United States
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.
Pressure Cycling Of Type 1 Pressure Vessels with Gaseous Hydrogen
Sep 2011
Publication
Type 1 steel pressure vessels are commonly used for the transport of pressurized gases including gaseous hydrogen. In the majority of cases these cylinders experience relatively few pressure cycles over their lifetime perhaps in the hundreds. In emerging markets such as hydrogen-powered industrial trucks hydrogen fuel systems are expected to experience thousands of cycles over just a few year period. This study investigates the fatigue life of Type 1 steel pressure vessels by subjecting full- scale vessels to pressure cycles with gaseous hydrogen between nominal pressure of 3.5 and 43.8 MPa. In addition engineered defects were machined on the inside of several pressure vessels for comparison to fatigue crack growth measurements on materials sectioned from these pressure vessels. As-manufactured pressure vessels have sustained >35000 cycles with failure while vessels with machined defects leaked before bursting after 8000 to 15000 pressure cycles. The measured number of cycles to failure in these pressure vessels is two to three times greater than predicted using conservative methods based on fatigue crack growth rates measured in gaseous hydrogen.
Hypothetical Accident Scenario Modelling for Condensed Hydrogen Storage Materials
Sep 2011
Publication
Hydrogen is seen as an ideal energy carrier for stationary and mobile applications. However the use of high energy density condensed hydrogen storage materials such as NH3BH3 comes with risks associated with their high reactivity with water exposure and their decomposition products reactivity in air. To predict their behaviour under these circumstances idealized finite element models of hypothetical accident scenarios have been developed. Empirical thermodynamic calculations based on precise thermal gravimetric analysis (TGA) and calorimetric experiments have been performed in order to quantify the energy and hydrogen release rates and to quantify the reaction products resulting from water and air exposure.
Risk Mitigation Strategies for Hydrogen Storage Materials
Sep 2011
Publication
Hydrogen is seen as an ideal energy carrier for stationary and mobile applications. However the use of high energy density materials such as hydrides comes with the drawback of risks associated to their high reactivity towards air and water exposure. We have developed novel strategies to mitigate these risks. These strategies were evaluated using standard UN tests and isothermal calorimetric measurements. Cycling experiments were conducted to assess the impact of the mitigants on the modified materials derived from 8LiH•3Mg(NH2)2 system. In some cases our results show an improvement in kinetics when compared to the unmodified material. Effective mitigants were also discovered for aluminium hydride (alane) and lithium borohydride completely inhibiting ignition.
Dispersion and Burning Behavior of Hydrogen Released in a Full-scale Residential Garage in the Presence and Absence of Conventional Automobiles
Sep 2011
Publication
Experiments are described in which hydrogen was released at the center of the floor of a real-scale enclosure having dimensions of a typical two-car residential garage. Real-time hydrogen concentrations were monitored at a number of locations. The hydrogen/air mixtures were ignited at pre-determined local volume fractions ranging from 8% to 29%. The combustion behavior and structural effects were monitored using combinations of high-speed pressure transducers and ionization gauges standard thermocouples hydrogen sensors and digital infrared and high-speed video cameras. Experiments were performed both for empty garages and garages with conventional automobiles parked above the hydrogen release location.
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.
Hydrogen Safety Training for Laboratory Researchers and Technical Personnel
Sep 2011
Publication
We have developed a web-based hydrogen safety class and are developing a hands-on hydrogen safety class. The 4-h web-based class is directed to laboratory researchers who need basic hydrogen safety information (free online access at http://www.h2labsafety.org/) and it addresses hydrogen fundamentals: properties pressure and cryogenic safety emergency response and codes and standards. Technical operators in charge of building and testing experimental hydrogen equipment will also soon benefit from a more comprehensive 3-day hands-on safety class that will present detailed information for installation testing and operation of hydrogen pressurized systems. The hands-on class includes a full day of classroom instruction followed by two days of laboratory work where students assemble test and operate a pressure system based on a schematic and component description.
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.
Safety of Hydrogen Powered Industrial Trucks, Lessons Learned and Existing Codes and Standards Gaps
Sep 2011
Publication
This paper provides an introduction to the powered industrial truck application of fuel cell power systems the safety similarities with the automotive application and safety lessons learned. Fuel Cell niche markets have proven their value to many early adopters. How has the automotive market provided a springboard for these niche applications? How are niche markets revealing gaps in current safety approaches? What is different about the powered industrial truck application and what new codes and standards are needed to accommodate those differences?
Optimal Hydrogen Carrier: Holistic Evaluation of Hydrogen Storage and Transportation Concepts for Power Generation, Aviation, and Transportation
Oct 2022
Publication
The storage of excess electrical generation enabled through the electrolytic production of hydrogen from water would allow “load-shifting” of power generation. This paves the way for hydrogen as an energy carrier to be further used as a zero‑carbon fuel for land air and sea transportation. However challenges in hydrogen storage and transportation ultimately pose restrictions on its wider adaption along horizontal and vertical vectors. This paper investigates chemical energy carriers ranging from small molecules such as ammonia and methane to formic acid as well as other more complex hydrocarbons in response to this timely engineering problem. The hydrogenation and dehydrogenation of such carrier molecules require energy lowering the effective net heating value of hydrogen up to 32 %. Different carrier approaches are discussed in the light of availability energetics water requirements and suitability for applications in power generation shipping trucking and aviation supplemented by a comprehensive safety review making this study unique in its field. It is found that hydrogen delivered without a carrier is ideal for power generation applications due to the large quantities required. Aviation would benefit from either ammonia or hydrogen and is generally a field challenging to decarbonize. Ammonia appears also to be a good medium for shipping hydrogen between continents and to power container ships due to its high energy density and lower liquid temperature compared with hydrogen. At the same time ammonia can also be used to power the ship's engine. Long-haul trucking would benefit the most from cryogenic or compressed hydrogen due to the lower quantities required and purity requirements of the fuel cells.
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.
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.
Mixing and Warming of Cryogenic Hydrogen Releases
Sep 2017
Publication
Laboratory measurements were made on the concentration and temperature fields of cryogenic hydrogen jets. Images of spontaneous Raman scattering from a pulsed planar laser sheet were used to measure the concentration and temperature fields from varied releases. Jets with up to 5 bar pressure with near-liquid temperatures at the release point were characterized in this work. This data is relevant for characterizing unintended leaks from piping connected to cryogenic hydrogen storage tanks such as might be encountered at a hydrogen fuel cell vehicle fuelling station. The average centerline mass fraction was observed to decay at a rate similar to room temperature hydrogen jets while the half-width of the Gaussian profiles of mass fraction were observed to spread more slowly than for room temperature hydrogen. This suggests that the mixing and models for cryogenic hydrogen may be different than for room temperature hydrogen. Results from this work were also compared to a one-dimensional (streamwise) model. Good agreement was seen in terms of temperature and mass fraction. In subsequent work a validated version of this model will be exercised to quantitatively assess the risk at hydrogen fuelling stations with cryogenic hydrogen on-site.
Modeling of Hydrogen Pressurization and Extraction in Cryogenic Pressure Vessels Due to Vacuum Insulation Failure
Sep 2017
Publication
We have analyzed vacuum insulation failure in an automotive cryogenic pressure vessel (also known as cryo-compressed vessel) storing hydrogen (H2). Vacuum insulation failure increases heat transfer into cryogenic vessels by about a factor of 100 potentially leading to rapid pressurization and venting to avoid exceeding maximum allowable working pressure (MAWP). H2 release to the environment may be dangerous if the vehicle is located in a closed space (e.g. a garage or tunnel) at the moment of insulation failure. We therefore consider utilization of the hydrogen in the vehicle fuel cell and electricity dissipation through operation of vehicle accessories or battery charging as an alternative to releasing hydrogen to the environment. We consider two strategies: initiating hydrogen extraction immediately after vacuum insulation failure or waiting until MAWP is reached before extraction. The results indicate that cryogenic pressure vessels have thermodynamic advantages that enable slowing down hydrogen release to moderate levels that can be consumed in the fuel cell and dissipated onboard the vehicle even in the worst case when the vacuum fails with a vessel storing hydrogen at maximum refuel density (70 g/L at 300 bar). The two proposed strategies are therefore feasible and the best alternative can be chosen based on economic and/or implementation constraints.
Hydrogen Safety Sensor Performance and Use Gap Analysis
Sep 2017
Publication
Hydrogen sensors are recognized as an important technology for facilitating the safe implementation of hydrogen as an alternative fuel and there are numerous reports of a sensor alarm successfully preventing a potentially serious event. However gaps in sensor metrological specifications as well as in their performance for some applications exist. The U.S. Department of Energy (DOE) Fuel Cell Technologies Office published a short list of critical gaps in the 2007 and 2012 Multiyear Project Plans; more detailed gap analyses were independently performed by the Joint Research Centre (JRC) and the National Renewable Energy Laboratory (NREL). There have been however some significant advances in sensor technologies since these assessments including the commercial availability of hydrogen sensors with fast response times (t90 < 1 s which had been an elusive DOE target since 2007) improved robustness to chemical poisons improved selectivity and improved lifetime and stability. These improvements however have not been universal and typically pertain to select platforms or models. Moreover as hydrogen markets grow and new applications are being explored more demands will be imposed on sensor performance. The hydrogen sensor laboratories at NREL and the JRC are currently updating the hydrogen safety sensor gap analysis through direct interaction with international stakeholders in the hydrogen community especially end users. NREL and the JRC are currently organizing a series of workshops (in Europe and the United States) with sensor developers end-users and other stakeholders in 2017 to identify technology gaps and to develop a path forward to address them. One workshop was held on May 10 in Brussels Belgium at the Headquarters of the Fuel Cell and Hydrogen Joint Undertaking. A second workshop is planned at NREL in Golden CO USA. This paper reviews improvements in sensor technologies in the past 5 to 10 years identifies gaps in sensor performance and use requirements and identifies potential research strategies to address the gaps. The outcomes of the Hydrogen Sensors Workshops are also summarized.
Fatigue and Fracture of High-hardenability Steels for Thick-walled Hydrogen Pressure Vessels
Sep 2017
Publication
Stationary pressure vessels for the storage of large volumes of gaseous hydrogen at high pressure (>70 MPa) are typically manufactured from Cr-Mo steels. These steels display hydrogen-enhanced fatigue crack growth but pressure vessels can be manufactured using defect-tolerant design methodologies. However storage volumes are limited by the wall thickness that can be reliably manufactured for quench and tempered Cr-Mo steels typically not more than 25-35 mm. High-hardenability steels can be manufactured with thicker walls which enables larger diameter pressure vessels and larger storage volumes. The goal of this study is to assess the fracture and fatigue response of high hardenability Ni-Cr-Mo pressure vessel steels for use in high-pressure hydrogen service at pressure in excess of 1000 bar. Standardized fatigue crack growth tests were performed in gaseous hydrogen at frequency of 1Hz and for R-ratios in the range of 0.1 to 0.7. Elastic-plastic fracture toughness measurements were also performed. The measured fatigue and fracture behavior is placed into the context of previous studies on fatigue and fracture of Cr-Mo steels for gaseous hydrogen.
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.
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.
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.
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.
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