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.
Measurement of Fatigue Crack Growth Rates for Steels in Hydrogen Containment Components
Sep 2009
Publication
The objective of this work was to enable the safe design of hydrogen pressure vessels by measuring the fatigue crack growth rates of ASME code-qualified steels in high-pressure hydrogen gas. While a design framework has recently been established for high-pressure hydrogen vessels a material property database does not exist to support the design calculations. This study addresses such voids in the database by measuring the fatigue crack growth rates of three different heats of ASME SA-372 Grade J steel in 100 MPa hydrogen gas. Results showed that the fatigue crack growth rates were similar for all three steel heats although the highest-strength steel appeared to exhibit the highest growth rates. Hydrogen accelerated the fatigue crack growth rates of the steels by as much as two orders of magnitude relative to anticipated crack growth rates in inert environments. Despite such dramatic effects of hydrogen on the fatigue crack growth rates measurement of these properties enables reliable definition of the design life of steel hydrogen containment vessels.
Developing a Hydrogen Fuel Cell Vehicle (HFCV) Energy Consumption Model for Transportation Applications
Jan 2022
Publication
This paper presents a simple hydrogen fuel cell vehicle (HFCV) energy consumption model. Simple fuel/energy consumption models have been developed and employed to estimate the energy and environmental impacts of various transportation projects for internal combustion engine vehicles (ICEVs) battery electric vehicles (BEVs) and hybrid electric vehicles (HEVs). However there are few published results on HFCV energy models that can be simply implemented in transportation applications. The proposed HFCV energy model computes instantaneous energy consumption utilizing instantaneous vehicle speed acceleration and roadway grade as input variables. The mode accurately estimates energy consumption generating errors of 0.86% and 2.17% relative to laboratory data for the fuel cell estimation and the total energy estimation respectively. Furthermore this work validated the proposed model against independent data and found that the new model accurately estimated the energy consumption producing an error of 1.9% and 1.0% relative to empirical data for the fuel cell and the total energy estimation respectively. The results demonstrate that transportation engineers policy makers automakers and environmental engineers can use the proposed model to evaluate the energy consumption effects of transportation projects and connected and automated vehicle (CAV) transportation applications within microscopic traffic simulation models.
Ignition Limits For Combustion of Unintended Hydrogen Releases- Experimental and Theoretical Results
Sep 2009
Publication
The ignition limits of hydrogen/air mixtures in turbulent jets are necessary to establish safety distances based on ignitable hydrogen location for safety codes and standards development. Studies in turbulent natural gas jets have shown that the mean fuel concentration is insufficient to determine the flammable boundaries of the jet. Instead integration of probability density functions (PDFs) of local fuel concentration within the quiescent flammability limits termed the flammability factor (FF) was shown to provide a better representation of ignition probability (PI). Recent studies in turbulent hydrogen jets showed that the envelope of ignitable gas composition (based on the mean hydrogen concentration) did not correspond to the known flammability limits for quiescent hydrogen/air mixtures. The objective of this investigation is to validate the FF approach to the prediction of ignition in hydrogen leak scenarios. The PI within a turbulent hydrogen jet was determined using a pulsed Nd:YAG laser as the ignition source. Laser Rayleigh scattering was used to characterize the fuel concentration throughout the jet. Measurements in methane and hydrogen jets exhibit similar trends in the ignition contour which broadens radially until an axial location is reached after which the contour moves inward to the centerline. Measurements of the mean and fluctuating hydrogen concentration are used to characterize the local composition statistics conditional on whether the laser spark results in a local ignition event or complete light-up of a stable jet flame. The FF is obtained through direct integration of local PDFs. A model was developed to predict the FF using a presumed PDF with parameters obtained from experimental data and computer simulations. Intermittency effects that are important in the shear layer are incorporated in a composite PDF. By comparing the computed FF with the measured PI we have validated the flammability factor approach for application to ignition of hydrogen jets.
Experimental Characterization and Modelling of Helium Dispersion in a ¼ - Scale Two-Car Residential Garage
Sep 2009
Publication
A series of experiments are described in which helium was released at a constant rate into a 1.5 m × 1.5 m × 0.75 m enclosure designed as a ¼-scale model of a two car garage. The purpose was to provide reference data sets for testing and validating computational fluid dynamics (CFD) models and to experimentally characterize the effects of a number of variables on the mixing behaviour within an enclosure and the exchange of helium with the surroundings. Helium was used as a surrogate for hydrogen and the total volume released was scaled as the amount that would be released by a typical hydrogen fuelled automobile with a full tank. Temporal profiles of helium were measured at seven vertical locations within the enclosure during and following one hour and four hour releases. Idealized vents in one wall sized to provide air exchange rates typical of actual garages were used. The effects of vent size number and location were investigated using three different vent combinations. The dependence on leak location was considered by releasing helium from three different points within the enclosure. It is shown that the National Institute of Standards and Technology (NIST) CFD code Fire Dynamics Simulator (FDS) provides time resolved predictions for helium concentrations that agree well with the experimental measurements.
A Review on Advanced Manufacturing for Hydrogen Storage Applications
Dec 2021
Publication
Hydrogen is a notoriously difficult substance to store yet has endless energy applications. Thus the study of long-term hydrogen storage and high-pressure bulk hydrogen storage have been the subject of much research in the last several years. To create a research path forward it is important to know what research has already been done and what is already known about hydrogen storage. In this review several approaches to hydrogen storage are addressed including high-pressure storage cryogenic liquid hydrogen storage and metal hydride absorption. Challenges and advantages are offered based on reported research findings. Since the project looks closely at advanced manufacturing techniques for the same are outlined as well. There are seven main categories into which most rapid prototyping styles fall. Each is briefly explained and illustrated as well as some generally accepted advantages and drawbacks to each style. An overview of hydrogen adsorption on metal hydrides carbon fibers and carbon nanotubes are presented. The hydrogen storage capacities of these materials are discussed as well as the differing conditions in which the adsorption was performed under. Concepts regarding storage shape and materials accompanied by smaller-scale advanced manufacturing options for hydrogen storage are also presented.
Analysis of Composite Hydrogen Storage Cylinders under Transient Thermal Loads
Sep 2007
Publication
In order to ensure safe operation of hydrogen storage cylinders under adverse conditions one should be able to predict the extremities under which these cylinders are capable of operating without failing catastrophically. It is therefore necessary to develop a comprehensive model which can predict the behavior and failure of composite storage cylinders when subjected to various types of loading conditions and operating environments. In the present work a finite element model has been developed to analyze composite hydrogen storage cylinders subjected to transient localized thermal loads and internal pressure. The composite cylinder consists of an aluminium liner that serves as a hydrogen gas permeation barrier. A filament-wound carbon/epoxy composite laminate placed over the liner provides the desired load bearing capacity. A glass/epoxy layer or other material is placed over the carbon/epoxy laminate to provide damage resistance for the carbon/epoxy laminates. A doubly curved composite shell element accounting for transverse shear deformation and geometric nonlinearity is used. A temperature dependent material model has been developed and implemented in ABAQUS using user subroutine. A failure model based on Hashin's failure theory is used to predict the various types of failure in the cylinder. A progressive damage model has also been implemented to account for reduction in modulus due to failure. A sublaminate model has been developed to save computational time and reduce the complications in the analysis. A numerical study is conducted to analyze a typical hydrogen storage cylinder and possible failure trends due to localized thermal loading and internal pressure is presented.
Risk Quantification of Hydride Based Hydrogen Storage Systems for Automotive Applications
Sep 2009
Publication
For hydrogen fuelled vehicles to attain significant market penetration it is essential that any potential risks be controlled within acceptable levels. To achieve this goal on-board vehicle hydrogen storage systems should undergo risk analyses during early concept development and design phases. By so doing the process of eliminating safety-critical failure modes will help guide storage system development and be more efficient to implement than if undertaken after the design-freeze stage. The focus of this paper is the development of quantitative risk analyses of storage systems which use onboard reversible materials such as conventional AB5 metal hydrides the complex hydride NaAlH4 or other material candidates currently being researched. Collision of a vehicle having such a hydrogen storage system was selected as a dominant accident initiator and a probabilistic event tree model has been developed for this initiator. The event tree model contains a set of comprehensive mutually exclusive accident sequences. The event tree represents chronological ordering of key events that are postulated to occur sequentially in time during the accident progression. Each event may represent occurrence of a phenomenon (e.g. hydride chemical reaction and dust cloud explosion) or a hardware failure (e.g. hydride storage vessel rupture). Event tree branch probabilities can be quantified using fault tree models or basic events with probability distributions. A fault tree model for hydride dust cloud explosion is provided as an example. Failure probabilities assigned to the basic events in the fault tree can be estimated from test results published data or expert opinion elicitation. To account for variabilities in the probabilities assigned to fault tree basic events and hence to propagate uncertainties in event tree sequences Monte Carlo sampling and Latin Hypercube sampling were employed and the statistics of the results from both techniques were compared.
Blending Hydrogen into Natural Gas Pipeline Networks: A Review of Key Issues
Mar 2013
Publication
The United States has 11 distinct natural gas pipeline corridors: five originate in the Southwest four deliver natural gas from Canada and two extend from the Rocky Mountain region. This study assesses the potential to deliver hydrogen through the existing natural gas pipeline network as a hydrogen and natural gas mixture to defray the cost of building dedicated hydrogen pipelines.
Modeling of Hydrogen Pressurization and Extraction in Cryogenic Pressure Vessels Due to Vacuum Insulation Failure
Sep 2017
Publication
We have analyzed vacuum insulation failure in an automotive cryogenic pressure vessel (also known as cryo-compressed vessel) storing hydrogen (H2). Vacuum insulation failure increases heat transfer into cryogenic vessels by about a factor of 100 potentially leading to rapid pressurization and venting to avoid exceeding maximum allowable working pressure (MAWP). H2 release to the environment may be dangerous if the vehicle is located in a closed space (e.g. a garage or tunnel) at the moment of insulation failure. We therefore consider utilization of the hydrogen in the vehicle fuel cell and electricity dissipation through operation of vehicle accessories or battery charging as an alternative to releasing hydrogen to the environment. We consider two strategies: initiating hydrogen extraction immediately after vacuum insulation failure or waiting until MAWP is reached before extraction. The results indicate that cryogenic pressure vessels have thermodynamic advantages that enable slowing down hydrogen release to moderate levels that can be consumed in the fuel cell and dissipated onboard the vehicle even in the worst case when the vacuum fails with a vessel storing hydrogen at maximum refuel density (70 g/L at 300 bar). The two proposed strategies are therefore feasible and the best alternative can be chosen based on economic and/or implementation constraints.
Clean Energy and Fuel Storage
Aug 2019
Publication
Clean energy and fuel storage is often required for both stationary and automotive applications. Some of the clean energy and fuel storage technologies currently under extensive research and development are hydrogen storage direct electric storage mechanical energy storage solar-thermal energy storage electrochemical (batteries and supercapacitors) and thermochemical storage. The gravimetric and volumetric storage capacity energy storage density power output operating temperature and pressure cycle life recyclability and cost of clean energy or fuel storage are some of the factors that govern efficient energy and fuel storage technologies for potential deployment in energy harvesting (solar and wind farms) stations and on-board vehicular transportation. This Special Issue thus serves the need to promote exploratory research and development on clean energy and fuel storage technologies while addressing their challenges to a practical and sustainable infrastructure.
Hydrogen Safety Sensor Performance and Use Gap Analysis
Sep 2017
Publication
Hydrogen sensors are recognized as an important technology for facilitating the safe implementation of hydrogen as an alternative fuel and there are numerous reports of a sensor alarm successfully preventing a potentially serious event. However gaps in sensor metrological specifications as well as in their performance for some applications exist. The U.S. Department of Energy (DOE) Fuel Cell Technologies Office published a short list of critical gaps in the 2007 and 2012 Multiyear Project Plans; more detailed gap analyses were independently performed by the Joint Research Centre (JRC) and the National Renewable Energy Laboratory (NREL). There have been however some significant advances in sensor technologies since these assessments including the commercial availability of hydrogen sensors with fast response times (t90 < 1 s which had been an elusive DOE target since 2007) improved robustness to chemical poisons improved selectivity and improved lifetime and stability. These improvements however have not been universal and typically pertain to select platforms or models. Moreover as hydrogen markets grow and new applications are being explored more demands will be imposed on sensor performance. The hydrogen sensor laboratories at NREL and the JRC are currently updating the hydrogen safety sensor gap analysis through direct interaction with international stakeholders in the hydrogen community especially end users. NREL and the JRC are currently organizing a series of workshops (in Europe and the United States) with sensor developers end-users and other stakeholders in 2017 to identify technology gaps and to develop a path forward to address them. One workshop was held on May 10 in Brussels Belgium at the Headquarters of the Fuel Cell and Hydrogen Joint Undertaking. A second workshop is planned at NREL in Golden CO USA. This paper reviews improvements in sensor technologies in the past 5 to 10 years identifies gaps in sensor performance and use requirements and identifies potential research strategies to address the gaps. The outcomes of the Hydrogen Sensors Workshops are also summarized.
Mixing and Warming of Cryogenic Hydrogen Releases
Sep 2017
Publication
Laboratory measurements were made on the concentration and temperature fields of cryogenic hydrogen jets. Images of spontaneous Raman scattering from a pulsed planar laser sheet were used to measure the concentration and temperature fields from varied releases. Jets with up to 5 bar pressure with near-liquid temperatures at the release point were characterized in this work. This data is relevant for characterizing unintended leaks from piping connected to cryogenic hydrogen storage tanks such as might be encountered at a hydrogen fuel cell vehicle fuelling station. The average centerline mass fraction was observed to decay at a rate similar to room temperature hydrogen jets while the half-width of the Gaussian profiles of mass fraction were observed to spread more slowly than for room temperature hydrogen. This suggests that the mixing and models for cryogenic hydrogen may be different than for room temperature hydrogen. Results from this work were also compared to a one-dimensional (streamwise) model. Good agreement was seen in terms of temperature and mass fraction. In subsequent work a validated version of this model will be exercised to quantitatively assess the risk at hydrogen fuelling stations with cryogenic hydrogen on-site.
International Association for Hydrogen Safety ‘Research Priorities Workshop’, September 2018, Buxton, UK
Sep 2018
Publication
Hydrogen has the potential to be used by many countries as part of decarbonising the future energy system. Hydrogen can be used as a fuel ‘vector’ to store and transport energy produced in low-carbon ways. This could be particularly important in applications such as heating and transport where other solutions for low and zero carbon emission are difficult. To enable the safe uptake of hydrogen technologies it is important to develop the international scientific evidence base on the potential risks to safety and how to control them effectively. The International Association for Hydrogen Safety (known as IA HySAFE) is leading global efforts to ensure this. HSE hosted the 2018 IA HySAFE Biennial Research Priorities Workshop. A panel of international experts presented during nine key topic sessions: (1) Industrial and National Programmes; (2) Applications; (3) Storage; (4) Accident Physics – Gas Phase; (5) Accident Physics – Liquid/ Cryogenic Behaviour; (6) Materials; (7) Mitigation Sensors Hazard Prevention and Risk Reduction; (8) Integrated Tools for Hazard and Risk Assessment; (9) General Aspects of Safety.<br/>This report gives an overview of each topic made by the session chairperson. It also gives further analysis of the totality of the evidence presented. The workshop outputs are shaping international activities on hydrogen safety. They are helping key stakeholders to identify gaps in knowledge and expertise and to understand and plan for potential safety challenges associated with the global expansion of hydrogen in the energy system.
Fuel Cell Codes and Standards Resource
Jan 2021
Publication
Although hydrogen has been used in industry for decades its use as a fuel for vehicles or stationary power generation in consumer environments is relatively new. As such hydrogen and fuel cell codes and standards are in various stages of development. Industry manufacturers the government and other safety experts are working with codes and standards development organizations to prepare review and promulgate technically-sound codes and standards for hydrogen and fuel cell technologies and systems.
Codes and standards are being adopted revised or developed for vehicles; fuel delivery and storage; fueling service and parking facilities; and vehicle fueling interfaces. Codes and standards are also being adopted revised or developed for stationary and portable fuel cells and interfaces as well as hydrogen generators. A list of current of international codes and standards is available on the Fuel Cells Codes and Standards Resource.
Link to website
Codes and standards are being adopted revised or developed for vehicles; fuel delivery and storage; fueling service and parking facilities; and vehicle fueling interfaces. Codes and standards are also being adopted revised or developed for stationary and portable fuel cells and interfaces as well as hydrogen generators. A list of current of international codes and standards is available on the Fuel Cells Codes and Standards Resource.
Link to website
Technology Assessment of Hydrogen Firing of Process Heaters
Apr 2011
Publication
In conjunction with John Zink Co. LLC the Chevron Energy Technology Company conducted a three part study evaluating potential issues with switching refinery process heaters from fuel gas to hydrogen fuel for the purpose of greenhouse gas emissions reduction via CO2 capture and storage.
The focus was on the following areas:
The focus was on the following areas:
- Heater performance
- Burner performance and robustness
- Fuel gas system retrofit requirements
Blind-prediction: Estimating the Consequences of Vented Hydrogen Deflagrations for Homogeneous Mixtures in a 20-foot ISO Container
Sep 2017
Publication
Trygve Skjold,
Helene Hisken,
Sunil Lakshmipathy,
Gordon Atanga,
Marco Carcassi,
Martino Schiavetti,
James R. Stewart,
A. Newton,
James R. Hoyes,
Ilias C. Tolias,
Alexandros G. Venetsanos,
Olav Roald Hansen,
J. Geng,
Asmund Huser,
Sjur Helland,
Romain Jambut,
Ke Ren,
Alexei Kotchourko,
Thomas Jordan,
Jérome Daubech,
Guillaume Lecocq,
Arve Grønsund Hanssen,
Chenthil Kumar,
Laurent Krumenacker,
Simon Jallais,
D. Miller and
Carl Regis Bauwens
This paper summarises the results from a blind-prediction study for models developed for estimating the consequences of vented hydrogen deflagrations. The work is part of the project Improving hydrogen safety for energy applications through pre-normative research on vented deflagrations (HySEA). The scenarios selected for the blind-prediction entailed vented explosions with homogeneous hydrogen-air mixtures in a 20-foot ISO container. The test program included two configurations and six experiments i.e. three repeated tests for each scenario. The comparison between experimental results and model predictions reveals reasonable agreement for some of the models and significant discrepancies for others. It is foreseen that the first blind-prediction study in the HySEA project will motivate developers to improve their models and to update guidelines for users of the models.
Safety Code Equivalencies in Hydrogen Infrastructure Deployment
Sep 2019
Publication
Various studies and market trends show that the number of hydrogen fuelling stations will increase to the thousands in the US by 2050. NFPA 2 Hydrogen Technologies Code (NFPA2) the nationally adopted primary code governing hydrogen safety is relatively new and hydrogen vehicle technology is a relatively new and rapidly developing technology. In order to effectively aid and accelerate the deployment of standardized retail hydrogen fuelling facilities the permitting of hydrogen fuelling stations employing outdoor bulk liquid storage in the state of California.
In an effort to better understand how the applicants consultants and more importantly the Authorities Having Jurisdiction (AHJ)s are interpreting and applying the NFPA 2 especially for complex applications the newest hydrogen stations with the largest amount of bulk hydrogen storage in urban environment settings were identified and the permit applications and permit approval outcomes of the said stations were analysed. Utilizing the pubic record request process LH2 station permit applications were reviewed along with the approval outcomes directly from the municipalities that issued the permits. AHJs with H2 station permitting experience were interviewed. Case studies of permit hydrogen fuelling station permit applications were then complied to document both the perspectives of the applicant and the AHJ and the often iterative and collaborative nature of permitting.
The current permitting time for Liquid Hydrogen (LH2) stations can range from 9 to 18 months in the California. Five out of the six LH2 stations applications required Alternative Means & Methods (AM&Ms) proposals and deviations from the prescriptive requirements of the Code were granted. Furthermore AHJs often requested additional documents and studies specific to application parameters in addition to NFPA 2 requirements.
In an effort to better understand how the applicants consultants and more importantly the Authorities Having Jurisdiction (AHJ)s are interpreting and applying the NFPA 2 especially for complex applications the newest hydrogen stations with the largest amount of bulk hydrogen storage in urban environment settings were identified and the permit applications and permit approval outcomes of the said stations were analysed. Utilizing the pubic record request process LH2 station permit applications were reviewed along with the approval outcomes directly from the municipalities that issued the permits. AHJs with H2 station permitting experience were interviewed. Case studies of permit hydrogen fuelling station permit applications were then complied to document both the perspectives of the applicant and the AHJ and the often iterative and collaborative nature of permitting.
The current permitting time for Liquid Hydrogen (LH2) stations can range from 9 to 18 months in the California. Five out of the six LH2 stations applications required Alternative Means & Methods (AM&Ms) proposals and deviations from the prescriptive requirements of the Code were granted. Furthermore AHJs often requested additional documents and studies specific to application parameters in addition to NFPA 2 requirements.
Compliance Measurements of Fuel Cell Electric Vehicle Exhaust
Sep 2019
Publication
The NREL Sensor Laboratory has been developing an analyzer that can verify compliance to the international United Nations Global Technical Regulation number 13 (GTR 13--Global Technical Regulation on Hydrogen and Fuel Cell Vehicles) prescriptive requirements pertaining to allowable hydrogen levels in the exhaust of fuel cell electric vehicles (FCEV) [1]. GTR 13 prescribes that the FCEV exhaust shall remain below 4 vol% H2 over a 3-second moving average and shall not at any time exceed 8 vol% H2 as verified with an analyzer with a response time (t90) of 300 ms or faster. GTR 13 has been implemented and is to serve as the basis for national regulations pertaining to hydrogen powered vehicle safety in the United States Canada Japan and the European Union. In the U.S. vehicle safety is overseen by the Department of Transportation (DOT) through the Federal Motor Vehicle Safety Standards (FMVSS) and in Canada by Transport Canada through the Canadian Motor Vehicle Safety Standard (CMVSS). The NREL FCEV exhaust analyzer is based upon a low-cost commercial hydrogen sensor with a response time (t90) of less than 250 ms. A prototype analyzer and gas probe assembly have been constructed and tested that can interface to the gas sampling system used by Environment and Climate Change Canada’s (ECCC) Emission Research and Measurement Section (ERMS) for the exhaust gas analysis. Through a partnership with Transport Canada ECCC will analyze the hydrogen level in the exhaust of a commercial FCEV. ECCC will use the NREL FCEV Exhaust Gas analyzer to perform these measurements. The analyzer was demonstrated on a FCEV operating under simulated road conditions using a chassis dynamometer at a private facility.
Ignitability and Mixing of Underexpanded Hydrogen Jets
Sep 2011
Publication
Reliable methods are needed to predict ignition boundaries that result from compressed hydrogen bulk storage leaks without complex modelling. To support the development of these methods a new high-pressure stagnation chamber has been integrated into Sandia National Laboratories’ Turbulent Combustion Laboratory so that relevant compressed gas release scenarios can be replicated. For the present study a jet with a 10:1 pressure ratio issuing from a small 0.75 mm radius nozzle has been examined. Jet exit shock structure was imaged by Schlieren photography while quantitative Planar Laser Rayleigh Scatter imaging was used to measure instantaneous hydrogen mole fractions downstream of the Mach disk. Measured concentration statistics and ignitable boundary predictions compared favorably to analytic reconstructions of downstream jet dispersion behaviour. Model results were produced from subsonic jet dispersion models and by invoking self-similarity jet scaling arguments with length scaling by experimentally measured effective source radii. Similar far field reconstructions that relied on various notional nozzle models to account for complex jet exit shock phenomena failed to satisfactorily predict the experimental findings. These results indicate further notional nozzle refinement is needed to improve the prediction fidelity. Moreover further investigation is required to understand the effect of different pressure ratios on measured virtual origins used in the jet dispersion model.
Hypothetical Accident Scenario Modelling for Condensed Hydrogen Storage Materials
Sep 2011
Publication
Hydrogen is seen as an ideal energy carrier for stationary and mobile applications. However the use of high energy density condensed hydrogen storage materials such as NH3BH3 comes with risks associated with their high reactivity with water exposure and their decomposition products reactivity in air. To predict their behaviour under these circumstances idealized finite element models of hypothetical accident scenarios have been developed. Empirical thermodynamic calculations based on precise thermal gravimetric analysis (TGA) and calorimetric experiments have been performed in order to quantify the energy and hydrogen release rates and to quantify the reaction products resulting from water and air exposure.
Hydrogen Emergency Response Training for First Responders
Sep 2011
Publication
The U.S. Department of Energy supports the implementation of hydrogen fuel cell technologies by providing hydrogen safety and emergency response training to first responders. A collaboration was formed to develop and deliver a one-day course that uses a mobile fuel cell vehicle (FCV) burn prop designed and built by Kidde Fire Trainers. This paper describes the development of the training curriculum including the design and operation of the FCV prop; describes the successful delivery of this course to over 300 participants at three training centers in California; and discusses feedback and observations received on the course. Photographs and video clips of the training sessions will be presented.
Hydrogen Flames in Tubes- Critical Run-up Distances
Sep 2007
Publication
The hazard associated with flame acceleration to supersonic speeds in hydrogen mixtures is discussed. A set of approximate models for evaluation of the run-up distances to supersonic flames in relatively smooth tubes and tubes with obstacles is presented. The model for smooth tubes is based on general relationships between the flame area turbulent burning velocity and the flame speed combined with an approximate description for the boundary layer thickness ahead of an accelerated flame. The unknown constants of the model are evaluated using experimental data. This model is then supplemented with the model for the minimum run-up distance for FA in tubes with obstacles developed earlier. On the basis of these two models solutions for the determination of the critical runup distances for FA and deflagration to detonation transition in tubes and channels for various hydrogen mixtures initial temperature and pressure tube size and tube roughness are presented.
Risk Mitigation Strategies for Hydrogen Storage Materials
Sep 2011
Publication
Hydrogen is seen as an ideal energy carrier for stationary and mobile applications. However the use of high energy density materials such as hydrides comes with the drawback of risks associated to their high reactivity towards air and water exposure. We have developed novel strategies to mitigate these risks. These strategies were evaluated using standard UN tests and isothermal calorimetric measurements. Cycling experiments were conducted to assess the impact of the mitigants on the modified materials derived from 8LiH•3Mg(NH2)2 system. In some cases our results show an improvement in kinetics when compared to the unmodified material. Effective mitigants were also discovered for aluminium hydride (alane) and lithium borohydride completely inhibiting ignition.
The International Energy Agency Hydrogen Implementing Agreement Task on Hydrogen Safety
Sep 2009
Publication
The International Energy Agency’s Hydrogen Implementing Agreement (www.ieahia.org) initiated a collaborative task on hydrogen safety in 1994 and this has proved to an effective method of pooling expert knowledge to address the most significant problems associated with the barriers to the commercial adoption of hydrogen energy. Presently there are approximately 10 countries participating in the task and it has proven a valuable method of efficiently combining efforts and resources. The task is now in the fifth year of a six year term and will end in October 2010. This paper will describe the scope of the task the progress made and plans for future work. There are also a number of other tasks underway and this paper will give a brief summary of those activities. Because of the nature of the International Energy Agency which is an international agreement between governments it is intended that such collaboration will complement other efforts to help build the technology base around which codes and standards can be developed. This paper describes the specific scope and work plan for the collaboration that has been developed to date.
Updated Jet Flame Radiation Modelling with Corrections for Buoyancy and Wind
Sep 2013
Publication
Radiative heat fluxes from small to medium-scale hydrogen jet flames (<10 m) compare favorably to theoretical predictions provided the product species thermal emittance and optical flame thickness are corrected for. However recent heat flux measurements from two large-scale horizontally orientated hydrogen flames (17.4 and 45.9 m respectively) revealed that current methods underpredicted the flame radiant fraction by 40% or more. Newly developed weighted source flame radiation models have demonstrated substantial improvement in the heat flux predictions particularly in the near-field and allow for a sensible way to correct potential ground surface reflective irradiance. These updated methods are still constrained by the fact that the flame is assumed to have a linear trajectory despite buoyancy effects that can result in significant flame deformation. The current paper discusses a method to predict flame centerline trajectories via a one-dimensional flame integral model which enables optimized placement of source emitters for weighted multi-source heat flux prediction methods. Flame shape prediction from choked releases was evaluated against flame envelope imaging and found to depend heavily on the notional nozzle model formulation used to compute the density weighted effective nozzle diameter. Nonetheless substantial improvement in the prediction of downstream radiative heat flux values occurred when emitter placement was corrected by the flame integral model regardless of the notional nozzle model formulation used.
Hourly Modelling of Thermal Hydrogen Electricity Markets
Jul 2020
Publication
The hourly operation of Thermal Hydrogen electricity markets is modelled. The economic values for all applicable chemical commodities are quantified (syngas ammonia methanol and oxygen) and an hourly electricity model is constructed to mimic the dispatch of key technologies: bi-directional power plants dual-fuel heating systems and plug-in fuel-cell hybrid electric vehicles. The operation of key technologies determines hourly electricity prices and an optimization model adjusts the capacity to minimize electricity prices yet allow all generators to recover costs. We examine 12 cost scenarios for renewables nuclear and natural gas; the results demonstrate emissionsfree ‘energy-only’ electricity markets whose supply is largely dominated by renewables. The economic outcome is made possible in part by seizing the full supply-chain value from electrolysis (both hydrogen and oxygen) which allows an increased willingness to pay for (renewable) electricity. The wholesale electricity prices average $25–$45/ MWh or just slightly higher than the assumed levelized cost of renewable energy. This implies very competitive electricity prices particularly given the lack of need for ‘scarcity’ pricing capacity markets dedicated electricity storage or underutilized electric transmission and distribution capacity.
Hydrogen Compatibility of Austenitic Stainless Steel Tubing and Orbital Tube Welds
Sep 2013
Publication
Refueling infrastructure for use in gaseous hydrogen powered vehicles requires extensive manifolding for delivering the hydrogen from the stationary fuel storage at the refueling station to the vehicle as well as from the mobile storage on the vehicle to the fuel cell or combustion engine. Manifolds for gas handling often use welded construction (as opposed to compression fittings) to minimize gas leaks. Therefore it is important to understand the effects of hydrogen on tubing and tubing welds. This paper provides a brief overview of on-going studies on the effects of hydrogen precharging on the tensile properties of austenitic stainless tubing and orbital tube welds of several austenitic stainless steels.
Regulations, Codes, and Standards (RCS) For Large Scale Hydrogen Systems
Sep 2017
Publication
Hydrogen has potential applications that require larger-scale storage use and handling systems than currently are employed in emerging-market fuel cell applications. These potential applications include hydrogen generation and storage systems that would support electrical grid systems. There has been extensive work evaluating regulations codes and standards (RCS) for the emerging fuel cell market such as the infrastructure required to support fuel cell electric vehicles. However there has not been a similar RCS evaluation and development process for these larger systems. This paper presents an evaluation of the existing RCS in the United States for large-scale systems and identifies potential RCS gaps. This analysis considers large-scale hydrogen technologies that are currently being employed in limited use but may be more widely used as large-scale applications expand. The paper also identifies areas of potential safety research that would need to be conducted to fill the RCS gaps. U.S. codes define bulk hydrogen storage systems but do not define large-scale systems. This paper evaluates potential applications to define a large-scale hydrogen system relative to the systems employed in emerging technologies such as hydrogen fuelling stations. These large-scale systems would likely be of similar size to or larger than industrial hydrogen systems.
Validation of Two-Layer Model for Underexpanded Hydrogen Jets
Sep 2019
Publication
Previous studies have shown that the two-layer model more accurately predicts hydrogen dispersion than the conventional notional nozzle models without significantly increasing the computational expense. However the model was only validated for predicting the concentration distribution and has not been adequately validated for predicting the velocity distributions. In the present study particle imaging velocimetry (PIV) was used to measure the velocity field of an underexpanded hydrogen jet released at 10 bar from a 1.5 mm diameter orifice. The two-layer model was the used to calculate the inlet conditions for a two-dimensional axisymmetric CFD model to simulate the hydrogen jet downstream of the Mach disk. The predicted velocity spreading and centerline decay rates agreed well with the PIV measurements. The predicted concentration distribution was consistent with data from previous planar Rayleigh scattering measurements used to verify the concentration distribution predictions in an earlier study. The jet spreading was also simulated using several widely used notional nozzle models combined with the integral plume model for comparison. These results show that the velocity and concentration distributions are both better predicted by the two-layer model than the notional nozzle models to complement previous studies verifying only the predicted concentration profiles. Thus this study shows that the two-layer model can accurately predict the jet velocity distributions as well as the concentration distributions as verified earlier. Though more validation studies are needed to improve confidence in the model and increase the range of validity the present work indicates that the two-layer model is a promising tool for fast accurate predictions of the flow fields of underexpanded hydrogen jets.
Controlled Hydrogen Fleet and Infrastructure Demonstration and Validation Project
Dec 2011
Publication
This report summarizes the work conducted under U.S. Department of Energy (DOE) under contract DE-FC36-04GO14285 by Mercedes-Benz & Research Development North America (MBRDNA) Chrysler Daimler Mercedes Benz USA (MBUSA) BP DTE Energy and NextEnergy to validate fuel cell technologies for infrastructure transportation as well as assess technology and commercial readiness for the market. The Mercedes Team together with its partners tested the technology by operating and fuelling hydrogen fuel cell vehicles under real world conditions in varying climate terrain and driving conditions. Vehicle and infrastructure data was collected to monitor the progress toward the hydrogen vehicle and infrastructure performance targets of $2.00 to 3.00/gge hydrogen production cost and 2000-hour fuel cell durability. Finally to prepare the public for a hydrogen economy outreach activities were designed to promote awareness and acceptance of hydrogen technology. DTE BP and NextEnergy established hydrogen filling stations using multiple technologies for on-site hydrogen generation storage and dispensing. DTE established a hydrogen station in Southfield Michigan while NextEnergy and BP worked together to construct one hydrogen station in Detroit. BP constructed another fueling station in Burbank California and provided a full-time hydrogen trailer at San Francisco California and a hydrogen station located at Los Angeles International Airportmore.
Low-carbon Hydrogen Via Integration of Steam Methane Reforming with Molten Carbonate Fuel Cells at Low Fuel Utilization
Feb 2021
Publication
Hydrogen production is critical to many modern chemical processes – ammonia synthesis petroleum refining direct reduction of iron and more. Conventional approaches to hydrogen manufacture include steam methane reforming and autothermal reforming which today account for the lion's share of hydrogen generation. Without CO2 capture these processes emit about 8.7 kg of CO2 for each kg of H2 produced. In this study a molten carbonate fuel cell system with CO2 capture is proposed to retrofit the flue gas stream of an existing Steam Methane Reforming plant rated at 100000 Nm3 h−1 of 99.5% pure H2. The thermodynamic analysis shows direct CO2 emissions can be reduced by more than 95% to 0.4 to 0.5 kg CO2 /kg H2 while producing 17% more hydrogen (with an increase in natural gas input of approximately 37%). Because of the additional power and hydrogen generation of the carbonate fuel cell the efficiency debit associated with CO2 capture is quite small reducing the SMR efficiency from 76.6% without capture to 75.6% with capture. In comparison the use of standard amine technology for CO2 capture reduces the efficiency below 70%. This demonstrates the synergistic nature of the carbonate fuel cells which can reform natural gas to H2 while simultaneously capturing CO2 from the SMR flue gas and producing electricity giving rise to a total system with very low emissions yet high efficiency.
The Renewable Hydrogen–Methane (RHYME) Transportation Fuel: A Practical First Step in the Realization of the Hydrogen Economy
Feb 2022
Publication
The permanent introduction of green hydrogen into the energy economy would require that a discriminating selection be made of its use in the sectors where its value is optimal in terms of relative cost and life cycle reduction in carbon dioxide emissions. Consequently hydrogen can be used as an energy storage medium when intermittent wind and solar power exceed certain penetration in the grid likely above 40% and in road transportation right away to begin displacing gasoline and diesel fuels. To this end the proposed approach is to utilize current technologies represented by PHEV in light-duty and HEV in heavy-duty vehicles where a high-performance internal combustion engine is used with a fuel comprised of 15–20% green hydrogen and 85–89% green methane depending on vehicle type. This fuel designated as RHYME takes advantage of the best attributes of hydrogen and methane results in lower life cycle carbon dioxide emissions than BEVs or FCEVs and offers a cost-effective and pragmatic approach both locally as well as globally in establishing hydrogen as part of the energy economy over the next ten to thirty years.
Stress–Corrosion Cracking of AISI 316L Stainless Steel in Seawater Environments: Effect of Surface Machining
Oct 2020
Publication
To understand the effect of surface machining on the resistance of AISI 316L to SCC (stress–corrosion cracking) in marine environments we tested nuts surface-machined by different methods in a seawater-spraying chamber. Two forms of cracks were observed: on the machined surface and underneath it. On the surface cracks connected with the pitting sites were observed to propagate perpendicular to the hoop-stress direction identifying them as stress–corrosion cracks. Under the surface catastrophic transgranular cracks developed likely driven by hydrogen embrittlement caused by the chloride-concentrating level of humidity in the testing environment. Under constant testing conditions significantly different SCC resistance was observed depending on how the nuts had been machined. Statistical evaluation of the nut surface-crack density indicates that machining by a “form” tool yields a crack density one order of magnitude lower than machining by a “single-point” tool. Microstructural analysis of form-tool-machined nuts revealed a homogeneous deformed subsurface zone with nanosized grains leading to enhanced surface hardness. Apparently the reduced grain size and/or the associated mechanical hardening improve resistance to SCC. The nanograin subsurface zone was not observed on nuts machined by a single-point tool. Surface roughness measurements indicate that single-point-tool-machined nuts have a rougher surface than form-tool machined nuts. Apparently surface roughness reduces SCC resistance by increasing the susceptibility to etch attack in Cl--rich solutions. The results of X-ray diffractometry and transmission electron microscopy diffractometry indicate that machining with either tool generates a small volume fraction (< 0.01) of strain-induced martensite. However considering the small volume fraction and absence of martensite in regions of cracking martensite is not primarily responsible for SCC in marine environments.
Role of Hydrogen in a Low-Carbon Electric Power System: A Case Study
Jan 2021
Publication
The European Union set a 2050 decarbonization target in the Paris Agreement to reduce carbon emissions by 90–95% relative to 1990 emission levels. The path toward achieving those deep decarbonization targets can take various shapes but will surely include a portfolio of economy-wide low-carbon energy technologies/options. The growth of the intermittent renewable power sources in the grid mix has helped reduce the carbon footprint of the electric power sector. Under the need for decarbonizing the electric power sector we simulated a low-carbon power system. We investigated the role of hydrogen for future electric power systems under current cost projections. The model optimizes the power generation mix economically for a given carbon constraint. The generation mix consists of intermittent renewable power sources (solar and wind) and dispatchable gas turbine and combined cycle units fuelled by natural gas with carbon capture and sequestration as well as hydrogen. We created several scenarios with battery storage options pumped hydro hydrogen storage and demand-side response (DSR). The results show that energy storage replaces power generation and pumped hydro entirely replaces battery storage under given conditions. The availability of pumped hydro storage and demand-side response reduced the total cost as well as the combination of solar photovoltaic and pumped hydro storage. Demand-side response reduces relatively costly dispatchable power generation reduces annual power generation halves the shadow carbon price and is a viable alternative to energy storage. The carbon constrain defines the generation mix and initializes the integration of hydrogen (H2). Although the model rates power to gas with hydrogen as not economically viable in this power system under the given conditions and assumptions hydrogen is important for hard-to-abate sectors and enables sector coupling in a real energy system. This study discusses the potential for hydrogen beyond this model approach and shows the differences between cost optimization models and real-world feasibility.
Resource Assessment for Hydrogen Production
Jul 2020
Publication
This analysis was conducted in support of the U.S. Department of Energy's H2@Scale initiative and this report examines the resources required to meet demand for an additional 10 million metric tonnes (MMT) of hydrogen in 2040. The technical potential of hydrogen production from fossil nuclear and renewable energy resources is presented. Updated maps describe the geographical distribution of hydrogen production potential from renewable energy resources. The results conclude that the technical resource availability of domestic energy resources is sufficient to meet an additional 10 MMT of hydrogen demand in 2040 without placing significant pressure on existing resources. While this level of hydrogen demand could result in a significant increase in renewable energy consumption in particular the technical potential of each resource is estimated to be sufficient to meet the demand. Future research to enable the large-scale integration of hydrogen in the U.S. energy and other sectors will include analyzing the geographic distribution of resources in relation to hydrogen demand for a variety of applications. Additional techno-economic analysis is also needed to understand the economic potential of hydrogen in other industries beyond transportation; such analysis is currently being undertaken by a multi-lab project initiated by DOE in 2016. Finally information from techno-economic analyses should be used to continually update and inform R&D targets for energy production hydrogen production and hydrogen utilization technologies.
Reversible Hydrogen Storage Using Nanocomposites
Jul 2020
Publication
In the field of energy storage recently investigated nanocomposites show promise in terms of high hydrogen uptake and release with enhancement in the reaction kinetics. Among several carbonaceous nanovariants like carbon nanotubes (CNTs) fullerenes and graphitic nanofibers reveal reversible hydrogen sorption characteristics at 77 K due to their van der Waals interaction. The spillover mechanism combining Pd nanoparticles on the host metal-organic framework (MOF) show room temperature uptake of hydrogen. Metal or complex hydrides either in the nanocomposite form and its subset nanocatalyst dispersed alloy phases illustrate the concept of nanoengineering and nanoconfinement of particles with tailor-made properties for reversible hydrogen storage. Another class of materials comprising polymeric nanostructures such as conducting polyaniline and their functionalized nanocomposites are versatile hydrogen storage materials because of their unique size high specific surface-area pore-volume and bulk properties. The salient features of nanocomposite materials for reversible hydrogen storage are reviewed and discussed.
Hydrogen-Based Energy Storage Systems for Large-Scale Data Center Applications
Nov 2021
Publication
Global demand for data and data access has spurred the rapid growth of the data center industry. To meet demands data centers must provide uninterrupted service even during the loss of primary power. Service providers seeking ways to eliminate their carbon footprint are increasingly looking to clean and sustainable energy solutions such as hydrogen technologies as alternatives to traditional backup generators. In this viewpoint a survey of the current state of data centers and hydrogen-based technologies is provided along with a discussion of the hydrogen storage and infrastructure requirements needed for large-scale backup power applications at data centers.
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
Impact of Hydrogen/Natural Gas Blends on Partially Premixed Combustion Equipment: NOx Emission and Operational Performance
Feb 2022
Publication
Several North American utilities are planning to blend hydrogen into gas grids as a short‐ term way of addressing the scalable demand for hydrogen and as a long‐term decarbonization strat‐ egy for ‘difficult‐to‐electrify’ end uses. This study documents the impact of 0–30% hydrogen blends by volume on the performance emissions and safety of unadjusted equipment in a simulated use environment focusing on prevalent partially premixed combustion designs. Following a thorough literature review the authors describe three sets of results: operating standard and “ultra‐low NOx” burners from common heating equipment in “simulators” with hydrogen/methane blends up to 30% by volume in situ testing of the same heating equipment and field sampling of a wider range of equipment with 0–10% hydrogen/natural gas blends at a utility‐owned training facility. The equipment was successfully operated with up to 30% hydrogen‐blended fuels with limited visual changes to flames and key trends emerged: (a) a decrease in the input rate from 0 to 30% H2 up to 11% often in excess of the Wobbe Index‐based predictions; (b) NOx and CO emissions are flat or decline (air‐free or energy‐adjusted basis) with increasing hydrogen blending; and (c) a minor de‐ crease (1.2%) or increase (0.9%) in efficiency from 0 to 30% hydrogen blends for standard versus ultra‐low NOx‐type water heaters respectively.
Safety Standard for Hydrogen and Hydrogen Systems Guidelines for Hydrogen System Design, Materials Selection, Operations, Storage and Transportation
Jan 1997
Publication
The NASA Safety Standard which establishes a uniform process for hydrogen system design materials selection operation storage and transportation is presented. The guidelines include suggestions for safely storing handling and using hydrogen in gaseous (GH2) liquid (LH2) or slush (SLH2) form whether used as a propellant or non-propellant. The handbook contains 9 chapters detailing properties and hazards facility design design of components materials compatibility detection and transportation. Chapter 10 serves as a reference and the appendices contained therein include: assessment examples; scaling laws explosions blast effects and fragmentation; codes standards and NASA directives; and relief devices along with a list of tables and figures abbreviations a glossary and an index for ease of use. The intent of the handbook is to provide enough information that it can be used alone but at the same time reference data sources that can provide much more detail if required.
Green Synthesis of Olefin-linked Covalent Organic Frameworks for Hydrogen Fuel Cell Applications
Mar 2021
Publication
Green synthesis of crystalline porous materials for energy-related applications is of great significance but very challenging. Here we create a green strategy to fabricate a highly crystalline olefin-linked pyrazine-based covalent organic framework (COF) with high robustness and porosity under solvent-free conditions. The abundant nitrogen sites high hydrophilicity and well-defined one-dimensional nanochannels make the resulting COF an ideal platform to confine and stabilize the H3PO4 network in the pores through hydrogen-bonding interactions. The resulting material exhibits low activation energy (Ea) of 0.06 eV and ultrahigh proton conductivity across a wide relative humidity (10–90 %) and temperature range (25–80 °C). A realistic proton exchange membrane fuel cell using the olefin-linked COF as the solid electrolyte achieve a maximum power of 135 mW cm−2 and a current density of 676 mA cm−2 which exceeds all reported COF materials.
Sub-second and Ppm-level Optical Sensing of Hydrogen Using Templated Control of Nano-hydride Geometry and Composition
Apr 2021
Publication
The use of hydrogen as a clean and renewable alternative to fossil fuels requires a suite of flammability mitigating technologies particularly robust sensors for hydrogen leak detection and concentration monitoring. To this end we have developed a class of lightweight optical hydrogen sensors based on a metasurface of Pd nano-patchy particle arrays which fulfills the increasing requirements of a safe hydrogen fuel sensing system with no risk of sparking. The structure of the optical sensor is readily nano-engineered to yield extraordinarily rapid response to hydrogen gas (<3 s at 1 mbar H2) with a high degree of accuracy (<5%). By incorporating 20% Ag Au or Co the sensing performances of the Pd-alloy sensor are significantly enhanced especially for the Pd80Co20 sensor whose optical response time at 1 mbar of H2 is just ~0.85 s while preserving the excellent accuracy (<2.5%) limit of detection (2.5 ppm) and robustness against aging temperature and interfering gases. The superior performance of our sensor places it among the fastest and most sensitive optical hydrogen sensors.
A Solar Thermal Sorption-enhanced Steam Methane Reforming (SE-SMR) Approach and its Performance Assessment
Feb 2022
Publication
This paper proposes an integration of concentrating solar power (CSP) with a sorption-enhanced steam methane reforming (SE-SMR) process and assesses its overall solar-to-fuel conversion performance. A thermodynamic treatment of the SE-SMR process for H2 production is presented and evaluated in an innovative two reactors system configuration using CSP as a heat input. Four metal carbonate/metal oxide pairs are considered and the equilibrium thermodynamics reveals that CaCO3/CaO pair is the most suitable candidate for this process. Additionally a reactor-scale thermodynamic model is developed to determine the optimum operating conditions for the process. For the carbonation step temperatures between 700 and 900 K and steam-to-methane ratio ≥4 are found to be the most favorable. Furthermore an advanced process model which utilizes operating conditions determined from the reactor-scale model is developed to evaluate the process efficiency. The model predicts that the proposed process can achieve a solar-to-fuel efficiency ~41% for calcination temperature of 1500 K and carbonation temperature of 800 K without considering any solid heat recovery. An additional 2.5% increase in the process efficiency is feasible with the consideration of the solid heat recovery. This study shows the thermodynamic feasibility of integrating the SE-SMR process with CSP technologies.
Ex Situ Thermo-catalytic Upgrading of Biomass Pyrolysis Vapors Using a Traveling Wave Microwave Reactor
Sep 2016
Publication
Microwave heating offers a number of advantages over conventional heating methods such as rapid and volumetric heating precise temperature control energy efficiency and lower temperature gradient. In this article we demonstrate the use of 2450 MHz microwave traveling wave reactor to heat the catalyst bed for thermo-catalytic upgrading of pyrolysis vapors. HZSM-5 catalyst was tested at three different temperatures (290 330 and 370°C) at a catalyst to biomass ratio of 2. Results were compared with conventional heating and induction heating method of catalyst bed. The yields of aromatic compounds and coke deposition were dependent on temperature and method of heating. Microwave heating yielded higher aromatic compounds and lower coke deposition. Microwave heating was also energy efficient compared to conventional reactors. The rate of catalyst deterioration was lower for catalyst heated in microwave system.
Microwave Absorption of Aluminum/Hydrogen Treated Titanium Dioxide Nanoparticles
Dec 2018
Publication
Interactions between incident electromagnetic energy and matter are of critical importance for numerous civil and military applications such as photocatalysis solar cells optics radar detection communications information processing and transport et al. Traditional mechanisms for such interactions in the microwave frequency mainly rely on dipole rotations and magnetic domain resonance. In this study we present the first report of the microwave absorption of Al/H2 treated TiO2 nanoparticles where the Al/H2 treatment not only induces structural and optical property changes but also largely improves the microwave absorption performance of TiO2 nanoparticles. Moreover the frequency of the microwave absorption can be finely controlled with the treatment temperature and the absorption efficiency can reach optimal values with a careful temperature tuning. A large reflection loss of −58.02 dB has been demonstrated with 3.1 mm TiO2 coating when the treating temperature is 700 °C. The high efficiency of microwave absorption is most likely linked to the disordering-induced property changes in the materials. Along with the increased microwave absorption properties are largely increased visible-light and IR absorptions and enhanced electrical conductivity and reduced skin-depth which is likely related to the interfacial defects within the TiO2 nanoparticles caused by the Al/H2 treatment.
Dual Z-scheme Charge Transfer in TiO2–Ag–Cu2O Composite for Enhanced Photocatalytic Hydrogen Generation
Apr 2015
Publication
Photocatalytic hydrogen generation is one of the most promising solutions to convert solar power into green chemical energy. In this work a multi-component TiO2–Ag–Cu2O composite was obtained through simple impregnation-calcination of Cu2O and subsequent photodeposition of Ag onto electrospun TiO2 nanotubes. The resulting TiO2–Ag–Cu2O photocatalyst exhibits excellent photocatalytic H2 evolution activity due to the synergetic effect of Ag and Cu2O on electrospun TiO2nanotubes. A dual Z-scheme charge transfer pathway for photocatalytic reactions over TiO2–Ag–Cu2O composite was proposed and discussed. This work provides a prototype for designing Z-scheme photocatalyst with Ag as an electron mediator.
Raw Biomass Electroreforming Coupled to Green Hydrogen Generation
Mar 2021
Publication
Despite the tremendous progress of coupling organic electrooxidation with hydrogen generation in a hybrid electrolysis electroreforming of raw biomass coupled to green hydrogen generation has not been reported yet due to the rigid polymeric structures of raw biomass. Herein we electrooxidize the most abundant natural amino biopolymer chitin to acetate with over 90% yield in hybrid electrolysis. The overall energy consumption of electrolysis can be reduced by 15% due to the thermodynamically and kinetically more favorable chitin oxidation over water oxidation. In obvious contrast to small organics as the anodic reactant the abundance of chitin endows the new oxidation reaction excellent scalability. A solar-driven electroreforming of chitin and chitin-containing shrimp shell waste is coupled to safe green hydrogen production thanks to the liquid anodic product and suppression of oxygen evolution. Our work thus demonstrates a scalable and safe process for resource upcycling and green hydrogen production for a sustainable energy future.
Decarbonization of Australia’s Energy System: Integrated Modelling of the Transformation of Electricity, Transportation, and Industrial Sectors
Jul 2020
Publication
To achieve the Paris Agreement’s long-term temperature goal current energy systems must be transformed. Australia represents an interesting case for energy system transformation modelling: with a power system dominated by fossil fuels and specifically with a heavy coal component there is at the same time a vast potential for expansion and use of renewables. We used the multi-sectoral Australian Energy Modelling System (AUSeMOSYS) to perform an integrated analysis of implications for the electricity transport and selected industry sectors to the mid-century. The state-level resolution allows representation of regional discrepancies in renewable supply and the quantification of inter-regional grid extensions necessary for the physical integration of variable renewables. We investigated the impacts of different CO2 budgets and selected key factors on energy system transformation. Results indicate that coal-fired generation has to be phased out completely by 2030 and a fully renewable electricity supply achieved in the 2030s according to the cost-optimal pathway implied by the 1.5 °C Paris Agreement-compatible carbon budget. Wind and solar PV can play a dominant role in decarbonizing Australia’s energy system with continuous growth of demand due to the strong electrification of linked energy sectors.
Overview of Biomass Conversion to Electricity and Hydrogen and Recent Developments in Low-Temperature Electrochemical Approaches
Nov 2020
Publication
Biomass is plant or animal material that stores both chemical and solar energies and that is widely used for heat production and various industrial processes. Biomass contains a large amount of the element hydrogen so it is an excellent source for hydrogen production. Therefore biomass is a sustainable source for electricity or hydrogen production. Although biomass power plants and reforming plants have been commercialized it remains a difficult challenge to develop more effective and economic technologies to further improve the conversion efficiency and reduce the environmental impacts in the conversion process. The use of biomass-based flow fuel cell technology to directly convert biomass to electricity and the use of electrolysis technology to convert biomass into hydrogen at a low temperature are two new research areas that have recently attracted interest. This paper first briefly introduces traditional technologies related to the conversion of biomass to electricity and hydrogen and then reviews the new developments in flow biomass fuel cells (FBFCs) and biomass electrolysis for hydrogen production (BEHP) in detail. Further challenges in these areas are discussed.
Quantifying the Potential of Renewable Natural Gas to Support a Reformed Energy Landscape: Estimates for New York State
Jun 2021
Publication
Public attention to climate change challenges our locked-in fossil fuel-dependent energy sector. Natural gas is replacing other fossil fuels in our energy mix. One way to reduce the greenhouse gas (GHG) impact of fossil natural gas is to replace it with renewable natural gas (RNG). The benefits of utilizing RNG are that it has no climate change impact when combusted and utilized in the same applications as fossil natural gas. RNG can be injected into the gas grid used as a transportation fuel or used for heating and electricity generation. Less common applications include utilizing RNG to produce chemicals such as methanol dimethyl ether and ammonia. The GHG impact should be quantified before committing to RNG. This study quantifies the potential production of biogas (i.e. the precursor to RNG) and RNG from agricultural and waste sources in New York State (NYS). It is unique because it is the first study to provide this analysis. The results showed that only about 10% of the state’s resources are used to generate biogas of which a small fraction is processed to RNG on the only two operational RNG facilities in the state. The impact of incorporating a second renewable substitute for fossil natural gas “green” hydrogen is also analyzed. It revealed that injecting RNG and “green” hydrogen gas into the pipeline system can reduce up to 20% of the state’s carbon emissions resulting from fossil natural gas usage which is a significant GHG reduction. Policy analysis for NYS shows that several state and federal policies support RNG production. However the value of RNG can be increased 10-fold by applying a similar incentive policy to California’s Low Carbon Fuel Standard (LCFS).
Recent Advances in Carbon Dioxide Conversion: A Circular Bioeconomy Perspective
Jun 2021
Publication
Managing the concentration of atmospheric CO2 requires a multifaceted engineering strategy which remains a highly challenging task. Reducing atmospheric CO2 (CO2R) by converting it to value-added chemicals in a carbon neutral footprint manner must be the ultimate goal. The latest progress in CO2R through either abiotic (artificial catalysts) or biotic (natural enzymes) processes is reviewed herein. Abiotic CO2R can be conducted in the aqueous phase that usually leads to the formation of a mixture of CO formic acid and hydrogen. By contrast a wide spectrum of hydrocarbon species is often observed by abiotic CO2R in the gaseous phase. On the other hand biotic CO2R is often conducted in the aqueous phase and a wide spectrum of value-added chemicals are obtained. Key to the success of the abiotic process is understanding the surface chemistry of catalysts which significantly governs the reactivity and selectivity of CO2R. However in biotic CO2R operation conditions and reactor design are crucial to reaching a neutral carbon footprint. Future research needs to look toward neutral or even negative carbon footprint CO2R processes. Having a deep insight into the scientific and technological aspect of both abiotic and biotic CO2R would advance in designing efficient catalysts and microalgae farming systems. Integrating the abiotic and biotic CO2R such as microbial fuel cells further diversifies the spectrum of CO2R.
Hydrogen Fuel Cell Vehicles; Current Status and Future Prospect
Jun 2019
Publication
The hazardous effects of pollutants from conventional fuel vehicles have caused the scientific world to move towards environmentally friendly energy sources. Though we have various renewable energy sources the perfect one to use as an energy source for vehicles is hydrogen. Like electricity hydrogen is an energy carrier that has the ability to deliver incredible amounts of energy. Onboard hydrogen storage in vehicles is an important factor that should be considered when designing fuel cell vehicles. In this study a recent development in hydrogen fuel cell engines is reviewed to scrutinize the feasibility of using hydrogen as a major fuel in transportation systems. A fuel cell is an electrochemical device that can produce electricity by allowing chemical gases and oxidants as reactants. With anodes and electrolytes the fuel cell splits the cation and the anion in the reactant to produce electricity. Fuel cells use reactants which are not harmful to the environment and produce water as a product of the chemical reaction. As hydrogen is one of the most efficient energy carriers the fuel cell can produce direct current (DC) power to run the electric car. By integrating a hydrogen fuel cell with batteries and the control system with strategies one can produce a sustainable hybrid car
Nickel-Based Electrocatalysts for Water Electrolysis
Feb 2022
Publication
Currently hydrogen production is based on the reforming process leading to the emission of pollutants; therefore a substitute production method is imminently required. Water electrolysis is an ideal alternative for large-scale hydrogen production as it does not produce any carbon-based pollutant byproducts. The production of green hydrogen from water electrolysis using intermittent sources (e.g. solar and eolic sources) would facilitate clean energy storage. However the electrocatalysts currently required for water electrolysis are noble metals making this potential option expensive and inaccessible for industrial applications. Therefore there is a need to develop electrocatalysts based on earth-abundant and low-cost metals. Nickel-based electrocatalysts are a fitting alternative because they are economically accessible. Extensive research has focused on developing nickel-based electrocatalysts for hydrogen and oxygen evolution. Theoretical and experimental work have addressed the elucidation of these electrochemical processes and the role of heteroatoms structure and morphology. Even though some works tend to be contradictory they have lit up the path for the development of efficient nickel-based electrocatalysts. For these reasons a review of recent progress is presented herein.
Water Photo-Oxidation Reaction on Clean and Doped Two-Dimensional Graphitic C2N
Apr 2020
Publication
In the search for new efficient photo-catalysts for hydrogen production through water splitting the main attention has been paid to tuning the band gap width and its position with respect to vacuum level. However actual electro-catalytic activity for the water oxidation reaction on a catalyst surface is no less important than those quantities. In this work we evaluate from first principles the thermodynamics of the reaction on relatively new candidates for water splitting: two-dimensional C2N and that doped with phosphorus. We find that the 4-step reaction usually expected for water splitting will not proceed on these systems resulting in oxygen atoms left strongly adsorbed to the surface. Another option a 3-step reaction is also found to be unfavorable. We also test an effect of higher oxygen coverage on the reaction thermodynamics as suggested elsewhere. We find that indeed the doubled O-coverage makes the 4-step reaction feasible for the doped C2N. However an unacceptably high anode potential is required to make this reaction proceed. We thus conclude that the materials under consideration may not be efficient electro-catalysts for water splitting.
Spin Pinning Effect to Reconstructed Oxyhydroxide Layer on Ferromagnetic Oxides for Enhanced Water Oxidation
Jun 2021
Publication
Producing hydrogen by water electrolysis suffers from the kinetic barriers in the oxygen evolution reaction (OER) that limits the overall efficiency. With spin-dependent kinetics in OER to manipulate the spin ordering of ferromagnetic OER catalysts (e.g. by magnetization) can reduce the kinetic barrier. However most active OER catalysts are not ferromagnetic which makes the spin manipulation challenging. In this work we report a strategy with spin pinning effect to make the spins in paramagnetic oxyhydroxides more aligned for higher intrinsic OER activity. The spin pinning effect is established in oxideFM/oxyhydroxide interface which is realized by a controlled surface reconstruction of ferromagnetic oxides. Under spin pinning simple magnetization further increases the spin alignment and thus the OER activity which validates the spin effect in rate-limiting OER step. The spin polarization in OER highly relies on oxyl radicals (O∙) created by 1st dehydrogenation to reduce the barrier for subsequent O-O coupling.
Storable Energy Production from Wind over Water
Apr 2020
Publication
The current status of a project is described which aims to demonstrate the technical and economic feasibility of converting the vast wind energy available over the globe’s oceans and lakes into storable energy. To this end autonomous high-performance sailing ships are equipped with hydrokinetic turbines whose output is stored either in electric batteries or is fed into electrolysers to produce hydrogen which then is compressed and stored in tanks. In the present paper the previous analytical studies which showed the potential of this “energy ship concept” are summarized and progress on its hardware demonstration is reported involving the conversion of a model sailboat to autonomous operation. The paper concludes with a discussion of the potential of this concept to achieve the IPCC-mandated requirement of reducing the global CO2 emissions by about 45% by 2030 reaching net zero by 2050.
A Combined Chemical-Electrochemical Process to Capture CO2 and Produce Hydrogen and Electricity
Sep 2021
Publication
Several carbon sequestration technologies have been proposed to utilize carbon dioxide (CO2 ) to produce energy and chemical compounds. However feasible technologies have not been adopted due to the low efficiency conversion rate and high-energy requirements. Process intensification increases the process productivity and efficiency by combining chemical reactions and separation operations. In this work we present a model of a chemical-electrochemical cyclical process that can capture carbon dioxide as a bicarbonate salt. The proposed process also produces hydrogen and electrical energy. Carbon capture is enhanced by the reaction at the cathode that displaces the equilibrium into bicarbonate production. Literature data show that the cyclic process can produce stable operation for long times by preserving ionic balance using a suitable ionic membrane that regulates ionic flows between the two half-cells. Numerical simulations have validated the proof of concept. The proposed process could serve as a novel CO2 sequestration technology while producing electrical energy and hydrogen.
Direct Evidence for Solid-like Hydrogen in a Nanoporous Carbon Hydrogen Storage Material at Supercritical Temperatures
Jul 2015
Publication
Here we report direct physical evidence that confinement of molecular hydrogen (H2) in an optimized nanoporous carbon results in accumulation of hydrogen with characteristics commensurate with solid H2 at temperatures up to 67 K above the liquid vapor critical temperature of bulk H2. This extreme densification is attributed to confinement of H2 molecules in the optimally sized micropores and occurs at pressures as low as 0.02 MPa. The quantities of contained solid-like H2 increased with pressure and were directly evaluated using in situ inelastic neutron scattering and confirmed by analysis of gas sorption isotherms. The demonstration of the existence of solid-like H2 challenges the existing assumption that supercritical hydrogen confined in nanopores has an upper limit of liquid H2 density. Thus this insight offers opportunities for the development of more accurate models for the evaluation and design of nanoporous materials for high capacity adsorptive hydrogen storage.
Towards Ecological Alternatives in Bearing Lubrication
Jun 2021
Publication
Hydrogen is the cleanest fuel available because its combustion product is water. The internal combustion engine can in principle and without significant modifications run on hydrogen to produce mechanical energy. Regarding the technological solution leading to compact engines a question to ask is the following: Can combustion engine systems be lubricated with hydrogen? In general since many applications such as in turbomachines is it possible to use the surrounding gas as a lubricant? In this paper journal bearings global parameters are calculated and compared for steady state and dynamic conditions for different gas constituents such as air pentafluoropropane helium and hydrogen. Such a bearing may be promising as an ecological alternative to liquid lubrication.
Economic Analysis of a High-pressure Urban Pipeline Concept (HyLine) for Delivering Hydrogen to Retail Fueling Stations
Nov 2019
Publication
Reducing the cost of delivering hydrogen to fuelling stations and dispensing it into fuel cell electric vehicles (FCEVs) is one critical element of efforts to increase the cost-competitiveness of FCEVs. Today hydrogen is primarily delivered to stations by trucks. Pipeline delivery is much rarer: one urban U.S. station has been supplied with 800-psi hydrogen from an industrial hydrogen pipeline since 2011 and a German station on the edge of an industrial park has been supplied with 13000-psi hydrogen from a pipeline since 2006. This article compares the economics of existing U.S. hydrogen delivery methods with the economics of a high-pressure scalable intra-city pipeline system referred to here as the “HyLine” system. In the HyLine system hydrogen would be produced at urban industrial or commercial sites compressed to 15000 psi stored at centralized facilities delivered via high-pressure pipeline to retail stations and dispensed directly into FCEVs. Our analysis of retail fuelling station economics in Los Angeles suggests that as FCEV demand for hydrogen in an area becomes sufficiently dense pipeline hydrogen delivery gains an economic advantage over truck delivery. The HyLine approach would also enable cheaper dispensed hydrogen compared with lower-pressure pipeline delivery owing to economies of scale associated with integrated compression and storage. In the largest-scale fuelling scenario analyzed (a network of 24 stations with capacities of 1500 kg/d each and hydrogen produced via steam methane reforming) HyLine could potentially achieve a profited hydrogen cost of $5.3/kg which is approximately equivalent to a gasoline cost of $2.7/gal (assuming FCEVs offer twice the fuel economy of internal combustion engine vehicles and vehicle cost is competitive). It is important to note that significant effort would be required to develop technical knowledge codes and standards that would enable a HyLine system to be viable. However our preliminary analysis suggests that the HyLine approach merits further consideration based on its potential economic advantages. These advantages could also include the value of minimizing retail space used by hydrogen compression and storage sited at fuelling stations which is not reflected in our analysis.
Optimization of Component Sizing for a Fuel Cell-Powered Truck to Minimize Ownership Cost
Mar 2019
Publication
In this study we consider fuel cell-powered electric trucks (FCETs) as an alternative to conventional medium- and heavy-duty vehicles. FCETs use a battery combined with onboard hydrogen storage for energy storage. The additional battery provides regenerative braking and better fuel economy but it will also increase the initial cost of the vehicle. Heavier reliance on stored hydrogen might be cheaper initially but operational costs will be higher because hydrogen is more expensive than electricity. Achieving the right tradeoff between these power and energy choices is necessary to reduce the ownership cost of the vehicle. This paper develops an optimum component sizing algorithm for FCETs. The truck vehicle model was developed in Autonomie a platform for modelling vehicle energy consumption and performance. The algorithm optimizes component sizes to minimize overall ownership cost while ensuring that the FCET matches or exceeds the performance and cargo capacity of a conventional vehicle. Class 4 delivery truck and class 8 linehaul trucks are shown as examples. We estimate the ownership cost for various hydrogen costs powertrain components ownership periods and annual vehicle miles travelled.
How Green is Blue Hydrogen?
Jul 2021
Publication
Hydrogen is often viewed as an important energy carrier in a future decarbonized world. Currently most hydrogen is produced by steam reforming of methane in natural gas (“gray hydrogen”) with high carbon dioxide emissions. Increasingly many propose using carbon capture and storage to reduce these emissions producing so-called “blue hydrogen” frequently promoted as low emissions. We undertake the first effort in a peer-reviewed paper to examine the lifecycle greenhouse gas emissions of blue hydrogen accounting for emissions of both carbon dioxide and unburned fugitive methane. Far from being low carbon greenhouse gas emissions from the production of blue hydrogen are quite high particularly due to the release of fugitive methane. For our default assumptions (3.5% emission rate of methane from natural gas and a 20-year global warming potential) total carbon dioxide equivalent emissions for blue hydrogen are only 9%-12% less than for gray hydrogen. While carbon dioxide emissions are lower fugitive methane emissions for blue hydrogen are higher than for gray hydrogen because of an increased use of natural gas to power the carbon capture. Perhaps surprisingly the greenhouse gas footprint of blue hydrogen is more than 20% greater than burning natural gas or coal for heat and some 60% greater than burning diesel oil for heat again with our default assumptions. In a sensitivity analysis in which the methane emission rate from natural gas is reduced to a low value of 1.54% greenhouse gas emissions from blue hydrogen are still greater than from simply burning natural gas and are only 18%-25% less than for gray hydrogen. Our analysis assumes that captured carbon dioxide can be stored indefinitely an optimistic and unproven assumption. Even if true though the use of blue hydrogen appears difficult to justify on climate ground
Carbon Capture from Biogas by Deep Eutectic Solvents A COSMO Study to Evaluate the Effect of Impurities on Solubility and Selectivity
Jun 2021
Publication
Deep eutectic solvents (DES) are compounds of a hydrogen bond donor (HBD) and a hydrogen bond acceptor (HBA) that contain a depressed melting point compared to their individual constituents. DES have been studied for their use as carbon capture media and biogas upgrading. However contaminants’ presence in biogas might affect the carbon capture by DES. In this study conductor-like screening model for real solvents (COSMO-RS) was used to determine the effect of temperature pressure and selective contaminants on five DES’ namely choline chloride-urea choline chloride-ethylene glycol tetra butyl ammonium chloride-ethylene glycol tetra butyl ammonium bromide-decanoic acid and tetra octyl ammonium chloride-decanoic acid. Impurities studied in this paper are hydrogen sulfide ammonia water nitrogen octamethyltrisiloxane and decamethylcyclopentasiloxane. At infinite dilution CO2 solubility dependence upon temperature in each DES was examined by means of Henry’s Law constants. Next the systems were modeled from infinite dilution to equilibrium using the modified Raoults’ Law where CO2 solubility dependence upon pressure was examined. Finally solubility of CO2 and CH4 in the various DES were explored with the presence of varying mole percent of selective contaminants. Among the parameters studied it was found that the HBD of the solvent is the most determinant factor for the effectiveness of CO2 solubility. Other factors affecting the solubility are alkyl chain length of the HBA the associated halogen and the resulting polarity of the DES. It was also found that choline chloride-urea is the most selective to CO2 but has the lowest CO2 solubility and is the most polar among other solvents. On the other hand tetraoctylammonium chloride-decanoic acid is the least selective has the highest maximum CO2 solubility is the least polar and is the least affected by its environment.
Quaternary Hydrides Pd1-y-zAgyCuzHx Embedded Atom Method Potentials for Hydrogen Energy Applications
Jan 2021
Publication
The Pd-H system has attracted extensive attention. Pd can absorb considerable amount of H at room temperature this ability is reversible so it is suitable for multiple energy applications. Pd-Ag alloys possess higher H permeability solubility and narrower miscibility gap with better mechanical properties than pure Pd but sulfur poisoning remains an issue. Pd-Cu alloys have excellent resistance to sulfur and carbon monoxide poisoning and hydrogen embrittlement good mechanical properties and broader temperature working environments over pure Pd but relatively lower hydrogen permeability and solubility than pure Pd and Pd-Ag alloys. This suggests that alloying Pd with Ag and Cu to create Pd-Ag-Cu ternary alloys can optimize the overall performance and substantially lowers the cost. Thus in this paper we provide the first embedded atom method potentials for the quaternary hydrides Pd1-y-zAgyCuzHx. The fully analytical potentials are fitted utilizing the central atom method without performing time-consuming molecular dynamics simulations.
Influence of Cs Promoter on Ethanol Steam-Reforming Selectivity of Pt/m-ZrO2 Catalysts at Low Temperature
Sep 2021
Publication
The decarboxylation pathway in ethanol steam reforming ultimately favors higher selectivity to hydrogen over the decarbonylation mechanism. The addition of an optimized amount of Cs to Pt/m-ZrO2 catalysts increases the basicity and promotes the decarboxylation route converting ethanol to mainly H2 CO2 and CH4 at low temperature with virtually no decarbonylation being detected. This offers the potential to feed the product stream into a conventional methane steam reformer for the production of hydrogen with higher selectivity. DRIFTS and the temperature-programmed reaction of ethanol steam reforming as well as fixed bed catalyst testing revealed that the addition of just 2.9% Cs was able to stave off decarbonylation almost completely by attenuating the metallic function. This occurs with a decrease in ethanol conversion of just 16% relative to the undoped catalyst. In comparison with our previous work with Na this amount is—on an equivalent atomic basis—just 28% of the amount of Na that is required to achieve the same effect. Thus Cs is a much more efficient promoter than Na in facilitating decarboxylation.
Fire Safety of Hydrogen-Fuelled Vehicles- System-Level Bonfire Test
Sep 2005
Publication
The European Community requires a vehicle-level bonfire test for vehicles using plastic fuel tanks for conventional fuels (ECE R-34 Annex 5). A similar test could be applied to hydrogen-fuelled vehicles. It would test a realistic vehicle with its complete fuel and safety systems. An advantage of such a test is that the same test could be applied independent of the hydrogen storage technology (compressed gas liquid or hydride). There are currently standards for bonfire testing of a bare Compressed Natural Gas (CNG) tank and its Pressure Relief Device (PRD). This standard is FMVSS 304 in the U.S. and ISO 15869-1 in Europe. Japan has a similar standard. It requires that a bare tank and its associated PRD be subjected to a propane flame for 20 minutes. The tank must either survive or safely vent its contents. No modern composite wound tank is expected to survive for 20 minutes – so this is not a tank test but really a PRD test. The test procedure requires the PRD to be shielded from direct impingement of the flames – but the shield is not well specified. If it shields the PRD too well the PRD will not activate and the tank will burst. This paper describes the results of a CNG and a hydrogen tank burst from such tests. The mechanical energy released is enormous. It is simply unacceptable to allow the tank to burst – the PRD and venting system must work. Organizations in the U.S Europe and Japan are in the process of modifying the CNG tank bonfire test for compressed hydrogen storage. A bare tank with a single PRD is not a good simulation of a hydrogen fuel system installed in an actual vehicle. There will usually be multiple tanks plumbed together at either the tank pressure or at the intermediate pressure (after the pressure regulator). There may be more than one PRD. The tank may be shielded (from debris) or insulated to protect it from an underbody pool fire. Also the heat transfer from the simulated pool fire (propane flame) will be very different when mounted in a vehicle versus the bare tank test. A vehicle-level pool fire test will alleviate these problems. It is therefore recommended that the bare tank test be replaced by or augmented with a vehicle-level bonfire test similar to ECE R-34 Annex 5.
Hydrogen Wide Area Monitoring of LH2 Releases at HSE for the PRESLHY Project
Sep 2021
Publication
The characterization of liquid hydrogen (LH2) releases has been identified as an international research priority to facilitate the safe use of hydrogen as an energy carrier. Empirical field measurements such as those afforded by Hydrogen Wide Area Monitoring can elucidate the behavior of LH2 releases which can then be used to support and validate dispersion models. Hydrogen Wide Area Monitoring can be defined as the quantitative three-dimensional spatial and temporal profiling of planned or unintentional hydrogen releases. The NREL Sensor Laboratory developed a Hydrogen Wide Area Monitor (HyWAM) based upon a distributed array of hydrogen sensors. The NREL Sensor Laboratory and the Health and Safety Executive (HSE) formally committed to collaborate on profiling GH2 and LH2 releases which allowed for the integration of the NREL HyWAM into the HSE LH2 release behavior investigation supported by the FCH JU Prenormative Research for the Safe Use of Liquid Hydrogen (PRESLHY) program. A HyWAM system was deployed consisting of 32 hydrogen measurement points and co-located temperature sensors distributed downstream of the LH2 release apparatus developed by HSE. In addition the HyWAM deployment was supported by proximal wind and weather monitors. In a separate presentation at this conference “HSE Experimental Summary for the Characterisation Dispersion and Electrostatic Hazards of LH2 for the PRESLHY Project” HSE researchers summarize the experimental apparatus and protocols utilized in the HSE LH2 releases that were performed under the auspices of PRESLHY. As a supplement to the HSE presentation this presentation will focus on the spatial and temporal behavior LH2 releases as measured by the NREL HyWAM. Correlations to ambient conditions such as wind speed and direction plume temperature and hydrogen concentrations will be discussed in addition to the design and performance of the NREL HyWAM and its potential for improving hydrogen facility safety.
Toward Design of Synergistically Active Carbon-Based Catalysts for Electrocatalytic Hydrogen Evolution
Apr 2014
Publication
Replacement of precious catalyst with cost-effective alternatives would be significantly beneficial for hydrogen production via electrocatalytic hydrogen evolution reaction (HER). All candidates thus far are exclusively metallic catalysts which suffer inherent corrosion and oxidation susceptibility during acidic proton-exchange membrane electrolysis. Herein based on theoretical predictions we designed and synthesized nitrogen (N) and phosphorus (P) dual-doped graphene as a non-metallic electrocatalyst for sustainable and efficient hydrogen production. The N and Phetero-atoms could coactivate the adjacent C atom in the graphene matrix by affecting its valence orbital energy levels to induce a synergistically enhanced reactivity toward HER. As a result the dual-doped graphene showed higher electrocatalytic HER activity than single-doped ones and comparable performance to some of the traditional metallic catalysts.
Nickel Sulfides Supported by Carbon Spheres as Efficient Catalysts for Hydrogen Evolution Reaction
Jun 2021
Publication
Ni3S2 and NiS supported on carbon spheres are successfully synthesized by a facile hydrothermal method. And then a series of physical characterizations included XRD (X-ray diffraction) EDS (energy dispersive spectroscopy) FESEM (field emission scanning electron microscopy) and XPS (X-ray photo-electron spectroscopy) were used to analyze the samples. XRD was used to confirm that NiNi3S2 S2 and NiS were successfully fabricated. FESEM indicated that Ni3S2 and NiS disperse well on carbon spheres. Electrochemical tests showed that nickel sulfides supported by carbon spheres exhibited excellent hydrogen evolution performance. The excellent catalytic activity is attributed to the synergistic effect of carbon spheres and transition metal sulfides of which the carbon spheres act to enhance the electrical conductivity and the dispersion of Ni3S2 and NiS thus providing more active sites for the hydrogen evolution reaction.
Physicochemical Properties of Proton-conducting SmNiO3 Epitaxial Films
Mar 2019
Publication
Proton conducting SmNiO3 (SNO) thin films were grown on (001) LaAlO3 substrates for systematically investigating the proton transport properties. X-ray Diffraction and Atomic Force Microscopy studies reveal that the as-grown SNO thin films have good single crystallinity and smooth surface morphology. The electrical conductivity measurements in air indicate a peak at 473 K in the temperature dependence of the resistance of the SNO films probably due to oxygen loss on heating. A Metal-Insulator-Transition occurs at 373 K for the films after annealing at 873 K in air. In a hydrogen atmosphere (3% H2/97% N2) an anomalous peak in the resistance is found at 685 K on the first heating cycle. Electrochemical Impedance Spectroscopy studies as a function of temperature indicate that the SNO films have a high ionic conductivity (0.030 S/cm at 773 K) in a hydrogen atmosphere. The activation energy for proton conductivity was determined to be 0.23 eV at 473–773 K and 0.37 eV at 773–973 K respectively. These findings demonstrate that SNO thin films have good proton conductivity and are good candidate electrolytes for low temperature proton-conducting Solid Oxide Fuel Cells.
Economic Value of Flexible Hydrogen-based Polygeneration Energy Systems
Jan 2016
Publication
Polygeneration energy systems (PES) have the potential to provide a flexible high-efficiency and low-emissions alternative for power generation and chemical synthesis from fossil fuels. This study aims to assess the economic value of fossil-fuel PES which rely on hydrogen as an intermediate product. Our analysis focuses on a representative PES configuration that uses coal as the primary energy input and produces electricity and fertilizer as end-products. We derive a series of propositions that assess the cost competitiveness of the modeled PES under both static and flexible operation modes. The result is a set of metrics that quantify the levelized cost of hydrogen the unit profit-margin of PES and the real option values of ‘diversification’ and ‘flexibility’ embedded in PES. These metrics are subsequently applied to assess the economics of Hydrogen Energy California (HECA) a PES currently under development in California. Under our technical and economic assumptions HECA’s levelized cost of hydrogen is estimated at 1.373 $/kgh. The profitability of HECA as a static PES increases in the share of hydrogen converted to fertilizer rather than electricity. However when configured as a flexible PES HECA almost breaks even on a pre-tax basis. Diversification and flexibility are valuable for HECA when polygeneration is compared to static monogeneration of electricity but these two real options have no value when comparing polygeneration to static monogeneration of fertilizers.
National Training Facility for Hydrogen Safety. Five year plan for HAMMER
Sep 2005
Publication
A suitably trained emergency response force is an essential component for safe implementation of any type of fuel infrastructure. Because of the relative newness of hydrogen as a fuel however appropriate emergency response procedures are not yet well understood by responder workforces across the United States and around the world. A significant near-term training effort is needed to ensure that the future hydrogen infrastructure can be developed and operated with acceptable incident risk. Efforts are presently underway at the HAMMER site in Washington State to develop curricula related to hydrogen properties and behavior identification of problems (e.g. incorrect equipment installation) and appropriate response and other relevant information intended for classroom instruction. In addition a number of hands-on training props are planned for realistic simulation of hydrogen incidents in order to convey proper response procedures in high-pressure cryogenic high leakage or other high-risk accident situations. Surveys of emergency responders fire marshals regulatory authorities manufacturers and others are being undertaken to ensure that the capabilities developed and offered at HAMMER will meet the acknowledged need. This paper describes the training curricula and props anticipated at HAMMER and is intended to provide useful information to others planning similar training programs.
Enhancing Safety of Hydrogen Containment Components Through Materials Testing Under In-service Conditions
Oct 2015
Publication
The capabilities in the Hydrogen Effects on Materials Laboratory (HEML) at Sandia National Laboratories and the related materials testing activities that support standards development and technology deployment are reviewed. The specialized systems in the HEML allow testing of structural materials under in-service conditions such as hydrogen gas pressures up to 138 MPa temperatures from ambient to 203 K and cyclic mechanical loading. Examples of materials testing under hydrogen gas exposure featured in the HEML include stainless steels for fuel cell vehicle balance of plant components and Cr-Mo steels for stationary seamless pressure vessels.
The Pressure Peaking Phenomenon: Validation for Unignited Releases in Laboratory-scale Enclosure
Oct 2015
Publication
This study is aimed at the validation of the pressure peaking phenomenon against laboratory-scale experiments. The phenomenon was discovered recently as a result of analytical and numerical studies performed at Ulster University. The phenomenon is characterized by the existence of a peak on the overpressure transient in an enclosure with vent(s) at some conditions. The peak overpressure can significantly exceed the steady-state pressure and jeopardise a civil structure integrity causing serious life safety and property protection problems. However the experimental validation of the phenomenon was absent until recently. The validation experiments were performed at Karlsruhe Institute of Technology within the framework of the HyIndoor project. Tests were carried out with release of three different gases (air helium and hydrogen) within a laboratory-scale enclosure of about 1 m3 volume with a vent of comparatively small size. The model of pressure peaking phenomenon reproduced closely the experimental pressure dynamics within the enclosure for all three used gases. The prediction of pressure peaking phenomenon consists of two steps which are explained in detail. Examples of calculation for typical hydrogen applications are presented.
Comparison of Two-layer Model for High Pressure Hydrogen Jets with Notional Nozzle Model Predictions and Experimental Data
Oct 2015
Publication
A two-layer reduced order model of high pressure hydrogen jets was developed which includes partitioning of the flow between the central core jet region leading to the Mach disk and the supersonic slip region around the core. The flow after the Mach disk is subsonic while the flow around the Mach disk is supersonic with a significant amount of entrained air. This flow structure significantly affects the hydrogen concentration profiles downstream. The predictions of this model are compared to previous experimental data for high pressure hydrogen jets up to 20 MPa and to notional nozzle models and CFD models for pressures up to 35 MPa using ideal gas properties. The results show that this reduced order model gives better predictions of the mole fraction distributions than previous models for highly underexpanded jets. The predicted locations of the 4% lower flammability limit also show that the two-layer model much more accurately predicts the measured locations than the notional nozzle models. The comparisons also show that the CFD model always underpredicts the measured mole fraction concentrations.
Hydrogen Safety Training for Laboratory Researchers and Technical Personnel
Sep 2011
Publication
We have developed a web-based hydrogen safety class and are developing a hands-on hydrogen safety class. The 4-h web-based class is directed to laboratory researchers who need basic hydrogen safety information (free online access at http://www.h2labsafety.org/) and it addresses hydrogen fundamentals: properties pressure and cryogenic safety emergency response and codes and standards. Technical operators in charge of building and testing experimental hydrogen equipment will also soon benefit from a more comprehensive 3-day hands-on safety class that will present detailed information for installation testing and operation of hydrogen pressurized systems. The hands-on class includes a full day of classroom instruction followed by two days of laboratory work where students assemble test and operate a pressure system based on a schematic and component description.
Safety of Hydrogen Powered Industrial Trucks, Lessons Learned and Existing Codes and Standards Gaps
Sep 2011
Publication
This paper provides an introduction to the powered industrial truck application of fuel cell power systems the safety similarities with the automotive application and safety lessons learned. Fuel Cell niche markets have proven their value to many early adopters. How has the automotive market provided a springboard for these niche applications? How are niche markets revealing gaps in current safety approaches? What is different about the powered industrial truck application and what new codes and standards are needed to accommodate those differences?
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.
Dispersion and Burning Behavior of Hydrogen Released in a Full-scale Residential Garage in the Presence and Absence of Conventional Automobiles
Sep 2011
Publication
Experiments are described in which hydrogen was released at the center of the floor of a real-scale enclosure having dimensions of a typical two-car residential garage. Real-time hydrogen concentrations were monitored at a number of locations. The hydrogen/air mixtures were ignited at pre-determined local volume fractions ranging from 8% to 29%. The combustion behavior and structural effects were monitored using combinations of high-speed pressure transducers and ionization gauges standard thermocouples hydrogen sensors and digital infrared and high-speed video cameras. Experiments were performed both for empty garages and garages with conventional automobiles parked above the hydrogen release location.
Applying Risk Management Strategies Prudently
Sep 2011
Publication
During the current global financial crisis the term “Risk Management” is often heard. Just as the causes for the financial problems are elusive so is a complete definition of what Risk Management means. The answer is highly dependent upon your perceptions of “risk” and your appetite for assuming risks. The proposed paper will explore these issues with some brief case studies as they apply to hydrogen industrial applications hydrogen refuelling stations and fuel cell technologies for distributed generation.
Specifically the paper will identify the various risk exposures from the perspective of the project developers original equipment suppliers end users project funding sources and traditional insurance providers. What makes this evaluation intriguing is that it is a mixed bag of output capacities Combine Heat & Power (CHP) potential and technology maturity. Therefore the application considerations must be part of any overall Risk Management program.
Specifically the paper will identify the various risk exposures from the perspective of the project developers original equipment suppliers end users project funding sources and traditional insurance providers. What makes this evaluation intriguing is that it is a mixed bag of output capacities Combine Heat & Power (CHP) potential and technology maturity. Therefore the application considerations must be part of any overall Risk Management program.
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