United States
Natural and Forced Ventilation of Buoyant Gas Released In a Full-Scale Garage, Comparison of Model Predictions and Experimental Data
Sep 2011
Publication
An increase in the number of hydrogen-fuelled applications in the marketplace will require a better understanding of the potential for fires and explosion associated with the unintended release of hydrogen within a structure. Predicting the temporally evolving hydrogen concentration in a structure with unknown release rates leak sizes and leak locations is a challenging task. A simple analytical model was developed to predict the natural and forced mixing and dispersion of a buoyant gas released in a partially enclosed compartment with vents at multiple levels. The model is based on determining the instantaneous compartment over-pressure that drives the flow through the vents and assumes that the helium released under the automobile mixes fully with the surrounding air. Model predictions were compared with data from a series of experiments conducted to measure the volume fraction of a buoyant gas (at 8 different locations) released under an automobile placed in the center of a full-scale garage (6.8 m × 5.4 m × 2.4 m). Helium was used as a surrogate gas for safety concerns. The rate of helium released under an automobile was scaled to represent 5 kg of hydrogen released over 4 h. CFD simulations were also performed to confirm the observed physical phenomena. Analytical model predictions for helium volume fraction compared favourably with measured experimental data for natural and forced ventilation. Parametric studies are presented to understand the effect of release rates vent size and location on the predicted volume fraction in the garage. Results demonstrate the applicability of the model to effectively and rapidly reduce the flammable concentration of hydrogen in a compartment through forced ventilation.
Overview of the DOE Hydrogen Safety, Codes and Standards Program part 4- Hydrogen Sensors
Oct 2015
Publication
Hydrogen sensors are recognized as a critical element in the safety design for any hydrogen system. In this role sensors can perform several important functions including indication of unintended hydrogen releases activation of mitigation strategies to preclude the development of dangerous situations activation of alarm systems and communication to first responders and to initiate system shutdown. The functionality of hydrogen sensors in this capacity is decoupled from the system being monitored thereby providing an independent safety component that is not affected by the system itself. The importance of hydrogen sensors has been recognized by DOE and by the Fuel Cell Technologies Office’s Safety and Codes Standards (SCS) program in particular which has for several years supported hydrogen safety sensor research and development. The SCS hydrogen sensor programs are currently led by the National Renewable Energy Laboratory Los Alamos National Laboratory and Lawrence Livermore National Laboratory. The current SCS sensor program encompasses the full range of issues related to safety sensors including development of advance sensor platforms with exemplary performance development of sensor-related code and standards outreach to stakeholders on the role sensors play in facilitating deployment technology evaluation and support on the proper selection and use of sensors.
Overview of the DOE Hydrogen Safety, Codes and Standards Program Part 3- Advances in Research and Development to Enhance the Scientific Basis for Hydrogen Regulations, Codes and Standards
Oct 2015
Publication
Hydrogen fuels are being deployed around the world as an alternative to traditional petrol and battery technologies. As with all fuels regulations codes and standards are a necessary component of the safe deployment of hydrogen technologies. There has been a focused effort in the international hydrogen community to develop codes and standards based on strong scientific principles to accommodate the relatively rapid deployment of hydrogen-energy systems. The need for science-based codes and standards has revealed the need to advance our scientific understanding of hydrogen in engineering environments. This brief review describes research and development activities with emphasis on scientific advances that have aided the advancement of hydrogen regulations codes and standards for hydrogen technologies in four key areas: (1) the physics of high-pressure hydrogen releases (called hydrogen behaviour); (2) quantitative risk assessment; (3) hydrogen compatibility of materials; and (4) hydrogen fuel quality.
Quantifying the Potential Consequences of a Detonation in a Hydrogen Jet Release
Sep 2019
Publication
The unconfined release of high-pressure hydrogen can create a large flammable jet with the potential to generate significant damage. To properly understand the separation distances necessary to protect the immediate surroundings it is important to accurately assess the potential consequences. In these events the possibility for a detonation cannot be excluded and would generally result in the worst case scenario from the standpoint of damaging overpressure. The strong concentration gradients created by a jet release however raises the question of what portion of the flammable cloud should be considered. Often all of the fuel within the limits of fast-flame acceleration or even all of the fuel within the flammability range is considered which typically comprises the majority of the flammable cloud. In this work prior detonation studies are reviewed to illustrate the inherently unstable nature of detonations with a focus on the critical dimensions and concentration gradients that can support a propagating detonation wave. These criteria are then applied to the flammable cloud concentration distributions generated by an unconfined jet release of hydrogen. By evaluating these limits it is found that the portion of the flammable cloud that is likely to participate is significantly reduced. These results are compared with existing experimental data on the ignition of unconfined hydrogen releases and the peak pressures that were measured are consistent with a detonation of a mass of fuel that is equivalent to the model prediction for the mass of fuel within the detonable limits. This work demonstrates how the critical conditions for detonation propagation can be used to estimate the portion of a hydrogen release that could participates in a detonation and how these criteria can be readily incorporated into existing dispersion modelling approaches.
Hydrogen Strategy - Enabling a Low-Carbon Economy
Jul 2020
Publication
This document summarizes current hydrogen technologies and communicates the U.S. Department of Energy (DOE) Office of Fossil Energy's (FE's) strategic plan to accelerate research development and deploymnet of hydrogen technologies in the United States. It also describes ongoing FE hydrogen-related research and development (R&D). Hydrogen from fossil fuels is a versatile energy carrier and can play an important role in the transition to a low-carbon economy.
Advanced Hydrogen and CO2 Capture Technology for Sour Syngas
Apr 2011
Publication
A key challenge for future clean power or hydrogen projects via gasification is the need to reduce the overall cost while achieving significant levels of CO2 capture. The current state of the art technology for capturing CO2 from sour syngas uses a physical solvent absorption process (acid gas removal–AGR) such as Selexol™ or Rectisol® to selectively separate H2S and CO2 from the H2. These two processes are expensive and require significant utility consumption during operation which only escalates with increasing levels of CO2 capture. Importantly Air Products has developed an alternative option that can achieve a higher level of CO2 capture than the conventional technologies at significantly lower capital and operating costs. Overall the system is expected to reduce the cost of CO2 capture by over 25%.<br/>Air Products developed this novel technology by leveraging years of experience in the design and operation of H2 pressure swing adsorption (PSA) systems in its numerous steam methane reformers. Commercial PSAs typically operate on clean syngas and thus need an upstream AGR unit to operate in a gasification process. Air Products recognized that a H2 PSA technology adapted to handle sour feedgas (Sour PSA) would enable a new and enhanced improvement to a gasification system. The complete Air Products CO2 Capture technology (CCT) for sour syngas consists of a Sour PSA unit followed by a low-BTU sour oxycombustion unit and finally a CO2 purification / compression system.
Hydrogen Monitoring Requirements in the Global Technical Regulation on Hydrogen and Fuel Cell Vehicles
Oct 2015
Publication
The United Nations Economic Commission for Europe Global Technical Regulation (GTR) Number 13 (Global Technical Regulation on Hydrogen and Fuel Cell Vehicles) is the defining document regulating safety requirements in hydrogen vehicles and in particular fuel cell electric vehicles (FCEVs). GTR Number 13 has been formally adopted and will serve as the basis for the national regulatory standards for FCEV safety in North America (led by the United States) Japan Korea and the European Union. The GTR defines safety requirements for these vehicles including specifications on the allowable hydrogen levels in vehicle enclosures during in-use and post-crash conditions and on the allowable hydrogen emissions levels in vehicle exhaust during certain modes of normal operation. However in order to be incorporated into national regulations that is to be legally binding methods to verify compliance with the specific requirements must exist. In a collaborative program the Sensor Laboratories at the National Renewable Energy Laboratory in the United States and the Joint Research Centre Institute for Energy and Transport in the Netherlands have been evaluating and developing analytical methods that can be used to verify compliance with the hydrogen release requirements as specified in the GTR.
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.
Hydrogen Wide Area Monitoring of LH2 Releases
Sep 2019
Publication
The characterization of liquid hydrogen (LH2) releases has been identified as an international research priority to expand the safe use of hydrogen as an energy carrier. The elucidation of LH2 release behavior will require the development of dispersion and other models guided and validated by empirical field measurements such as those afforded by Hydrogen Wide Area Monitoring (HyWAM). HyWAM can be defined as the quantitative spatial and temporal three-dimensional monitoring of planned or unintentional hydrogen releases. With support provided through the FCH JU Prenormative Research for the Safe Use of Liquid Hydrogen (PRESLHY) program HSE performed a series of LH2 releases to characterize the dispersion and pooling behavior of cold hydrogen releases. The NREL Sensor Laboratory developed a HyWAM system based upon a distributed array of point sensors that is amenable for profiling cold hydrogen plumes. The NREL Sensor Laboratory and HSE formally committed to collaborate on profiling the LH2 releases. This collaboration included the integration of the NREL HyWAM into the HSE LH2 release hardware. This was achieved through a deployment plan jointly developed by the NREL and HSE personnel. Under this plan the NREL Sensor Laboratory provided multiple HyWAM modules that accommodated 32 sampling points for near-field hydrogen profiling during the HSE PRESLHY LH2 releases. The NREL HyWAM would be utilized throughout the LH2 release study performed under PRESLHY by HSE including Work Package 3 (WP3—Release and Mixing--Rainout) and subsequent work packages (WP4—Ignition and WP5—Combustion). Under the auspices of the PRESLHY WP6 (Implementation) data and findings from the HSE LH2 Releases are to be made available to stakeholders in the hydrogen community. Comprehensive data analysis and dissemination is ongoing but the integration of the NREL HyWAM into the HSE LH2 Release Apparatus and its performance as well as some key outcomes of the LH2 releases in WP3 are presented.
Department of Energy Hydrogen Program Plan
Nov 2020
Publication
The Department of Energy (DOE) Hydrogen Program Plan (the Program Plan or Plan) outlines the strategic high-level focus areas of DOE’s Hydrogen Program (the Program). The term Hydrogen Program refers not to any single office within DOE but rather to the cohesive and coordinated effort of multiple offices that conduct research development and demonstration (RD&D) activities on hydrogen technologies. This terminology and the coordinated efforts on hydrogen among relevant DOE offices have been in place since 2004 and provide an inclusive and strategic view of how the Department coordinates activities on hydrogen across applications and sectors. This version of the Plan updates and expands upon previous versions including the Hydrogen Posture Plan and the DOE Hydrogen and Fuel Cells Program Plan and provides a coordinated high-level summary of hydrogen related activities across DOE.
The 2006 Hydrogen Posture Plan fulfilled the requirement in the Energy Policy Act of 2005 (EPACT 2005) that the Energy Secretary transmit to Congress a coordinated plan for DOE’s hydrogen and fuel cell activities. For historical context the original Posture Plan issued in 2004 outlined a coordinated plan for DOE and the U.S. Department of Transportation to meet the goals of the Hydrogen Fuel Initiative (HFI) and implement the 2002 National Hydrogen Energy Technology Roadmap. The HFI was launched in 2004 to accelerate research development and demonstration (RD&D) of hydrogen and fuel cell technologies for use in transportation electricity generation and portable power applications. The Roadmap provided a blueprint for the public and private efforts required to fulfill a long-term national vision for hydrogen energy as outlined in A National Vision of America’s Transition to a Hydrogen Economy—to 2030 and Beyond. Both the Roadmap and the Vision were developed out of meetings involving DOE industry academia non-profit organizations and other stakeholders. The Roadmap the Vision the Posture Plans the 2011 Program Plan and the results of key stakeholder workshops continue to form the underlying basis for this current edition of the Program Plan.
This edition of the Program Plan reflects the Department’s focus on conducting coordinated RD&D activities to enable the adoption of hydrogen technologies across multiple applications and sectors. It includes content from the various plans and documents developed by individual offices within DOE working on hydrogen-related activities including: the Office of Fossil Energy's Hydrogen Strategy: Enabling a Low Carbon Economy the Office of Energy Efficiency and Renewable Energy’s Hydrogen and Fuel Cell Technologies Office Multi-year RD&D Plan the Office of Nuclear Energy’s Integrated Energy Systems 2020 Roadmap and the Office of Science’s Basic Research Needs for the Hydrogen Economy. Many of these documents are also in the process of updates and revisions and will be posted online.
Through this overarching document the reader will gain information on the key RD&D needs to enable the largescale use of hydrogen and related technologies—such as fuel cells and turbines—in the economy and how the Department’s various offices are addressing those needs. The Program will continue to periodically revise the Plan along with all program office RD&D plans to reflect technological progress programmatic changes policy decisions and updates based on stakeholder input and reviews.
The 2006 Hydrogen Posture Plan fulfilled the requirement in the Energy Policy Act of 2005 (EPACT 2005) that the Energy Secretary transmit to Congress a coordinated plan for DOE’s hydrogen and fuel cell activities. For historical context the original Posture Plan issued in 2004 outlined a coordinated plan for DOE and the U.S. Department of Transportation to meet the goals of the Hydrogen Fuel Initiative (HFI) and implement the 2002 National Hydrogen Energy Technology Roadmap. The HFI was launched in 2004 to accelerate research development and demonstration (RD&D) of hydrogen and fuel cell technologies for use in transportation electricity generation and portable power applications. The Roadmap provided a blueprint for the public and private efforts required to fulfill a long-term national vision for hydrogen energy as outlined in A National Vision of America’s Transition to a Hydrogen Economy—to 2030 and Beyond. Both the Roadmap and the Vision were developed out of meetings involving DOE industry academia non-profit organizations and other stakeholders. The Roadmap the Vision the Posture Plans the 2011 Program Plan and the results of key stakeholder workshops continue to form the underlying basis for this current edition of the Program Plan.
This edition of the Program Plan reflects the Department’s focus on conducting coordinated RD&D activities to enable the adoption of hydrogen technologies across multiple applications and sectors. It includes content from the various plans and documents developed by individual offices within DOE working on hydrogen-related activities including: the Office of Fossil Energy's Hydrogen Strategy: Enabling a Low Carbon Economy the Office of Energy Efficiency and Renewable Energy’s Hydrogen and Fuel Cell Technologies Office Multi-year RD&D Plan the Office of Nuclear Energy’s Integrated Energy Systems 2020 Roadmap and the Office of Science’s Basic Research Needs for the Hydrogen Economy. Many of these documents are also in the process of updates and revisions and will be posted online.
Through this overarching document the reader will gain information on the key RD&D needs to enable the largescale use of hydrogen and related technologies—such as fuel cells and turbines—in the economy and how the Department’s various offices are addressing those needs. The Program will continue to periodically revise the Plan along with all program office RD&D plans to reflect technological progress programmatic changes policy decisions and updates based on stakeholder input and reviews.
State-of-the-Art and Research Priorities in Hydrogen Safety
Sep 2013
Publication
On October 16-17 2012 the International Association for Hydrogen Safety (HySafe) in cooperation with the Institute for Energy and Transport of the Joint Research Centre of the European Commission (JRC IET Petten) held a two-day workshop dedicated to Hydrogen Safety Research Priorities. The workshop was hosted by Federal Institute for Materials Research and Testing (BAM) in Berlin Germany. The main idea of the Workshop was to bring together stakeholders who can address the existing knowledge gaps in the area of the hydrogen safety including identification and prioritization of such gaps from the standpoint of scientific knowledge both experimental and theoretical including numerical. The experience highlighting these gaps which was obtained during both practical applications (industry) and risk assessment should serve as reference point for further analysis. The program included two sections: knowledge gaps as they are addressed by industry and knowledge gaps and state-of-the-art by research. In the current work the main results of the workshop are summarized and analysed.
ISO 19880-1, Hydrogen Fueling Station and Vehicle Interface Safety Technical Report
Oct 2015
Publication
Hydrogen Infrastructures are currently being built up to support the initial commercialization of the fuel cell vehicle by multiple automakers. Three primary markets are presently coordinating a large build up of hydrogen stations: Japan; USA; and Europe to support this. Hydrogen Fuelling Station General Safety and Performance Considerations are important to establish before a wide scale infrastructure is established.
This document introduces the ISO Technical Report 19880-1 and summarizes main elements of the proposed standard. Note: this ICHS paper is based on the draft TR 19880 and is subject to change when the document is published in 2015. International Standards Organisation (ISO) Technical Committee (TC) 197 Working Group (WG) 24 has been tasked with the preparation of the ISO standard 19880-1 to define the minimum requirements considered applicable worldwide for the hydrogen and electrical safety of hydrogen stations. This report includes safety considerations for hydrogen station equipment and components control systems and operation. The following systems are covered specifically in the document as shown in Figure 1:
This document introduces the ISO Technical Report 19880-1 and summarizes main elements of the proposed standard. Note: this ICHS paper is based on the draft TR 19880 and is subject to change when the document is published in 2015. International Standards Organisation (ISO) Technical Committee (TC) 197 Working Group (WG) 24 has been tasked with the preparation of the ISO standard 19880-1 to define the minimum requirements considered applicable worldwide for the hydrogen and electrical safety of hydrogen stations. This report includes safety considerations for hydrogen station equipment and components control systems and operation. The following systems are covered specifically in the document as shown in Figure 1:
- H2 production / supply delivery system
- Compression
- Gaseous hydrogen buffer storage;
- Pre-cooling device;
- Gaseous hydrogen dispensers.
- Hydrogen Fuelling Vehicle Interface
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.
Can the Addition of Hydrogen to Natural Gas Reduce the Explosion Risk?
Sep 2009
Publication
One of the main benefits sought by including hydrogen in the alternative fuels mix is emissions reduction – eventually by 100%. However in the near term there is a very significant cost differential between fossil fuels and hydrogen. Hythane (a blend of hydrogen and natural gas) can act as a viable next step on the path to an ultimate hydrogen economy as a fuel blend consisting of 8−30 % hydrogen in methane can reduce emissions while not requiring significant changes in existing infrastructure. This work seeks to evaluate whether hythane may be safer than both hydrogen and methane under certain conditions. This is due to the fact hythane combines the positive safety properties of hydrogen (strong buoyancy high diffusivity) and methane (much lower flame speeds and narrower flammability limits as compared to hydrogen). For this purpose several different mixture compositions (e.g. 8 % 20 % and 30 % hydrogen) are considered. The evaluation of (a) dispersion characteristics (which are more positive than for methane) (b) combustion characteristics (which are closer to methane than hydrogen) and (c) Combined dispersion + explosion risk is performed. This risk is expected to be comparable to that of pure methane possibly lower in some situations and definitely lower than for pure hydrogen. The work is performed using the CFD software FLACS that has been well-validated for safety studies of both natural gas/methane and hydrogen systems. The first part of the work will involve validating the flame speeds and flammability limits predicted by FLACS against values available in literature. The next part of the work involves validating the overpressures predicted by the CFD tool for combustion of premixed mixtures of methane and hydrogen with air against available experimental data. In the end practical systems such as vehicular tunnels garages etc. is used to demonstrate positive safety benefits of hythane with comparisons to similar simulations for both hydrogen and methane.
Hydrogen Systems Component Safety
Sep 2013
Publication
The deployment of hydrogen technologies particularly the deployment of hydrogen dispensing systems for passenger vehicles requires that hydrogen components perform reliably in environments where they have to meet the following performance parameters:
The paper will use incident frequency data from NREL’s Technology Validation project to more quantitatively identify safety concerns in hydrogen dispensing and storage systems.
- Perform safely where the consumer will be operating the dispensing equipment
- Dispense hydrogen at volumes comparable to gasoline dispensing stations in timeframes comparable to gasoline stations
- Deliver a fueling performance that is within the boundaries of consumer tolerance
- Perform with maintenance/incident frequencies comparable to gasoline dispensing systems
The paper will use incident frequency data from NREL’s Technology Validation project to more quantitatively identify safety concerns in hydrogen dispensing and storage systems.
An Assessment on the Quantification of Hydrogen Releases Through Oxygen Displacement Using Oxygen
Sep 2013
Publication
Contrary to several reports in the recent literature the use of oxygen sensors for indirectly monitoring ambient hydrogen concentration has serious drawbacks. This method is based on the assumption that a hydrogen release will displace oxygen which is quantified using oxygen sensors. Despite its shortcomings the draft Hydrogen Vehicle Global Technical Regulation lists this method as a means to monitor hydrogen leaks to verify vehicle fuel system integrity. Experimental evaluations that were designed to impartially compare the ability of commercial oxygen and hydrogen sensors to reliably measure and report hydrogen concentration changes are presented. Numerous drawbacks are identified and discussed.
Fundamental Combustion Properties of Oxygen Enriched Hydrogen-air Mixtures Relevant to Safety Analysis Experimental and Simulation Study
Oct 2015
Publication
In order to face the coming shortage of fossil energies a number of alternative methods of energy production are being considered. One promising approach consists in using hydrogen in replacement of the conventional fossil fuels or as an additive to these fuels. In addition to conventional hydro-electric and fission-based nuclear plants electric energy could be obtained in the future using nuclear fusion as investigated within the framework of the ITER project International Thermonuclear Experimental Reactor. However the operation of ITER may rise safety problems including the formation of a flammable dust/hydrogen/air atmosphere. A first step towards the accurate assessment of accidental explosion in ITER consists in better characterizing the risk of explosion in gaseous hydrogen-containing mixtures. In the present study laminar burning speeds ignition delay-times behind reflected shock wave and detonation cell sizes were measured over wide ranges of composition and equivalence ratios. The performances of five detailed reaction models were evaluated with respect to the present data.
3D Risk Management for Hydrogen Installations (HY3DRM)
Oct 2015
Publication
This paper introduces the 3D risk management (3DRM) concept with particular emphasis on hydrogen installations (Hy3DRM). The 3DRM framework entails an integrated solution for risk management that combines a detailed site-specific 3D geometry model a computational fluid dynamics (CFD) tool for simulating flow-related accident scenarios methodology for frequency analysis and quantitative risk assessment (QRA) and state-of-the-art visualization techniques for risk communication and decision support. In order to reduce calculation time and to cover escalating accident scenarios involving structural collapse and projectiles the CFD-based consequence analysis can be complemented with empirical engineering models reduced order models or finite element analysis (FEA). The paper outlines the background for 3DRM and presents a proof-of-concept risk assessment for a hypothetical hydrogen filling station. The prototype focuses on dispersion fire and explosion scenarios resulting from loss of containment of gaseous hydrogen. The approach adopted here combines consequence assessments obtained with the CFD tool FLACS-Hydrogen from Gexcon and event frequencies estimated with the Hydrogen Risk Assessment Models (HyRAM) tool from Sandia to generate 3D risk contours for explosion pressure and radiation loads. For a given population density and set of harm criteria it is straightforward to extend the analysis to include personnel risk as well as risk-based design such as detector optimization. The discussion outlines main challenges and inherent limitations of the 3DRM concept as well as prospects for further development towards a fully integrated framework for risk management in organizations.
Experimental Investigation of Spherical-flame Acceleration in Lean Hydrogen-air Mixtures
Oct 2015
Publication
Large-scale experiments examining spherical-flame acceleration in lean hydrogen-air mixtures were performed in a 64 m3 constant-pressure enclosure. Equivalence ratios ranging from 0.33 to 0.57 were examined using detailed front tracking for flame diameters up to 1.2 m through the use of a Background Oriented Schlieren (BOS) technique. From these measurements the critical radii for onset of instability for these mixtures on the order of 2–3 cm were obtained. In addition the laminar burning velocity and rate of flame acceleration as a function of radius were also measured.
Overview of the DOE Hydrogen Safety, Codes and Standards Program Part 1- Regulations, Codes and Standards (RCS) for Hydrogen Technologies - An Historical Overview
Oct 2015
Publication
RCS for hydrogen technologies were first developed approximately sixty years ago when hydrogen was being sold as an industrial commodity. The advent of new hydrogen technologies such as Fuel Cell Electric Vehicles (FCEVs) created a need for new RCS. These RCS have been developed with extensive support from the US DOE. These new hydrogen technologies are approaching commercial deployment and this process will produce information on RCS field performance that will create more robust RCS.
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.
Overview of the DOE Hydrogen Safety, Codes and Standards Program part 2- Hydrogen and Fuel Cells, Emphasizing Safety to Enable Commercialization
Oct 2015
Publication
Safety is of paramount importance in all facets of the research development demonstration and deployment work of the U.S. Department of Energy’s (DOE) Fuel Cell Technologies Program. The Safety Codes and Standards sub-program (SC&S) facilitates deployment and commercialization of fuel cell and hydrogen technologies by developing and disseminating information and knowledge resources for their safe use. A comprehensive safety management program utilizing the Hydrogen Safety Panel to raise safety consciousness at the project level and developing/disseminating a suite of safety knowledge resources is playing an integral role in DOE and SC&S efforts. This paper provides examples of accomplishments achieved while reaching a growing and diverse set of stakeholders involved in research development and demonstration; design and manufacturing; deployment and operations. The work of the Hydrogen Safety Panel highlights new knowledge and the insights gained through interaction with project teams. Various means of collaboration to enhance the value of the program’s safety knowledge tools and training resources are illustrated and the direction of future initiatives to reinforce the commitment to safety is discussed.
Application of Quantitative Risk Assessment for Performance-based Permitting of Hydrogen Fueling Stations
Oct 2015
Publication
NFPA 2 Hydrogen Technologies Code allows the use of risk-informed approaches to permitting hydrogen fuelling installations through the use of performance-based evaluations of specific hydrogen hazards. However the hydrogen fuelling industry in the United States has been reluctant to implement the performance-based option because the perception is that the required effort is cost prohibitive and there is no guarantee that the Authority Having Jurisdiction (AHJ) would accept the results. This report provides a methodology for implementing a performance-based design of an outdoor hydrogen refuelling station that does not comply with specific prescriptive separation distances. Performance-based designs are a code-compliant alternative to meeting prescriptive requirements. Compliance is demonstrated by evaluating a compliant prescriptive-based refuelling station design with a performance-based design approach using Quantitative Risk Assessment (QRA) methods and hydrogen risk tools. This template utilizes the Sandia-developed QRA tool Hydrogen Risk Analysis Model (HyRAM) to calculate risk values when developing risk-equivalent designs. HyRAM combines reduced-order deterministic models that characterize hydrogen release and flame behaviour with probabilistic risk models to quantify risk values. Each project is unique and this template is not intended to cover unique site-specific characteristics. Instead example content and a methodology are provided for a representative hydrogen refuelling site which can be built upon for new hydrogen applications.
Continuous Codes and Standards Improvement (CCSI)
Oct 2015
Publication
As of 2014 the majority of the Codes and Standards required to initially deploy hydrogen technologies infrastructure in the US have been promulgated1. These codes and standards will be field tested through their application to actual hydrogen technologies projects. CCSI is process of identifying code issues that arise during project deployment and then develop codes solutions to these issues. These solutions would typically be proposed amendments to codes and standards. The process is continuous because of technology and the state of safety knowledge develops there will be a need for monitoring the application of codes and standards and improving them based on information gathered during their application. This paper will discuss code issues that have surfaced through hydrogen technologies infrastructure project deployment and potential code changes that would address these issues. The issues that this paper will address include:
- Setback distances for bulk hydrogen storage
- Code mandated hazard analyses
- Sensor placement and communication
- The use of approved equipment
- System monitoring and maintenance requirements
HYRAM: A Methodology and Toolkit for Quantitative Risk Assessment of Hydrogen Systems
Oct 2015
Publication
HyRAM is a methodology and accompanying software toolkit which is being developed to provide a platform for integration of state-of-the-art validated science and engineering models and data relevant to hydrogen safety. As such the HyRAM software toolkit establishes a standard methodology for conducting quantitative risk assessment (QRA) and consequence analysis relevant to assessing the safety of hydrogen fueling and storage infrastructure. The HyRAM toolkit integrates fast-running deterministic and probabilistic models for quantifying risk of accident scenarios for predicting physical effects and for characterizing the impact of hydrogen hazards (thermal effects from jet fires thermal and pressure effects from deflagrations and detonations). HyRAM incorporates generic probabilities for equipment failures for nine types of hydrogen system components generic probabilities for hydrogen ignition and probabilistic models for the impact of heat flux and pressure on humans and structures. These are combined with fast-running computationally and experimentally validated models of hydrogen release and flame behaviour. HyRAM can be extended in scope via user contributed models and data. The QRA approach in HyRAM can be used for multiple types of analyses including codes and standards development code compliance safety basis development and facility safety planning. This manuscript discusses the current status and vision for HyRAM.
An Overview of Hydrogen Safety Sensors and Requirements
Sep 2009
Publication
There exists an international commitment to increase the utilization of hydrogen as a clean and renewable alternative to carbon-based fuels. The availability of hydrogen safety sensors is critical to assure the safe deployment of hydrogen systems. Already the use of hydrogen safety sensors is required for the indoor fueling of fuel cell powered forklifts (e.g. NFPA 52 Vehicular Fuel Systems Code [1]). Additional Codes and Standards specific to hydrogen detectors are being developed [2 3] which when adopted will impose mandatory analytical performance metrics. There are a large number of commercially available hydrogen safety sensors. Because end-users have a broad range of sensor options for their specific applications the final selection of an appropriate sensor technology can be complicated. Facility engineers and other end-users are expected to select the optimal sensor technology choice. However some sensor technologies may not be a good fit for a given application. Informed decisions require an understanding of the general analytical performance specifications that can be expected by a given sensor technology. Although there are a large number of commercial sensors most can be classified into relatively few specific sensor types (e.g. electrochemical metal oxide catalytic bead and others). Performance metrics of commercial sensors produced on a specific platform may vary between manufacturers but to a significant degree a specific platform has characteristic analytical trends advantages and limitations. Knowledge of these trends facilitates the selection of the optimal technology for a specific application (i.e. indoor vs. outdoor environments). An understanding of the various sensor options and their general analytical performance specifications would be invaluable in guiding the selection of the most appropriate technology for the designated application.
Self-Ignition of Hydrogen Jet Fires By Electrostatic Discharge Induced By Entrained Particulates
Sep 2011
Publication
The potential for particulates entrained in hydrogen releases to generate electrostatic charge and induce electrostatic discharge ignitions was investigated. A series of tests were performed in which hydrogen was released through a 3.75-mm-diameter orifice from an initial pressure of 140 bar. Electrostatic field sensors were used to characterize the electrification of known quantities of iron oxide particulates deliberately entrained in the release. The ignition experiments focused on using charged particulates to induce spark discharges from isolated conductors and corona discharges. A total of 12 ignition events were observed. The results show that electrification of entrained particulates is a viable self-ignition mechanism of hydrogen releases.
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.
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.
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.
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.
Validated Equivalent Source Model for an Under-expanded Hydrogen Jet
Oct 2015
Publication
As hydrogen fuel cell vehicles become more widely adopted by consumers the demand for refuelling stations increases. Most vehicles require high-pressure (either 350 or 700 bar) hydrogen and therefore the refuelling infrastructure must support these pressures. Fast running reduced order physical models of releases from high-pressure sources are needed so that quantitative risk assessment can guide the safety certification of these stations. A release from a high pressure source is choked at the release point forming the complex shock structures of an under-expanded jet before achieving a characteristic Gaussian pro le for velocity density mass fraction etc. downstream. Rather than using significant computational resources to resolve the shock structure an equivalent source model can be used to quickly and accurately describe the ow in terms of velocity diameter and thermodynamic state after the shock structure. In this work we present correlations for the equivalent boundary conditions of a subsonic jet as a high-pressure jet downstream of the shock structure. Schlieren images of under-expanded jets are used to show that the geometrical structure of under-expanded jets scale with the square root of the static to ambient pressure ratio. Correlations for an equivalent source model are given and these parameters are also found to scale with square root of the pressure ratio. We present our model as well as planar laser Rayleigh scattering validation data for static pressures up to 60 bar.
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.
Design of an Efficient, High Purity Hydrogen Generation Apparatus and Method for a Sustainable, Closed Clean Energy Cycle
Jul 2015
Publication
In this paper we present a detailed design study of a novel apparatus for safely generating hydrogen (H2) on demand according to a novel method using a controlled chemical reaction between water (H2O) and sodium (Na) metal that yields hydrogen gas of sufficient purity for direct use in fuel cells without risk of contaminating sensitive catalysts. The apparatus consists of a first pressure vessel filled with liquid H2O with an overpressure of nitrogen (N2) gas above the H2O reactant and a second pressure vessel that stores solid Na reactant. Hydrogen gas is generated above the solid Na when H2O reactant is introduced using a regulator that senses when the downstream pressure of H2 gas above the solid Na reactant has dropped below a threshold value. The sodium hydroxide (NaOH) byproduct of the hydrogen producing reaction is collected within the apparatus for later reprocessing by electrolysis to recover the Na reactant.
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.
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.
Characteristic of Cryogenic Hydrogen Flames from High-aspect Ratio Nozzles
Sep 2019
Publication
Unintentional leaks at hydrogen fuelling stations have the potential to form hydrogen jet flames which pose a risk to people and infrastructure. The heat flux from these jet flames are often used to develop separation distances between hydrogen components and buildings lot-lines etc. The heat flux and visible flame length is well understood for releases from round nozzles but real unintended releases would be expected to be be higher aspect-ratio cracks. In this work we measured the visible flame length and heat-flux characteristics of cryogenic hydrogen flames from high-aspect ratio nozzles. We compare this data to flames of both cryogenic and compressed hydrogen from round nozzles. The aspect ratio of the release does not affect the flame length or heat flux significantly for a given mass flow under the range of conditions studied. The engineering correlations presented in this work that enable the prediction of flame length and heat flux can be used to assess risk at hydrogen fuelling stations with liquid hydrogen and develop science-based separation distances for these stations.
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.
Hydrogen and Fuel Cell Stationary Applications: Key Findings of Modelling and Experimental Work in the Hyper Project
Sep 2009
Publication
Síle Brennan,
A. Bengaouer,
Marco Carcassi,
Gennaro M. Cerchiara,
Andreas Friedrich,
O. Gentilhomme,
William G. Houf,
N. Kotchourko,
Alexei Kotchourko,
Sergey Kudriakov,
Dmitry Makarov,
Vladimir V. Molkov,
Efthymia A. Papanikolaou,
C. Pitre,
Mark Royle,
R. W. Schefer,
G. Stern,
Alexandros G. Venetsanos,
Anke Veser,
Deborah Willoughby,
Jorge Yanez and
Greg H. Evans
"This paper summarises the modelling and experimental programme in the EC FP6 project HYPER. A number of key results are presented and the relevance of these findings to installation permitting guidelines (IPG) for small stationary hydrogen and fuel cell systems is discussed. A key aim of the activities was to generate new scientific data and knowledge in the field of hydrogen safety and where possible use this data as a basis to support the recommendations in the IPG. The structure of the paper mirrors that of the work programme within HYPER in that the work is described in terms of a number of relevant scenarios as follows: 1. high pressure releases 2. small foreseeable releases 3. catastrophic releases and 4. the effects of walls and barriers. Within each scenario the key objectives activities and results are discussed.<br/>The work on high pressure releases sought to provide information for informing safety distances for high-pressure components and associated fuel storage activities on both ignited and unignited jets are reported. A study on small foreseeable releases which could potentially be controlled through forced or natural ventilation is described. The aim of the study was to determine the ventilation requirements in enclosures containing fuel cells such that in the event of a foreseeable leak the concentration of hydrogen in air for zone 2 ATEX is not exceeded. The hazard potential of a possibly catastrophic hydrogen leakage inside a fuel cell cabinet was investigated using a generic fuel cell enclosure model. The rupture of the hydrogen feed line inside the enclosure was considered and both dispersion and combustion of the resulting hydrogen air mixture were examined for a range of leak rates and blockage ratios. Key findings of this study are presented. Finally the scenario on walls and barriers is discussed; a mitigation strategy to potentially reduce the exposure to jet flames is to incorporate barriers around hydrogen storage equipment. Conclusions of experimental and modelling work which aim to provide guidance on configuration and placement of these walls to minimise overall hazards is presented. "
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.
QRA Including Utility for Decision Support of H2 Infrastructure Licensing
Sep 2011
Publication
Rational decision making in land use planning and licensing of H2 infrastructure surrounded by other industrial activities and population should take account of individual and societal risks. QRA produces a risk matrix of potential consequences versus event probabilities that is shrouded in ambiguity and lacking transparency. NIMBY and conflict are lurking. To counter these issues risk analysts should therefore also determine the utilities of decision alternatives which describe desirability of benefits on a single scale. Rationally weighing risks versus benefits results in more transparent and defendable decisions. Example risk analyses of two types of refuelling stations and three hydrogen supply transportation types applying Influence Diagram/BBNs are worked out. Keywords: risk assessment influence diagram decision making land use planning
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.
Advancing the Hydrogen Safety Knowledge Base
Sep 2013
Publication
The International Energy Agency's Hydrogen Implementing Agreement (IEA HIA) was established in 1977 to pursue collaborative hydrogen research and development and information exchange among its member countries. Information and knowledge dissemination is a key aspect of the work within IEA HIA tasks and case studies technical reports and presentations/publications often result from the collaborative efforts. The work conducted in hydrogen safety under Task 31 and its predecessor Task 19 can positively impact the objectives of national programs even in cases for which a specific task report is not published. The interactions within Task 31 illustrate how technology information and knowledge exchange among participating hydrogen safety experts serve the objectives intended by the IEA HIA.
First Responder Training Supporting Commercialization of Hydrogen and Fuel Cell Technologies
Oct 2015
Publication
A properly trained first responder community is critical to the successful introduction of hydrogen fuel cell applications and their transformation in how we use energy. Providing resources with accurate information and current knowledge is essential to the delivery of effective hydrogen and fuel cell-related first responder training. The California Fuel Cell Partnership and the Pacific Northwest National Laboratory have over 15 years of experience in developing and delivering hydrogen safety-related first responder training materials and programs. A National Hydrogen and Fuel Cell Emergency Response Training Resource was recently released. This training resource serves the delivery of a variety of training regimens. Associated materials are adaptable for different training formats ranging from high-level overview presentations to more comprehensive classroom training. This paper presents what has been learned from the development and delivery of hydrogen safety-related first responder training programs (online classroom hands-on) by the respective organizations. The collaborative strategy being developed for enhancing training materials and methods for greater accessibility based on stakeholder input will be discussed.
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.
Experimental Investigation of Hydrogen Release and Ignition from Fuel Cell Powered Forklifts in Enclosed Spaces
Sep 2011
Publication
Due to rapid growth in the use of hydrogen powered fuel cell forklifts within warehouse enclosures Sandia National Laboratories has worked to develop scientific methods that support the creation of new hydrogen safety codes and standards for indoor refuelling operations. Based on industry stakeholder input conducted experiments were devised to assess the utility of modelling approaches used to analyze potential consequences from ignited hydrogen leaks in facilities certified according to existing code language. Release dispersion and combustion characteristics were measured within a scaled test facility located at SRI International's Corral Hollow Test Site. Moreover the impact of mitigation measures such as active/passive ventilation and pressure relief panels was investigated. Since it is impractical to experimentally evaluate all possible facility configurations and accident scenarios careful characterization of the experimental boundary conditions has been performed so that collected datasets can be used to validate computational modelling approaches.
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.
Hydrogen Fuel-Cell Forklift Vehicle Releases In Enclosed Spaces
Sep 2011
Publication
Sandia National Laboratories has worked with stakeholders and original equipment manufacturers (OEMs) to develop scientific data that can be used to create risk-informed hydrogen codes and standards for the safe operation of indoor hydrogen fuel-cell forklifts. An important issue is the possibility of an accident inside a warehouse or other enclosed space where a release of hydrogen from the high-pressure gaseous storage tank could occur. For such scenarios computational fluid dynamics (CFD) simulations have been used to model the release and dispersion of gaseous hydrogen from the vehicle and to study the behavior of the ignitable hydrogen cloud inside the warehouse or enclosure. The overpressure arising as a result of ignition and subsequent deflagration of the hydrogen cloud within the warehouse has been studied for different ignition delay times and ignition locations. Both ventilated and unventilated warehouses have been considered in the analysis. Experiments have been performed in a scaled warehouse test facility and compared with simulations to validate the results of the computational analysis.
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.
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.
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).
Detection of Hydrogen Released In a Full-Scale Residential Garage
Sep 2011
Publication
Experiments were conducted to assess detectability of a low-level leak of hydrogen gas and the uniformity of hydrogen concentration at selected sensor placement locations in a realistic setting. A 5%2hydrogen/95%2nitrogen gas mixture was injected at a rate of 350 L/min for about 3/4 hour into a 93m3 residential garage space through a 0.09 m2 square open-top dispersion box located on the floor. Calibrated catalytic sensors were placed on ceiling and wall locations and the sensors detected hydrogen early in the release and continued to measure concentrations to peak and diminishing levels. Experiments were conducted with and without a car parked over the dispersion box. The results show that a car positioned over the dispersion box tends to promote dilution of the hydrogen cause a longer time for locations to reach a fixed threshold and produce lower peak concentrations than with no car present.
Validation Testing In Support Of Hydrogen Codes and Standards Developments
Sep 2011
Publication
New codes and standards are being developed to facilitate the safe deployment of emerging hydrogen technologies. Hydrogen markets will benefit from standards that address the specific properties of hydrogen hydrogen effects on strength of materials and hydrogen compressed gas storage at pressures up to 70 MPa. The need for validation of new hydrogen requirements has been identified by codes and standards technical committees. The US Department of Energy (DOE) office of Energy Efficiency and Renewable Energy (EERE) has tasked the National Renewable Energy Laboratory (NREL) with the role of supporting hydrogen codes and standards research and development needs. NREL has provided validation test support to several new standards development efforts including pressure testing of 70 MPa on board vehicle storage systems flaw testing of stationary hydrogen tanks fill protocols for hydrogen fuel dispensing and hydrogen compatibility testing for hydrogen pressure relief devices (HPRD’s). Validation test results are presented for these four specific standards development needs.
Real World Hydrogen Technology Validation
Sep 2011
Publication
The Department of Energy the Department of Defense's Defense Logistics Agency and the Department of Transportation's Federal Transit Administration have funded learning demonstrations and early market deployments to provide insight into applications of hydrogen technologies on the road in the warehouse and as stationary power. NREL's analyses validate the technology in real-world applications reveal the status of the technology and facilitate the development of hydrogen and fuel cell technologies manufacturing and operations. This paper presents the maintenance safety and operation data of fuel cells in multiple applications with the reported incidents near misses and frequencies. NREL has analyzed records of more than 225000 kilograms of hydrogen that have been dispensed through more than 108000 hydrogen fills with an excellent safety record.
Hydrogen Fueling Standardization: Enabling ZEVs with "Same as Today" Fueling and FCEV Range and Safety
Oct 2015
Publication
Zero Emission Vehicles (ZEVs) are necessary to help reduce the emissions in the transportation sector which is responsible for 40% of overall greenhouse gas emissions. There are two types of ZEVs Battery Electric Vehicles (BEVs) and Fuel Cell Electric Vehicles (FCEVs) Commercial Success of BEVs has been challenging thus far also due to limited range and very long charging duration. FCEVs using H2 infrastructure with SAE J2601 and J2799 standards can be consistently fuelled in a safe manner fast and resulting in a range similar to conventional vehicles. Specifically fuelling with SAE J2601 with the SAE J2799 enables FCEVs to fill with hydrogen in 3-5 minutes and to achieve a high State of Charge (SOC) resulting in 300+ mile range without exceeding the safety storage limits. Standardized H2 therefore gives an advantage to the customer over electric charging. SAE created this H2 fuelling protocol based on modelling laboratory and field tests. These SAE standards enable the first generation of commercial FCEVs and H2 stations to achieve a customer acceptable fueling similar to today's experience. This report details the advantages of hydrogen and the validation of H2 fuelling for the SAE standards.
Component Availability Effects for Pressure Relief Valves Used at Hydrogen Fueling Stations
Sep 2017
Publication
There are times in engineering when it seems that safety and equipment cost reduction are conflicting priorities. This could be the case for pressure relief valves and vent stack sizing. This paper explores the role that component availability (particularly variety in flow and orifice diameters) plays in the engineer’s decision of a relief valve. This paper outlines the guidelines and assumptions in sizing and selecting pressure relief devices (PRDs) found in a typical high pressure hydrogen fueling station. It also provides steps in sizing the station common vent stack where the discharge gas is to be routed to prior being released into the atmosphere. This paper also explores the component availability landscape for hydrogen station designers and identifies opportunities for improvement in the supply chain of components as hydrogen fueling stations increase in number and size. American Society of Mechanical Engineers Boiler and Pressure Vessel Code Section VIII (ASME BPVC Section VIII) Compressed Gas Association S-1.3 (CGA S-1.3) and American Petroleum Institute 520 (API 520) standards provide specific design criteria for hydrogen pressure relief valves. Results of these calculations do not match the available components. The available safety relief valves are 50 to 87 times larger than the required calculated flow capacities. Selecting a significantly oversized safety relief valve affects the vent stack design as the stack design requires sizing relative to the actual flowrate of the safety relief valve. The effect on the vent stack size in turn negatively affects site safety radiation threshold set back distances.
Effect of Initial Turbulence on Vented Explosion Over Pressures from Lean Hydrogen-air Deflagrations
Sep 2013
Publication
To examine the effect of initial turbulence on vented explosions experiments were performed for lean hydrogen–air mixtures with hydrogen concentrations ranging from 12 to 15% vol. at elevated initial turbulence. As expected it was found that an increase in initial turbulence increased the overall flame propagation speed and this increased flame propagation speed translated into higher peak overpressures during the external explosion. The peak pressures generated by flame–acoustic interactions however did not vary significantly with initial turbulence. When flame speeds measurements were examined it was found that the burning velocity increased with flame radius as a power function of radius with a relatively constant exponent over the range of weak initial turbulence studied and did not vary systematically with initial turbulence. Instead the elevated initial turbulence increased the initial flame propagation velocities of the various mixtures. The initial turbulence thus appears to act primarily by generating higher initial flame wrinkling while having a minimal effect on the growth rate of the wrinkles. For practical purposes of modelling flame propagation and pressure generation in vented explosions the increase in burning velocity due to turbulence is suggested to be approximated by a single constant factor that increases the effective burning velocity of the mixture. When this approach is applied to a previously developed vent sizing correlation the correlation performs well for almost all of the peaks. It was found however that in certain situations this approach significantly under predicts the flame–acoustic peak. This suggests that further research may be necessary to better understand the influence of initial turbulence on the development of flame–acoustic peaks in vented explosions.
Deploying Fuel Cell Systems, What Have We Learned
Sep 2013
Publication
The Hydrogen Safety Panel brings a broad cross-section of expertise from the industrial government and academic sectors to help advise the U.S. Department of Energy's (DOE) Fuel Cell Technologies Office through its work in hydrogen safety codes and standards. The Panel's initiatives in reviewing safety plans conducting safety evaluations identifying safety-related technical data gaps and supporting safety knowledge tools and databases cover the gamut from research and development to demonstration. The Panel's recent work has focused on the safe deployment of hydrogen and fuel cell systems in support of DOE efforts to accelerate fuel cell commercialization in early market applications: vehicle refuelling material handling equipment backup power for warehouses and telecommunication sites and portable power devices. This paper summarizes the work and learnings from the Panel's early efforts the transition to its current focus and the outcomes and conclusions from recent work on the deployment of hydrogen and fuel cell systems.
Discussion of Lessons Learned from a Hydrogen Release
Sep 2013
Publication
Just in line with any emerging alternative transportation fuel incidents involving hydrogen used as transportation fuel are learning opportunities for this new and growing industry. This paper includes discussion of many topics in hydrogen safety surrounding the installation operation and maintenance of commercial hydrogen stations or compression storage and dispensing systems.
What is an Explosion?
Sep 2013
Publication
We are going to focus our discussion on “Explosions” its definitions from a scientific regulatory and societal perspective. We will point out that as defined these definitions are not consistent and lead to ambiguity. Of particular interest to this work is how this current ambiguity affects the emerging Regulation Codes and Standards (RCS) as applied to hydrogen technologies. While this manuscript has its roots in combustion science with extension to both the standard development and regulatory communities for hazards at large the unique behavior of hydrogen in many configurations motivates examining the relevant definitions and language used in these communities. We will point out the ambiguities how this leads to confusion in supporting definitions and how it leads to overly restrictive RCS for hydrogen applications. We will then suggest terminology which is not ambiguous internally self-consistent and allows appropriate RCS to be promulgated to ensure the safety of the public and capital to ensure the correct response of first responders and allow cost effective development of hydrogen technologies in our infrastructure.
Empirical Profiling of Cold Hydrogen Plumes Formed from Venting of LH2 Storage Vessels
Sep 2017
Publication
Liquid hydrogen (LH2) storage is viewed as a viable approach to assure sufficient hydrogen capacity at commercial fuelling stations. Presently LH2 is produced at remote facilities and then transported to the end-use site by road vehicles (i.e. LH2 tanker trucks). Venting of hydrogen to depressurize the transport storage tank is a routine part of the LH2 delivery and site transfer process. The behaviour of cold hydrogen plumes has not been well characterized because of the sparsity of empirical field data which can lead to overly conservative safety requirements. Committee members of the National Fire Protection Association (NFPA) Standard 2 [1] formed the Hydrogen Storage Safety Task Group which consists of hydrogen producers safety experts and computational fluid dynamics modellers has identified the lack of understanding of hydrogen dispersion during LH2 venting of storage vessels as a critical gap for establishing safety distances at LH2 facilities especially commercial hydrogen fuelling stations. To address this need the National Renewable Energy Laboratory Sensor Laboratory in collaboration with the NFPA Hydrogen Storage Task Group developed a prototype Cold Hydrogen Plume Analyzer to empirically characterize the hydrogen plume formed during LH2 storage tank venting. The prototype analyzer was field deployed during an actual LH2 venting process. Critical findings included
- Hydrogen above the lower flammable limit (LFL) was detected as much as 2 m lower than the release point which is not predicted by existing models.
- Personal monitors detected hydrogen at ground level although at levels below the LFL.
- A small but inconsistent correlation was found between oxygen depletion and the hydrogen concentration.
- A negligible to non-existent correlation was found between in-situ temperature measurements and the hydrogen concentration.
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.
Polymer Behaviour in High Pressure Hydrogen, Helium and Argon Environments as Applicable to the Hydrogen Infrastructure
Sep 2017
Publication
Polymers for O-rings valve seats gaskets and other sealing applications in the hydrogen infrastructure face extreme conditions of high-pressure H2 (0.1 to 100 MPa) during normal operation. To fill current knowledge gaps and to establish standard test methods for polymers in H2 environments these materials can be tested in laboratory scale H2 manifolds mimicking end use pressure and temperature conditions. Beyond the influence of high pressure H2 the selection of gases used for leak detection in the H2 test manifold their pressures and times of exposure gas types relative diffusion and permeation rates are all important influences on the polymers being tested. These effects can be studied ex-situ with post-exposure characterization. In a previous study four polymers (Viton A Buna N High Density Polyethylene (HDPE) and Polytetrafluoroethylene (PTFE)) commonly used in the H2 infrastructure were exposed to high-pressure H2 (100 MPa). The observed effects of H2 were consistent with typical polymer property-structure relationships; in particular H2 affected elastomers more than thermoplastics. However since high pressure He was used for purging and leak detection prior to filling with H2 a study of the influence of the purge gas on these polymers was considered necessary to isolate the effects of H2 from those of the purge gas. Therefore in this study Viton A Buna N and PTFE were exposed to the He purge procedure without the subsequent H2 exposure. Additionally six polymers Viton A Buna N PTFE Polyoxymethylene (POM) Polyamide 11 (Nylon) and Ethylenepropylenediene monomer rubber (EPDM) were subjected to high pressure Ar (100 MPa) followed by high pressure H2 (100 MPa) under the same static isothermal conditions to identify the effect of a purge gas with a significantly larger molecular size than He. Viton A and Buna N elastomers are more prone to irreversible changes as a result of H2 exposure from both Ar and He leak tests as indicated by influences on storage modulus extent of swelling and increased compression set. EPDM even though it is an elastomer is not as prone to high-pressure gas influences. The thermoplastics are generally less influenced by high pressure regardless of the gas type. Conclusions from these experiments will provide insight into the influence of purging processes and purge gases on the subsequent testing in high pressure gaseous H2. Control for the influence of purging on testing results is essential for the development of robust test methods for evaluating the effects of H2 and other high-pressure gases on the properties of polymers.
Regulations, Codes, and Standards (RCS) for Multi-fuel Motor Vehicle Dispensing Station
Sep 2017
Publication
In the United States requirements for liquid motor vehicle fuelling stations have been in place for many years. Requirements for motor vehicle fuelling stations for gaseous fuels including hydrogen are relatively new. These requirements have in the United States been developed along different code and standards paths. The liquid fuels have been addressed in a single document and the gaseous fuels have been addressed in documents specific to an individual gas. The result of these parallel processes is that multi-fuel stations are subject to requirements in several fuelling regulations codes and standards (RCS). This paper describes a configuration of a multi-fuel motor vehicle fuelling station and provides a detailed breakdown of the codes and standards requirements. The multi-fuel station would dispense what the U.S. Department of Energy defines as the six key alternative fuels: biodiesel electricity ethanol hydrogen natural gas and propane. The paper will also identify any apparent gaps in RCS and potential research projects that could help fill these gaps.
Ultrasonic-assisted Catalytic Transfer Hydrogenation for Upgrading Pyrolysis-oil
Feb 2021
Publication
Recent interest in biomass-based fuel blendstocks and chemical compounds has stimulated research efforts on conversion and upgrading pathways which are considered as critical commercialization drivers. Existing pre-/post-conversion pathways are energy intense (e.g. pyrolysis and hydrogenation) and economically unsustainable thus more efficient process solutions can result in supporting the renewable fuels and green chemicals industry. This study proposes a process including biomass conversion and bio-oil upgrading using mixed fast and slow pyrolysis conversion pathway as well as sono-catalytic transfer hydrogenation (SCTH) treatment process. The proposed SCTH treatment employs ammonium formate as a hydrogen transfer additive and palladium supported on carbon as the catalyst. Utilizing SCTH bio-oil molecular bonds were broken and restructured via the phenomena of cavitation rarefaction and hydrogenation with the resulting product composition investigated using ultimate analysis and spectroscopy. Additionally an in-line characterization approach is proposed using near-infrared spectroscopy calibrated by multivariate analysis and modelling. The results indicate the potentiality of ultrasonic cavitation catalytic transfer hydrogenation and SCTH for incorporating hydrogen into the organic phase of bio-oil. It is concluded that the integration of pyrolysis with SCTH can improve bio-oil for enabling the production of fuel blendstocks and chemical compounds from lignocellulosic biomass.
The Potential of Gas Switching Partial Oxidation Using Advanced Oxygen Carriers for Efficient H2 Production with Inherent CO2 Capture
May 2021
Publication
The hydrogen economy has received resurging interest in recent years as more countries commit to net-zero CO2 emissions around the mid-century. “Blue” hydrogen from natural gas with CO2 capture and storage (CCS) is one promising sustainable hydrogen supply option. Although conventional CO2 capture imposes a large energy penalty advanced process concepts using the chemical looping principle can produce blue hydrogen at efficiencies even exceeding the conventional steam methane reforming (SMR) process without CCS. One such configuration is gas switching reforming (GSR) which uses a Ni-based oxygen carrier material to catalyze the SMR reaction and efficiently supply the required process heat by combusting an off-gas fuel with integrated CO2 capture. The present study investigates the potential of advanced La-Fe-based oxygen carrier materials to further increase this advantage using a gas switching partial oxidation (GSPOX) process. These materials can overcome the equilibrium limitations facing conventional catalytic SMR and achieve direct hydrogen production using a water-splitting reaction. Results showed that the GSPOX process can achieve mild efficiency improvements relative to GSR in the range of 0.6–4.1%-points with the upper bound only achievable by large power and H2 co-production plants employing a highly efficient power cycle. These performance gains and the avoidance of toxicity challenges posed by Ni-based oxygen carriers create a solid case for the further development of these advanced materials. If successful results from this work indicate that GSPOX blue hydrogen plants can outperform an SMR benchmark with conventional CO2 capture by more than 10%-points both in terms of efficiency and CO2 avoidance.
Hydrogen is Essential for Sustainability
Nov 2018
Publication
Sustainable energy conversion requires zero emissions of greenhouse gases and criteria pollutants using primary energy sources that the earth naturally replenishes quickly like renewable resources. Solar and wind power conversion technologies have become cost effective recently but challenges remain to manage electrical grid dynamics and to meet end-use requirements for energy dense fuels and chemicals. Renewable hydrogen provides the best opportunity for a zero emissions fuel and is the best feedstock for production of zero emission liquid fuels and some chemical and heat end-uses. Renewable hydrogen can be made at very high efficiency using electrolysis systems that are dynamically operated to complement renewable wind and solar power dynamics. Hydrogen can be stored within the existing natural gas system to provide low cost massive storage capacity that (1) could be sufficient to enable a 100% zero emissions grid; (2) has sufficient energy density for end-uses including heavy duty transport; (3) is a building block for zero emissions fertilizer and chemicals; and (4) enables sustainable primary energy in all sectors of the economy.
Durability of Anion Exchange Membrane Water Electrolyzers
Apr 2021
Publication
Interest in the low-cost production of clean hydrogen is growing. Anion exchange membrane water electrolyzers (AEMWEs) are considered one of the most promising sustainable hydrogen production technologies because of their ability to split water using platinum group metal-free catalysts less expensive anode flow fields and bipolar plates. Critical to the realization of AEMWEs is understanding the durability-limiting factors that restrict the long-term use of these devices. This article presents both durability-limiting factors and mitigation strategies for AEMWEs under three operation modes i.e. pure water-fed (no liquid electrolyte) concentrated KOH-fed and 1 wt% K2CO3-fed operating at a differential pressure of 100 psi. We examine extended-term behaviors of AEMWEs at the single-cell level and connect their behavior with the electrochemical chemical and mechanical instability of single-cell components. Finally we discuss the pros and cons of AEMWEs under these operation modes and provide direction for long-lasting AEMWEs with highly efficient hydrogen production capabilities.
Advanced Optimal Planning for Microgrid Technologies Including Hydrogen and Mobility at a Real Microgrid Testbed
Apr 2021
Publication
This paper investigates the optimal planning of microgrids including the hydrogen energy system through mixed-integer linear programming model. A real case study is analyzed by extending the only microgrid lab facility in Austria. The case study considers the hydrogen production via electrolysis seasonal storage and fuelling station for meeting the hydrogen fuel demand of fuel cell vehicles busses and trucks. The optimization is performed relative to two different reference cases which satisfy the mobility demand by diesel fuel and utility electricity based hydrogen fuel production respectively. The key results indicate that the low emission hydrogen mobility framework is achieved by high share of renewable energy sources and seasonal hydrogen storage in the microgrid. The investment optimization scenarios provide at least 66% and at most 99% carbon emission savings at increased costs of 30% and 100% respectively relative to the costs of the diesel reference case (current situation)
Utilization and Recycling of End of Life Plastics for Sustainable and Clean Industrial Processes Including the Iron and Steel Industry
Aug 2019
Publication
About 400 million tonnes of plastics are produced per annum worldwide. End-of-life of plastics disposal contaminates the waterways aquifers and limits the landfill areas. Options for recycling plastic wastes include feedstock recycling mechanical /material recycling industrial energy recovery municipal solid waste incineration. Incineration of plastics containing E-Wastes releases noxious odours harmful gases dioxins HBr polybrominated diphenylethers and other hydrocarbons. This study focusses on recycling options in particular feedstock recycling of plastics in high-temperature materials processing for a sustainable solution to the plastic wastes not suitable for recycling. Of the 7% CO2 emissions attributed to the iron and steel industry worldwide ∼30% of the carbon footprint is reduced using the waste plastics compared to other carbon sources in addition to energy savings. Plastics have higher H2 content than the coal. Hydrogen evolved from the plastics acts as the reductant alongside the carbon monoxide. Hydrogen reduction of iron ore in presence of plastics increases the reaction rates due to higher diffusion of H2 compared to CO. Plastic replacement reduces the process temperature by at least 100–200 °C due to the reducing gases (hydrogen) which enhance the energy efficiency of the process. Similarly plastics greatly reduce the emissions in other high carbon footprint process such as magnesia production while contributing to energy.
Using Additives to Control the Decomposition Temperature of Sodium Borohydride
May 2020
Publication
Hydrogen (H2) shows great promise as zero-carbon emission fuel but there are several challenges to overcome in regards to storage and transportation to make it a more universal energy solution. Gaseous hydrogen requires high pressures and large volume tanks while storage of liquid hydrogen requires cryogenic temperatures; neither option is ideal due to cost and the hazards involved. Storage in the solid state presents an attractive alternative and can meet the U.S. Department of Energy (DOE) constraints to find materials containing > 7 % H2 (gravimetric weight) with a maximum H2 release under 125 °C.
While there are many candidate hydrogen storage materials the vast majority are metal hydrides. Of the hydrides this review focuses solely on sodium borohydride (NaBH4) which is often not covered in other hydride reviews. However as it contains 10.6% (by weight) H2 that can release at 133 ± 3 JK−1mol−1 this inexpensive material has received renewed attention. NaBH4 should decompose to H2g) Na(s) and B(s) and could be recycled into its original form. Unfortunately metal to ligand charge transfer in NaBH4 induces high thermodynamic stability creating a high decomposition temperature of 530 °C. In an effort make H2 more accessible at lower temperatures researchers have incorporated additives to destabilize the structure.
This review highlights metal additives that have successfully reduced the decomposition temperature of NaBH4 with temperatures ranging from 522 °C (titanium (IV) fluoride) to 379 °C (niobium (V) fluoride). We describe synthetic methods employed chemical pathways taken and the challenges of boron derivative formation on H2 cycling. Though no trends can be found across all additives it is our hope that compiling the data here will enable researchers to gain a better understanding of the additives’ influence and to determine how a new system might be designed to make NaBH4 a more viable H2 fuel source.
While there are many candidate hydrogen storage materials the vast majority are metal hydrides. Of the hydrides this review focuses solely on sodium borohydride (NaBH4) which is often not covered in other hydride reviews. However as it contains 10.6% (by weight) H2 that can release at 133 ± 3 JK−1mol−1 this inexpensive material has received renewed attention. NaBH4 should decompose to H2g) Na(s) and B(s) and could be recycled into its original form. Unfortunately metal to ligand charge transfer in NaBH4 induces high thermodynamic stability creating a high decomposition temperature of 530 °C. In an effort make H2 more accessible at lower temperatures researchers have incorporated additives to destabilize the structure.
This review highlights metal additives that have successfully reduced the decomposition temperature of NaBH4 with temperatures ranging from 522 °C (titanium (IV) fluoride) to 379 °C (niobium (V) fluoride). We describe synthetic methods employed chemical pathways taken and the challenges of boron derivative formation on H2 cycling. Though no trends can be found across all additives it is our hope that compiling the data here will enable researchers to gain a better understanding of the additives’ influence and to determine how a new system might be designed to make NaBH4 a more viable H2 fuel source.
Ignition of Hydrogen-air Mixtures Under Volumetric Expansion Conditions
Sep 2017
Publication
A better understanding of chemical kinetics under volumetric expansion is important for a number of situations relevant to industrial safety including detonation diffraction and direct initiation reflected shock-ignition at obstacles ignition behind a decaying shock among others. The ignition of stoichiometric hydrogen-air mixtures was studied using 0D numerical simulations with time-dependent specific volume variations. The competition between chemical energy release and expansion-induced cooling was characterized for different cooling rates and mathematical forms describing the shock decay rate. The critical conditions for reaction quenching were systematically determined and the thermo-chemistry dynamics were analyzed near the critical conditions.
Ignition of Hydrogen-air Mixtures by Moving Heated Particles
Oct 2015
Publication
Studying thermal ignition mechanisms is a key step for evaluating many ignition hazards. In the present work two-dimensional simulations with detailed chemistry are used to study the reaction pathways of the transient flow and ignition of a stoichiometric hydrogen-air mixture by moving hot spheres. For temperatures above the ignition threshold ignition takes place after a short time between the front stagnation point and separation location depending upon the sphere's surface temperature. Closer to the threshold the volume of gas adjacent to the separation region ignites homogeneously after a longer time. These results demonstrate the importance of boundary layer development and flow separation in the ignition process.
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.
Biomass Derived Porous Nitrogen Doped Carbon for Electrochemical Devices
Mar 2017
Publication
Biomass derived porous nanostructured nitrogen doped carbon (PNC) has been extensively investigated as the electrode material for electrochemical catalytic reactions and rechargeable batteries. Biomass with and without containing nitrogen could be designed and optimized to prepare PNC via hydrothermal carbonization pyrolysis and other methods. The presence of nitrogen in carbon can provide more active sites for ion absorption improve the electronic conductivity increase the bonding between carbon and sulfur and enhance the electrochemical catalytic reaction. The synthetic methods of natural biomass derived PNC heteroatomic co- or tri-doping into biomass derived carbon and the application of biomass derived PNC in rechargeable Li/Na batteries high energy density Li–S batteries supercapacitors metal-air batteries and electrochemical catalytic reaction (oxygen reduction and evolution reactions hydrogen evolution reaction) are summarized and discussed in this review. Biomass derived PNCs deliver high performance electrochemical storage properties for rechargeable batteries/supercapacitors and superior electrochemical catalytic performance toward hydrogen evolution oxygen reduction and evolution as promising electrodes for electrochemical devices including battery technologies fuel cell and electrolyzer.
Evaluation of Decarbonization Technologies for ASEAN Countries via an Integrated Assessment Tool
May 2022
Publication
A new assessment tool for evaluating decarbonization technologies that considers each technology’s sustainability security affordability readiness and impact for a specific country is proposed. This tool is applied to a set of decarbonization technologies for the power transport and industry sectors for the ten Southeast Asian countries that constitute ASEAN. This results in a list of the most promising decarbonization technologies as well as the remaining issues that need more research and development. This study reveals several common themes for ASEAN’s decarbonization. First carbon capture and storage (CCS) is a key technology for large-scale CO2 emission. Second for countries that rely heavily on coal for power generation switching to gas can halve their CO2 emission in the power sector and should be given high priority. Third hydropower and bioenergy both have high potential for the majority of ASEAN countries if their sustainability issues can be resolved satisfactorily. Fourth replacing conventional vehicles by electric vehicles is the overarching theme in the road transport sector but will result in increased demand for electricity. In the medium to long term the use of hydrogen for marine fuel and biofuels for aviation fuel are preferred solutions for the marine and aviation transport sectors. Fifth for the industry sector installing CCS in industrial plants should be given priority but replacing fossil fuels by blue hydrogen for high-temperature heating is the preferred long-term solution.
A Manganese Hydride Molecular Sieve for Practical Hydrogen Storage Under Ambient Conditions
Dec 2018
Publication
A viable hydrogen economy has thus far been hampered by the lack of an inexpensive and convenient hydrogen storage solution meeting all requirements especially in the areas of long hauls and delivery infrastructure. Current approaches require high pressure and/or complex heat management systems to achieve acceptable storage densities. Herein we present a manganese hydride molecular sieve that can be readily synthesized from inexpensive precursors and demonstrates a reversible excess adsorption performance of 10.5 wt% and 197 kgH2 m-3 at 120 bar at ambient temperature with no loss of activity after 54 cycles. Inelastic neutron scattering and computational studies confirm Kubas binding as the principal mechanism. The thermodynamically neutral adsorption process allows for a simple system without the need for heat management using moderate pressure as a toggle. A storage material with these properties will allow the DOE system targets for storage and delivery to be achieved providing a practical alternative to incumbents such as 700 bar systems which generally provide volumetric storage values of 40 kgH2 m-3 or less while retaining advantages over batteries such as fill time and energy density. Reasonable estimates for production costs and loss of performance due to system implementation project total energy storage costs roughly 5 times cheaper than those for 700 bar tanks potentially opening doors for increased adoption of hydrogen as an energy vector.
Comparison of Conventional vs. Modular Hydrogen Refuelling Stations and On-Site Production vs. Delivery
Mar 2017
Publication
To meet the needs of public and private stakeholders involved in the development construction and operation of hydrogen fuelling stations needed to support the widespread roll-out of hydrogen fuel cell electric vehicles this work presents publicly available station templates and analyses. These ‘Reference Stations’ help reduce the cost and speed the deployment of hydrogen stations by providing a common baseline with which to start a design enable quick assessment of potential sites for a hydrogen station identify contributors to poor economics and suggest areas of research. This work presents layouts bills of materials piping and instrumentation diagrams and detailed analyses of five new station designs. In the near term delivered hydrogen results in a lower cost of hydrogen compared to on-site production via steam methane reforming or electrolysis although the on-site production methods have other advantages. Modular station concepts including on-site production can reduce lot sizes from conventional assemble-on-site stations.
IPHE Regulations Codes and Standards Working Group-type IV COPV Round Robin Testing
Oct 2015
Publication
This manuscript presents the results of a multi-lateral international activity intended to understand how to execute a cycle stress test as specified in a chosen standard (GTR SAE ISO EIHP …). The purpose of this work was to establish a harmonized test method protocol to ensure that the same results would be achieved regardless of the testing facility. It was found that accurate temperature measurement of the working fluid is necessary to ensure the test conditions remain within the tolerances specified. Continuous operation is possible with adequate cooling of the working fluid but this becomes more demanding if the cycle frequency increases. Recommendations for future test system design and operation are presented.
Large-Scale Hydrogen Deflagrations and Detonations
Sep 2005
Publication
Large-scale deflagration and detonation experiments of hydrogen and air mixtures provide fundamental data needed to address accident scenarios and to help in the evaluation and validation of numerical models. Several different experiments of this type were performed. Measurements included flame front time of arrival (TOA) using ionization probes blast pressure heat flux high-speed video standard video and infrared video. The large-scale open-space tests used a hemispherical 300-m3 facility that confined the mixture within a thin plastic tent that was cut prior to initiating a deflagration. Initial homogeneous hydrogen concentrations varied from 15% to 30%. An array of large cylindrical obstacles was placed within the mixture for some experiments to explore turbulent enhancement of the combustion. All tests were ignited at the bottom center of the facility using either a spark or in one case a small quantity of high explosive to generate a detonation. Spark-initiated deflagration tests were performed within the tunnel using homogeneous hydrogen mixtures. Several experiments were performed in which 0.1 kg and 2.2 kg of hydrogen were released into the tunnel with and without ventilation. For some tunnel tests obstacles representing vehicles were used to investigate turbulent enhancement. A test was performed to investigate any enhancement of the deflagration due to partial confinement produced by a narrow gap between aluminium plates. The attenuation of a blast wave was investigated using a 4-m-tall protective blast wall. Finally a large-scale hydrogen jet experiment was performed in which 27 kg of hydrogen was released vertically into the open atmosphere in a period of about 30 seconds. The hydrogen plume spontaneously ignited early in the release.
Validation of Flacs-Hydrogen CFD Consequence Prediction Model Against Large Scale H2 Explosion Experiments in the Flame Facility
Sep 2005
Publication
The FLACS CFD-tool for consequence prediction has been developed continuously since 1980. The initial focus was explosion safety on offshore oil platforms in recent years the tool is also applied to study dispersion hydrogen safety dust explosions and more. A development project sponsored by Norsk Hydro Statoil and Ishikawajima Heavy Industries (IHI) was carried out to improve the modelling and validation of hydrogen dispersion and explosions. In this project GexCon carried out 200 small-scale experiments on dispersion and explosion with H2 and mixtures with H2 and CO or N2. Experiments with varying confinement congestion concentration and ignition location were performed. Since the main purpose of the tests was to produce good validation data all tests were simulated with the FLACS-HYDROGEN tool. The simulations confirmed the ability to predict explosions effects for the wide range of scenarios studied. A few examples of comparisons will be shown. To build confidence in a consequence prediction model it is important that the scales used for validation are as close as possible to reality. Since the hazard to people and facilities and the risk will generally increase with scale validation against large-scale experiments is important. In the 1980s a series of large-scale explosion experiments with H2 was carried out in the Sandia FLAME facility and sponsored by the US Nuclear Regulatory Commission. The FLAME facility is a 30.5m x 1.83m x 2.44m channel tests were performed with H2 concentrations from 7% to 30% with varying degree of top venting (0% 13% and 50%) and congestion (with or without baffles blocking 33% of the channel cross-section). A wide range of flame speeds and overpressures were observed. Comparisons are made between FLACS simulations and FLAME tests. The main conclusion from this validation study is that the precision when predicting H2 explosion consequences with FLACS has been improved to a very acceptable level
Risk Assessment for Hydrogen Codes and Standards
Sep 2005
Publication
The development and promulgation of codes and standards are essential to establish a market-receptive environment for commercial hydrogen-based products and systems. The focus of the U.S. Department of Energy (DOE) is to conduct the research and development (R&D) needed to strengthen the scientific basis for technical requirements incorporated in national and international standards codes and regulations. In the U.S. the DOE and its industry partners have formed a Codes and Standards Tech Team (CSTT) to help guide the R&D. The CSTT has adopted an R&D Roadmap to achieve a substantial and verified database of the properties and behaviour of hydrogen and the performance characteristics of emerging hydrogen technology applications sufficient to enable the development of effective codes and standards for these applications. However to develop a more structured approach to the R&D described above the CSTT conducted a workshop on Risk Assessment for Hydrogen Codes and Standards in March 2005. The purpose of the workshop was to attain a consensus among invited experts on the protocols and data needed to address the development of risk-informed standards codes and regulations for hydrogen used as an energy carrier by consumers. Participants at the workshop identified and assessed requirements methodologies and applicability of risk assessment (RA) tools to develop a framework to conduct RA activities to address for example hydrogen fuel distribution delivery on-site storage and dispensing and hydrogen vehicle servicing and parking. The CSTT was particularly interested in obtaining the advice of RA experts and representatives of standards and model code developing organizations and industry on how data generated by R&D can be turned into information that is suitable for hydrogen codes and standards development. The paper reports on the results of the workshop and the RA activities that the DOE’s program on hydrogen safety codes and standards will undertake. These RA activities will help structure a comprehensive R&D effort that the DOE and its industry partners are undertaking to obtain the data and conduct the analysis and testing needed to establish a scientific and technical basis for hydrogen standards codes and regulations.
Analysis of Buoyancy-driven Ventilation of Hydrogen from Buildings
Sep 2007
Publication
When hydrogen gas is used or stored within a building as with a hydrogen-powered vehicle parked in a residential garage any leakage of unignited H2 will mix with indoor air and may form a flammable mixture. One approach to safety engineering relies on buoyancy-driven passive ventilation of H2 from the building through vents to the outside. To discover relationships between design variables we combine two types of analysis: (1) a simplified 1-D steady-state analysis of buoyancy-driven ventilation and (2) CFD modelling using FLUENT 6.3. The simplified model yields a closed-form expression relating the H2 concentration to vent area height and discharge coefficient; leakage rate; and a stratification factor. The CFD modelling includes 3-D geometry; H2 cloud formation; diffusion momentum convection and thermal effects; and transient response. We modelled a typical residential two-car garage with 5 kg of H2 stored in a fuel tank; leakage rates of 5.9 to 82 L/min (tank discharge times of 12 hours to 1 week); a variety of vent sizes and heights; and both isothermal and nonisothermal conditions. This modelling indicates a range of the stratification factor needed to apply the simplified model for vent sizing as well as a more complete understanding of the dynamics of H2 movement within the building. A significant thermal effect occurs when outdoor temperature is higher than indoor temperature so that thermocirculation opposes the buoyancy-driven ventilation of H2. This circumstance leads to higher concentrations of H2 in the building relative to an isothermal case. In an unconditioned space such as a residential garage this effect depends on the thermal coupling of indoor air to outdoor air the ground (under a concrete slab floor) and an adjacent conditioned space in addition to temperatures. We use CFD modelling to explore the magnitude of this effect under rather extreme conditions.
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.
Collaborative Activities On Hydrogen Safety under the International Energy Agency’s Hydrogen Implementing
Sep 2005
Publication
In October 2004 the International Energy Agency Hydrogen Implementing Agreement (www.ieahia.org) approved the initiation of a collaborative task on hydrogen safety. During the past twelve months a work plan has been established and several member countries have committed to participate. Because of the nature of the International Energy Agency which is an international agreement between governments it is hoped that such collaboration will complement other cooperative efforts to help build the technology base around which codes and standards can be developed. In this way the new task on hydrogen safety will further the IEA Hydrogen Agreement in fulfilling its mission to accelerate the commercial introduction of hydrogen energy. This paper describes the specific scope and work plan for the collaboration that has been developed to date.
Evaluation of Safety Distances Related to Unconfined Hydrogen Explosions
Sep 2005
Publication
A simple approximate method for evaluation of blast effects and safety distances for unconfined hydrogen explosions is presented. The method includes models for flame speeds hydrogen distribution blast parameters and blast damage criteria. An example of the application of this methodology for hydrogen releases in three hypothetical obstructed areas with different levels of congestion is presented. The severity of the blast effect of unconfined hydrogen explosions is shown to depend strongly on the level of congestion for relatively small releases. Extremely large releases of hydrogen are predicted to be less sensitive to the congestion level.
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.
Study of Hydrogen Diffusion and Deflagration in a Closed System
Sep 2007
Publication
A total of 12 ventilation experiments with various combinations of hydrogen release rates and ventilation speeds were performed in order to study how ventilation speed and release rate effect the hydrogen concentration in a closed system. The experiential facility was constructed out of steel plates and beams in the shape of a rectangular enclosure. The volume of the test facility was about 60m3. The front face of the enclosure was covered by a plastic film in order to allow visible and infrared cameras to capture images of the flame. The inlet and outlet vents were located on the lower front face and the upper backside panel respectively. Hydrogen gas was released toward the ceiling from the center of the floor. The hydrogen gas was released at constant rate in each test. The hydrogen release rate ranged from 0.002 m3/s to 0.02 m3/s. Ventilation speeds were 0.1 0.2 and 0.4 m3/s respectively. Ignition was attempted at the end of the hydrogen release by using multiple continuous spark ignition modules on the ceiling and next to the release point. Time evolution of hydrogen concentration was measured using evacuated sample bottles. Overpressure and impulse inside and outside the facility were also measured. The mixture was ignited by a spark ignition module mounted on the ceiling in eight of eleven tests. In the other three tests the mixture was ignited by spark ignition modules mounted next to the nozzle. Overpressures generated by the hydrogen deflagration in most of these tests were low and represented a small risk to people or property. The primary risk associated with the hydrogen deflagrations studied in these tests was from the fire. The maximum concentration is proportional to the ratio of the hydrogen release rate to the ventilation speed within the range of parameters tested. Therefore a required ventilation speed can be estimated from the assumed hydrogen leak rate within the experimental conditions described 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.
Modeling of Sudden Hydrogen Expansion from Cryogenic Pressure Vessel Failure
Sep 2011
Publication
We have modelled sudden hydrogen expansion from a cryogenic pressure vessel. This model considers real gas equations of state single and two-phase flow and the specific “vessel within vessel” geometry of cryogenic vessels. The model can solve sudden hydrogen expansion for initial pressures up to 1210 bar and for initial temperatures ranging from 27 to 400 K. For practical reasons our study focuses on hydrogen release from 345 bar with temperatures between 62 K and 300 K. The pressure vessel internal volume is 151 L. The results indicate that cryogenic pressure vessels may offer a safety advantage with respect to compressed hydrogen vessels because i) the vacuum jacket protects the pressure vessel from environmental damage ii) hydrogen when released discharges first into an intermediate chamber before reaching the outside environment and iii) working temperature is typically much lower and thus the hydrogen has less energy. Results indicate that key expansion parameters such as pressure rate of energy release and thrust are all considerably lower for a cryogenic vessel within vessel geometry as compared to ambient temperature compressed gas vessels. Future work will focus on taking advantage of these favourable conditions to attempt fail-safe cryogenic vessel designs that do not harm people or property even after catastrophic failure of the inner pressure vessel.
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.
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.
Risk-Informed Separation Distances For Hydrogen Refuelling Stations
Sep 2007
Publication
The development of an infrastructure for the future hydrogen economy will require the simultaneous development of a set of codes and standards. As part of the U.S. Department of Energy Hydrogen Fuel Cells & Infrastructure Technologies Program Sandia National Laboratories is developing the technical basis for assessing the safety of hydrogen-based systems for use in the development/modification of relevant codes and standards. This work includes experimentation and modelling to understand the fluid mechanics and dispersion of hydrogen for different release scenarios including investigations of hydrogen combustion and subsequent heat transfer from hydrogen flames. The resulting technical information is incorporated into engineering models that are used for assessment of different hydrogen release scenarios and for input into quantitative risk assessments (QRA) of hydrogen facilities. The QRAs are used to identify and quantify scenarios for the unintended release of hydrogen and to identify the significant risk contributors at different types of hydrogen facilities. The results of the QRAs are one input into a risk-informed codes and standards development process that can also include other considerations by the code and standard developers. This paper describes an application of QRA methods to help establish one key code requirement: the minimum separation distances between a hydrogen refuelling station and other facilities and the public at large. An example application of the risk-informed approach has been performed to illustrate its utility and to identify key parameters that can influence the resulting selection of separation distances. Important parameters that were identified include the selected consequence measures and risk criteria facility operating parameters (e.g. pressure and volume) and the availability of mitigation features (e.g. automatic leak detection and isolation). The results also indicate the sensitivity of the results to key modelling assumptions and the component leakage rates used in the QRA models.
Safety Considerations for Hydrogen Test Cells
Sep 2009
Publication
The properties of hydrogen compared to conventional fuels such as gasoline and diesel are substantially different requiring adaptations to the design and layout of test cells for hydrogen fuelled engines and vehicles. A comparison of hydrogen fuel properties versus conventional fuels in this paper provides identification of requirements that need to be adapted to design a safe test cell. Design examples of actual test cells are provided to showcase the differences in overall layout and ventilation safety features fuel supply and metering and emissions measurements. Details include requirements for ventilation patterns the necessity for engine fume hoods as well as hydrogen specific intake and exhaust design. The unique properties of hydrogen in particular the wide flammability limits and nonvisible flames also require additional safety features such as hydrogen sensors and flame cameras. A properly designed and implemented fuel supply system adds to the safety of the test cell by minimizing the amount of hydrogen that can be released. Apart from this the properties of hydrogen also require different fuel consumption measurement systems pressure levels of the fuel supply system additional ventilation lines strategically placed safety solenoids combined with appropriate operational procedures. The emissions measurement for hydrogen application has to be expanded to include the amount of unburned hydrogen in the exhaust as a measurement of completeness of combustion. This measurement can also be used as a safety feature to avoid creation of ignitable hydrogen-air mixtures in the engine exhaust. The considerations provided in this paper lead to the conclusion that hydrogen IC engines can be safely tested however properly designed test cell and safety features have to be included to mitigate the additional hazards related to the change in fuel characteristics.
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.
For a Successful Arrival of the Hydrogen Economy Improve Now the Confidence Level of Risk Assessments
Sep 2009
Publication
For large-scale distribution and use of energy carriers classified as hazardous material in many countries as a method to assist land use planning to grant licenses to design a safe installation and to operate it safely some form of risk analysis and assessment is applied. Despite many years of experience the methods have still their weaknesses even the most elaborated ones as e.g. shown by the large spread in results when different teams perform an analysis on a same plant as was done in EU projects. Because a fuel as hydrogen with its different properties will come new in the daily use of many people incidents may happen and risks will be discussed. HySafe and other groups take good preparatory action in this respect and work in the right direction as appears from various documents produced. However already a superficial examination of the results so far tells that further cooperative work is indispensable. To avoid criticism skepticism and frustration not only the positive findings should be described and general features of the methods but the community has also to give strong guidance with regard to the uncertainties. Scenario development appears to be very dependent on insight and experience of an individual analyst leak and ignition probability may vary over a wide range of values Computational Fluid Dynamics or CFD models may lead to very different result. The Standard Benchmark Exercise Problems SBEPs are a good start but shall produce guidelines or recommendations for CFD use or even perhaps certification of models. Where feasible narrowing of possible details of scenarios to the more probable ones taking into account historical incident data and schematizing in bowties more explicit use of confidence intervals on e.g. failure rates and ignition probability estimates will help. Further knowledge gaps should be defined.
The Hydrogen Safety Program of the US Department of Energy
Sep 2005
Publication
Demonstrated safety in the production distribution and use of hydrogen will be critical to successful implementation of a hydrogen infrastructure. Recognizing the importance of this issue the U.S. Department of Energy has established the Hydrogen Safety Program to ensure safe operations of its hydrogen research and development program as well as to identify and address needs for new knowledge and technologies in the future hydrogen economy. Activities in the Safety Program range across the entire safety spectrum including: R&D devoted to investigation of hydrogen behaviour physical characteristics materials compatibility and risk analysis; inspection and investigation into the safety procedures and practices of all hydrogen projects supported by DOE funds; development of critical technologies for safe hydrogen systems such as sensors and design techniques; and safety training and education for emergency responders code inspectors and the general public. Throughout its activities the Safety Program encourages the open sharing of information to enable widespread benefit from any lessons learned or new information developed.
This paper provides detailed descriptions of the various activities of the DOE Hydrogen Safety Program and includes some example impacts already achieved from its implementation.
This paper provides detailed descriptions of the various activities of the DOE Hydrogen Safety Program and includes some example impacts already achieved from its implementation.
The Potential of Hydrogen Hydrate as a Future Hydrogen Storage Medium
Dec 2020
Publication
Hydrogen is recognized as the “future fuel” and the most promising alternative of fossil fuels due to its remarkable properties including exceptionally high energy content per unit mass (142 MJ/kg) low mass density and massive environmental and economical upsides. A wide spectrum of methods in H2 production especially carbon-free approaches H2purification and H2storage have been investigated to bring this energy source closer to the technological deployment. Hydrogen hydrates are among the most intriguing material paradigms for H2storage due to their appealing properties such as low energy consumption for charge and discharge safety cost-effectiveness and favorable environmental features. Here we comprehensively discuss the progress in understanding of hydrogen clathrate hydrates with an emphasis on charging/discharging rate of H2 (i.e. hydrate formation and dissociation rates) and the storage capacity. A thorough understanding on phase equilibrium of the hydrates and its variation through different materials is provided. The path toward ambient temperature and pressure hydrogen batteries with high storage capacity is elucidated. We suggest that the charging rate of H2 in this storage medium and long cyclic performance are more immediate challenges than storage capacity for technological translation of this storage medium. This review and provided outlook establish a groundwork for further innovation on hydrogen hydrate systems for promising future of hydrogen fuel.
Research Requirements to Move the Bar Forward Using Aqueous Formate Salts as H2 Carriers for Energy Storage Applications
Nov 2020
Publication
In this perspective on hydrogen carriers we focus on the needs for the development of robust active catalysts for the release of H2 from aqueous formate solutions which are non-flammable non-toxic thermally stable and readily available at large scales at reasonable cost. Formate salts can be stockpiled in the solid state or dissolved in water for long term storage and transport using existing infrastructure. Furthermore formate salts are readily regenerated at moderate pressures using the same catalyst as for the H2 release. There have been several studies focused on increasing the activity of catalysts to release H2 at moderate temperatures i.e. < 80 °C below the operating temperature of a proton exchange membrane (PEM) fuel cell. One significant challenge to enable the use of aqueous formate salts as hydrogen carriers is the deactivation of the catalyst under operating conditions. In this work we provide a review of the most efficient heterogeneous catalysts that have been described in the literature their proposed modes of deactivation and the strategies reported to reactivate them. We discuss potential pathways that may lead to deactivation and strategies to mitigate it in a variety of H2 carrier applications. We also provide an example of a potential use case employing formate salts solutions using a fixed bed reactor for seasonal storage of energy for a microgrid application.
Current Status of Automotive Fuel Cells for Sustainable Transport
May 2019
Publication
Automotive proton-exchange membrane fuel cells (PEMFCs) have finally reached a state of technological readiness where several major automotive companies are commercially leasing and selling fuel cell electric vehicles including Toyota Honda and Hyundai. These now claim vehicle speed and acceleration refueling time driving range and durability that rival conventional internal combustion engines and in most cases outperform battery electric vehicles. The residual challenges and areas of improvement which remain for PEMFCs are performance at high current density durability and cost. These are expected to be resolved over the coming decade while hydrogen infrastructure needs to become widely available. Here we briefly discuss the status of automotive PEMFCs misconceptions about the barriers that platinum usage creates and the remaining hurdles for the technology to become broadly accepted and implemented.
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