizing of Hydrogen Induced Cracking in Pressure Vessels Using Phased Array Ultrasonic Data Processing
Jul 2016
Publication
Pressure vessels operating in sour service conditions in refinery environments can be subject to the risk of H₂S cracking resulting from the hydrogen entering into the material. This risk which is related to the specific working conditions and to the quality of the steel used shall be properly managed in order to maintain the highest safety at a cost-effective level.<br/>Nowadays the typical management strategy is based on a risk based inspection (RBI) evaluation to define the inspection plan used in conjunction with a fitness for service (FFS) approach in defining if the vessel although presenting dangerous defects such as cracks can still be considered “fit for purpose” for a given time window based on specific fracture mechanics analysis.<br/>These vessels are periodically subject to non-destructive evaluation typically ultrasonic testing. Phased Array (PA) ultrasonic is the latest technology more and more used for this type of application.<br/>This paper presents the design and development of an optimized Phased Array ultrasonic inspection technique for the detection and sizing of hydrogen induced cracking (HIC) type flaws used as reference for comparison. Materials used containing natural operational defects were inspected in “as-service” conditions.<br/>Samples have then been inspected by means of a “full matrix capture” (FMC) acquisition process followed by “total focusing method” (TFM) data post processing. FCM-TFM data have been further post-processed and then used to create a 3D geometrical reconstruction of the volume inspected. Results obtained show the significant improvement that FMC/TFM has over traditional PA inspection techniques both in terms of sensitivity and resolution for this specific type of defect. Moreover since the FMC allows for the complete time domain signal to be captured from every element of a linear array probe the full set of data is available for post-processing.<br/>Finally the possibility to reconstruct the geometry of the component from the scans including the defects present in its volume represents the ideal solution for a reliable data transferring process to the engineering function for the subsequent FFS analysis.
Options for Producing Low-carbon Hydrogen at Scale
Feb 2018
Publication
Low-carbon hydrogen has the potential to play a significant role in tackling climate change and poor air quality. This policy briefing considers how hydrogen could be produced at a useful scale to power vehicles heat homes and supply industrial processes.
Four groups of hydrogen production technologies are examined:
Thermochemical Routes to Hydrogen
These methods typically use heat and fossil fuels. Steam methane reforming is the dominant commercial technology and currently produces hydrogen on a large scale but is not currently low carbon. Carbon capture is therefore essential with this process. Innovative technology developments may also help and research is underway. Alternative thermal methods of creating hydrogen indicate biomass gasification has potential. Other techniques at a low technology readiness level include separation of hydrogen from hydrocarbons using microwaves.
Electrolytic Routes to Hydrogen
Electrolytic hydrogen production also known as electrolysis splits water into hydrogen and oxygen using electricity in an electrolysis cell. Electrolysis produces pure hydrogen which is ideal for low temperature fuel cells for example in electric vehicles. Commercial electrolysers are on the market and have been in use for many years. Further technology developments will enable new generation electrolysers to be commercially competitive when used at scale with fluctuating renewable energy sources.
Biological Routes to Hydrogen
Biological routes usually involve the conversion of biomass to hydrogen and other valuable end products using microbial processes. Methods such as anaerobic digestion are feasible now at a laboratory and small pilot scale. This technology may prove to have additional or greater impact and value as route for the production of high value chemicals within a biorefinery concept.
Solar to Fuels Routes to Hydrogen
A number of experimental techniques have been reported the most developed of which is ‘solar to fuels’ - a suite of technologies that typically split water into hydrogen and oxygen using solar energy. These methods have close parallels with the process of photosynthesis and are often referred to as ‘artificial photosynthesis’ processes. The research is promising though views are divided on its ultimate utility. Competition for space will always limit the scale up of solar to fuels.
The briefing concludes that steam methane reforming and electrolysis are the most likely technologies to be deployed to produce low-carbon hydrogen at volume in the near to mid-term providing that the challenges of high levels of carbon capture (for steam methane reforming) and cost reduction and renewable energy sources (for electrolysis) can be overcome.
Four groups of hydrogen production technologies are examined:
Thermochemical Routes to Hydrogen
These methods typically use heat and fossil fuels. Steam methane reforming is the dominant commercial technology and currently produces hydrogen on a large scale but is not currently low carbon. Carbon capture is therefore essential with this process. Innovative technology developments may also help and research is underway. Alternative thermal methods of creating hydrogen indicate biomass gasification has potential. Other techniques at a low technology readiness level include separation of hydrogen from hydrocarbons using microwaves.
Electrolytic Routes to Hydrogen
Electrolytic hydrogen production also known as electrolysis splits water into hydrogen and oxygen using electricity in an electrolysis cell. Electrolysis produces pure hydrogen which is ideal for low temperature fuel cells for example in electric vehicles. Commercial electrolysers are on the market and have been in use for many years. Further technology developments will enable new generation electrolysers to be commercially competitive when used at scale with fluctuating renewable energy sources.
Biological Routes to Hydrogen
Biological routes usually involve the conversion of biomass to hydrogen and other valuable end products using microbial processes. Methods such as anaerobic digestion are feasible now at a laboratory and small pilot scale. This technology may prove to have additional or greater impact and value as route for the production of high value chemicals within a biorefinery concept.
Solar to Fuels Routes to Hydrogen
A number of experimental techniques have been reported the most developed of which is ‘solar to fuels’ - a suite of technologies that typically split water into hydrogen and oxygen using solar energy. These methods have close parallels with the process of photosynthesis and are often referred to as ‘artificial photosynthesis’ processes. The research is promising though views are divided on its ultimate utility. Competition for space will always limit the scale up of solar to fuels.
The briefing concludes that steam methane reforming and electrolysis are the most likely technologies to be deployed to produce low-carbon hydrogen at volume in the near to mid-term providing that the challenges of high levels of carbon capture (for steam methane reforming) and cost reduction and renewable energy sources (for electrolysis) can be overcome.
Water Photo-Electrooxidation Using Mats of TiO2 Nanorods, Surface Sensitized by a Metal–Organic Framework of Nickel and 1,2-Benzene Dicarboxylic Acid
Apr 2021
Publication
Photoanodes comprising a transparent glass substrate coated with a thin conductive film of fluorine-doped tin oxide (FTO) and a thin layer of a photoactive phase have been fabricated and tested with regard to the photo-electro-oxidation of water into molecular oxygen. The photoactive layer was made of a mat of TiO2 nanorods (TDNRs) of micrometric thickness. Individual nanorods were successfully photosensitized with nanoparticles of a metal–organic framework (MOF) of nickel and 12-benzene dicarboxylic acid (BDCA). Detailed microstructural information was obtained from SEM and TEM analysis. The chemical composition of the active layer was determined by XRD XPS and FTIR analysis. Optical properties were determined by UV–Vis spectroscopy. The water photooxidation activity was evaluated by linear sweep voltammetry and the robustness was assessed by chrono-amperometry. The OER (oxygen evolution reaction) photo-activity of these photoelectrodes was found to be directly related to the amount of MOF deposited on the TiO2 nanorods and was therefore maximized by adjusting the MOF content. The microscopic reaction mechanism which controls the photoactivity of these photoelectrodes was analyzed by photo-electrochemical impedance spectroscopy. Microscopic rate parameters are reported. These results contribute to the development and characterization of MOF-sensitized OER photoanodes.
Energy Transition: Measurement Needs Within the Hydrogen Industry
Dec 2017
Publication
Hydrogen in the UK is beginning to shift from hypothetical debates to practical demonstration projects. An ever-growing evidence base has showcased how the costs of hydrogen and its barriers to entry are reducing such that it now has practical potential to contribute to the decarbonisation of the UK's energy sector.
Despite this hydrogen has yet to have wide commercial uptake due in part to a number of barriers where measurement plays a critical role. To accelerate the shift towards the hydrogen economy these challenges have been identified and prioritised by NPL.
The report Energy transition: Measurement needs within the hydrogen industry outlines the challenges identified. The highest priority issues are:
This Document can be downloaded from their website
Despite this hydrogen has yet to have wide commercial uptake due in part to a number of barriers where measurement plays a critical role. To accelerate the shift towards the hydrogen economy these challenges have been identified and prioritised by NPL.
The report Energy transition: Measurement needs within the hydrogen industry outlines the challenges identified. The highest priority issues are:
- Material development for fuel cells and electrolysers to reduce costs and assess critical degradation mechanisms – extending lifetime and durability is key to the commercialisation of these technologies.
- Impact assessment of added odorant to hydrogen to aid leak detection. Measurement of its impact during pipeline transportation and on the end-use application (particularly fuel cell technology) will be important to provide assurance that it will not affect lifetime and durability.
- Determination of the blend ratio when hydrogen is mixed with natural gas in the gas grid. Accurate flow rate measurement and validated metering methods are needed to ensure accurate billing of the consumer.
- Measurement of the combustion properties of hydrogen including flame detection and propagation temperature and nitrogen oxides (NOx) emissions should it be used for heat applications to ensure existing and new appliances are suitable for hydrogen.
- Assessment of the suitability of existing gas infrastructure and materials for hydrogen transportation. Building an understanding of what adaptations might need to be made to avoid for example air permeation metal embrittlement and hydrogen leakage.
- Validated techniques for hydrogen storage which will require measurement of the efficiency and capacity of each mechanism through robust metering leakage detection and purity analysis to ensure they are optimised for the storage of hydrogen gas.
This Document can be downloaded from their website
Criticality and Life-Cycle Assessment of Materials Used in Fuel-Cell and Hydrogen Technologies
Mar 2021
Publication
The purpose of this paper is to obtain relevant data on materials that are the most commonly used in fuel-cell and hydrogen technologies. The focus is on polymer-electrolyte-membrane fuel cells solid-oxide fuel cells polymer-electrolyte-membrane water electrolysers and alkaline water electrolysers. An innovative methodological approach was developed for a preliminary material assessment of the four technologies. This methodological approach leads to a more rapid identification of the most influential or critical materials that substantially increase the environmental impact of fuel-cell and hydrogen technologies. The approach also assisted in amassing the life-cycle inventories—the emphasis here is on the solid-oxide fuel-cell technology because it is still in its early development stage and thus has a deficient materials’ database—that were used in a life-cycle assessment for an in-depth material-criticality analysis. All the listed materials—that either are or could potentially be used in these technologies—were analysed to give important information for the fuel-cell and hydrogen industries the recycling industry the hydrogen economy as well as policymakers. The main conclusion from the life-cycle assessment is that the polymer-electrolyte membrane water electrolysers have the highest environmental impacts; lower impacts are seen in polymer-electrolyte-membrane fuel cells and solid-oxide fuel cells while the lowest impacts are observed in alkaline water electrolysers. The results of the material assessment are presented together for all the considered materials but also separately for each observed technology.
Controllable H2 Generation by Formic Acid Decomposition on a Novel Pd/Templated Carbon Catalyst
Nov 2020
Publication
A novel Pd/templated carbon catalyst (Pd/TC) was developed characterized and tested in the dehydrogenation of formic acid (FA) under mild conditions with the possibility to control the H2 generation rate in the absence or presence of HCOONa (SF) by adjusting the Pd:FA and/or FA:SF ratios. The characterization results of the templated carbon obtained by the chemical vapor deposition of acetylene on NaY zeolite revealed different structural and morphological properties compared to other C-based supports. Therefore it was expected to induce a different catalytic behavior for the Pd/TC catalyst. Indeed the TC-supported Pd catalyst exhibited superior activity in the decomposition of FA even at room temperature with turnover frequencies (TOFs) of up to 143.7 and 218.8 h−1 at 60 °C. The H2 generation rate increased with an increasing temperature while the H2 yield increased with a decreasing FA concentration. Constant generation of gaseous flow (H2 + CO2) was achieved for 11 days by the complete dehydrogenation of FA at room temperature using a 2 M FA solution and Pd:FA = 1:2100. The presence of SF in the reaction medium significantly enhanced the H2 generation rate (535 h−1 for FA:SF = 3:1 and 60 °C).
Improve Hydrogen Economy for Vehicular Fuel Cell System via Investigation and Control of Optimal Operating Oxygen Excess Ratio
Apr 2022
Publication
This study investigates and controls the optimal operating oxygen excess ratio (OER) for PEMFC which effectively prevents oxygen starvation and improves the hydrogen economy of proton exchange membrane fuel cells (PEMFC). Firstly the PEMFC output characteristic model and the five-order nonlinear air supply system model are established. Moreover an adaptive algebraic observer was developed to observe the partial pressure of gas in PEMFC and further reconstruct OER. Secondly to achieve the minimum hydrogen consumption under the required power the reference OER is determined by analyzing the PEMFC system output power with its minimum current. Finally the super-twisting algorithm is adopted to track reference OER. Simulation results show that the average absolute observation errors of oxygen nitrogen and cathode pressures under the Highway Fuel Economy Test are 1351.1 Pa (5.1%) 1724.2 Pa (0.9%) and 409.9 Pa (1.6%) respectively. The OER adjust average absolute error is 0.03. Compared with the commonly used fixed OER (e.g. OER of 1.5 and 2.3) the optimal OER strategy can reduce the hydrogen consumption of the PEMFC system by 5.2% and 1.8% respectively. Besides a DSP hardware in loop test is conducted to show the real-time performance of the proposed optimal method.
Life Cycle Assessment of Fuel Cell Vehicles Considering the Detailed Vehicle Components: Comparison and Scenario Analysis in China Based on Different Hydrogen Production Schemes
Aug 2019
Publication
Numerous studies concerning the life cycle assessment of fuel cell vehicles (FCVs) have been conducted. However little attention has been paid to the life cycle assessment of an FCV from the perspective of the detailed vehicle components. This work conducts the life cycle assessment of Toyota Mirai with all major components considered in a Chinese context. Both the vehicle cycle and the fuel cycle are included. Both comprehensive resources and energy consumption and comprehensive environmental emissions of the life cycles are investigated. Potential environmental impacts are further explored based on CML 2001 method. Then different hydrogen production schemes are compared to obtain the most favorable solution. To explore the potential of the electrolysis the scenario analysis of the power structure is conducted. The results show that the most mineral resources are consumed in the raw material acquisition stage the most fossil energy is consumed in the use stage and global warming potential (GWP) value is fairly high in all life cycle stages of Toyota Mirai using electrolyzed hydrogen. For hydrogen production schemes the scenario analysis indicates that simply by optimizing the power structure the environmental impact of the electrolysis remains higher than other schemes. When using the electricity from hydropower or wind power the best choice will be the electrolysis.
A Process for Hydrogen Production from the Catalytic Decomposition of Formic Acid over Iridium—Palladium Nanoparticles
Jun 2021
Publication
The present study investigates a process for the selective production of hydrogen from the catalytic decomposition of formic acid in the presence of iridium and iridium–palladium nanoparticles under various conditions. It was found that a loading of 1 wt.% of 2% palladium in the presence of 1% iridium over activated charcoal led to a 43% conversion of formic acid to hydrogen at room temperature after 4 h. Increasing the temperature to 60 °C led to further decomposition and an improvement in conversion yield to 63%. Dilution of formic acid from 0.5 to 0.2 M improved the decomposition reaching conversion to 81%. The reported process could potentially be used in commercial applications.
Enhanced Hydrogen Generation Efficiency of Methanol using Dielectric Barrier Discharge Plasma Methodology and Conducting Sea Water as an Electrode
Aug 2020
Publication
In this work methanol decomposition method has been discussed for the production of hydrogen gas with the application of plasma. A simple dielectric barrier discharge (DBD) plasma reactor was designed for this purpose with two types of electrode. The DBD plasma reactor was experimented by substituting one of the metal electrodes with feebly conducting sea water which yielded better efficiency in producing hydrogen gas. Experimental parameters such as; discharge voltage and time were varied by maintaining a discharge gap of 1.5 mm and the plasma discharge characteristics were studied. Filamentary type micro-discharges were found to be formed which was observed as numerous streamer clusters in the current waveform. Gas chromatographic study confirmed the production of hydrogen gas with residence time around 3.6 min. Although the concentration (%) of H2 was high (98.1 %) and consistent with copper electrode assembly the rate of formation and concentration was found to be the highest (98.7 %) for water electrode for specific discharge voltage. The energy efficiency was found to be 0.5 mol H2/kWh and 1.2 mol H2/kWh for metal (Cu) and water electrodes respectively. The electrode material significantly affects the plasma condition and hence the rate of hydrogen production. Compositional analysis of the water used as electrode showed a minimal change in the composition even after the completion of the experiment as compared to the untreated water. Methanol degradation study shows the presence of untreated methanol in the residue of the plasma reactor which has been confirmed from the absorption spectra.
Instantaneous Hydrogen Production from Ammonia by Non-thermal Arc Plasma Combining with Catalyst
Jul 2021
Publication
Owing to the storage and transportation problems of hydrogen fuel exploring new methods of the realtime hydrogen production from ammonia becomes attractive. In this paper non-thermal arc plasma (NTAP) combining with NiO/Al2O3 catalyst is developed to produce hydrogen from ammonia with high efficiency and large scale. The effects of ammonia gas flow rate and discharge power on the gas temperature electron density the hydrogen production rate and energy efficiency were investigated. Experimental results show that the optical emission spectrum of NTAP working with pure ammonia medium was dominated by the atom spectrum of Hα Hβ and molecular spectrum of NH component. Under the optimum experimental condition of plasma discharge the highest energy efficiency of hydrogen production reached 783.4 L/kW·h at NH3 gas flow rate of 30 SLM. When the catalyst was added and heated by the NTAP simultaneously the energy efficiency further increased to 1080.0 L/kW·h.
Hydrogeochemical Modeling to Identify Potential Risks of Underground Hydrogen Storage in Depleted Gas Fields
Nov 2018
Publication
Underground hydrogen storage is a potential way to balance seasonal fluctuations in energy production from renewable energies. The risks of hydrogen storage in depleted gas fields include the conversion of hydrogen to CH4(g) and H2S(g) due to microbial activity gas–water–rock interactions in the reservoir and cap rock which are connected with porosity changes and the loss of aqueous hydrogen by diffusion through the cap rock brine. These risks lead to loss of hydrogen and thus to a loss of energy. A hydrogeochemical modeling approach is developed to analyze these risks and to understand the basic hydrogeochemical mechanisms of hydrogen storage over storage times at the reservoir scale. The one-dimensional diffusive mass transport model is based on equilibrium reactions for gas–water–rock interactions and kinetic reactions for sulfate reduction and methanogenesis. The modeling code is PHREEQC (pH-REdox-EQuilibrium written in the C programming language). The parameters that influence the hydrogen loss are identified. Crucial parameters are the amount of available electron acceptors the storage time and the kinetic rate constants. Hydrogen storage causes a slight decrease in porosity of the reservoir rock. Loss of aqueous hydrogen by diffusion is minimal. A wide range of conditions for optimized hydrogen storage in depleted gas fields is identified.
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