United States
Exchange Current Density of Reversible Solid Oxide Cell Electrodes
Mar 2022
Publication
Reversible solid oxide cells (r-SOCs) can be operated in either solid oxide fuel cell or solid oxide electrolysis cell mode. They are expected to become important in the support of renewable energy due to their high efficiency for both power generation and hydrogen generation. The exchange current density is one of the most important parameters in the quantification of electrode performance in solid oxide cells. In this study four different fuel electrodes and two different air electrodes are fabricated using different materials and the microstructures are compared. The temperature fuel humidification and oxygen concentration at the air electrode are varied to obtain the apparent exchange current density for the different electrode materials. In contrast to ruthenium-and-gadolinia-doped ceria (Rh-GDC) as well as nickel-and-gadolinia-doped ceria (Ni-GDC) electrodes significant differences in the apparent exchange current density were observed between electrolysis and fuel cell modes for the nickel-scandia-stabilized zirconia (Ni-ScSZ) cermet. Variation of gas concentration revealed that surface adsorption sites were almost completely vacant for all these electrodes. The apparent exchange current densities obtained in this study are useful as a parameter for simulation of the internal properties of r-SOCs.
Experimental Investigation of Hydrogen Jet Fire Mitigation by Barrier Walls
Sep 2009
Publication
Hydrogen jet flames resulting from ignition of unintended releases can be extensive in length and pose significant radiation and impingement hazards. One possible mitigation strategy to reduce exposure to jet flames is to incorporate barriers around hydrogen storage and delivery equipment. While reducing the extent of unacceptable consequences the walls may introduce other hazards if not properly configured. This paper describes experiments carried out to characterize the effectiveness of different barrier wall configurations at reducing the hazards created by jet fires. The hazards that are evaluated are the generation of overpressure during ignition the thermal radiation produced by the jet flame and the effectiveness of the wall at deflecting the flame.<br/>The tests were conducted against a vertical wall (1-wall configuration) and two “3-wall” configurations that consisted of the same vertical wall with two side walls of the same dimensions angled at 135° and 90°. The hydrogen jet impinged on the center of the central wall in all cases. In terms of reducing the radiation heat flux behind the wall the 1-wall configuration performed best followed by the 3-wall 135° configuration and the 3-wall 90°. The reduced shielding efficiency of the three-wall configurations was probably due to the additional confinement created by the side walls that limited the escape of hot gases to the sides of the wall and forced the hot gases to travel over the top of the wall.<br/>The 3-wall barrier with 135° side walls exhibited the best overall performance. Overpressures produced on the release side of the wall were similar to those produced in the 1-wall configuration. The attenuation of overpressure and impulse behind the wall was comparable to that of the three-wall configuration with 90° side walls. The 3-wall 135° configuration’s ability to shield the back side of the wall from the heat flux emitted from the jet flame was comparable to the 1-wall and better than the 3-wall 90° configuration. The ratio of peak overpressure (from in front of the wall and from behind the wall) showed that the 3-wall 135° configuration and the 3-wall 90° configuration had a similar effectiveness. In terms of the pressure mitigation the 3-wall configurations performed significantly better than the 1-wall configuration
Deflagration Safety Study of Mixtures of Hydrogen and Natural Gas in a Semi-open Space
Sep 2007
Publication
In the transition to a hydrogen economy it is likely that hydrogen will be used or stored in close proximity to other flammable fuels and gases. Accidents can occur that result in the release of two or more fuels such as hydrogen and natural gas that can mix and form a hazard. A series of five medium-scale semi-open-space deflagration experiments have been conducted with hydrogen natural gas and air mixtures. The natural gas consisted of 90% methane 6% ethane 3% propane and 1% butane by volume. Mixtures of hydrogen and natural gas were created with the hydrogen mole fraction in the fuel varying from 1.000 to 0.897 and the natural gas mole fraction varying from 0.000 to 0.103. The hydrogen and natural gas mixture was then released inside a 5.27-m³ thin plastic tent. The stoichiometric fuel-air mixtures were ignited with a 40-J spark located at the bottom center of the tent. Overpressure and impulse data were collected using pressure transducers located within the mixture volume and in the free field. Flame front time-of-arrival was measured using fast response thermocouples and infrared video. Flame speeds relative to a fixed observer were measured between 36.2 m/s and 19.7 m/s. Average peak overpressures were measured between 2.0 kPa and 0.3 kPa. The addition of natural gas inhibited the combustion when the hydrogen mole fraction was less than or equal to 0.949. For these mixtures there was a significant decrease in overpressures. When the hydrogen mole fraction in the fuel was between 0.999 and 0.990 the overpressures were slightly higher than for the case of hydrogen alone. This could be due to experimental scatter or there may be a slight enhancement of the combustion when a very small amount of natural gas was present. From a safety standpoint variation in overpressure was small and should have little effect on safety considerations.
Recent Progress and Approaches on Transition Metal Chalcogenides for Hydrogen Production
Dec 2021
Publication
Development of efficient and affordable photocatalysts is of great significance for energy production and environmental sustainability. Transition metal chalcogenides (TMCs) with particle sizes in the 1–100 nm have been used for various applications such as photocatalysis photovoltaic and energy storage due to their quantum confinement effect optoelectronic behavior and their stability. In particular TMCs and their heterostructures have great potential as an emerging inexpensive and sustainable alternative to metal-based catalysts for hydrogen evolution. Herein the methods used for the fabrication of TMCs characterization techniques employed and the different methods of solar hydrogen production by using different TMCs as photocatalyst are reviewed. This review provides a summary of TMC photocatalysts for hydrogen production.
Simulations of Hydrogen Releases from a Storage Tanks- Dispersion and Consequences of Ignition
Sep 2005
Publication
We present results from hydrogen dispersion simulations from a pressurized reservoir at constant flow rate in the presence and absence of a wall. The dispersion simulations are performed using a commercial finite volume solver. Validation of the approach is discussed. Constant concentration envelopes corresponding to the 2% 4% and 15% hydrogen concentration in air are calculated for a subcritical vertical jet and for an equivalent subcritical horizontal jet from a high pressure reservoir. The consequences of ignition and the resulting overpressure are calculated for subcritical horizontal and vertical hydrogen jets and in the latter case compared to available experimental data.
PRD Hydrogen Release and Dispersion, a Comparison of CFD Results Obtained from Using Ideal and Real Gas Law Properties.
Sep 2005
Publication
In this paper CFD techniques were applied to the simulations of hydrogen release from a 400-bar tank to ambient through a Pressure Relieve Device (PRD) 6 mm (¼”) opening. The numerical simulations using the TOPAZ software developed by Sandia National Laboratory addressed the changes of pressure density and flow rate variations at the leak orifice during release while the PHOENICS software package predicted extents of various hydrogen concentration envelopes as well as the velocities of gas mixture for the dispersion in the domain. The Abel-Noble equation of state (AN-EOS) was incorporated into the CFD model implemented through the TOPAZ and PHOENICS software to accurately predict the real gas properties for hydrogen release and dispersion under high pressures. The numerical results were compared with those obtained from using the ideal gas law and it was found that the ideal gas law overestimates the hydrogen mass release rates by up to 35% during the first 25 seconds of release. Based on the findings the authors recommend that a real gas equation of state be used for CFD predictions of high-pressure PRD releases.
Hydrogen Embrittlement of Medium Mn Steels
Feb 2021
Publication
Recent research efforts to develop advanced–/ultrahigh–strength medium-Mn steels have led to the development of a variety of alloying concepts thermo-mechanical processing routes and microstructural variants for these steel grades. However certain grades of advanced–/ultrahigh–strength steels (A/UHSS) are known to be highly susceptible to hydrogen embrittlement due to their high strength levels. Hydrogen embrittlement characteristics of medium–Mn steels are less understood compared to other classes of A/UHSS such as high Mn twinning–induced plasticity steel because of the relatively short history of the development of this steel class and the complex nature of multiphase fine-grained microstructures that are present in medium–Mn steels. The motivation of this paper is to review the current understanding of the hydrogen embrittlement characteristics of medium or intermediate Mn (4 to 15 wt pct) multiphase steels and to address various alloying and processing strategies that are available to enhance the hydrogen-resistance of these steel grades.
Everything About Hydrogen Podcast: Is This the End of the Diesel Train?
Jan 2020
Publication
For this show the team are taking a dive into the world of hydrogen trains and who better to speak to this space than Mike Muldoon Head of Business Development and Marketing for Alstom UK&I. Alstom have been the pioneers of hydrogen powered rail and in addition to two operating trains in Germany have secured over Eur500 million of orders for hydrogen trains. On the show we talk to Mike about why Alstom see hydrogen as a key part of the evolution of the rail industry towards zero emissions and why hydrogen today is such a compelling proposition for operators and investors.
The podcast can be found on their website
The podcast can be found on their website
Vented Explosion Overpressures From Combustion of Hydrogen and Hydrocarbon Mixtures
Sep 2009
Publication
Experimental data obtained for hydrogen mixtures in a room-size enclosure are presented and compared with data for propane and methane mixtures. This set of data was also used to develop a three-dimensional gas dynamic model for the simulation of gaseous combustion in vented enclosures. The experiments were performed in a 64 m3 chamber with dimensions of 4.6 × 4.6 × 3.0 m and a vent opening on one side and vent areas of either 2.7 or 5.4 m2 were used. Tests were performed for three ignition locations at the wall opposite the vent at the center of the chamber or at the center of the wall containing the vent. Hydrogen–air mixtures with concentrations close 18% vol. were compared with stoichiometric propane–air and methane–air mixtures. Pressure data as function of time and flame time-of-arrival data were obtained both inside and outside the chamber near the vent. Modelling was based on a Large Eddy Simulation (LES) solver created using the OpenFOAM CFD toolbox using sub-grid turbulence and flame wrinkling models. A comparison of these simulations with experimental data is discussed.
Environmental Reactivity of Solid State Hydride Materials
Sep 2009
Publication
In searching for high gravimetric and volumetric density hydrogen storage systems it is inevitable that higher energy density materials will be used. In order to make safe and commercially acceptable condensed phase hydrogen storage systems it is important to understand quantitatively the hazards involved in using and handling these materials and to develop appropriate mitigation strategies to handle potential material exposure events. A crucial aspect of the development of risk identification and mitigation strategies is the development of rigorous environmental reactivity testing standards and procedures. This will allow for the identification of potential hazards and implementation of risk mitigation strategies. Modified testing procedures for shipping air and/or water sensitive materials as codified by the United Nations have been used to evaluate two potential hydrogen storage materials 2LiBH4·MgH2 and NH3BH3. The modified U.N. procedures include identification of self-reactive substances pyrophoric substances and gas-emitting substances with water contact. The results of these tests for air and water contact sensitivity will be compared to the pure material components where appropriate (e.g. LiBH4 and MgH2). The water contact tests are divided into two scenarios dependent on the hydride to water mole ratio and heat transport characteristics. Air contact tests were run to determine whether a substance will spontaneously react with air in a packed or dispersed form. Relative to 2LiBH4·MgH2 the chemical hydride NH3BH3 was observed to be less environmentally reactive.
Simulation of Small-Scale Releases from Liquid Hydrogen Storage Systems
Sep 2009
Publication
Knowledge of the concentration field and flammability envelope from small-scale leaks is important for the safe use of hydrogen. These small-scale leaks may occur from leaky fittings or o-ring seals on liquid hydrogen-based systems. The present study focuses on steady-state leaks with large amounts of pressure drop along the leak path such that hydrogen enters the atmosphere at near atmospheric pressure (i.e. Very low Mach number). A three-stage buoyant turbulent entrainment model is developed to predict the properties (trajectory hydrogen concentration and temperature) of a jet emanating from the leak. Atmospheric hydrogen properties (temperature and quality) at the leak plane depend on the storage pressure and whether the leak occurs from the saturated vapor space or saturated liquid space. In the first stage of the entrainment model ambient temperature air (295 K) mixes with the leaking hydrogen (20–30 K) over a short distance creating an ideal gas mixture at low temperature (∼65 K). During this process states of hydrogen and air are determined from equilibrium thermodynamics using models developed by NIST. In the second stage of the model (also relatively short in distance) the radial distribution of hydrogen concentration and velocity in the jet develops into a Gaussian profile characteristic of free jets. The third and by far the longest stage is the part of the jet trajectory where flow is fully developed. Results show that flammability envelopes for cold hydrogen jets are generally larger than those of ambient temperature jets. While trajectories for ambient temperature jets depend solely on the leak densimetric Froude number results from the present study show that cold jet trajectories depend on the Froude number and the initial jet density ratio. Furthermore the flammability envelope is influenced by the hydrogen concentration in the jet at the beginning of fully developed flow.
Modeling of 2LiBH4+MgH2 Hydrogen Storage System Accident Scenarios Using Empirical and Theoretical Thermodynamics
Sep 2009
Publication
It is important to understand and quantify the potential risk resulting from accidental environmental exposure of condensed phase hydrogen storage materials under differing environmental exposure scenarios. This paper describes a modelling and experimental study with the aim of predicting consequences of the accidental release of 2LiBH4+MgH2 from hydrogen storage systems. The methodology and results developed in this work are directly applicable to any solid hydride material and/or accident scenario using appropriate boundary conditions and empirical data.
The ability to predict hydride behaviour for hypothesized accident scenarios facilitates an assessment of the risk associated with the utilization of a particular hydride. To this end an idealized finite volume model was developed to represent the behaviour of dispersed hydride from a breached system. Semi-empirical thermodynamic calculations and substantiating calorimetric experiments were performed in order to quantify the energy released energy release rates and to quantify the reaction products resulting from water and air exposure of a lithium borohydride and magnesium hydride combination.
The hydrides LiBH4 and MgH2 were studied individually in the as-received form and in the 2:1 “destabilized” mixture. Liquid water hydrolysis reactions were performed in a Calvet calorimeter equipped with a mixing cell using neutral water. Water vapor and oxygen gas phase reactivity measurements were performed at varying relative humidities and temperatures by modifying the calorimeter and utilizing a gas circulating flow cell apparatus. The results of these calorimetric measurements were compared with standardized United Nations (UN) based test results for air and water reactivity and used to develop quantitative kinetic expressions for hydrolysis and air oxidation in these systems. Thermodynamic parameters obtained from these tests were then inputted into a computational fluid dynamics model to predict both the hydrogen generation rates and concentrations along with localized temperature distributions. The results of these numerical simulations can be used to predict ignition events and the resultant conclusions will be discussed.
The ability to predict hydride behaviour for hypothesized accident scenarios facilitates an assessment of the risk associated with the utilization of a particular hydride. To this end an idealized finite volume model was developed to represent the behaviour of dispersed hydride from a breached system. Semi-empirical thermodynamic calculations and substantiating calorimetric experiments were performed in order to quantify the energy released energy release rates and to quantify the reaction products resulting from water and air exposure of a lithium borohydride and magnesium hydride combination.
The hydrides LiBH4 and MgH2 were studied individually in the as-received form and in the 2:1 “destabilized” mixture. Liquid water hydrolysis reactions were performed in a Calvet calorimeter equipped with a mixing cell using neutral water. Water vapor and oxygen gas phase reactivity measurements were performed at varying relative humidities and temperatures by modifying the calorimeter and utilizing a gas circulating flow cell apparatus. The results of these calorimetric measurements were compared with standardized United Nations (UN) based test results for air and water reactivity and used to develop quantitative kinetic expressions for hydrolysis and air oxidation in these systems. Thermodynamic parameters obtained from these tests were then inputted into a computational fluid dynamics model to predict both the hydrogen generation rates and concentrations along with localized temperature distributions. The results of these numerical simulations can be used to predict ignition events and the resultant conclusions will be discussed.
Effect of Hydrogen Concentration on Vented Explosion Overpressures from Lean Hydrogen–air Deflagrations
Sep 2011
Publication
Experimental data from vented explosion tests using lean hydrogen–air mixtures with concentrations from 12 to 19% vol. are presented. A 63.7-m3 chamber was used for the tests with a vent size of either 2.7 or 5.4 m2. The tests were focused on the effect of hydrogen concentration ignition location vent size and obstacles on the pressure development of a propagating flame in a vented enclosure. The dependence of the maximum pressure generated on the experimental parameters was analyzed. It was confirmed that the pressure maxima are caused by pressure transients controlled by the interplay of the maximum flame area the burning velocity and the overpressure generated outside of the chamber by an external explosion. A model proposed earlier to estimate the maximum pressure for each of the main pressure transients was evaluated for the various hydrogen concentrations. The effect of the Lewis number on the vented explosion overpressure is discussed.
Wide Area and Distributed Hydrogen Sensors
Sep 2009
Publication
Recent advances in optical sensors show promise for the development of new wide area monitoring and distributed optical network hydrogen detection systems. Optical hydrogen sensing technologies reviewed here are: 1) open path Raman scattering systems 2) back scattering from chemically treated solid polymer matrix optical fiber sensor cladding; and 3) schlieren and shearing interferometry imaging. Ultrasonic sensors for hydrogen release detection are also reviewed. The development status of these technologies and their demonstrated results in sensor path length low hydrogen concentration detection ability and response times are described and compared to the corresponding status of hydrogen spot sensor network technologies.
Compatibility and Suitability of Existing Steel Pipelines for Transport of Hydrogen and Hydrogen-natural Gas Blends
Sep 2017
Publication
Hydrogen is being considered as a pathway to decarbonize large energy systems and for utility-scale energy storage. As these applications grow transportation infrastructure that can accommodate large quantities of hydrogen will be needed. Many millions of tons of hydrogen are already consumed annually some of which is transported in dedicated hydrogen pipelines. The materials and operation of these hydrogen pipeline systems however are managed with more constraints than a conventional natural gas pipeline. Transitional strategies for deep decarbonization of energy systems include blending hydrogen into existing natural gas systems where the materials and operations may not have the same controls. This study explores the hydrogen compatibility of existing pipeline steels and the suitability of these steels in hydrogen pipeline systems. Representative fracture and fatigue properties of pipeline grade steels in gaseous hydrogen are summarized from the literature. These properties are then considered in idealized design life calculations to inform materials performance for a typical gas pipeline.
Pressure Cycling Of Type 1 Pressure Vessels with Gaseous Hydrogen
Sep 2011
Publication
Type 1 steel pressure vessels are commonly used for the transport of pressurized gases including gaseous hydrogen. In the majority of cases these cylinders experience relatively few pressure cycles over their lifetime perhaps in the hundreds. In emerging markets such as hydrogen-powered industrial trucks hydrogen fuel systems are expected to experience thousands of cycles over just a few year period. This study investigates the fatigue life of Type 1 steel pressure vessels by subjecting full- scale vessels to pressure cycles with gaseous hydrogen between nominal pressure of 3.5 and 43.8 MPa. In addition engineered defects were machined on the inside of several pressure vessels for comparison to fatigue crack growth measurements on materials sectioned from these pressure vessels. As-manufactured pressure vessels have sustained >35000 cycles with failure while vessels with machined defects leaked before bursting after 8000 to 15000 pressure cycles. The measured number of cycles to failure in these pressure vessels is two to three times greater than predicted using conservative methods based on fatigue crack growth rates measured in gaseous hydrogen.
Fundamental Safety Testing and Analysis of Solid State Hydrogen Storage Materials and Systems
Sep 2007
Publication
Hydrogen is seen as the future automobile energy storage media due to its inherent cleanliness upon oxidation and its ready utilization in fuel cell applications. Its physical storage in light weight low volume systems is a key technical requirement. In searching for ever higher gravimetric and volumetric density hydrogen storage materials and systems it is inevitable that higher energy density materials will be studied and used. To make safe and commercially acceptable systems it is important to understand quantitatively the risks involved in using and handling these materials and to develop appropriate risk mitigation strategies to handle unforeseen accidental events. To evaluate these materials and systems an IPHE sanctioned program was initiated in 2006 partnering laboratories from Europe North America and Japan. The objective of this international program is to understanding the physical risks involved in synthesis handling and utilization of solid state hydrogen storage materials and to develop methods to mitigate these risks. This understanding will support ultimate acceptance of commercially high density hydrogen storage system designs. An overview of the approaches to be taken to achieve this objective will be given. Initial experimental results will be presented on environmental exposure of NaAlH4 a candidate high density hydrogen storage compound. The tests to be shown are based on United Nations recommendations for the transport of hazardous materials and include air and water exposure of the hydride at three hydrogen charge levels in various physical configurations. Additional tests developed by the American Society for Testing and Materials were used to quantify the dust cloud ignition characteristics of this material which may result from accidental high energy impacts and system breach. Results of these tests are shown along with necessary risk mitigation techniques used in the synthesis and fabrication of a prototype hydrogen storage system.
A Study of Barrier Walls for Mitigation of Unintended Releases of Hydrogen
Sep 2009
Publication
Hydrogen jet flames resulting from ignition of unintended releases can be extensive in length and pose significant radiation and impingement hazards. Depending on the leak diameter and source pressure the resulting consequence distances can be unacceptably large. One possible mitigation strategy to reduce exposure to jet flames is to incorporate barriers around hydrogen storage and delivery equipment. An experimental and modeling program has been performed at Sandia National Laboratories to better characterize the effectiveness of barrier walls to reduce hazards. This paper describes the experimental and modeling program and presents results obtained for various barrier configurations. The experimental measurements include flame deflection using standard and infrared video and high-speed movies (500 fps) to study initial flame propagation from the ignition source. Measurements of the ignition overpressure wall deflection radiative heat flux and wall and gas temperature were also made at strategic locations. The modeling effort includes three-dimensional calculations of jet flame deflection by the barriers computations of the thermal radiation field around barriers predicted overpressure from ignition and the computation of the concentration field from deflected unignited hydrogen releases. The various barrier designs are evaluated in terms of their mitigation effectiveness for the associated hazards present. The results show that barrier walls are effective at deflecting jet flames in a desired direction and can help attenuate the effects of ignition overpressure and flame radiative heat flux.
Using Hydrogen Safety Best Practices and Learning From Safety Events
Sep 2009
Publication
A best practice is a technique or methodology that has reliably led to a desired result. A wealth of experience regarding the safe use and handling of hydrogen exists as a result of an extensive history in a wide variety of industrial and aerospace settings. Hydrogen Safety Best Practices (www.h2bestpractices.org) captures this vast knowledge base and makes it publicly available to those working with hydrogen and related systems including those just starting to work with hydrogen. This online manual is organized under a number of hierarchical technical content categories. References including publications and other online links that deal with the safety aspects of hydrogen are compiled for easy access. This paper discusses the development of Hydrogen Safety Best Practices as a safety knowledge tool the nature of its technical content and the steps taken to enhance its value and usefulness. Specific safety event examples are provided to illustrate the link between technical content in the online best practices manual and a companion safety knowledge tool Hydrogen Incident Reporting and Lessons Learned (www.h2incidents.org) which encourages the sharing of lessons learned and other safety event information.
Novel Wide-area Hydrogen Sensing Technology
Sep 2007
Publication
Element One Inc. is developing novel indicators for hydrogen gas for applications as a complement to conventional electronic hydrogen sensors or as a low-cost alternative in situations where an electronic signal is not needed. The indicator consists of a thin film coating or a pigment of a transition metal oxide such as tungsten oxide or molybdenum oxide with a catalyst such as platinum or palladium. The oxide is partially reduced in the presence of hydrogen in concentrations as low as 300 parts per million and changes from transparent to a dark colour. The colour change is fast and easily seen from a distance. In air the colour change reverses quickly when the source of hydrogen gas is removed in the case of tungsten oxide or is nearly irreversible in the case of molybdenum oxide. A number of possible implementations have been successfully demonstrated in the laboratory including hydrogen indicating paints tape cautionary decals and coatings for hydrogen storage tanks. These and other implementations may find use in vehicles stationary appliances piping refuelling stations and in closed spaces such as maintenance and residential garages for hydrogen-fuelled vehicles. The partially reduced transition metal oxide becomes semi conductive and increases its electrical conductivity by several orders of magnitude when exposed to hydrogen. The integration of this electrical resistance sensor with an RFID tag may extend the ability of these sensors to record and transmit a history of the presence or absence of leaked hydrogen over long distances. Over long periods of exposure to the atmosphere the indicator’s response may slow due to catalyst degradation. Our current emphasis is on controlling this degradation. The kinetics of the visual indicators is being investigated along with their durability in collaboration with the NASA Kennedy Space Center.
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