Japan
Fast Synthesis of TiNi by Mechanical Alloying and its Hydrogenation Properties
Mar 2019
Publication
Mechanical alloying is widely used for the synthesis of hydrogen storage materials. However amorphization and contamination triggered by long-time milling are serious drawbacks for obtaining efficient hydrogen storage. In this work short-time ball milling synthesis is explored for a representative hydride forming compound: TiNi. Through structural morphological and chemical characterizations we evidence that formation of TiNi is complete in only 20 min with minor Fe contamination (0.2 wt%). Cross-sectional analysis of powder stuck on milling balls reveals that alloy formation occurs through the interdiffusion between thin layers of co-laminated pure elements. Hydrogenation thermodynamics and kinetics of short-time mechanically alloyed TiNi are similar to those of coarse-grained compounds obtained by classical high-temperature melting. Mechanical alloying is a suitable method for fast and energy-efficient synthesis of intermetallic compounds such as TiNi.
Effectiveness of a Blower in Reducing the Hazard of Hydrogen Leaking from a Hydrogen-fueled Vehicle
Sep 2013
Publication
To handle a hydrogen fuel cell vehicle (HFCV) safely after its involvement in an accident it is necessary to provide appropriate emergency response information to the first responder. In the present study a forced wind of 10 m/s or faster with and without a duct was applied to a vehicle leaking hydrogen gas at a rate of 2000 NL/min. Then hydrogen concentrations were measured around the vehicle and an ignition test was conducted to evaluate the effectiveness of forced winds and the safety of emergency response under forced wind conditions. The results: 1) Forced winds of 10 m/s or faster caused the hydrogen concentrations in the vicinity of the vehicle to decline to less than the lower flammability limit and the hydrogen gas in the various sections of the vehicles were so diluted that even if ignition occurred the blast-wave pressure was moderate. 2) When the first responder had located the hydrogen leakage point in the vehicle it was possible to lower the hydrogen concentrations around the vehicle by aiming the wind duct towards the leakage point and blowing winds at 10 m/s from the duct exit.
Numerical Investigation of Vented Hydrogen-air Deflagration in a Chamber
Oct 2015
Publication
This paper shows numerical investigation related to hydrogen-air deflagration venting. The aim of this study is to clarify the influence of concentration gradient on the pressure histories and peak pressures in a chamber. The numerical analysis target is a 27 m3 cubic chamber which has 2.6 m2 vent area on the sidewall. The vent opening pressure is set to be gauge 10 kPa. Two different conditions of the hydrogen concentration are assumed which are uniform and gradient. In the uniform case 15 20 25 30 and 35 vol.% concentrations are assumed. In the gradient case the concentration linearly increases from 0 vol.% (at the ground) to 30 40 50 60 70 vol.% (at the ceiling). The initial total mass of hydrogen inside the chamber is the same as the uniform case. Moreover three different ignition points are assumed: on the rear center and the front of the chamber relative to the vent. The deflagrations are initiated by a single ignition source. In most gradient cases the highest peak is lower than in the uniform case though the initial total mass of hydrogen inside the chamber is the same as in the uniform case. This is because the generated burned gas per time is smaller in the gradient case than in the uniform case. In 15 vol.% gradient case however the peak pressure gets higher than in the uniform case. This is because in 15 vol.% gradient case the burning velocity around the ignition point gets faster and the flame surface gets larger which induces larger amount of burned gas per time.
Steam Condensation Effect in Hydrogen Venting from a BWR Reactor Building
Oct 2015
Publication
In the accident of Fukushima Daiichi nuclear power plants hydrogen was accumulated in the reactor buildings and exploded. To prevent such explosions hydrogen venting from reactor buildings is considered. When the gas mixture is released to a reactor building through a reactor containment together with the hydrogen some amount of steam might also be released. The steam condenses if the building atmosphere is below the saturation temperature and it affects the hydrogen behaviour. In this study the condensation effect to the hydrogen venting is evaluated using CFD analyses by comparing the case where a hydrogen-nitrogen mixture is released and the case where a hydrogen-steam mixture is released.
Public Perception on Hydrogen Infrastructure in Japan
Oct 2015
Publication
A public survey was conducted in March 2015 in Japan asking public awareness knowledge perception and acceptance regarding hydrogen hydrogen infrastructure and fuel cell vehicle adopting the same key questions contained in the public surveys conducted six and seven years ago. Changes in answers between two different times of survey implementation were analyzed by comparing results of current survey to those of the previous surveys. Regression analyses were conducted and revealed influence of respondents’ awareness knowledge and perception about hydrogen hydrogen infrastructure and fuel cell vehicle on their acceptance on hydrogen station. We found a large increase in the awareness and relatively a small improvement on knowledge on hydrogen energy hydrogen infrastructure and fuel cell vehicle from the previous surveys. In contrast we did not find much changes in perception of risk and benefit perception on hydrogen society and hydrogen station and public acceptance of hydrogen infrastructure. Through the regression analyses we found large influences of negative risk perception of hydrogen itself and technology of hydrogen station and perception of necessity of hydrogen station on public acceptance of hydrogen station and the small influence of time background on the acceptance. Through the results of analyses implications to public communication in building public infrastructure are presented.
Low-carbon Energy Transition With the Sun and Forest: Solar-driven Hydrogen Production from Biomass
Nov 2021
Publication
There is a need to derive hydrogen from renewable sources and the innovative stewardship of two natural resources namely the Sun and forest could provide a new pathway. This paper provides the first comparative analysis of solar-driven hydrogen production from environmental angles. A novel hydrogen production process proposed in this paper named Solar-Driven Advanced Biomass Indirect-Gasification (SABI-Hydrogen) shows promise toward achieving continuous operation and scalability the two key challenges to meet future energy needs. The calculated Global Warming Potential for 1 kg of solar-driven hydrogen production is 1.04 kg CO2-eq/kg H2 less than half of the current biomass gasification process which emits 2.67 kg CO2-eq/kg H2. Further SABI-Hydrogen demonstrates the least-carbon intensive pathway among all current hydrogen production methods. Thus solar-driven hydrogen production from biomass could lead to a sustainable supply essential for a low-carbon energy transition.
A Study on Dispersion Resulting From Liquefied Hydrogen Spilling
Oct 2015
Publication
For massive utilization of hydrogen energy it is necessary to transport a large quantity of hydrogen by liquefied hydrogen carriers. However the current rule on ships carrying liquefied hydrogen in bulks do not address the maritime transport of liquefied hydrogen and the safety assessment of liquefied hydrogen carriage is thus very important. In the present study we spilled liquefied hydrogen and LNG (Liquefied Natural Gas) on the surface of various materials and compared the difference of their spread and dispersion. Liquefied hydrogen immediately dispersed upward compared to LNG. Furthermore we also measured the flammability limit of low temperature hydrogen gas. Its range at low temperature was narrower than the range at normal temperature.
Visualization of Auto-ignition Phenomenon Under the Controlled Burst Pressure
Oct 2015
Publication
A high-pressure hydrogen jet released into the air has the possibility of igniting in a tube without any ignition source. The mechanism of this phenomenon called spontaneous ignition is considered to be that hydrogen diffuses into the hot air caused by the shock wave from diaphragm rupture and the hydrogen-oxidizer mixed region is formed enough to start chemical reaction. Recently flow visualization studies on the spontaneous ignition process have been conducted to understand its detailed mechanism but such ignition has not yet been well clarified. In this study the spontaneous ignition phenomenon was observed in a rectangular tube. The results confirm the presence of a flame at the wall of the tube when the shock wave pressure reaches 1.2–1.5 MPa in more than 9 MPa burst pressure and that ignition occurs near the wall followed by multiple ignitions as the shock wave propagates with the ignitions eventually combining to form a flame.
Numerical Simulations of Spontaneous Ignition of High-pressure Hydrogen Based on Detailed Chemical Kinetics
Sep 2013
Publication
A two-dimensional (2-D) simulation of spontaneous ignition of high-pressure hydrogen in a length of duct is conducted in order to explore its underlying ignition mechanisms. The present study adopts a 2-D rectangular duct (i.e. not axisymmetric geometry) and focuses on the effects of initial diaphragm shape on the spontaneous ignitions. The Navier-Stokes equations with a detailed chemical kinetics mechanism are solved in a manner of direct numerical simulation. The detailed mechanisms of spontaneous ignition are discussed for each initial diaphragm shape. For a straight diaphragm shape it is found that the ignition occurs only near the wall due to the adiabatic wall condition while the three ignition events: ignitions due to leading shock wave reflection at the wall hydrogen penetration into shock-heated air near the wall and deep penetration of hydrogen into shock-heated air behind the leading shock wave are identified for a largely deformed diaphragm shape.
Numerical Study on Detailed Mechanism of H2-Air Flame Jet Ignition
Sep 2013
Publication
Jet ignition was recognized in the 1970s and has since been applied to automobile engines such as the Honda CVCC. In the 1990s jet ignition was observed in explosions and was seen as a problem that may relate to jet ignition. Our group presented jet ignition experimentally and numerically in 1999 and later using LIF measurements with the same experimental vessel as used in 1999. However the detailed mechanism of jet ignition was not clarified at that time. The target of this study is to clarify how jet ignition happens and to understand the detailed mechanism of flame jet ignition.
TPR-XAFS Study for Hydrogen Recombination Reaction of Platinum Metal Nanoparticle Catalysts
Sep 2017
Publication
Proper management of hydrogen gas is very important for safety of nuclear power plants. Hydrogen removal system by hydrogen recombination reaction (water formation reaction) on a catalyst is one of the candidates for avoiding hydrogen explosion. We have observed in situ and time-resolved structure change of platinum metal nanoparticle catalyst during hydrogen recombination reaction by using simultaneous measurement of temperature-programmed reaction and X-ray absorption fine structure (TPR-XAFS). A poisoning effect by carbon monoxide on catalytic activity was focused. It was found that the start of hydrogen recombination reaction is closely connected with the occurrence of the decomposition of adsorbed carbon monoxide molecules and creation of surface oxide layer on platinum metal nanoparticles.
Outward Propagation Velocity and Acceleration Characteristics in Hydrogen-air Deflagration
Oct 2015
Publication
Propagation characteristics of hydrogen-air deflagration need to be understood for an accurate risk assessment. Especially flame propagation velocity is one of the most important factors. Propagation velocity of outwardly propagating flame has been estimated from burning velocity of a flat flame considering influence of thermal expansion at a flame front; however this conventional method is not enough to estimate an actual propagation velocity because flame propagation is accelerated owing to cellular flame front caused by intrinsic instability in hydrogen-air deflagration. Therefore it is important to understand the dynamic propagation characteristics of hydrogen-air deflagration. We performed explosion tests in a closed chamber which has 300 mm diameter windows and observed flame propagation phenomena by using Schlieren photography. In the explosion experiments hydrogen-air mixtures were ignited at atmospheric pressure and room temperature and in the range of equivalence ratio from 0.2 to 1.0. Analyzing the obtained Schlieren images flame radius and flame propagation velocity were measured. As the result cellular flame fronts formed and flame propagations of hydrogen–air mixture were accelerated at the all equivalence ratios. In the case of equivalent ratio φ = 0.2 a flame floated up and could not propagate downward because the influence of buoyancy exceeded a laminar burning velocity. Based upon these propagation characteristics a favorable estimation method of flame propagation velocity including influence of flame acceleration was proposed. Moreover the influence of intrinsic instability on propagation characteristics was elucidated.
Hydrogen Storage Mechanism in Sodium-Based Graphene Nanoflakes: A Density Functional Theory Study
Jan 2022
Publication
Carbon materials such as graphene nanoflakes carbon nanotubes and fullerene can be widely used to store hydrogen and doping these materials with lithium (Li) generally increases their H2 -storage densities. Unfortunately Li is expensive; therefore alternative metals are required to realize a hydrogen-based society. Sodium (Na) is an inexpensive element with chemical properties that are similar to those of lithium. In this study we used density functional theory to systematically investigate how hydrogen molecules interact with Na-doped graphene nanoflakes. A graphene nanoflake (GR) was modeled by a large polycyclic aromatic hydrocarbon composed of 37 benzene rings with GR-Na-(H2 )n and GR-Na+ -(H2 )n (n = 0–12) clusters used as hydrogen storage systems. Data obtained for the Na system were compared with those of the Li system. The single-H2 GR-Li and GR-Na systems (n = 1) exhibited binding energies (per H2 molecule) of 3.83 and 2.72 kcal/mol respectively revealing that the Li system has a high hydrogen-storage ability. This relationship is reversed from n = 4 onwards; the Na systems exhibited larger or similar binding energies for n = 4–12 than the Li-systems. The present study strongly suggests that Na can be used as an alternative metal to Li in H2 -storage applications. The H2 -storage mechanism in the Na system is also discussed based on the calculated results.
Fatigue and Fracture of High-hardenability Steels for Thick-walled Hydrogen Pressure Vessels
Sep 2017
Publication
Stationary pressure vessels for the storage of large volumes of gaseous hydrogen at high pressure (>70 MPa) are typically manufactured from Cr-Mo steels. These steels display hydrogen-enhanced fatigue crack growth but pressure vessels can be manufactured using defect-tolerant design methodologies. However storage volumes are limited by the wall thickness that can be reliably manufactured for quench and tempered Cr-Mo steels typically not more than 25-35 mm. High-hardenability steels can be manufactured with thicker walls which enables larger diameter pressure vessels and larger storage volumes. The goal of this study is to assess the fracture and fatigue response of high hardenability Ni-Cr-Mo pressure vessel steels for use in high-pressure hydrogen service at pressure in excess of 1000 bar. Standardized fatigue crack growth tests were performed in gaseous hydrogen at frequency of 1Hz and for R-ratios in the range of 0.1 to 0.7. Elastic-plastic fracture toughness measurements were also performed. The measured fatigue and fracture behavior is placed into the context of previous studies on fatigue and fracture of Cr-Mo steels for gaseous hydrogen.
Numerical Simulation on Low-speed Hydrogen Jet Diffusion
Oct 2015
Publication
The numerical simulation for the hydrogen jet experiments performed by Schefer et al. is conducted using the compressible multicomponent Navier-Stokes equations with the preconditioning method. The simulated results for the hydrogen jet agree with the theoretical results of Tollmien. As far as comparing with the experiments by Schefer et al. the concentration profiles along the radial direction agree with the present numerical results and that along the centerline also agree well with the experimental results after the data are normalized by the equivalent nozzle diameter. It is confirmed that the spread of the jet width from the jet exit to downstream is affected by the Kelvin-Helmholtz instability. It is also confirmed that the jet flow field is formed alternately by the high pressure region and the low pressure one to cause the jet flow fluctuation.
Reversible Ammonia-based and Liquid Organic Hydrogen Carriers for High-density Hydrogen Storage: Recent Progress
Feb 2019
Publication
Liquid hydrogen carriers are considered to be attractive hydrogen storage options because of their ease of integration into existing chemical transportation infrastructures when compared with liquid or compressed hydrogen. The development of such carriers forms part of the work of the International Energy Agency Task 32: Hydrogen-Based Energy Storage. Here we report the state-of-the-art for ammonia-based and liquid organic hydrogen carriers with a particular focus on the challenge of ensuring easily regenerable high-density hydrogen storage.
Effect of Carbon Monoxide on Polymer Electrolyte Fuel Cell Performance with a Hydrogen Circulation System
Feb 2022
Publication
The effect of carbon monoxide (CO) on the performance of polymer electrolyte fuel cells (PEFCs) with either a hydrogen circulation system or a hydrogen one-way pass system is investigated and compared. The voltage drop induced by adding 0.2 ppm of CO to the PEFC with the hydrogen circulation system was less than one-tenth of that observed in the PEFC with the hydrogen one-way pass system at 1000 mA cm–2 and a cell temperature of 60 °C. Gas analysis results showed that CO concentration in the hydrogen circulation system was lower than the initially supplied CO concentration. In the hydrogen circulation system permeated oxygen from the cathode should enhance CO oxidation. This should lead to decrease the CO concentration and mitigate the voltage drop in the hydrogen circulation system.
A Multiobjective Optimization of a Catalyst Distribution in a Methane/Steam Reforming Reactor Using a Genetic Algorithm
May 2020
Publication
The presented research focuses on an optimization design of a catalyst distribution inside a small-scale methane/steam reforming reactor. A genetic algorithm was used for the multiobjective optimization which included the search for an optimum of methane conversion rate and a minimum of the difference between highest and lowest temperatures in the reactor. For the sake of computational time the maximal number of the segment with different catalyst densities was set to be thirty in this study. During the entire optimization process every part of the reactor could be filled either with a catalyst material or non-catalytic metallic foam. In both cases the porosity and pore size was also specified. The impact of the porosity and pore size on the active reaction surface and permeability was incorporated using graph theory and three-dimensional digital material representation. Calculations start with the generation of a random set of possible reactors each with a different catalyst distribution. The algorithm calls reforming simulation over each of the reactors and after obtaining concentration and temperature fields the algorithms calculated fitness function. The properties of the best reactors are combined to generate a new population of solutions. The procedure is repeated and after meeting the coverage criteria the optimal catalyst distribution was proposed. The paper is summarized with the optimal catalyst distribution for the given size and working conditions of the system.
Ammonia as Effective Hydrogen Storage: A Review on Production, Storage and Utilization
Jun 2020
Publication
Ammonia is considered to be a potential medium for hydrogen storage facilitating CO2-free energy systems in the future. Its high volumetric hydrogen density low storage pressure and stability for long-term storage are among the beneficial characteristics of ammonia for hydrogen storage. Furthermore ammonia is also considered safe due to its high auto ignition temperature low condensation pressure and lower gas density than air. Ammonia can be produced from many different types of primary energy sources including renewables fossil fuels and surplus energy (especially surplus electricity from the grid). In the utilization site the energy from ammonia can be harvested directly as fuel or initially decomposed to hydrogen for many options of hydrogen utilization. This review describes several potential technologies in current conditions and in the future for ammonia production storage and utilization. Ammonia production includes the currently adopted Haber–Bosch electrochemical and thermochemical cycle processes. Furthermore in this study the utilization of ammonia is focused mainly on the possible direct utilization of ammonia due to its higher total energy efficiency covering the internal combustion engine combustion for gas turbines and the direct ammonia fuel cell. Ammonia decomposition is also described in order to give a glance at its progress and problems. Finally challenges and recommendations are also given toward the further development of the utilization of ammonia for hydrogen storage.
Materials for Hydrogen-based Energy Storage - Past, Recent Progress and Future Outlook
Dec 2019
Publication
Michael Hirscher,
Volodymyr A. Yartys,
Marcello Baricco,
José Bellosta von Colbe,
Didier Blanchard,
Robert C. Bowman Jr.,
Darren P. Broom,
Craig Buckley,
Fei Chang,
Ping Chen,
Young Whan Cho,
Jean-Claude Crivello,
Fermin Cuevas,
William I. F. David,
Petra E. de Jongh,
Roman V. Denys,
Martin Dornheim,
Michael Felderhoff,
Yaroslav Filinchuk,
George E. Froudakis,
David M. Grant,
Evan MacA. Gray,
Bjørn Christian Hauback,
Teng He,
Terry D. Humphries,
Torben R. Jensen,
Sangryun Kim,
Yoshitsugu Kojima,
Michel Latroche,
Hai-wen Li,
Mykhaylo V. Lototskyy,
Joshua W. Makepeace,
Kasper T. Møller,
Lubna Naheed,
Peter Ngene,
Dag Noreus,
Magnus Moe Nygård,
Shin-ichi Orimo,
Mark Paskevicius,
Luca Pasquini,
Dorthe B. Ravnsbæk,
M. Veronica Sofianos,
Terrence J. Udovic,
Tejs Vegge,
Gavin Walker,
Colin Webb,
Claudia Weidenthaler and
Claudia Zlotea
Globally the accelerating use of renewable energy sources enabled by increased efficiencies and reduced costs and driven by the need to mitigate the effects of climate change has significantly increased research in the areas of renewable energy production storage distribution and end-use. Central to this discussion is the use of hydrogen as a clean efficient energy vector for energy storage. This review by experts of Task 32 “Hydrogen-based Energy Storage” of the International Energy Agency Hydrogen TCP reports on the development over the last 6 years of hydrogen storage materials methods and techniques including electrochemical and thermal storage systems. An overview is given on the background to the various methods the current state of development and the future prospects. The following areas are covered; porous materials liquid hydrogen carriers complex hydrides intermetallic hydrides electro-chemical storage of energy thermal energy storage hydrogen energy systems and an outlook is presented for future prospects and research on hydrogen-based energy storage
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