United States
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.
Large Transition State Stabilization From a Weak Hydrogen Bond
Jul 2020
Publication
A series of molecular rotors was designed to study and measure the rate accelerating effects of an intramolecular hydrogen bond. The rotors form a weak neutral O–H⋯O[double bond length as m-dash]C hydrogen bond in the planar transition state (TS) of the bond rotation process. The rotational barrier of the hydrogen bonding rotors was dramatically lower (9.9 kcal mol−1) than control rotors which could not form hydrogen bonds. The magnitude of the stabilization was significantly larger than predicted based on the independently measured strength of a similar O–H⋯O[double bond length as m-dash]C hydrogen bond (1.5 kcal mol−1). The origins of the large transition state stabilization were studied via experimental substituent effect and computational perturbation analyses. Energy decomposition analysis of the hydrogen bonding interaction revealed a significant reduction in the repulsive component of the hydrogen bonding interaction. The rigid framework of the molecular rotors positions and preorganizes the interacting groups in the transition state. This study demonstrates that with proper design a single hydrogen bond can lead to a TS stabilization that is greater than the intrinsic interaction energy which has applications in catalyst design and in the study of enzyme mechanisms.
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.
Thermal Hydrogen: An Emissions Free Hydrocarbon Economy
Apr 2017
Publication
Envisioned below is an energy system named Thermal Hydrogen developed to enable economy-wide decarbonization. Thermal Hydrogen is an energy system where electric and/or heat energy is used to split water (or CO2) for the utilization of both by-products: hydrogen as energy storage and pure oxygen as carbon abatement. Important advantages of chemical energy carriers are long term energy storage and extended range for electric vehicles. These minimize the need for the most capital intensive assets of a fully decarbonized energy economy: low carbon power plants and batteries. The pure oxygen pre-empts the gas separation process of “Carbon Capture and Sequestration” (CCS) and enables hydrocarbons to use simpler more efficient thermodynamic cycles. Thus the “externality” of water splitting pure oxygen is increasingly competitive hydrocarbons which happen to be emissions free. Methods for engineering economy-wide decarbonization are described below as well as the energy supply carrier and distribution options offered by the system.
Achieving High-rate Hydrogen Recovery from Wastewater Using Customizable Alginate Polymer Gel Matrices Encapsulating Biomass
Jul 2018
Publication
In addition to methane gas higher-value resources such as hydrogen gas are produced during anaerobic wastewater treatment. They are however immediately consumed by other organisms. To recover these high-value resources not only do the desired phenotypes need to be retained in the anaerobic reactor but the undesired ones need to be washed out. In this study a well-established alginate-based polymer gel with and without a coating layer was used to selectively encapsulate hydrogen-producing biomass in beads to achieve high-rate recovery of hydrogen during anaerobic wastewater treatment. The effect of cross-linking agents Ca2+ Sr2+ and Ba2+ as well as a composite coating on the beads consisting of alternating layers of polyethylenimine and silica hydrogel were investigated with respect to their performance specifically their mass transfer characteristics and their differential ability to retain the encapsulated biomass. Although the coating reduced the escape rate of encapsulated biomass from the beads all alginate polymer matrices without coating effectively retained biomass. Fast diffusion of dissolved organic carbon (DOC) through the polymer gel was observed in both Ca-alginate and Sr-alginate without coating. The coating however decreased either the diffusivity or the permeability of the DOC depending on whether the DOC was from synthetic wastewater (more lipids and proteins) or real brewery wastewater (more sugars). Consequently the encapsulation system with coating became diffusion limited when brewery wastewater with high chemical oxygen demand was fed resulting in a lower hydrogen production rate than the uncoated encapsulation systems. In all cases the encapsulated biomass was able to produce hydrogen even at a hydraulic residence time of 45 min. Although there are limitations to this system the used of encapsulated biomass for resource recovery from wastewater shows promise particularly for high-rate systems in which the retention of specific phenotypes is desired.
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.
Very Low-cost Visual and Wireless Sensors for Effective Hydrogen Gas Leak Detection
Sep 2013
Publication
Element One Inc. Boulder CO is developing novel hydrogen gas leak indicators to improve the safety and maintenance operations of hydrogen production and chemical processing facilities and hydrogen fueling stations. These technologies can be used to make visual gas leak indicators such as paints decals and conformal plastic films as well as RF sensors for wireless networks. The primary advantage of the Element One hydrogen gas indicators is their low cost and easy deployment which allows them to be used ubiquitously at each and every potential hydrogen leak site. They have the potential to convert safety problems into routine maintenance problems thereby improving overall safety and decreasing operational costs.
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.
Understanding Composition–property Relationships in Ti–Cr–V–Mo Alloys for Optimisation of Hydrogen Storage in Pressurised Tanks
Jun 2014
Publication
The location of hydrogen within Ti–Cr–V–Mo alloys has been investigated during hydrogen absorption and desorption using in situ neutron powder diffraction and inelastic neutron scattering. Neutron powder diffraction identifies a low hydrogen equilibration pressure body-centred tetragonal phase that undergoes a martensitic phase transition to a face-centred cubic phase at high hydrogen equilibration pressures. The average location of the hydrogen in each phase has been identified from the neutron powder diffraction data although inelastic neutron scattering combined with density functional theory calculations show that the local structure is more complex than it appears from the average structure. Furthermore the origin of the change in dissociation pressure and hydrogen trapping on cycling in Ti–Cr–V–Mo alloys is discussed.
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
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.
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.
Addressing Hydrogen Embrittlement of Metals in the Sae J2579 Fuel Cell Vehicle Tank Standard
Sep 2013
Publication
The SAE Technical Information Report (TIR) J2579 (Technical Information Report for Fuel Systems in Fuel Cell and Other Hydrogen Vehicles) has been created to address the safety performance of hydrogen storage and handling systems on vehicles. Safety qualification of the compressed hydrogen storage system is demonstrated through performance testing on prototype containment vessels. The two performance tests currently included in the SAE J2579 for evaluating unacceptable leakage and burst do not account for the potential effects of hydrogen embrittlement on structural integrity. This report describes efforts to address hydrogen embrittlement of structural metals in the framework of performance-based safety qualification. New safety qualification pathways that account for hydrogen embrittlement in the SAE J2579 include an additional pneumatic performance test using hydrogen gas or materials tests that demonstrate acceptable hydrogen embrittlement resistance of candidate structural metals.
The Hydrogen Executive Leadership Panel (HELP) Initiative for Emergency Responder Training
Sep 2007
Publication
In close cooperation with their Canadian counterparts United States public safety authorities are taking the first steps towards creating a proper infrastructure to ensure the safe use of the new hydrogen fuel cells now being introduced commercially. Currently public safety officials are being asked to permit hydrogen fuel cells for stationary power and as emergency power backups for the telecommunications towers that exist everywhere. Consistent application of the safety codes is difficult – in part because it is new – yet it is far more complex to train emergency responders to deal safely with the inevitable hydrogen incidents. The US and Canadian building and fire codes and standards are similar but not identical. The US and Canadian rules are unlikely to be useful to other nations without modification to suit different regulatory systems. However emergency responder safety training is potentially more universal. The risks strategies and tactics are unlikely to differ much by region. The Hydrogen Executive Leadership Panel (HELP) made emergency responder safety training its first priority because the transition to hydrogen depends on keeping incidents small and inoffensive and the public and responders safe from harm. One might think that advising 1.2 million firefighters and 800000 law enforcement officers about hydrogen risks is no more complicated than adding guidance to a website. One would be wrong. The term “training” has specific legal implications which may vary by state. For hazardous materials federal requirements apply. Insurance companies place training requirements on the policies they sell to fire departments including the thousands of small all-volunteer departments which may operate as private corporations. Union contracts may define training and promotions may be based on satisfactorily completed certain levels of training. Emergency responders could no sooner learn how to extinguish a<br/>hydrogen fire by reading a webpage than a person could learn to ride a bicycle by reading a book. Procedures must be learned by listening reading and then doing. Regular practice is necessary. As new hydrogen applications are commercialized additional responder training may be necessary. This highlights another obstacle emergency responders’ ability to travel distances and take the time to undergo training. Historically fire academies established adjunct instructor programs and satellite academies to bring the training to firefighters. The large well-equipped academies are typically used for specialized training. States rarely have enough instructors and instructors often must take the time to create a course outline research each point and produce a program that is informative useful and holds the attention of responders. The challenge of training emergency responders seems next to impossible but public safety authorities are asked to tackle the impossible every day and a model exists to move forward in the U.S. Over the past few years the National Association of State Fire Marshals and U.S. Department of Transportation enlisted the help of emergency responders and industry to create a standardized approach to train emergency responders to deal with pipeline incidents. A curriculum and training materials were created and more than 26000 sets have been distributed for free to public safety agencies nationwide. More than 8000 instructors have been trained to use these materials that are now part of the regular training in 23 states. Using this model HELP intends to ensure that all emergency responders are trained to address hydrogen risks. The model and the rigorous scenario analysis and review used to developing the operational and technical training is addressed in this paper.
Facilitating the Safest Possible Transition from Fossil to Hydrogen Fuels- Hydrogen Executive Leadership Panel
Sep 2005
Publication
In recent years federal and state safety authorities have worked to bring emergency planners and responders together with industry the scientific community and consumers to ensure high levels of safety with gas and liquid pipelines and more recently with liquefied natural gas terminals. The U.S. Department of Transportation (DOT) is the federal authority on the safe transportation of energy and the National Association of State Fire Marshals (NASFM) represents state-level safety authorities. Together they have produced firefighter safety training materials technical guidance and information for use in communities considering new energy infrastructure and conducted research to support these activities. In 2004 the DOT-NASFM partnership established the Hydrogen Executive Leadership Panel (HELP) to ensure a safe transition from fossil fuels to hydrogen fuel cells. HELP brings together senior policy-level experts from all sectors to understand and recommend mitigation strategies for the risks associated with the transportation and use of hydrogen in motor vehicles. The initial group includes experts from the United States Canada and Europe. HELP will be supported by an advisory committee of emergency planners and responders—individuals well-equipped to describe real-world scenarios of greatest concern—and by a second advisory committee of engineers and scientists who will help translate the real-world scenarios into useful technical solutions. By September 2005 HELP expects to define the initial real-world scenarios of greatest concern and bring together teams of experts to collaborate with automakers energy producers government authorities consumers and public safety officials. Much work lies ahead including creating guidance for hydrogen powered automobiles emergency response safety training establishing test methods to reflect real-world incident scenarios and modifying state and local building and fire codes. The HELP leadership will present its strategic plan and first report at the International Conference on Hydrogen Safety in September 2005.
Risk-Informed Process and Tools for Permitting Hydrogen Fueling Stations
Sep 2007
Publication
The permitting process for hydrogen fueling stations varies from country to country. However a common step in the permitting process is the demonstration that the proposed fueling station meets certain safety requirements. Currently many permitting authorities rely on compliance with well known codes and standards as a means to permit a facility. Current codes and standards for hydrogen facilities require certain safety features specify equipment made of material suitable for hydrogen environment and include separation or safety distances. Thus compliance with the code and standard requirements is widely accepted as evidence of a safe design. However to ensure that a hydrogen facility is indeed safe the code and standard requirements should be identified using a risk-informed process that utilizes an acceptable level of risk. When compliance with one or more code or standard requirements is not possible an evaluation of the risk associated with the exemptions to the requirements should be understood and conveyed to the Authority Having Jurisdiction (AHJ). Establishment of a consistent risk assessment toolset and associated data is essential to performing these risk evaluations. This paper describes an approach for risk-informing the permitting process for hydrogen fueling stations that relies primarily on the establishment of risk-informed codes and standards. The proposed risk-informed process begins with the establishment of acceptable risk criteria associated with the operation of hydrogen fueling stations. Using accepted Quantitative Risk Assessment (QRA) techniques and the established risk criteria the minimum code and standard requirements necessary to ensure the safe operation of hydrogen facilities can be identified. Risk informed permitting processes exist in some countries and are being developed in others. To facilitate consistent risk-informed approaches the participants in the International Energy Agency (IEA) Task 19 on hydrogen safety are working to identify acceptable risk criteria QRA models and supporting data.
Hydrogen Safety and Permitting Hydrogen Fueling Stations
Sep 2007
Publication
Two key aspects of hydrogen safety are (1) incorporating data and analysis from research development and demonstration (RD&D) into the codes and standards development process; and (2) adopting and enforcing these codes and standards by state and local permitting officials. This paper describes work that the U.S. Department of Energy (DOE) is sponsoring to address these aspects of hydrogen safety. For the first DOE is working with the automobile and energy industries to identify and address high priority RD&D to establish a sound scientific basis for requirements that are incorporated in hydrogen codes and standards. The high priority RD&D needs are incorporated and tracked in an RD&D Roadmap adopted by the Codes and Standards Technical Team of the FreedomCAR and Fuel Partnership. DOE and its national laboratories conduct critical RD&D and work with key standards and model code development organizations to help incorporate RD&D results into the codes and standards process. To address the second aspect DOE has launched an initiative to facilitate the permitting process for hydrogen fueling stations (HFS). A key element of this initiative will be a Web-based information repository a toolkit that includes information fact sheets networking charts to encourage information exchange among code officials who have permitted or are in the process of permitting HFS templates to show whether a proposed station footprint conforms to requirements in the jurisdiction and a database of requirements incorporated in key codes and standards. The information repository will be augmented by workshops for code officials and station developers in jurisdictions that are likely to have HFS in the near future.
Incident Reporting- Learning from Experience
Sep 2007
Publication
Experience makes a superior teacher. Sharing the details surrounding safety events is one of the best ways to help prevent their recurrence elsewhere. This approach requires an open non-punitive environment to achieve broad benefits. The Hydrogen Incident Reporting Tool (www.h2incidents.org) is intended to facilitate the sharing of lessons learned and other relevant information gained from actual experiences using and working with hydrogen and hydrogen systems. Its intended audience includes those involved in virtually any aspect of hydrogen technology systems and use with an emphasis towards energy and transportation applications. The database contains records of safety events both publicly available and/or voluntarily submitted. Typical records contain a general description of the occurrence contributing factors equipment involved and some detailing of consequences and changes that have been subsequently implemented to prevent recurrence of similar events in the future. The voluntary and confidential nature and other characteristics surrounding the database mean that any analysis of apparent trends in its contents cannot be considered statistically valid for a universal population. A large portion of reported incidents have occurred in a laboratory setting due to the typical background of the reporting projects for example. Yet some interesting trends are becoming apparent even at this early stage of the database’s existence and general lessons can already be taken away from these experiences. This paper discusses the database and a few trends that have already become apparent for the reported incidents. Anticipated future uses of this information are also described. This paper is intended to encourage wider participation and usage of the incidents reporting database and to promote the safety benefits offered by its contents.
A Rural Hydrogen Transportation Test Bed
Sep 2007
Publication
The University of Missouri-Rolla (UMR) through a hydrogen internal combustion engine vehicle evaluation participation agreement with the Ford Motor Company will establish a commuter bus service and hydrogen refueling at a station in rural Missouri near Ft. Leonard Wood (FLW). Initiated by a request from the U.S. Army Maneuver Support Center at FLW UMR is leading the effort to launch the commuter service between FLW and the neighboring towns of Rolla and Lebanon Missouri each of which are located approximately 40 km from the military base on Interstate-44 highway. The broad research training and education agenda for the rural hydrogen transportation test bed is to develop demonstrate evaluate and promote safe hydrogen-based technologies in a real world environment. With funds provided by the Defense Logistics Agency through the Air Force Research Laboratory this hydrogen initiative will build and operate a hydrogen fueling facility that includes on-site generation of hydrogen through electrolysis as well as selling a range of other traditional and alternative fuels.
Development of Standards for Evaluating Materials Compatibility with High-pressure Gaseous Hydrogen
Sep 2013
Publication
The Hydrogen Safety Codes and Standards program element of the US Department of Energy's Fuel Cell Technologies Office provides coordination and technical data for the development of domestic and international codes and standards related to hydrogen technologies. The materials compatibility program task at Sandia National Laboratories (Livermore CA) is focused on developing the technical basis for qualifying materials for hydrogen service i.e. accommodating hydrogen embrittlement. This presentation summarizes code development activities for qualifying materials for hydrogen service with emphasis on the scientific basis for the testing methodologies including fracture mechanics based measurements (fracture threshold and fatigue crack growth) total fatigue life measurements and full- scale pressure vessel testing.
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.
Kinetic Model of Incipient Hydride Formation in Zr Clad under Dynamic Oxide Growth Conditions
Feb 2020
Publication
The formation of elongated zirconium hydride platelets during corrosion of nuclear fuel clad is linked to its premature failure due to embrittlement and delayed hydride cracking. Despite their importance however most existing models of hydride nucleation and growth in Zr alloys are phenomenological and lack sufficient physical detail to become predictive under the variety of conditions found in nuclear reactors during operation. Moreover most models ignore the dynamic nature of clad oxidation which requires that hydrogen transport and precipitation be considered in a scenario where the oxide layer is continuously growing at the expense of the metal substrate. In this paper we perform simulations of hydride formation in Zr clads with a moving oxide/metal boundary using a stochastic kinetic diffusion/reaction model parameterized with state-of-the-art defect and solute energetics. Our model uses the solutions of the hydrogen diffusion problem across an increasingly-coarse oxide layer to define boundary conditions for the kinetic simulations of hydrogen penetration precipitation and dissolution in the metal clad. Our method captures the spatial dependence of the problem by discretizing all spatial derivatives using a stochastic finite difference scheme. Our results include hydride number densities and size distributions along the radial coordinate of the clad for the first 1.6 h of evolution providing a quantitative picture of hydride incipient nucleation and growth under clad service conditions.
Design of a Methanol Reformer for On-board Production of Hydrogen as Fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell Power System
Sep 2020
Publication
The method of Computational Fluid Dynamics is used to predict the process parameters and select the optimum operating regime of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system. The analysis uses a three reactions kinetics model for methanol steam reforming water gas shift and methanol decomposition reactions on Cu/ZnO/Al2O3 catalyst. Numerical simulations are performed at single channel level for a range of reformer operating temperatures and values of the molar flow rate of methanol per weight of catalyst at the reformer inlet. Two operating regimes of the fuel processor are selected which offer high methanol conversion rate and high hydrogen production while simultaneously result in a small reformer size and a reformate gas composition that can be tolerated by phosphoric acid-doped high temperature membrane electrode assemblies for proton exchange membrane fuel cells. Based on the results of the numerical simulations the reactor is sized and its design is optimized.
Highly Porous Organic Polymers for Hydrogen Fuel Storage
Apr 2019
Publication
Hydrogen (H2) is one of the best candidates to replace current petroleum energy resources due to its rich abundance and clean combustion. However the storage of H2presents a major challenge. There are two methods for storing H2 fuel chemical and physical both of which have some advantages and disadvantages. In physical storage highly porous organic polymers are of particular interest since they are low cost easy to scale up metal-free and environmentally friendly.
In this review highly porous polymers for H2 fuel storage are examined from five perspectives:
(a) brief comparison of H2 storage in highly porous polymers and other storage media;
(b) theoretical considerations of the physical storage of H2 molecules in porous polymers;
(c) H2 storage in different classes of highly porous organic polymers;
(d) characterization of microporosity in these polymers; and
(e) future developments for highly porous organic polymers for H2 fuel storage. These topics will provide an introductory overview of highly porous organic polymers in H2 fuel storage.
In this review highly porous polymers for H2 fuel storage are examined from five perspectives:
(a) brief comparison of H2 storage in highly porous polymers and other storage media;
(b) theoretical considerations of the physical storage of H2 molecules in porous polymers;
(c) H2 storage in different classes of highly porous organic polymers;
(d) characterization of microporosity in these polymers; and
(e) future developments for highly porous organic polymers for H2 fuel storage. These topics will provide an introductory overview of highly porous organic polymers in H2 fuel storage.
Cross-regional Drivers for CCUS Deployment
Jul 2020
Publication
CO2 capture utilization and storage (CCUS) is recognized as a uniquely important option in global efforts to control anthropogenic greenhouse-gas (GHG) emissions. Despite significant progress globally in advancing the maturity of the various component technologies and their assembly into full-chain demonstrations a gap remains on the path to widespread deployment in many countries. In this paper we focus on the importance of business models adapted to the unique technical features and sociopolitical drivers in different regions as a necessary component of commercial scale-up and how lessons might be shared across borders. We identify three archetypes for CCUS development—resource recovery green growth and low-carbon grids—each with different near-term issues that if addressed will enhance the prospect of successful commercial deployment. These archetypes provide a framing mechanism that can help to translate experience in one region or context to other locations by clarifying the most important technical issues and policy requirements. Going forward the archetype framework also provides guidance on how different regions can converge on the most effective use of CCUS as part of global deep-decarbonization efforts over the long term.
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.
Risk Reduction Potential of Accident Prevention and Mitigation Features
Sep 2011
Publication
Quantitative Risk Assessment (QRA) can help to establish a set of design and operational requirements in hydrogen codes and standards that will ensure safe operation of hydrogen facilities. By analyzing a complete set of possible accidents in a QRA the risk drivers for these facilities can be identified. Accident prevention and mitigation features can then be analyzed to determine which are the most effective in addressing these risk drivers and thus reduce the risk from possible accidents. Accident prevention features/methods such as proper material selection and preventative maintenance are included in the design and operation of facilities. Accident mitigation features are included to reduce or terminate the potential consequences from unintended releases of hydrogen. Mitigation features can be either passive or active in nature. Passive features do not require any component to function in order to prevent or mitigate a hydrogen release. Examples of passive mitigation features include the use of separation distances barriers and flow limiting orifices. Active mitigation features initiate when specific conditions occur during an accident in order to terminate an accident or reduce its consequences. Examples of active mitigation features include detection and isolation systems fire suppression systems and purging systems. A concept being pursued by the National Fire Protection Association (NFPA) hydrogen standard development is to take credit for prevention and mitigation features as a means to reduce separation distances at hydrogen facilities. By utilizing other mitigation features the risk from accidents can be decreased and risk-informed separation distances can be reduced. This paper presents some preliminary QRA results where the risk reduction potential for several active and passive mitigation features was evaluated. These measures include automatic leak detection and isolation systems the use of flow limiting orifices and the use of barriers. Reducing the number of risk-significant components in a system was also evaluated as an accident prevention method. In addition the potential reduction in separation distances if such measures were incorporated at a facility was also determined.
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.
Measurements of Effective Diffusion Coefficient of Helium and Hydrogen Through Gypsum
Sep 2011
Publication
An experimental apparatus which was based on the ¼-scale garage previously used for studying helium release and dispersion in our laboratory was used to obtain effective diffusion coefficients of helium and hydrogen (released as forming gas for safety reasons) through gypsum panel. Two types of gypsum panel were used in the experiments. Helium or forming gas was released into the enclosure from a Fischer burner1 located near the enclosure floor for a fixed duration and then terminated. Eight thermal-conductivity sensors mounted at different vertical locations above the enclosure floor were used to monitor the temporal and spatial gas concentrations. An electric fan was used inside the enclosure to mix the released gas to ensure a spatially uniform gas concentration to minimize stratification. The temporal variations of the pressure difference between the enclosure interior and the ambience were also measured. An analytical model was developed to extract the effective diffusion coefficients from the experimental data.
Use of Hydrogen Safety Sensors Under Anaerobic Conditions – Impact of Oxygen Content on Sensor Performance
Sep 2011
Publication
In any application involving the production storage or use of hydrogen sensors are important devices for alerting to the presence of leaked hydrogen. Hydrogen sensors should be accurate sensitive and specific as well as resistant to long term drift and varying environmental conditions. Furthermore as an integral element in a safety system sensor performance should not be compromised by operational parameters. For example safety sensors may be required to operate at reduced oxygen levels relative to air. In this work we evaluate and compare a number of sensor technologies in terms of their ability to detect hydrogen under conditions of varying oxygen concentration.
Introduction to Hydrogen Safety Engineering
Sep 2011
Publication
The viability and public acceptance of the hydrogen and fuel cell (HFC) systems and infrastructure depends on their robust safety engineering design education and training of the workforce regulators and other stakeholders in the state-of-the-art in the field. This can be provided only through building up and maturity of the hydrogen safety engineering (HSE) profession. HSE is defined as an application of scientific and engineering principles to the protection of life property and environment from adverse effects of incidents/accidents involving hydrogen. This paper describes a design framework and overviews a structure and contents of technical sub-systems for carrying out HSE. The approach is similar to British standard BS7974 for application of fire safety engineering to the design of buildings and expanded to reflect on specific for hydrogen safety related phenomena including but not limited to high pressure under-expanded leaks and dispersion spontaneous ignition of sudden hydrogen releases to air deflagrations and detonations etc. The HSE process includes three main steps. Firstly a qualitative design review is undertaken by a team that can incorporate owner hydrogen safety engineer architect representatives of authorities having jurisdiction e.g. fire services and other stakeholders. The team defines accident scenarios suggests trial safety designs and formulates acceptance criteria. Secondly a quantitative safety analysis of selected scenarios and trial designs is carried out by qualified hydrogen safety engineer(s) using the state-of-the-art knowledge in hydrogen safety science and engineering and validated models and tools. Finally the performance of a HFC system and/or infrastructure under the trial safety designs is assessed against predefined by the team acceptance criteria. This performance-based methodology offers the flexibility to assess trial safety designs using separately or simultaneously three approaches: deterministic comparative or combined probabilistic/deterministic.
From Research Results to Published Codes And Standards - Establishing Code Requirements For NFPA 55 Bulk Hydrogen Systems Separation Distances
Sep 2009
Publication
Performing research in the interest of providing relevant safety requirements is a valuable and essential endeavor but translating research results into enforceable requirements adopted into codes and standards a process sometimes referred to as codification can be a separate and challenging task. This paper discusses the process utilized to successfully translate research results related to bulk gaseous hydrogen storage separation (or stand-off) distances into code requirements in NFPA 55:Storage Use and Handling of Compressed Gases and Cryogenic Fluids in Portable and StationaryContainers Cylinders and Tanks and NFPA 2: Hydrogen Technologies. The process utilized can besummarized as follows: First the technical committees for the documents to be revised were engaged to confirm that the codification process was endorsed by the committee. Then a sub-committee referred to as a task group was formed. A chair must be elected or appointed. The chair should be a generalist with code enforcement or application experience. The task group was populated with several voting members of each technical committee. By having voting members as part of the task group the group becomes empowered and uniquely different from any other code proposal generating body. The task group was also populated with technical experts as needed but primarily the experts needed are the researchers involved. Once properly populated and empowered the task group must actively engage its members. The researchers must educate the code makers on the methods and limitations of their work and the code makers must take the research results and fill the gaps as needed to build consensus and create enforceable code language and generate a code change proposal that will be accepted. While this process seems simple there are pitfalls along the way that can impede or nullify the desired end result – changes to codes and standards. A few of these pitfalls include: wrong task group membership task group not empowered task group not supported in-person meetings not possible consensus not achieved. This paper focuses on the process used and how pitfalls can be avoided for future efforts.
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.
Hot Surface Ignition of Hydrogen-air Mixtures
Oct 2015
Publication
Hot surface ignition is relevant in the context of industrial safety. In the present work two-dimensional simulations with detailed chemistry and study of the reaction pathways of the buoyancy-driven flow and ignition of a stoichiometric hydrogen-air mixture by a rapidly heated surface (glowplug) are reported. Experimentally ignition is observed to occur regularly at the top of the glowplug; numerical results for hydrogen-air reproduce this trend and shed light on this behaviour. The simulations show the importance of flow separation in creating zones where convective losses are minimized and heat diffusion is maximized resulting in the critical conditions for ignition to take place.
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.
Predictions of Solid-State Hydrogen Storage System Contamination Processes
Sep 2009
Publication
Solid state materials such as metal and chemical hydrides have been proposed and developed for high energy density automotive hydrogen storage applications. As these materials are implemented into hydrogen storage systems developers must understand their behavior during accident scenarios or contaminated refueling events. An ability to predict thermal and chemical processes during contamination allows for the design of safe and effective hydrogen storage systems along with the development of appropriate codes and standards. A model for the transport of gases within an arbitrary-geometry reactive metal hydride bed (alane -AlH3) is presented in this paper. We have coupled appropriate Knudsen-regime permeability models for flow through packed beds with the fundamental heat transfer and chemical kinetic processes occurring at the particle level. Using experimental measurement to determine and validate model parameters we have developed a robust numerical model that can be utilized to predict processes in arbitrary scaled-up geometries during scenarios such as breach-in-tank or contaminated refueling. Results are presented that indicate the progression of a reaction front through a compacted alane bed as a result of a leaky fitting. The rate of this progression can be limited by; 1) restricting the flow of reactants into the bed through densification and 2) maximizing the rate of heat removal from the bed.
Development of Uniform Harm Criteria for Use in Quantitative Risk Analysis of the Hydrogen Infrastructure
Sep 2009
Publication
This paper discusses the preliminary results of the Risk Management subtask efforts within the International Energy Agency (IEA) Hydrogen Implementing Agreement (HIA) Task 19 on Hydrogen Safety to develop uniform harm criteria for use in the Quantitative Risk Assessments (QRAs) of hydrogen facilities. The IEA HIA Task 19 efforts are focused on developing guidelines and criteria for performing QRAs of hydrogen facilities. The performance of QRAs requires that the level of harm that is represented in the risk evaluation be established using deterministic models. The level of harm is a function of the type and level of hazard. The principle hazard associated with hydrogen facilities is uncontrolled accumulation of hydrogen in (semi) confined spaces and consecutive ignition. Another significant hazard is combustion of accidentally released hydrogen gas or liquid which may or may not happen instantaneously. The primary consequences from fire hazards consist of personnel injuries or fatalities or facility and equipment damage due to high air temperatures radiant heat fluxes or direct contact with hydrogen flames. The possible consequences of explosions on humans and structures or equipment include blast wave overpressure effects impact from fragments generated by the explosion the collapse of buildings and the heat effects from subsequent fire balls. A harm criterion is used to translate the consequences of an accident evaluated from deterministic models to a probability of harm to people structures or components. Different methods can be used to establish harm criteria including the use of threshold consequence levels and continuous functions that relate the level of a hazard to a probability of damage. This paper presents a survey of harm criteria that can be utilized in QRAs and makes recommendations on the criteria that should be utilized for hydrogen-related hazards.
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.
Statistical Analysis of Electrostatic Spark Ignition of Lean H2-O2-Ar Mixtures
Sep 2009
Publication
Determining the risk of accidental ignition of flammable mixtures is a topic of tremendous importance in industry and aviation safety. The concept of minimum ignition energy (MIE) has traditionally formed the basis for studying ignition hazards of fuels. In recent years however the viewpoint of ignition as a statistical phenomenon has formed the basis for studying ignition as this approach appears to be more consistent with the inherent variability in engineering test data. We have developed a very low energy capacitive spark ignition system to produce short sparks with fixed lengths of 1 to 2 mm. The ignition system is used to perform spark ignition tests in lean hydrogen oxygen-argon test mixtures over a range of spark energies. The test results are analyzed using statistical tools to obtain probability distributions for ignition versus spark energy demonstrating the statistical nature of ignition. The results also show that small changes in the hydrogen concentration lead to large changes in the ignition energy and dramatically different flame characteristics. A second low-energy spark ignition system is also developed to generate longer sparks with varying lengths up to 10 mm. A second set of ignition tests is performed in one of the test mixtures using a large range of park energies and lengths. The results are analyzed to obtain a probability distribution for ignition versus the spark energy per unit spark length. Preliminary results show that a single threshold MIE value does not exist and that the energy per unit length may be a more appropriate parameter for quantifying the risk of ignition.
Analysis of Jet Flames and Unignited Jets from Unintended Releases of Hydrogen
Sep 2007
Publication
A combined experimental and modeling program is being carried out at Sandia National Laboratories to characterize and predict the behavior of unintended hydrogen releases. In the case where the hydrogen leak remains unignited knowledge of the concentration field and flammability envelope is an issue of importance in determining consequence distances for the safe use of hydrogen. In the case where a high-pressure leak of hydrogen is ignited a classic turbulent jet flame forms. Knowledge of the flame length and thermal radiation heat flux distribution is important to safety. Depending on the effective diameter of the leak and the tank source pressure free jet flames can be extensive in length and pose significant radiation and impingement hazard resulting in consequence distances that are unacceptably large. One possible mitigation strategy to potentially reduce the exposure to jet flames is to incorporate barriers around hydrogen storage equipment. The reasoning is that walls will reduce the extent of unacceptable consequences due to jet releases resulting from accidents involving high-pressure equipment. While reducing the jet extent the walls may introduce other hazards if not configured properly. The goal of this work is to provide guidance on configuration and placement of these walls to minimize overall hazards using a quantitative risk assessment approach. Detailed Navier-Stokes calculations of jet flames and unignited jets are used to understand how hydrogen leaks and jet-flames interact with barriers. The effort is complemented by an experimental program that considers the interaction of jet flames and unignited jets with barriers.
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.
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.
Adapted Tube Cleaning Practices to Reduce Particulate Contamination at Hydrogen Fueling Stations
Sep 2017
Publication
The higher rate of component failure and downtime during initial operation in hydrogen stations is not well understood. The National Renewable Energy Laboratory (NREL) has been collecting failed components from retail and research hydrogen fuelling stations in California and Colorado and analyzing them using an optical zoom and scanning electron microscope. The results show stainless steel metal particulate contamination. While it is difficult to definitively know the origin of the contaminants a possible source of the metal particulates is improper tube cleaning practices. To understand the impact of different cleaning procedures NREL performed an experiment to quantify the particulates introduced from newly cut tubes. The process of tube cutting threading and bevelling which is performed most often during station fabrication is shown to introduce metal contaminants and thus is an area that could benefit from improved cleaning practices. This paper shows how these particulates can be reduced which could prevent station downtime and costly repair. These results are from the initial phase of a project in which NREL intends to further investigate the sources of particulate contamination in hydrogen stations.
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.
Comparison of NFPA and ISO Approaches for Evaluating Separation Distances
Sep 2011
Publication
The development of a set of safety codes and standards for hydrogen facilities is necessary to ensure they are designed and operated safely. To help ensure that a hydrogen facility meets an acceptable level of risk code and standard development organizations (SDOs) are utilizing risk-informed concepts in developing hydrogen codes and standards. Two SDOs the National Fire Protection Association (NFPA) and the International Organization for Standardization (ISO) through its Technical Committee (TC) 197 on hydrogen technologies have been developing standards for gaseous hydrogen facilities that specify the facilities have certain safety features use equipment made of material suitable for a hydrogen environment and have specified separation distances. Under Department of Energy funding Sandia National Laboratories (SNL) has been supporting efforts by both of these SDOs to develop the separation distances included in their respective standards. Important goals in these efforts are to use a defensible science-based approach to establish these requirements and to the extent possible harmonize the requirements. International harmonization of regulations codes and standards is critical for enabling global market penetration of hydrogen and fuel cell technologies.
Simulation of High-pressure Liquid Hydrogen Releases
Sep 2011
Publication
Sandia National Laboratories is working with stakeholders to develop scientific data for use by standards development organizations to create hydrogen codes and standards for the safe use of liquid hydrogen. Knowledge of the concentration field and flammability envelope for high-pressure hydrogen leaks is an issue of importance for the safe use of liquid hydrogen. Sandia National Laboratories is engaged in an experimental and analytical program to characterize and predict the behaviour of liquid hydrogen releases. This paper presents a model for computing hydrogen dilution distances for cold hydrogen releases. Model validation is presented for leaks of room temperature and 80 K high-pressure hydrogen gas. The model accounts for a series of transitions that occurs from a stagnate location in the tank to a point in the leak jet where the concentration of hydrogen in air at the jet centerline has dropped to 4% by volume. The leaking hydrogen is assumed to be a simple compressible substance with thermodynamic equilibrium between hydrogen vapor hydrogen liquid and air. For the multi-phase portions of the jet near the leak location the REFPROP equation of state models developed by NIST are used to account for the thermodynamics. Further downstream the jet develops into an atmospheric gas jet where the thermodynamics are described as a mixture of ideal gases (hydrogen–air mixture). Simulations are presented for dilution distances in under-expanded high-pressure leaks from the saturated vapor and saturated liquid portions of a liquid hydrogen storage tank at 10.34 barg (150 PSIG).
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.
Experimental Study of Hydrogen Release Accidents in a Vehicle Garage
Sep 2009
Publication
Storing a hydrogen fuel-cell vehicle in a garage poses a potential safety hazard because of the accidents that could arise from a hydrogen leak. A series of tests examined the risk involved with hydrogen releases and deflagrations in a structure built to simulate a one-car garage. The experiments involved igniting hydrogen gas that was released inside the structure and studying the effects of the deflagrations. The “garage” measured 2.72 m high 3.64 m wide and 6.10 m long internally and was constructed from steel using a reinforced design capable of withstanding a detonation. The front face of the garage was covered with a thin transparent plastic film. Experiments were performed to investigate extended-duration (20–40 min) hydrogen leaks. The effect that the presence of a vehicle in the garage has on the deflagration was also studied. The experiments examined the effectiveness of different ventilation techniques at reducing the hydrogen concentration in the enclosure. Ventilation techniques included natural upper and lower openings and mechanical ventilation systems. A system of evacuated sampling bottles was used to measure hydrogen concentration throughout the garage prior to ignition and at various times during the release. All experiments were documented with standard and infrared (IR) video. Flame front propagation was monitored with thermocouples. Pressures within the garage were measured by four pressure transducers mounted on the inside walls of the garage. Six free-field pressure transducers were used to measure the pressures outside the garage.
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.
Metal Hydride Hydrogen Compressors
Feb 2014
Publication
Metal hydride (MH) thermal sorption compression is an efficient and reliable method allowing a conversion of energy from heat into a compressed hydrogen gas. The most important component of such a thermal engine – the metal hydride material itself – should possess several material features in order to achieve an efficient performance in the hydrogen compression. Apart from the hydrogen storage characteristics important for every solid H storage material (e.g. gravimetric and volumetric efficiency of H storage hydrogen sorption kinetics and effective thermal conductivity) the thermodynamics of the metal–hydrogen systems is of primary importance resulting in a temperature dependence of the absorption/desorption pressures). Several specific features should be optimised to govern the performance of the MH-compressors including synchronisation of the pressure plateaus for multi-stage compressors reduction of slope of the isotherms and hysteresis increase of cycling stability and life time together with challenges in system design associated with volume expansion of the metal matrix during the hydrogenation.<br/>The present review summarises numerous papers and patent literature dealing with MH hydrogen compression technology. The review considers (a) fundamental aspects of materials development with a focus on structure and phase equilibria in the metal–hydrogen systems suitable for the hydrogen compression; and (b) applied aspects including their consideration from the applied thermodynamic viewpoint system design features and performances of the metal hydride compressors and major applications.
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