United States
Experimental Investigation of Hydrogen Jet Fire Mitigation by Barrier Walls
Sep 2009
Publication
Hydrogen jet flames resulting from ignition of unintended releases can be extensive in length and pose significant radiation and impingement hazards. One possible mitigation strategy to reduce exposure to jet flames is to incorporate barriers around hydrogen storage and delivery equipment. While reducing the extent of unacceptable consequences the walls may introduce other hazards if not properly configured. This paper describes experiments carried out to characterize the effectiveness of different barrier wall configurations at reducing the hazards created by jet fires. The hazards that are evaluated are the generation of overpressure during ignition the thermal radiation produced by the jet flame and the effectiveness of the wall at deflecting the flame.<br/>The tests were conducted against a vertical wall (1-wall configuration) and two “3-wall” configurations that consisted of the same vertical wall with two side walls of the same dimensions angled at 135° and 90°. The hydrogen jet impinged on the center of the central wall in all cases. In terms of reducing the radiation heat flux behind the wall the 1-wall configuration performed best followed by the 3-wall 135° configuration and the 3-wall 90°. The reduced shielding efficiency of the three-wall configurations was probably due to the additional confinement created by the side walls that limited the escape of hot gases to the sides of the wall and forced the hot gases to travel over the top of the wall.<br/>The 3-wall barrier with 135° side walls exhibited the best overall performance. Overpressures produced on the release side of the wall were similar to those produced in the 1-wall configuration. The attenuation of overpressure and impulse behind the wall was comparable to that of the three-wall configuration with 90° side walls. The 3-wall 135° configuration’s ability to shield the back side of the wall from the heat flux emitted from the jet flame was comparable to the 1-wall and better than the 3-wall 90° configuration. The ratio of peak overpressure (from in front of the wall and from behind the wall) showed that the 3-wall 135° configuration and the 3-wall 90° configuration had a similar effectiveness. In terms of the pressure mitigation the 3-wall configurations performed significantly better than the 1-wall configuration
National Training Facility for Hydrogen Safety. Five year plan for HAMMER
Sep 2005
Publication
A suitably trained emergency response force is an essential component for safe implementation of any type of fuel infrastructure. Because of the relative newness of hydrogen as a fuel however appropriate emergency response procedures are not yet well understood by responder workforces across the United States and around the world. A significant near-term training effort is needed to ensure that the future hydrogen infrastructure can be developed and operated with acceptable incident risk. Efforts are presently underway at the HAMMER site in Washington State to develop curricula related to hydrogen properties and behavior identification of problems (e.g. incorrect equipment installation) and appropriate response and other relevant information intended for classroom instruction. In addition a number of hands-on training props are planned for realistic simulation of hydrogen incidents in order to convey proper response procedures in high-pressure cryogenic high leakage or other high-risk accident situations. Surveys of emergency responders fire marshals regulatory authorities manufacturers and others are being undertaken to ensure that the capabilities developed and offered at HAMMER will meet the acknowledged need. This paper describes the training curricula and props anticipated at HAMMER and is intended to provide useful information to others planning similar training programs.
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.
Hydrogen or Batteries for Grid Storage? A Net Energy Analysis
Apr 2015
Publication
Energy storage is a promising approach to address the challenge of intermittent generation from renewables on the electric grid. In this work we evaluate energy storage with a regenerative hydrogen fuel cell (RHFC) using net energy analysis. We examine the most widely installed RHFC configuration containing an alkaline water electrolyzer and a PEM fuel cell. To compare RHFC's to other storage technologies we use two energy return ratios: the electrical energy stored on invested (ESOIe) ratio (the ratio of electrical energy returned by the device over its lifetime to the electrical-equivalent energy required to build the device) and the overall energy efficiency (the ratio of electrical energy returned by the device over its lifetime to total lifetime electrical-equivalent energy input into the system). In our reference scenario the RHFC system has an ESOIeratio of 59 more favorable than the best battery technology available today (Li-ion ESOIe= 35). (In the reference scenario RHFC the alkaline electrolyzer is 70% efficient and has a stack lifetime of 100 000 h; the PEM fuel cell is 47% efficient and has a stack lifetime of 10 000 h; and the round-trip efficiency is 30%.) The ESOIe ratio of storage in hydrogen exceeds that of batteries because of the low energy cost of the materials required to store compressed hydrogen and the high energy cost of the materials required to store electric charge in a battery. However the low round-trip efficiency of a RHFC energy storage system results in very high energy costs during operation and a much lower overall energy efficiency than lithium ion batteries (0.30 for RHFC vs. 0.83 for lithium ion batteries). RHFC's represent an attractive investment of manufacturing energy to provide storage. On the other hand their round-trip efficiency must improve dramatically before they can offer the same overall energy efficiency as batteries which have round-trip efficiencies of 75–90%. One application of energy storage that illustrates the trade-off between these different aspects of energy performance is capturing overgeneration (spilled power) for later use during times of peak output from renewables. We quantify the relative energetic benefit of adding different types of energy storage to a renewable generating facility using [EROI]grid. Even with 30% round-trip efficiency RHFC storage achieves the same [EROI]grid as batteries when storing overgeneration from wind turbines because its high ESOIeratio and the high EROI of wind generation offset the low round-trip efficiency.
Carbon Capture and Storage (CCS): The Way Forward
Mar 2018
Publication
Mai Bui,
Claire S. Adjiman,
André Bardow,
Edward J. Anthony,
Andy Boston,
Solomon Brown,
Paul Fennell,
Sabine Fuss,
Amparo Galindo,
Leigh A. Hackett,
Jason P. Hallett,
Howard J. Herzog,
George Jackson,
Jasmin Kemper,
Samuel Krevor,
Geoffrey C. Maitland,
Michael Matuszewski,
Ian Metcalfe,
Camille Petit,
Graeme Puxty,
Jeffrey Reimer,
David M. Reiner,
Edward S. Rubin,
Stuart A. Scott,
Nilay Shah,
Berend Smit,
J. P. Martin Trusler,
Paul Webley,
Jennifer Wilcox and
Niall Mac Dowell
Carbon capture and storage (CCS) is broadly recognised as having the potential to play a key role in meeting climate change targets delivering low carbon heat and power decarbonising industry and more recently its ability to facilitate the net removal of CO2 from the atmosphere. However despite this broad consensus and its technical maturity CCS has not yet been deployed on a scale commensurate with the ambitions articulated a decade ago. Thus in this paper we review the current state-of-the-art of CO2 capture transport utilisation and storage from a multi-scale perspective moving from the global to molecular scales. In light of the COP21 commitments to limit warming to less than 2 °C we extend the remit of this study to include the key negative emissions technologies (NETs) of bioenergy with CCS (BECCS) and direct air capture (DAC). Cognisant of the non-technical barriers to deploying CCS we reflect on recent experience from the UK's CCS commercialisation programme and consider the commercial and political barriers to the large-scale deployment of CCS. In all areas we focus on identifying and clearly articulating the key research challenges that could usefully be addressed in the coming decade.
Environmental Reactivity of Solid State Hydride Materials
Sep 2009
Publication
In searching for high gravimetric and volumetric density hydrogen storage systems it is inevitable that higher energy density materials will be used. In order to make safe and commercially acceptable condensed phase hydrogen storage systems it is important to understand quantitatively the hazards involved in using and handling these materials and to develop appropriate mitigation strategies to handle potential material exposure events. A crucial aspect of the development of risk identification and mitigation strategies is the development of rigorous environmental reactivity testing standards and procedures. This will allow for the identification of potential hazards and implementation of risk mitigation strategies. Modified testing procedures for shipping air and/or water sensitive materials as codified by the United Nations have been used to evaluate two potential hydrogen storage materials 2LiBH4·MgH2 and NH3BH3. The modified U.N. procedures include identification of self-reactive substances pyrophoric substances and gas-emitting substances with water contact. The results of these tests for air and water contact sensitivity will be compared to the pure material components where appropriate (e.g. LiBH4 and MgH2). The water contact tests are divided into two scenarios dependent on the hydride to water mole ratio and heat transport characteristics. Air contact tests were run to determine whether a substance will spontaneously react with air in a packed or dispersed form. Relative to 2LiBH4·MgH2 the chemical hydride NH3BH3 was observed to be less environmentally reactive.
Risk Quantification of Hydride Based Hydrogen Storage Systems for Automotive Applications
Sep 2009
Publication
For hydrogen fuelled vehicles to attain significant market penetration it is essential that any potential risks be controlled within acceptable levels. To achieve this goal on-board vehicle hydrogen storage systems should undergo risk analyses during early concept development and design phases. By so doing the process of eliminating safety-critical failure modes will help guide storage system development and be more efficient to implement than if undertaken after the design-freeze stage. The focus of this paper is the development of quantitative risk analyses of storage systems which use onboard reversible materials such as conventional AB5 metal hydrides the complex hydride NaAlH4 or other material candidates currently being researched. Collision of a vehicle having such a hydrogen storage system was selected as a dominant accident initiator and a probabilistic event tree model has been developed for this initiator. The event tree model contains a set of comprehensive mutually exclusive accident sequences. The event tree represents chronological ordering of key events that are postulated to occur sequentially in time during the accident progression. Each event may represent occurrence of a phenomenon (e.g. hydride chemical reaction and dust cloud explosion) or a hardware failure (e.g. hydride storage vessel rupture). Event tree branch probabilities can be quantified using fault tree models or basic events with probability distributions. A fault tree model for hydride dust cloud explosion is provided as an example. Failure probabilities assigned to the basic events in the fault tree can be estimated from test results published data or expert opinion elicitation. To account for variabilities in the probabilities assigned to fault tree basic events and hence to propagate uncertainties in event tree sequences Monte Carlo sampling and Latin Hypercube sampling were employed and the statistics of the results from both techniques were compared.
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.
Compatibility and Suitability of Existing Steel Pipelines for Transport of Hydrogen and Hydrogen-natural Gas Blends
Sep 2017
Publication
Hydrogen is being considered as a pathway to decarbonize large energy systems and for utility-scale energy storage. As these applications grow transportation infrastructure that can accommodate large quantities of hydrogen will be needed. Many millions of tons of hydrogen are already consumed annually some of which is transported in dedicated hydrogen pipelines. The materials and operation of these hydrogen pipeline systems however are managed with more constraints than a conventional natural gas pipeline. Transitional strategies for deep decarbonization of energy systems include blending hydrogen into existing natural gas systems where the materials and operations may not have the same controls. This study explores the hydrogen compatibility of existing pipeline steels and the suitability of these steels in hydrogen pipeline systems. Representative fracture and fatigue properties of pipeline grade steels in gaseous hydrogen are summarized from the literature. These properties are then considered in idealized design life calculations to inform materials performance for a typical gas pipeline.
Simulation of Small-Scale Releases from Liquid Hydrogen Storage Systems
Sep 2009
Publication
Knowledge of the concentration field and flammability envelope from small-scale leaks is important for the safe use of hydrogen. These small-scale leaks may occur from leaky fittings or o-ring seals on liquid hydrogen-based systems. The present study focuses on steady-state leaks with large amounts of pressure drop along the leak path such that hydrogen enters the atmosphere at near atmospheric pressure (i.e. Very low Mach number). A three-stage buoyant turbulent entrainment model is developed to predict the properties (trajectory hydrogen concentration and temperature) of a jet emanating from the leak. Atmospheric hydrogen properties (temperature and quality) at the leak plane depend on the storage pressure and whether the leak occurs from the saturated vapor space or saturated liquid space. In the first stage of the entrainment model ambient temperature air (295 K) mixes with the leaking hydrogen (20–30 K) over a short distance creating an ideal gas mixture at low temperature (∼65 K). During this process states of hydrogen and air are determined from equilibrium thermodynamics using models developed by NIST. In the second stage of the model (also relatively short in distance) the radial distribution of hydrogen concentration and velocity in the jet develops into a Gaussian profile characteristic of free jets. The third and by far the longest stage is the part of the jet trajectory where flow is fully developed. Results show that flammability envelopes for cold hydrogen jets are generally larger than those of ambient temperature jets. While trajectories for ambient temperature jets depend solely on the leak densimetric Froude number results from the present study show that cold jet trajectories depend on the Froude number and the initial jet density ratio. Furthermore the flammability envelope is influenced by the hydrogen concentration in the jet at the beginning of fully developed flow.
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.
Numerical Simulations of Cryogenic Hydrogen Cooling in Vortex Tubes with Smooth Transitions
Mar 2021
Publication
Improving efficiency of hydrogen cooling in cryogenic conditions is important for the wider applications of hydrogen energy systems. The approach investigated in this study is based on a Ranque-Hilsch vortex tube (RHVT) that generates temperature separation in a working fluid. The simplicity of RHVT is also a valuable characteristic for cryogenic systems. In the present work novel shapes of RHVT are computationally investigated with the goal to raise efficiency of the cooling process. Specifically a smooth transition is arranged between a vortex chamber where compressed gas is injected and the main tube with two exit ports at the tube ends. Flow simulations have been carried out using STAR-CCM+ software with the real-gas Redlich-Kwong model for hydrogen at temperatures near 70 K. It is determined that a vortex tube with a smooth transition of moderate size manifests about 7% improvement of the cooling efficiency when compared vortex tubes that use traditional vortex chambers with stepped transitions and a no-chamber setup with direct gas injection.
Mapping of Hydrogen Fuel Quality in Europe
Nov 2020
Publication
As part of FCH-JU funded HyCoRA project running from 2014 to 2017 28 gaseous and 13 particulate samples were collected from hydrogen refuelling stations in Europe. Samples were collected with commercial sampling instruments and analysis performed in compliance with prevailing fuel quality standards. Sampling was conducted with focus on diversity in feedstock as well as commissioning date of the HRS. Results indicate that the strategy for sampling was good. No evidence of impurity cross-over was observed. Parallel samples collected indicate some variation in analytical results. It was however found that fuel quality was generally good. Fourteen analytical results were in violation with the fuel tolerance limits. Therefore eight or 29% of the samples were in violation with the fuel quality requirements. Nitrogen oxygen and organics were the predominant impurities quantified. Particulate impurities were found to be within fuel quality specifications. No correlation between fuel quality and hydrogen feedstock or HRS commissioning date was found. Nitrogen to oxygen ratios gave no indication of samples being contaminated by air. A comparison of analytical results between two different laboratories were conducted. Some difference in analytical results were observed.
A Comparative Technoeconomic Analysis of Renewable Hydrogen Production Using Solar Energy
May 2016
Publication
A technoeconomic analysis of photoelectrochemical (PEC) and photovoltaic-electrolytic (PV-E) solar-hydrogen production of 10 000 kg H2 day−1 (3.65 kilotons per year) was performed to assess the economics of each technology and to provide a basis for comparison between these technologies as well as within the broader energy landscape. Two PEC systems differentiated primarily by the extent of solar concentration (unconcentrated and 10× concentrated) and two PV-E systems differentiated by the degree of grid connectivity (unconnected and grid supplemented) were analyzed. In each case a base-case system that used established designs and materials was compared to prospective systems that might be envisioned and developed in the future with the goal of achieving substantially lower overall system costs. With identical overall plant efficiencies of 9.8% the unconcentrated PEC and non-grid connected PV-E system base-case capital expenses for the rated capacity of 3.65 kilotons H2 per year were $205 MM ($293 per m2 of solar collection area (mS−2) $14.7 WH2P−1) and $260 MM ($371 mS−2 $18.8 WH2P−1) respectively. The untaxed plant-gate levelized costs for the hydrogen product (LCH) were $11.4 kg−1 and $12.1 kg−1 for the base-case PEC and PV-E systems respectively. The 10× concentrated PEC base-case system capital cost was $160 MM ($428 mS−2 $11.5 WH2P−1) and for an efficiency of 20% the LCH was $9.2 kg−1. Likewise the grid supplemented base-case PV-E system capital cost was $66 MM ($441 mS−2 $11.5 WH2P−1) and with solar-to-hydrogen and grid electrolysis system efficiencies of 9.8% and 61% respectively the LCH was $6.1 kg−1. As a benchmark a proton-exchange membrane (PEM) based grid-connected electrolysis system was analyzed. Assuming a system efficiency of 61% and a grid electricity cost of $0.07 kWh−1 the LCH was $5.5 kg−1. A sensitivity analysis indicated that relative to the base-case increases in the system efficiency could effect the greatest cost reductions for all systems due to the areal dependencies of many of the components. The balance-of-systems (BoS) costs were the largest factor in differentiating the PEC and PV-E systems. No single or combination of technical advancements based on currently demonstrated technology can provide sufficient cost reductions to allow solar hydrogen to directly compete on a levelized cost basis with hydrogen produced from fossil energy. Specifically a cost of CO2 greater than ∼$800 (ton CO2)−1 was estimated to be necessary for base-case PEC hydrogen to reach price parity with hydrogen derived from steam reforming of methane priced at $12 GJ−1 ($1.39 (kg H2)−1). A comparison with low CO2 and CO2-neutral energy sources indicated that base-case PEC hydrogen is not currently cost-competitive with electrolysis using electricity supplied by nuclear power or from fossil-fuels in conjunction with carbon capture and storage. Solar electricity production and storage using either batteries or PEC hydrogen technologies are currently an order of magnitude greater in cost than electricity prices with no clear advantage to either battery or hydrogen storage as of yet. Significant advances in PEC technology performance and system cost reductions are necessary to enable cost-effective PEC-derived solar hydrogen for use in scalable grid-storage applications as well as for use as a chemical feedstock precursor to CO2-neutral high energy-density transportation fuels. Hence such applications are an opportunity for foundational research to contribute to the development of disruptive approaches to solar fuels generation systems that can offer higher performance at much lower cost than is provided by current embodiments of solar fuels generators. Efforts to directly reduce CO2 photoelectrochemically or electrochemically could potentially produce products with higher value than hydrogen but many as yet unmet challenges include catalytic efficiency and selectivity and CO2 mass transport rates and feedstock cost. Major breakthroughs are required to obtain viable economic costs for solar hydrogen production but the barriers to achieve cost-competitiveness with existing large-scale thermochemical processes for CO2 reduction are even greater.
Measurement of Fatigue Crack Growth Rates for Steels in Hydrogen Containment Components
Sep 2009
Publication
The objective of this work was to enable the safe design of hydrogen pressure vessels by measuring the fatigue crack growth rates of ASME code-qualified steels in high-pressure hydrogen gas. While a design framework has recently been established for high-pressure hydrogen vessels a material property database does not exist to support the design calculations. This study addresses such voids in the database by measuring the fatigue crack growth rates of three different heats of ASME SA-372 Grade J steel in 100 MPa hydrogen gas. Results showed that the fatigue crack growth rates were similar for all three steel heats although the highest-strength steel appeared to exhibit the highest growth rates. Hydrogen accelerated the fatigue crack growth rates of the steels by as much as two orders of magnitude relative to anticipated crack growth rates in inert environments. Despite such dramatic effects of hydrogen on the fatigue crack growth rates measurement of these properties enables reliable definition of the design life of steel hydrogen containment vessels.
A Study of Barrier Walls for Mitigation of Unintended Releases of Hydrogen
Sep 2009
Publication
Hydrogen jet flames resulting from ignition of unintended releases can be extensive in length and pose significant radiation and impingement hazards. Depending on the leak diameter and source pressure the resulting consequence distances can be unacceptably large. One possible mitigation strategy to reduce exposure to jet flames is to incorporate barriers around hydrogen storage and delivery equipment. An experimental and modeling program has been performed at Sandia National Laboratories to better characterize the effectiveness of barrier walls to reduce hazards. This paper describes the experimental and modeling program and presents results obtained for various barrier configurations. The experimental measurements include flame deflection using standard and infrared video and high-speed movies (500 fps) to study initial flame propagation from the ignition source. Measurements of the ignition overpressure wall deflection radiative heat flux and wall and gas temperature were also made at strategic locations. The modeling effort includes three-dimensional calculations of jet flame deflection by the barriers computations of the thermal radiation field around barriers predicted overpressure from ignition and the computation of the concentration field from deflected unignited hydrogen releases. The various barrier designs are evaluated in terms of their mitigation effectiveness for the associated hazards present. The results show that barrier walls are effective at deflecting jet flames in a desired direction and can help attenuate the effects of ignition overpressure and flame radiative heat flux.
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.
Novel Wide-area Hydrogen Sensing Technology
Sep 2007
Publication
Element One Inc. is developing novel indicators for hydrogen gas for applications as a complement to conventional electronic hydrogen sensors or as a low-cost alternative in situations where an electronic signal is not needed. The indicator consists of a thin film coating or a pigment of a transition metal oxide such as tungsten oxide or molybdenum oxide with a catalyst such as platinum or palladium. The oxide is partially reduced in the presence of hydrogen in concentrations as low as 300 parts per million and changes from transparent to a dark colour. The colour change is fast and easily seen from a distance. In air the colour change reverses quickly when the source of hydrogen gas is removed in the case of tungsten oxide or is nearly irreversible in the case of molybdenum oxide. A number of possible implementations have been successfully demonstrated in the laboratory including hydrogen indicating paints tape cautionary decals and coatings for hydrogen storage tanks. These and other implementations may find use in vehicles stationary appliances piping refuelling stations and in closed spaces such as maintenance and residential garages for hydrogen-fuelled vehicles. The partially reduced transition metal oxide becomes semi conductive and increases its electrical conductivity by several orders of magnitude when exposed to hydrogen. The integration of this electrical resistance sensor with an RFID tag may extend the ability of these sensors to record and transmit a history of the presence or absence of leaked hydrogen over long distances. Over long periods of exposure to the atmosphere the indicator’s response may slow due to catalyst degradation. Our current emphasis is on controlling this degradation. The kinetics of the visual indicators is being investigated along with their durability in collaboration with the NASA Kennedy Space Center.
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.
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.
Developing a Hydrogen Fuel Cell Vehicle (HFCV) Energy Consumption Model for Transportation Applications
Jan 2022
Publication
This paper presents a simple hydrogen fuel cell vehicle (HFCV) energy consumption model. Simple fuel/energy consumption models have been developed and employed to estimate the energy and environmental impacts of various transportation projects for internal combustion engine vehicles (ICEVs) battery electric vehicles (BEVs) and hybrid electric vehicles (HEVs). However there are few published results on HFCV energy models that can be simply implemented in transportation applications. The proposed HFCV energy model computes instantaneous energy consumption utilizing instantaneous vehicle speed acceleration and roadway grade as input variables. The mode accurately estimates energy consumption generating errors of 0.86% and 2.17% relative to laboratory data for the fuel cell estimation and the total energy estimation respectively. Furthermore this work validated the proposed model against independent data and found that the new model accurately estimated the energy consumption producing an error of 1.9% and 1.0% relative to empirical data for the fuel cell and the total energy estimation respectively. The results demonstrate that transportation engineers policy makers automakers and environmental engineers can use the proposed model to evaluate the energy consumption effects of transportation projects and connected and automated vehicle (CAV) transportation applications within microscopic traffic simulation models.
H-Mat Hydrogen Compatibility of Polymers and Elastomers
Sep 2019
Publication
The H2@Scale program of the U.S. Department of Energy (DOE) Fuel Cell Technologies Office is supporting work on the hydrogen compatibility of polymers to improve the durability and reliability of materials for hydrogen infrastructure. The hydrogen compatibility program (H-Mat) seeks “to address the challenges of hydrogen degradation by elucidating the mechanisms of hydrogen-materials interactions with the goal of providing science-based strategies to design materials (micro)structures and morphology with improved resistance to hydrogen degradation.” This research has found hydrogen and pressure interactions with model rubber-material compounds demonstrating volume change and compression-set differences in the materials. The research leverages state-of-the-art capabilities of the DOE national labs. The materials were investigated using helium-ion microscopy which revealed significant morphological changes in the plasticizer incorporating compounds after exposure as evidenced by time-of-flight secondary ion mass spectrometry. Additional studies using transmission electron microscopy and nuclear magnetic resonance revealed that nanosized inclusions developed after gas decompression in rubber- and plasticizer-only materials; this is an indication of void formation at the nanometer level.
Opportunities and Challenges of Low-Carbon Hydrogen via Metallic Membranes
Jun 2020
Publication
Today electricity & heat generation transportation and industrial sectors together produce more than 80% of energy-related CO2 emissions. Hydrogen may be used as an energy carrier and an alternative fuel in the industrial residential and transportation sectors for either heating energy production from fuel cells or direct fueling of vehicles. In particular the use of hydrogen fuel cell vehicles (HFCVs) has the potential to virtually eliminate CO2 emissions from tailpipes and considerably reduce overall emissions from the transportation sector. Although steam methane reforming (SMR) is the dominant industrial process for hydrogen production environmental concerns associated with CO2 emissions along with the process intensification and energy optimization are areas that still require improvement. Metallic membrane reactors (MRs) have the potential to address both challenges. MRs operate at significantly lower pressures and temperatures compared with the conventional reactors. Hence the capital and operating expenses could be considerably lower compared with the conventional reactors. Moreover metallic membranes specifically Pd and its alloys inherently allow for only hydrogen permeation making it possible to produce a stream of up to 99.999+% purity.
For smaller and emerging hydrogen markets such as the semiconductor and fuel cell industries Pd-based membranes may be an appropriate technology based on the scales and purity requirements. In particular at lower hydrogen production rates in small-scale plants MRs with CCUS could be competitive compared to centralized H2 production. On-site hydrogen production would also provide a self-sufficient supply and further circumvent delivery delays as well as issues with storage safety. In addition hydrogen-producing MRs are a potential avenue to alleviate carbon emissions. However material availability Pd cost and scale-up potential on the order of 1.5 million m3/day may be limiting factors preventing wider application of Pd-based membranes.
Regarding the economic production of hydrogen the benchmark by the year 2020 has been determined and set in place by the U.S. DOE at less than $2.00 per kg of produced hydrogen. While the established SMR process can easily meet the set limit by DOE other carbon-free processes such as water electrolysis electron beam radiolysis and gliding arc technologies do not presently meet this requirement. In particular it is expected that the cost of hydrogen produced from natural gas without CCUS will remain the lowest among all of the technologies while the hydrogen cost produced from an SMR plant with solvent-based carbon capture could be twice as expensive as the conventional SMR without carbon capture. Pd-based MRs have the potential to produce hydrogen at competitive prices with SMR plants equipped with carbon capture.
Despite the significant improvements in the electrolysis technologies the cost of hydrogen produced by electrolysis may remain significantly higher in most geographical locations compared with the hydrogen produced from fossil fuels. The cost of hydrogen via electrolysis may vary up to a factor of ten depending on the location and the electricity source. Nevertheless due to its modular nature the electrolysis process will likely play a significant role in the hydrogen economy when implemented in suitable geographical locations and powered by renewable electricity.
This review provides a critical overview of the opportunities and challenges associated with the use of the MRs to produce high-purity hydrogen with low carbon emissions. Moreover a technoeconomic review of the potential methods for hydrogen production is provided and the drawbacks and advantages of each method are presented and discussed.
For smaller and emerging hydrogen markets such as the semiconductor and fuel cell industries Pd-based membranes may be an appropriate technology based on the scales and purity requirements. In particular at lower hydrogen production rates in small-scale plants MRs with CCUS could be competitive compared to centralized H2 production. On-site hydrogen production would also provide a self-sufficient supply and further circumvent delivery delays as well as issues with storage safety. In addition hydrogen-producing MRs are a potential avenue to alleviate carbon emissions. However material availability Pd cost and scale-up potential on the order of 1.5 million m3/day may be limiting factors preventing wider application of Pd-based membranes.
Regarding the economic production of hydrogen the benchmark by the year 2020 has been determined and set in place by the U.S. DOE at less than $2.00 per kg of produced hydrogen. While the established SMR process can easily meet the set limit by DOE other carbon-free processes such as water electrolysis electron beam radiolysis and gliding arc technologies do not presently meet this requirement. In particular it is expected that the cost of hydrogen produced from natural gas without CCUS will remain the lowest among all of the technologies while the hydrogen cost produced from an SMR plant with solvent-based carbon capture could be twice as expensive as the conventional SMR without carbon capture. Pd-based MRs have the potential to produce hydrogen at competitive prices with SMR plants equipped with carbon capture.
Despite the significant improvements in the electrolysis technologies the cost of hydrogen produced by electrolysis may remain significantly higher in most geographical locations compared with the hydrogen produced from fossil fuels. The cost of hydrogen via electrolysis may vary up to a factor of ten depending on the location and the electricity source. Nevertheless due to its modular nature the electrolysis process will likely play a significant role in the hydrogen economy when implemented in suitable geographical locations and powered by renewable electricity.
This review provides a critical overview of the opportunities and challenges associated with the use of the MRs to produce high-purity hydrogen with low carbon emissions. Moreover a technoeconomic review of the potential methods for hydrogen production is provided and the drawbacks and advantages of each method are presented and discussed.
Hourly Modelling of Thermal Hydrogen Electricity Markets
Jul 2020
Publication
The hourly operation of Thermal Hydrogen electricity markets is modelled. The economic values for all applicable chemical commodities are quantified (syngas ammonia methanol and oxygen) and an hourly electricity model is constructed to mimic the dispatch of key technologies: bi-directional power plants dual-fuel heating systems and plug-in fuel-cell hybrid electric vehicles. The operation of key technologies determines hourly electricity prices and an optimization model adjusts the capacity to minimize electricity prices yet allow all generators to recover costs. We examine 12 cost scenarios for renewables nuclear and natural gas; the results demonstrate emissionsfree ‘energy-only’ electricity markets whose supply is largely dominated by renewables. The economic outcome is made possible in part by seizing the full supply-chain value from electrolysis (both hydrogen and oxygen) which allows an increased willingness to pay for (renewable) electricity. The wholesale electricity prices average $25–$45/ MWh or just slightly higher than the assumed levelized cost of renewable energy. This implies very competitive electricity prices particularly given the lack of need for ‘scarcity’ pricing capacity markets dedicated electricity storage or underutilized electric transmission and distribution capacity.
Localized Plasticity and Associated Cracking in Stable and Metastable High-Entropy Alloys Pre-Charged with Hydrogen
Dec 2018
Publication
We investigated hydrogen embrittlement in Fe20Mn20Ni20Cr20Co and Fe30Mn10Cr10Co (at.%) alloys pre-charged with 100 MPa hydrogen gas by tensile testing at three initial strain rates of 10−4 10−3 and 10−2 s−1 at ambient temperature. The alloys are classified as stable and metastable austenite-based high-entropy alloys (HEAs) respectively. Both HEAs showed the characteristic hydrogen-induced degradation of tensile ductility. Electron backscatter diffraction analysis indicated that the reduction in ductility by hydrogen pre-charging was associated with localized plasticity-assisted intergranular crack initiation. It should be noted as an important finding that hydrogen-assisted cracking of the metastable HEA occurred not through a brittle mechanism but through localized plastic deformation in both the austenite and ε-martensite phases.
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.
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.
Blending Hydrogen into Natural Gas Pipeline Networks: A Review of Key Issues
Mar 2013
Publication
The United States has 11 distinct natural gas pipeline corridors: five originate in the Southwest four deliver natural gas from Canada and two extend from the Rocky Mountain region. This study assesses the potential to deliver hydrogen through the existing natural gas pipeline network as a hydrogen and natural gas mixture to defray the cost of building dedicated hydrogen pipelines.
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.
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.
Decarbonization Synergies From Joint Planning of Electricity and Hydrogen Production: A Texas Case Study
Oct 2020
Publication
Hydrogen (H2) shows promise as an energy carrier in contributing to emissions reductions from sectors which have been difficult to decarbonize like industry and transportation. At the same time flexible H2 production via electrolysis can also support cost-effective integration of high shares of variable renewable energy (VRE) in the power system. In this work we develop a least-cost investment planning model to co-optimize investments in electricity and H2 infrastructure to serve electricity and H2 demands under various low-carbon scenarios. Applying the model to a case study of Texas in 2050 we find that H2 is produced in approximately equal amounts from electricity and natural gas under the least-cost expansion plan with a CO2 price of $30–60/tonne. An increasing CO2 price favors electrolysis while increasing H2 demand favors H2 production from Steam Methane Reforming (SMR) of natural gas. H2 production is found to be a cost effective solution to reduce emissions in the electric power system as it provides flexibility otherwise provided by natural gas power plants and enables high shares of VRE with less battery storage. Additionally the availability of flexible electricity demand via electrolysis makes carbon capture and storage (CCS) deployment for SMR cost-effective at lower CO2 prices ($90/tonne CO2) than for power generation ($180/tonne CO2 ). The total emissions attributable to H2 production is found to be dependent on the H2 demand. The marginal emissions from H2 production increase with the H2 demand for CO2 prices less than $90/tonne CO2 due to shift in supply from electrolysis to SMR. For a CO2 price of $60/tonne we estimate the production weighted-average H2 price to be between $1.30–1.66/kg across three H2 demand scenarios. These findings indicate the importance of joint planning of electricity and H2 infrastructure for cost-effective energy system decarbonization.
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.
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.
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.
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
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.
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.
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.
Analysis of Composite Hydrogen Storage Cylinders under Transient Thermal Loads
Sep 2007
Publication
In order to ensure safe operation of hydrogen storage cylinders under adverse conditions one should be able to predict the extremities under which these cylinders are capable of operating without failing catastrophically. It is therefore necessary to develop a comprehensive model which can predict the behavior and failure of composite storage cylinders when subjected to various types of loading conditions and operating environments. In the present work a finite element model has been developed to analyze composite hydrogen storage cylinders subjected to transient localized thermal loads and internal pressure. The composite cylinder consists of an aluminium liner that serves as a hydrogen gas permeation barrier. A filament-wound carbon/epoxy composite laminate placed over the liner provides the desired load bearing capacity. A glass/epoxy layer or other material is placed over the carbon/epoxy laminate to provide damage resistance for the carbon/epoxy laminates. A doubly curved composite shell element accounting for transverse shear deformation and geometric nonlinearity is used. A temperature dependent material model has been developed and implemented in ABAQUS using user subroutine. A failure model based on Hashin's failure theory is used to predict the various types of failure in the cylinder. A progressive damage model has also been implemented to account for reduction in modulus due to failure. A sublaminate model has been developed to save computational time and reduce the complications in the analysis. A numerical study is conducted to analyze a typical hydrogen storage cylinder and possible failure trends due to localized thermal loading and internal pressure is presented.
Risk 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.
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?
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.
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.
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.
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.
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.
Safety Code Equivalencies in Hydrogen Infrastructure Deployment
Sep 2019
Publication
Various studies and market trends show that the number of hydrogen fuelling stations will increase to the thousands in the US by 2050. NFPA 2 Hydrogen Technologies Code (NFPA2) the nationally adopted primary code governing hydrogen safety is relatively new and hydrogen vehicle technology is a relatively new and rapidly developing technology. In order to effectively aid and accelerate the deployment of standardized retail hydrogen fuelling facilities the permitting of hydrogen fuelling stations employing outdoor bulk liquid storage in the state of California.
In an effort to better understand how the applicants consultants and more importantly the Authorities Having Jurisdiction (AHJ)s are interpreting and applying the NFPA 2 especially for complex applications the newest hydrogen stations with the largest amount of bulk hydrogen storage in urban environment settings were identified and the permit applications and permit approval outcomes of the said stations were analysed. Utilizing the pubic record request process LH2 station permit applications were reviewed along with the approval outcomes directly from the municipalities that issued the permits. AHJs with H2 station permitting experience were interviewed. Case studies of permit hydrogen fuelling station permit applications were then complied to document both the perspectives of the applicant and the AHJ and the often iterative and collaborative nature of permitting.
The current permitting time for Liquid Hydrogen (LH2) stations can range from 9 to 18 months in the California. Five out of the six LH2 stations applications required Alternative Means & Methods (AM&Ms) proposals and deviations from the prescriptive requirements of the Code were granted. Furthermore AHJs often requested additional documents and studies specific to application parameters in addition to NFPA 2 requirements.
In an effort to better understand how the applicants consultants and more importantly the Authorities Having Jurisdiction (AHJ)s are interpreting and applying the NFPA 2 especially for complex applications the newest hydrogen stations with the largest amount of bulk hydrogen storage in urban environment settings were identified and the permit applications and permit approval outcomes of the said stations were analysed. Utilizing the pubic record request process LH2 station permit applications were reviewed along with the approval outcomes directly from the municipalities that issued the permits. AHJs with H2 station permitting experience were interviewed. Case studies of permit hydrogen fuelling station permit applications were then complied to document both the perspectives of the applicant and the AHJ and the often iterative and collaborative nature of permitting.
The current permitting time for Liquid Hydrogen (LH2) stations can range from 9 to 18 months in the California. Five out of the six LH2 stations applications required Alternative Means & Methods (AM&Ms) proposals and deviations from the prescriptive requirements of the Code were granted. Furthermore AHJs often requested additional documents and studies specific to application parameters in addition to NFPA 2 requirements.
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.
Lessons Learned from Safety Events
Sep 2011
Publication
The Hydrogen Incident Reporting and Lessons Learned website (www.h2incidents.org) was launched in 2006 as a database-driven resource for sharing lessons learned from hydrogen-related safety events to raise safety awareness and encourage knowledge-sharing. The development of this database its first uses and subsequent enhancements have been described at the Second and Third International Conferences on Hydrogen Safety [1] [2]. Since 2009 continuing work has not only highlighted the value of safety lessons learned but enhanced how the database provides access to another safety knowledge tool Hydrogen Safety Best Practices (http://h2bestpractices.org). Collaborations with the International Energy Agency (IEA) Hydrogen Implementing Agreement (HIA) Task 19 – Hydrogen Safety and others have enabled the database to capture safety event learning’s from around the world. This paper updates recent progress highlights the new “Lessons Learned Corner” as one means for knowledge-sharing and examines the broader potential for collecting analyzing and using safety event information.
Hydrogen and Fuel Cell Vehicles UN Global Technical Regulation No. 13: Latest Updates Reflecting Heavy Duty Vehicles
Sep 2019
Publication
This paper provides a detailed technical description of the United Nations Global Technical Regulation No. 13 (UN GTR #13) 1998 Agreement and contracting party obligations phase 2 activity and safety provisions being discussed and developed for heavy duty hydrogen fuel cell vehicles.
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