United States
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.
Vented Explosion Overpressures From Combustion of Hydrogen and Hydrocarbon Mixtures
Sep 2009
Publication
Experimental data obtained for hydrogen mixtures in a room-size enclosure are presented and compared with data for propane and methane mixtures. This set of data was also used to develop a three-dimensional gas dynamic model for the simulation of gaseous combustion in vented enclosures. The experiments were performed in a 64 m3 chamber with dimensions of 4.6 × 4.6 × 3.0 m and a vent opening on one side and vent areas of either 2.7 or 5.4 m2 were used. Tests were performed for three ignition locations at the wall opposite the vent at the center of the chamber or at the center of the wall containing the vent. Hydrogen–air mixtures with concentrations close 18% vol. were compared with stoichiometric propane–air and methane–air mixtures. Pressure data as function of time and flame time-of-arrival data were obtained both inside and outside the chamber near the vent. Modelling was based on a Large Eddy Simulation (LES) solver created using the OpenFOAM CFD toolbox using sub-grid turbulence and flame wrinkling models. A comparison of these simulations with experimental data is discussed.
From Research Results to Published Codes And Standards - Establishing Code Requirements For NFPA 55 Bulk Hydrogen Systems Separation Distances
Sep 2009
Publication
Performing research in the interest of providing relevant safety requirements is a valuable and essential endeavor but translating research results into enforceable requirements adopted into codes and standards a process sometimes referred to as codification can be a separate and challenging task. This paper discusses the process utilized to successfully translate research results related to bulk gaseous hydrogen storage separation (or stand-off) distances into code requirements in NFPA 55:Storage Use and Handling of Compressed Gases and Cryogenic Fluids in Portable and StationaryContainers Cylinders and Tanks and NFPA 2: Hydrogen Technologies. The process utilized can besummarized as follows: First the technical committees for the documents to be revised were engaged to confirm that the codification process was endorsed by the committee. Then a sub-committee referred to as a task group was formed. A chair must be elected or appointed. The chair should be a generalist with code enforcement or application experience. The task group was populated with several voting members of each technical committee. By having voting members as part of the task group the group becomes empowered and uniquely different from any other code proposal generating body. The task group was also populated with technical experts as needed but primarily the experts needed are the researchers involved. Once properly populated and empowered the task group must actively engage its members. The researchers must educate the code makers on the methods and limitations of their work and the code makers must take the research results and fill the gaps as needed to build consensus and create enforceable code language and generate a code change proposal that will be accepted. While this process seems simple there are pitfalls along the way that can impede or nullify the desired end result – changes to codes and standards. A few of these pitfalls include: wrong task group membership task group not empowered task group not supported in-person meetings not possible consensus not achieved. This paper focuses on the process used and how pitfalls can be avoided for future efforts.
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.
Development of Standards for Evaluating Materials Compatibility with High-pressure Gaseous Hydrogen
Sep 2013
Publication
The Hydrogen Safety Codes and Standards program element of the US Department of Energy's Fuel Cell Technologies Office provides coordination and technical data for the development of domestic and international codes and standards related to hydrogen technologies. The materials compatibility program task at Sandia National Laboratories (Livermore CA) is focused on developing the technical basis for qualifying materials for hydrogen service i.e. accommodating hydrogen embrittlement. This presentation summarizes code development activities for qualifying materials for hydrogen service with emphasis on the scientific basis for the testing methodologies including fracture mechanics based measurements (fracture threshold and fatigue crack growth) total fatigue life measurements and full- scale pressure vessel testing.
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.
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.
Hydrogen Compatibility of Austenitic Stainless Steel Tubing and Orbital Tube Welds
Sep 2013
Publication
Refueling infrastructure for use in gaseous hydrogen powered vehicles requires extensive manifolding for delivering the hydrogen from the stationary fuel storage at the refueling station to the vehicle as well as from the mobile storage on the vehicle to the fuel cell or combustion engine. Manifolds for gas handling often use welded construction (as opposed to compression fittings) to minimize gas leaks. Therefore it is important to understand the effects of hydrogen on tubing and tubing welds. This paper provides a brief overview of on-going studies on the effects of hydrogen precharging on the tensile properties of austenitic stainless tubing and orbital tube welds of several austenitic stainless steels.
Hourly Modelling of Thermal Hydrogen Electricity Markets
Jul 2020
Publication
The hourly operation of Thermal Hydrogen electricity markets is modelled. The economic values for all applicable chemical commodities are quantified (syngas ammonia methanol and oxygen) and an hourly electricity model is constructed to mimic the dispatch of key technologies: bi-directional power plants dual-fuel heating systems and plug-in fuel-cell hybrid electric vehicles. The operation of key technologies determines hourly electricity prices and an optimization model adjusts the capacity to minimize electricity prices yet allow all generators to recover costs. We examine 12 cost scenarios for renewables nuclear and natural gas; the results demonstrate emissionsfree ‘energy-only’ electricity markets whose supply is largely dominated by renewables. The economic outcome is made possible in part by seizing the full supply-chain value from electrolysis (both hydrogen and oxygen) which allows an increased willingness to pay for (renewable) electricity. The wholesale electricity prices average $25–$45/ MWh or just slightly higher than the assumed levelized cost of renewable energy. This implies very competitive electricity prices particularly given the lack of need for ‘scarcity’ pricing capacity markets dedicated electricity storage or underutilized electric transmission and distribution capacity.
Hydrogen Strategy - Enabling a Low-Carbon Economy
Jul 2020
Publication
This document summarizes current hydrogen technologies and communicates the U.S. Department of Energy (DOE) Office of Fossil Energy's (FE's) strategic plan to accelerate research development and deploymnet of hydrogen technologies in the United States. It also describes ongoing FE hydrogen-related research and development (R&D). Hydrogen from fossil fuels is a versatile energy carrier and can play an important role in the transition to a low-carbon economy.
Carbon Negative Transportation Fuels - A Techno-Economic-Environmental Analysis of Biomass Pathways for Transportation
Feb 2022
Publication
Global warming and fossil fuel depletion have necessitated alternative sources of energy. Biomass is a promising fuel source because it is renewable and can be carbon negative even without carbon capture and storage. This study considers biomass as a clean renewable source for transportation fuels. An Aspen Plus process simulation model was built of a biomass gasification biorefinery with Fischer-Tropsch (FT) synthesis of liquid fuels. A GaBi life cycle assessment model was also built to determine the environmental impacts using a cradle-to-grave approach. Three different product pathways were considered: Fischer-Tropsch synthetic diesel hydrogen and electricity. An offgas autothermal reformer with a recycle loop was used to increase FT product yield. Different configurations and combinations of biorefinery products are considered. The thermal efficiency and cost of production of the FT liquid fuels are analyzed using the Aspen Plus process model. The greenhouse gas emissions profitability and mileage per kg biomass were compared. The mileage traveled per kilogram biomass was calculated using modern (2019-2021) diesel electric and hydrogen fuel cell vehicles. The overall thermal efficiency was found to be between 20-41% for FT fuels production between 58-61% for hydrogen production and around 25-26% for electricity production for this biorefinery. The lowest production costs were found to be $3.171/gal of FT diesel ($24.304/GJ) $1.860/kg of H2 ($15.779/GJ) and 13.332¢/kWh for electricity ($37.034/GJ). All configurations except one had net negative carbon emissions over the life cycle of the biomass. This is because carbon is absorbed in the trees initially and some of the carbon is sequestered in ash and unconverted char from the gasification process furthermore co-producing electricity while making transportation fuel offsets even more carbon emissions. Compared to current market rates for diesel hydrogen and electricity the most profitable biorefinery product is shown to be hydrogen while also having net negative carbon emissions. FT diesel can also be profitable but with a slimmer profit margin (not considering government credits) and still having net negative carbon emissions. However our biorefinery could not compete with current commercial electricity prices in the US. As oil hydrogen and electricity prices continue to change the economics of the biorefinery and the choice product will change as well. For our current biorefinery model hydrogen seems to be the most promising product choice for profit while staying carbon negative while FT diesel is the best choice for sequestering the most carbon and still being profitable. All code and data are given.
Updated Jet Flame Radiation Modelling with Corrections for Buoyancy and Wind
Sep 2013
Publication
Radiative heat fluxes from small to medium-scale hydrogen jet flames (<10 m) compare favorably to theoretical predictions provided the product species thermal emittance and optical flame thickness are corrected for. However recent heat flux measurements from two large-scale horizontally orientated hydrogen flames (17.4 and 45.9 m respectively) revealed that current methods underpredicted the flame radiant fraction by 40% or more. Newly developed weighted source flame radiation models have demonstrated substantial improvement in the heat flux predictions particularly in the near-field and allow for a sensible way to correct potential ground surface reflective irradiance. These updated methods are still constrained by the fact that the flame is assumed to have a linear trajectory despite buoyancy effects that can result in significant flame deformation. The current paper discusses a method to predict flame centerline trajectories via a one-dimensional flame integral model which enables optimized placement of source emitters for weighted multi-source heat flux prediction methods. Flame shape prediction from choked releases was evaluated against flame envelope imaging and found to depend heavily on the notional nozzle model formulation used to compute the density weighted effective nozzle diameter. Nonetheless substantial improvement in the prediction of downstream radiative heat flux values occurred when emitter placement was corrected by the flame integral model regardless of the notional nozzle model formulation used.
Experimental Study of Hydrogen Release Accidents in a Vehicle Garage
Sep 2009
Publication
Storing a hydrogen fuel-cell vehicle in a garage poses a potential safety hazard because of the accidents that could arise from a hydrogen leak. A series of tests examined the risk involved with hydrogen releases and deflagrations in a structure built to simulate a one-car garage. The experiments involved igniting hydrogen gas that was released inside the structure and studying the effects of the deflagrations. The “garage” measured 2.72 m high 3.64 m wide and 6.10 m long internally and was constructed from steel using a reinforced design capable of withstanding a detonation. The front face of the garage was covered with a thin transparent plastic film. Experiments were performed to investigate extended-duration (20–40 min) hydrogen leaks. The effect that the presence of a vehicle in the garage has on the deflagration was also studied. The experiments examined the effectiveness of different ventilation techniques at reducing the hydrogen concentration in the enclosure. Ventilation techniques included natural upper and lower openings and mechanical ventilation systems. A system of evacuated sampling bottles was used to measure hydrogen concentration throughout the garage prior to ignition and at various times during the release. All experiments were documented with standard and infrared (IR) video. Flame front propagation was monitored with thermocouples. Pressures within the garage were measured by four pressure transducers mounted on the inside walls of the garage. Six free-field pressure transducers were used to measure the pressures outside the garage.
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.
Deflagration Safety Study of Mixtures of Hydrogen and Natural Gas in a Semi-open Space
Sep 2007
Publication
In the transition to a hydrogen economy it is likely that hydrogen will be used or stored in close proximity to other flammable fuels and gases. Accidents can occur that result in the release of two or more fuels such as hydrogen and natural gas that can mix and form a hazard. A series of five medium-scale semi-open-space deflagration experiments have been conducted with hydrogen natural gas and air mixtures. The natural gas consisted of 90% methane 6% ethane 3% propane and 1% butane by volume. Mixtures of hydrogen and natural gas were created with the hydrogen mole fraction in the fuel varying from 1.000 to 0.897 and the natural gas mole fraction varying from 0.000 to 0.103. The hydrogen and natural gas mixture was then released inside a 5.27-m³ thin plastic tent. The stoichiometric fuel-air mixtures were ignited with a 40-J spark located at the bottom center of the tent. Overpressure and impulse data were collected using pressure transducers located within the mixture volume and in the free field. Flame front time-of-arrival was measured using fast response thermocouples and infrared video. Flame speeds relative to a fixed observer were measured between 36.2 m/s and 19.7 m/s. Average peak overpressures were measured between 2.0 kPa and 0.3 kPa. The addition of natural gas inhibited the combustion when the hydrogen mole fraction was less than or equal to 0.949. For these mixtures there was a significant decrease in overpressures. When the hydrogen mole fraction in the fuel was between 0.999 and 0.990 the overpressures were slightly higher than for the case of hydrogen alone. This could be due to experimental scatter or there may be a slight enhancement of the combustion when a very small amount of natural gas was present. From a safety standpoint variation in overpressure was small and should have little effect on safety considerations.
Recent Progress and Approaches on Transition Metal Chalcogenides for Hydrogen Production
Dec 2021
Publication
Development of efficient and affordable photocatalysts is of great significance for energy production and environmental sustainability. Transition metal chalcogenides (TMCs) with particle sizes in the 1–100 nm have been used for various applications such as photocatalysis photovoltaic and energy storage due to their quantum confinement effect optoelectronic behavior and their stability. In particular TMCs and their heterostructures have great potential as an emerging inexpensive and sustainable alternative to metal-based catalysts for hydrogen evolution. Herein the methods used for the fabrication of TMCs characterization techniques employed and the different methods of solar hydrogen production by using different TMCs as photocatalyst are reviewed. This review provides a summary of TMC photocatalysts for hydrogen production.
PRD Hydrogen Release and Dispersion, a Comparison of CFD Results Obtained from Using Ideal and Real Gas Law Properties.
Sep 2005
Publication
In this paper CFD techniques were applied to the simulations of hydrogen release from a 400-bar tank to ambient through a Pressure Relieve Device (PRD) 6 mm (¼”) opening. The numerical simulations using the TOPAZ software developed by Sandia National Laboratory addressed the changes of pressure density and flow rate variations at the leak orifice during release while the PHOENICS software package predicted extents of various hydrogen concentration envelopes as well as the velocities of gas mixture for the dispersion in the domain. The Abel-Noble equation of state (AN-EOS) was incorporated into the CFD model implemented through the TOPAZ and PHOENICS software to accurately predict the real gas properties for hydrogen release and dispersion under high pressures. The numerical results were compared with those obtained from using the ideal gas law and it was found that the ideal gas law overestimates the hydrogen mass release rates by up to 35% during the first 25 seconds of release. Based on the findings the authors recommend that a real gas equation of state be used for CFD predictions of high-pressure PRD releases.
Hydrogen Embrittlement of Medium Mn Steels
Feb 2021
Publication
Recent research efforts to develop advanced–/ultrahigh–strength medium-Mn steels have led to the development of a variety of alloying concepts thermo-mechanical processing routes and microstructural variants for these steel grades. However certain grades of advanced–/ultrahigh–strength steels (A/UHSS) are known to be highly susceptible to hydrogen embrittlement due to their high strength levels. Hydrogen embrittlement characteristics of medium–Mn steels are less understood compared to other classes of A/UHSS such as high Mn twinning–induced plasticity steel because of the relatively short history of the development of this steel class and the complex nature of multiphase fine-grained microstructures that are present in medium–Mn steels. The motivation of this paper is to review the current understanding of the hydrogen embrittlement characteristics of medium or intermediate Mn (4 to 15 wt pct) multiphase steels and to address various alloying and processing strategies that are available to enhance the hydrogen-resistance of these steel grades.
Simulations of Hydrogen Releases from a Storage Tanks- Dispersion and Consequences of Ignition
Sep 2005
Publication
We present results from hydrogen dispersion simulations from a pressurized reservoir at constant flow rate in the presence and absence of a wall. The dispersion simulations are performed using a commercial finite volume solver. Validation of the approach is discussed. Constant concentration envelopes corresponding to the 2% 4% and 15% hydrogen concentration in air are calculated for a subcritical vertical jet and for an equivalent subcritical horizontal jet from a high pressure reservoir. The consequences of ignition and the resulting overpressure are calculated for subcritical horizontal and vertical hydrogen jets and in the latter case compared to available experimental data.
Everything About Hydrogen Podcast: Is This the End of the Diesel Train?
Jan 2020
Publication
For this show the team are taking a dive into the world of hydrogen trains and who better to speak to this space than Mike Muldoon Head of Business Development and Marketing for Alstom UK&I. Alstom have been the pioneers of hydrogen powered rail and in addition to two operating trains in Germany have secured over Eur500 million of orders for hydrogen trains. On the show we talk to Mike about why Alstom see hydrogen as a key part of the evolution of the rail industry towards zero emissions and why hydrogen today is such a compelling proposition for operators and investors.
The podcast can be found on their website
The podcast can be found on their website
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.
Facilitating the Safest Possible Transition from Fossil to Hydrogen Fuels- Hydrogen Executive Leadership Panel
Sep 2005
Publication
In recent years federal and state safety authorities have worked to bring emergency planners and responders together with industry the scientific community and consumers to ensure high levels of safety with gas and liquid pipelines and more recently with liquefied natural gas terminals. The U.S. Department of Transportation (DOT) is the federal authority on the safe transportation of energy and the National Association of State Fire Marshals (NASFM) represents state-level safety authorities. Together they have produced firefighter safety training materials technical guidance and information for use in communities considering new energy infrastructure and conducted research to support these activities. In 2004 the DOT-NASFM partnership established the Hydrogen Executive Leadership Panel (HELP) to ensure a safe transition from fossil fuels to hydrogen fuel cells. HELP brings together senior policy-level experts from all sectors to understand and recommend mitigation strategies for the risks associated with the transportation and use of hydrogen in motor vehicles. The initial group includes experts from the United States Canada and Europe. HELP will be supported by an advisory committee of emergency planners and responders—individuals well-equipped to describe real-world scenarios of greatest concern—and by a second advisory committee of engineers and scientists who will help translate the real-world scenarios into useful technical solutions. By September 2005 HELP expects to define the initial real-world scenarios of greatest concern and bring together teams of experts to collaborate with automakers energy producers government authorities consumers and public safety officials. Much work lies ahead including creating guidance for hydrogen powered automobiles emergency response safety training establishing test methods to reflect real-world incident scenarios and modifying state and local building and fire codes. The HELP leadership will present its strategic plan and first report at the International Conference on Hydrogen Safety in September 2005.
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.
Hydrogen Flames in Tubes- Critical Run-up Distances
Sep 2007
Publication
The hazard associated with flame acceleration to supersonic speeds in hydrogen mixtures is discussed. A set of approximate models for evaluation of the run-up distances to supersonic flames in relatively smooth tubes and tubes with obstacles is presented. The model for smooth tubes is based on general relationships between the flame area turbulent burning velocity and the flame speed combined with an approximate description for the boundary layer thickness ahead of an accelerated flame. The unknown constants of the model are evaluated using experimental data. This model is then supplemented with the model for the minimum run-up distance for FA in tubes with obstacles developed earlier. On the basis of these two models solutions for the determination of the critical runup distances for FA and deflagration to detonation transition in tubes and channels for various hydrogen mixtures initial temperature and pressure tube size and tube roughness are presented.
A Rural Hydrogen Transportation Test Bed
Sep 2007
Publication
The University of Missouri-Rolla (UMR) through a hydrogen internal combustion engine vehicle evaluation participation agreement with the Ford Motor Company will establish a commuter bus service and hydrogen refueling at a station in rural Missouri near Ft. Leonard Wood (FLW). Initiated by a request from the U.S. Army Maneuver Support Center at FLW UMR is leading the effort to launch the commuter service between FLW and the neighboring towns of Rolla and Lebanon Missouri each of which are located approximately 40 km from the military base on Interstate-44 highway. The broad research training and education agenda for the rural hydrogen transportation test bed is to develop demonstrate evaluate and promote safe hydrogen-based technologies in a real world environment. With funds provided by the Defense Logistics Agency through the Air Force Research Laboratory this hydrogen initiative will build and operate a hydrogen fueling facility that includes on-site generation of hydrogen through electrolysis as well as selling a range of other traditional and alternative fuels.
Risk Assessment for Hydrogen Codes and Standards
Sep 2005
Publication
The development and promulgation of codes and standards are essential to establish a market-receptive environment for commercial hydrogen-based products and systems. The focus of the U.S. Department of Energy (DOE) is to conduct the research and development (R&D) needed to strengthen the scientific basis for technical requirements incorporated in national and international standards codes and regulations. In the U.S. the DOE and its industry partners have formed a Codes and Standards Tech Team (CSTT) to help guide the R&D. The CSTT has adopted an R&D Roadmap to achieve a substantial and verified database of the properties and behaviour of hydrogen and the performance characteristics of emerging hydrogen technology applications sufficient to enable the development of effective codes and standards for these applications. However to develop a more structured approach to the R&D described above the CSTT conducted a workshop on Risk Assessment for Hydrogen Codes and Standards in March 2005. The purpose of the workshop was to attain a consensus among invited experts on the protocols and data needed to address the development of risk-informed standards codes and regulations for hydrogen used as an energy carrier by consumers. Participants at the workshop identified and assessed requirements methodologies and applicability of risk assessment (RA) tools to develop a framework to conduct RA activities to address for example hydrogen fuel distribution delivery on-site storage and dispensing and hydrogen vehicle servicing and parking. The CSTT was particularly interested in obtaining the advice of RA experts and representatives of standards and model code developing organizations and industry on how data generated by R&D can be turned into information that is suitable for hydrogen codes and standards development. The paper reports on the results of the workshop and the RA activities that the DOE’s program on hydrogen safety codes and standards will undertake. These RA activities will help structure a comprehensive R&D effort that the DOE and its industry partners are undertaking to obtain the data and conduct the analysis and testing needed to establish a scientific and technical basis for hydrogen standards codes and regulations.
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
Analysis of Buoyancy-driven Ventilation of Hydrogen from Buildings
Sep 2007
Publication
When hydrogen gas is used or stored within a building as with a hydrogen-powered vehicle parked in a residential garage any leakage of unignited H2 will mix with indoor air and may form a flammable mixture. One approach to safety engineering relies on buoyancy-driven passive ventilation of H2 from the building through vents to the outside. To discover relationships between design variables we combine two types of analysis: (1) a simplified 1-D steady-state analysis of buoyancy-driven ventilation and (2) CFD modelling using FLUENT 6.3. The simplified model yields a closed-form expression relating the H2 concentration to vent area height and discharge coefficient; leakage rate; and a stratification factor. The CFD modelling includes 3-D geometry; H2 cloud formation; diffusion momentum convection and thermal effects; and transient response. We modelled a typical residential two-car garage with 5 kg of H2 stored in a fuel tank; leakage rates of 5.9 to 82 L/min (tank discharge times of 12 hours to 1 week); a variety of vent sizes and heights; and both isothermal and nonisothermal conditions. This modelling indicates a range of the stratification factor needed to apply the simplified model for vent sizing as well as a more complete understanding of the dynamics of H2 movement within the building. A significant thermal effect occurs when outdoor temperature is higher than indoor temperature so that thermocirculation opposes the buoyancy-driven ventilation of H2. This circumstance leads to higher concentrations of H2 in the building relative to an isothermal case. In an unconditioned space such as a residential garage this effect depends on the thermal coupling of indoor air to outdoor air the ground (under a concrete slab floor) and an adjacent conditioned space in addition to temperatures. We use CFD modelling to explore the magnitude of this effect under rather extreme conditions.
Analysis of Jet Flames and Unignited Jets from Unintended Releases of Hydrogen
Sep 2007
Publication
A combined experimental and modeling program is being carried out at Sandia National Laboratories to characterize and predict the behavior of unintended hydrogen releases. In the case where the hydrogen leak remains unignited knowledge of the concentration field and flammability envelope is an issue of importance in determining consequence distances for the safe use of hydrogen. In the case where a high-pressure leak of hydrogen is ignited a classic turbulent jet flame forms. Knowledge of the flame length and thermal radiation heat flux distribution is important to safety. Depending on the effective diameter of the leak and the tank source pressure free jet flames can be extensive in length and pose significant radiation and impingement hazard resulting in consequence distances that are unacceptably large. One possible mitigation strategy to potentially reduce the exposure to jet flames is to incorporate barriers around hydrogen storage equipment. The reasoning is that walls will reduce the extent of unacceptable consequences due to jet releases resulting from accidents involving high-pressure equipment. While reducing the jet extent the walls may introduce other hazards if not configured properly. The goal of this work is to provide guidance on configuration and placement of these walls to minimize overall hazards using a quantitative risk assessment approach. Detailed Navier-Stokes calculations of jet flames and unignited jets are used to understand how hydrogen leaks and jet-flames interact with barriers. The effort is complemented by an experimental program that considers the interaction of jet flames and unignited jets with barriers.
Collaborative Activities On Hydrogen Safety under the International Energy Agency’s Hydrogen Implementing
Sep 2005
Publication
In October 2004 the International Energy Agency Hydrogen Implementing Agreement (www.ieahia.org) approved the initiation of a collaborative task on hydrogen safety. During the past twelve months a work plan has been established and several member countries have committed to participate. Because of the nature of the International Energy Agency which is an international agreement between governments it is hoped that such collaboration will complement other cooperative efforts to help build the technology base around which codes and standards can be developed. In this way the new task on hydrogen safety will further the IEA Hydrogen Agreement in fulfilling its mission to accelerate the commercial introduction of hydrogen energy. This paper describes the specific scope and work plan for the collaboration that has been developed to date.
Fundamental Safety Testing and Analysis of Solid State Hydrogen Storage Materials and Systems
Sep 2007
Publication
Hydrogen is seen as the future automobile energy storage media due to its inherent cleanliness upon oxidation and its ready utilization in fuel cell applications. Its physical storage in light weight low volume systems is a key technical requirement. In searching for ever higher gravimetric and volumetric density hydrogen storage materials and systems it is inevitable that higher energy density materials will be studied and used. To make safe and commercially acceptable systems it is important to understand quantitatively the risks involved in using and handling these materials and to develop appropriate risk mitigation strategies to handle unforeseen accidental events. To evaluate these materials and systems an IPHE sanctioned program was initiated in 2006 partnering laboratories from Europe North America and Japan. The objective of this international program is to understanding the physical risks involved in synthesis handling and utilization of solid state hydrogen storage materials and to develop methods to mitigate these risks. This understanding will support ultimate acceptance of commercially high density hydrogen storage system designs. An overview of the approaches to be taken to achieve this objective will be given. Initial experimental results will be presented on environmental exposure of NaAlH4 a candidate high density hydrogen storage compound. The tests to be shown are based on United Nations recommendations for the transport of hazardous materials and include air and water exposure of the hydride at three hydrogen charge levels in various physical configurations. Additional tests developed by the American Society for Testing and Materials were used to quantify the dust cloud ignition characteristics of this material which may result from accidental high energy impacts and system breach. Results of these tests are shown along with necessary risk mitigation techniques used in the synthesis and fabrication of a prototype hydrogen storage system.
Addressing Hydrogen Embrittlement of Metals in the Sae J2579 Fuel Cell Vehicle Tank Standard
Sep 2013
Publication
The SAE Technical Information Report (TIR) J2579 (Technical Information Report for Fuel Systems in Fuel Cell and Other Hydrogen Vehicles) has been created to address the safety performance of hydrogen storage and handling systems on vehicles. Safety qualification of the compressed hydrogen storage system is demonstrated through performance testing on prototype containment vessels. The two performance tests currently included in the SAE J2579 for evaluating unacceptable leakage and burst do not account for the potential effects of hydrogen embrittlement on structural integrity. This report describes efforts to address hydrogen embrittlement of structural metals in the framework of performance-based safety qualification. New safety qualification pathways that account for hydrogen embrittlement in the SAE J2579 include an additional pneumatic performance test using hydrogen gas or materials tests that demonstrate acceptable hydrogen embrittlement resistance of candidate structural metals.
The Hydrogen Executive Leadership Panel (HELP) Initiative for Emergency Responder Training
Sep 2007
Publication
In close cooperation with their Canadian counterparts United States public safety authorities are taking the first steps towards creating a proper infrastructure to ensure the safe use of the new hydrogen fuel cells now being introduced commercially. Currently public safety officials are being asked to permit hydrogen fuel cells for stationary power and as emergency power backups for the telecommunications towers that exist everywhere. Consistent application of the safety codes is difficult – in part because it is new – yet it is far more complex to train emergency responders to deal safely with the inevitable hydrogen incidents. The US and Canadian building and fire codes and standards are similar but not identical. The US and Canadian rules are unlikely to be useful to other nations without modification to suit different regulatory systems. However emergency responder safety training is potentially more universal. The risks strategies and tactics are unlikely to differ much by region. The Hydrogen Executive Leadership Panel (HELP) made emergency responder safety training its first priority because the transition to hydrogen depends on keeping incidents small and inoffensive and the public and responders safe from harm. One might think that advising 1.2 million firefighters and 800000 law enforcement officers about hydrogen risks is no more complicated than adding guidance to a website. One would be wrong. The term “training” has specific legal implications which may vary by state. For hazardous materials federal requirements apply. Insurance companies place training requirements on the policies they sell to fire departments including the thousands of small all-volunteer departments which may operate as private corporations. Union contracts may define training and promotions may be based on satisfactorily completed certain levels of training. Emergency responders could no sooner learn how to extinguish a<br/>hydrogen fire by reading a webpage than a person could learn to ride a bicycle by reading a book. Procedures must be learned by listening reading and then doing. Regular practice is necessary. As new hydrogen applications are commercialized additional responder training may be necessary. This highlights another obstacle emergency responders’ ability to travel distances and take the time to undergo training. Historically fire academies established adjunct instructor programs and satellite academies to bring the training to firefighters. The large well-equipped academies are typically used for specialized training. States rarely have enough instructors and instructors often must take the time to create a course outline research each point and produce a program that is informative useful and holds the attention of responders. The challenge of training emergency responders seems next to impossible but public safety authorities are asked to tackle the impossible every day and a model exists to move forward in the U.S. Over the past few years the National Association of State Fire Marshals and U.S. Department of Transportation enlisted the help of emergency responders and industry to create a standardized approach to train emergency responders to deal with pipeline incidents. A curriculum and training materials were created and more than 26000 sets have been distributed for free to public safety agencies nationwide. More than 8000 instructors have been trained to use these materials that are now part of the regular training in 23 states. Using this model HELP intends to ensure that all emergency responders are trained to address hydrogen risks. The model and the rigorous scenario analysis and review used to developing the operational and technical training is addressed in this paper.
Incident Reporting- Learning from Experience
Sep 2007
Publication
Experience makes a superior teacher. Sharing the details surrounding safety events is one of the best ways to help prevent their recurrence elsewhere. This approach requires an open non-punitive environment to achieve broad benefits. The Hydrogen Incident Reporting Tool (www.h2incidents.org) is intended to facilitate the sharing of lessons learned and other relevant information gained from actual experiences using and working with hydrogen and hydrogen systems. Its intended audience includes those involved in virtually any aspect of hydrogen technology systems and use with an emphasis towards energy and transportation applications. The database contains records of safety events both publicly available and/or voluntarily submitted. Typical records contain a general description of the occurrence contributing factors equipment involved and some detailing of consequences and changes that have been subsequently implemented to prevent recurrence of similar events in the future. The voluntary and confidential nature and other characteristics surrounding the database mean that any analysis of apparent trends in its contents cannot be considered statistically valid for a universal population. A large portion of reported incidents have occurred in a laboratory setting due to the typical background of the reporting projects for example. Yet some interesting trends are becoming apparent even at this early stage of the database’s existence and general lessons can already be taken away from these experiences. This paper discusses the database and a few trends that have already become apparent for the reported incidents. Anticipated future uses of this information are also described. This paper is intended to encourage wider participation and usage of the incidents reporting database and to promote the safety benefits offered by its contents.
Risk-Informed Process and Tools for Permitting Hydrogen Fueling Stations
Sep 2007
Publication
The permitting process for hydrogen fueling stations varies from country to country. However a common step in the permitting process is the demonstration that the proposed fueling station meets certain safety requirements. Currently many permitting authorities rely on compliance with well known codes and standards as a means to permit a facility. Current codes and standards for hydrogen facilities require certain safety features specify equipment made of material suitable for hydrogen environment and include separation or safety distances. Thus compliance with the code and standard requirements is widely accepted as evidence of a safe design. However to ensure that a hydrogen facility is indeed safe the code and standard requirements should be identified using a risk-informed process that utilizes an acceptable level of risk. When compliance with one or more code or standard requirements is not possible an evaluation of the risk associated with the exemptions to the requirements should be understood and conveyed to the Authority Having Jurisdiction (AHJ). Establishment of a consistent risk assessment toolset and associated data is essential to performing these risk evaluations. This paper describes an approach for risk-informing the permitting process for hydrogen fueling stations that relies primarily on the establishment of risk-informed codes and standards. The proposed risk-informed process begins with the establishment of acceptable risk criteria associated with the operation of hydrogen fueling stations. Using accepted Quantitative Risk Assessment (QRA) techniques and the established risk criteria the minimum code and standard requirements necessary to ensure the safe operation of hydrogen facilities can be identified. Risk informed permitting processes exist in some countries and are being developed in others. To facilitate consistent risk-informed approaches the participants in the International Energy Agency (IEA) Task 19 on hydrogen safety are working to identify acceptable risk criteria QRA models and supporting data.
Hydrogen Safety and Permitting Hydrogen Fueling Stations
Sep 2007
Publication
Two key aspects of hydrogen safety are (1) incorporating data and analysis from research development and demonstration (RD&D) into the codes and standards development process; and (2) adopting and enforcing these codes and standards by state and local permitting officials. This paper describes work that the U.S. Department of Energy (DOE) is sponsoring to address these aspects of hydrogen safety. For the first DOE is working with the automobile and energy industries to identify and address high priority RD&D to establish a sound scientific basis for requirements that are incorporated in hydrogen codes and standards. The high priority RD&D needs are incorporated and tracked in an RD&D Roadmap adopted by the Codes and Standards Technical Team of the FreedomCAR and Fuel Partnership. DOE and its national laboratories conduct critical RD&D and work with key standards and model code development organizations to help incorporate RD&D results into the codes and standards process. To address the second aspect DOE has launched an initiative to facilitate the permitting process for hydrogen fueling stations (HFS). A key element of this initiative will be a Web-based information repository a toolkit that includes information fact sheets networking charts to encourage information exchange among code officials who have permitted or are in the process of permitting HFS templates to show whether a proposed station footprint conforms to requirements in the jurisdiction and a database of requirements incorporated in key codes and standards. The information repository will be augmented by workshops for code officials and station developers in jurisdictions that are likely to have HFS in the near future.
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.
Achieving High-rate Hydrogen Recovery from Wastewater Using Customizable Alginate Polymer Gel Matrices Encapsulating Biomass
Jul 2018
Publication
In addition to methane gas higher-value resources such as hydrogen gas are produced during anaerobic wastewater treatment. They are however immediately consumed by other organisms. To recover these high-value resources not only do the desired phenotypes need to be retained in the anaerobic reactor but the undesired ones need to be washed out. In this study a well-established alginate-based polymer gel with and without a coating layer was used to selectively encapsulate hydrogen-producing biomass in beads to achieve high-rate recovery of hydrogen during anaerobic wastewater treatment. The effect of cross-linking agents Ca2+ Sr2+ and Ba2+ as well as a composite coating on the beads consisting of alternating layers of polyethylenimine and silica hydrogel were investigated with respect to their performance specifically their mass transfer characteristics and their differential ability to retain the encapsulated biomass. Although the coating reduced the escape rate of encapsulated biomass from the beads all alginate polymer matrices without coating effectively retained biomass. Fast diffusion of dissolved organic carbon (DOC) through the polymer gel was observed in both Ca-alginate and Sr-alginate without coating. The coating however decreased either the diffusivity or the permeability of the DOC depending on whether the DOC was from synthetic wastewater (more lipids and proteins) or real brewery wastewater (more sugars). Consequently the encapsulation system with coating became diffusion limited when brewery wastewater with high chemical oxygen demand was fed resulting in a lower hydrogen production rate than the uncoated encapsulation systems. In all cases the encapsulated biomass was able to produce hydrogen even at a hydraulic residence time of 45 min. Although there are limitations to this system the used of encapsulated biomass for resource recovery from wastewater shows promise particularly for high-rate systems in which the retention of specific phenotypes is desired.
Low-carbon Hydrogen Via Integration of Steam Methane Reforming with Molten Carbonate Fuel Cells at Low Fuel Utilization
Feb 2021
Publication
Hydrogen production is critical to many modern chemical processes – ammonia synthesis petroleum refining direct reduction of iron and more. Conventional approaches to hydrogen manufacture include steam methane reforming and autothermal reforming which today account for the lion's share of hydrogen generation. Without CO2 capture these processes emit about 8.7 kg of CO2 for each kg of H2 produced. In this study a molten carbonate fuel cell system with CO2 capture is proposed to retrofit the flue gas stream of an existing Steam Methane Reforming plant rated at 100000 Nm3 h−1 of 99.5% pure H2. The thermodynamic analysis shows direct CO2 emissions can be reduced by more than 95% to 0.4 to 0.5 kg CO2 /kg H2 while producing 17% more hydrogen (with an increase in natural gas input of approximately 37%). Because of the additional power and hydrogen generation of the carbonate fuel cell the efficiency debit associated with CO2 capture is quite small reducing the SMR efficiency from 76.6% without capture to 75.6% with capture. In comparison the use of standard amine technology for CO2 capture reduces the efficiency below 70%. This demonstrates the synergistic nature of the carbonate fuel cells which can reform natural gas to H2 while simultaneously capturing CO2 from the SMR flue gas and producing electricity giving rise to a total system with very low emissions yet high efficiency.
International Association for Hydrogen Safety ‘Research Priorities Workshop’, September 2018, Buxton, UK
Sep 2018
Publication
Hydrogen has the potential to be used by many countries as part of decarbonising the future energy system. Hydrogen can be used as a fuel ‘vector’ to store and transport energy produced in low-carbon ways. This could be particularly important in applications such as heating and transport where other solutions for low and zero carbon emission are difficult. To enable the safe uptake of hydrogen technologies it is important to develop the international scientific evidence base on the potential risks to safety and how to control them effectively. The International Association for Hydrogen Safety (known as IA HySAFE) is leading global efforts to ensure this. HSE hosted the 2018 IA HySAFE Biennial Research Priorities Workshop. A panel of international experts presented during nine key topic sessions: (1) Industrial and National Programmes; (2) Applications; (3) Storage; (4) Accident Physics – Gas Phase; (5) Accident Physics – Liquid/ Cryogenic Behaviour; (6) Materials; (7) Mitigation Sensors Hazard Prevention and Risk Reduction; (8) Integrated Tools for Hazard and Risk Assessment; (9) General Aspects of Safety.<br/>This report gives an overview of each topic made by the session chairperson. It also gives further analysis of the totality of the evidence presented. The workshop outputs are shaping international activities on hydrogen safety. They are helping key stakeholders to identify gaps in knowledge and expertise and to understand and plan for potential safety challenges associated with the global expansion of hydrogen in the energy system.
Design of a Methanol Reformer for On-board Production of Hydrogen as Fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell Power System
Sep 2020
Publication
The method of Computational Fluid Dynamics is used to predict the process parameters and select the optimum operating regime of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system. The analysis uses a three reactions kinetics model for methanol steam reforming water gas shift and methanol decomposition reactions on Cu/ZnO/Al2O3 catalyst. Numerical simulations are performed at single channel level for a range of reformer operating temperatures and values of the molar flow rate of methanol per weight of catalyst at the reformer inlet. Two operating regimes of the fuel processor are selected which offer high methanol conversion rate and high hydrogen production while simultaneously result in a small reformer size and a reformate gas composition that can be tolerated by phosphoric acid-doped high temperature membrane electrode assemblies for proton exchange membrane fuel cells. Based on the results of the numerical simulations the reactor is sized and its design is optimized.
Research and Development of Hydrogen Carrier Based Solutions for Hydrogen Compression and Storage
Aug 2022
Publication
Martin Dornheim,
Lars Baetcke,
Etsuo Akiba,
Jose-Ramón Ares,
Tom Autrey,
Jussara Barale,
Marcello Baricco,
Kriston Brooks,
Nikolaos Chalkiadakis,
Véronique Charbonnier,
Steven Christensen,
José Bellosta von Colbe,
Mattia Costamagna,
Erika Michela Dematteis,
Jose-Francisco Fernández,
Thomas Gennett,
David Grant,
Tae Wook Heo,
Michael Hirscher,
Katherine Hurst,
Mykhaylo V. Lototskyy,
Oliver Metz,
Paola Rizzi,
Kouji Sakaki,
Sabrina Sartori,
Emmanuel Stamatakis,
Alastair D. Stuart,
Athanasios Stubos,
Gavin Walker,
Colin Webb,
Brandon Wood,
Volodymyr A. Yartys and
Emmanuel Zoulias
Industrial and public interest in hydrogen technologies has risen strongly recently as hydrogen is the ideal means for medium to long term energy storage transport and usage in combination with renewable and green energy supply. In a future energy system the production storage and usage of green hydrogen is a key technology. Hydrogen is and will in future be even more used for industrial production processes as a reduction agent or for the production of synthetic hydrocarbons especially in the chemical industry and in refineries. Under certain conditions material based systems for hydrogen storage and compression offer advantages over the classical systems based on gaseous or liquid hydrogen. This includes in particular lower maintenance costs higher reliability and safety. Hydrogen storage is possible at pressures and temperatures much closer to ambient conditions. Hydrogen compression is possible without any moving parts and only by using waste heat. In this paper we summarize the newest developments of hydrogen carriers for storage and compression and in addition give an overview of the different research activities in this field.
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.
Large Transition State Stabilization From a Weak Hydrogen Bond
Jul 2020
Publication
A series of molecular rotors was designed to study and measure the rate accelerating effects of an intramolecular hydrogen bond. The rotors form a weak neutral O–H⋯O[double bond length as m-dash]C hydrogen bond in the planar transition state (TS) of the bond rotation process. The rotational barrier of the hydrogen bonding rotors was dramatically lower (9.9 kcal mol−1) than control rotors which could not form hydrogen bonds. The magnitude of the stabilization was significantly larger than predicted based on the independently measured strength of a similar O–H⋯O[double bond length as m-dash]C hydrogen bond (1.5 kcal mol−1). The origins of the large transition state stabilization were studied via experimental substituent effect and computational perturbation analyses. Energy decomposition analysis of the hydrogen bonding interaction revealed a significant reduction in the repulsive component of the hydrogen bonding interaction. The rigid framework of the molecular rotors positions and preorganizes the interacting groups in the transition state. This study demonstrates that with proper design a single hydrogen bond can lead to a TS stabilization that is greater than the intrinsic interaction energy which has applications in catalyst design and in the study of enzyme mechanisms.
Highly Porous Organic Polymers for Hydrogen Fuel Storage
Apr 2019
Publication
Hydrogen (H2) is one of the best candidates to replace current petroleum energy resources due to its rich abundance and clean combustion. However the storage of H2presents a major challenge. There are two methods for storing H2 fuel chemical and physical both of which have some advantages and disadvantages. In physical storage highly porous organic polymers are of particular interest since they are low cost easy to scale up metal-free and environmentally friendly.
In this review highly porous polymers for H2 fuel storage are examined from five perspectives:
(a) brief comparison of H2 storage in highly porous polymers and other storage media;
(b) theoretical considerations of the physical storage of H2 molecules in porous polymers;
(c) H2 storage in different classes of highly porous organic polymers;
(d) characterization of microporosity in these polymers; and
(e) future developments for highly porous organic polymers for H2 fuel storage. These topics will provide an introductory overview of highly porous organic polymers in H2 fuel storage.
In this review highly porous polymers for H2 fuel storage are examined from five perspectives:
(a) brief comparison of H2 storage in highly porous polymers and other storage media;
(b) theoretical considerations of the physical storage of H2 molecules in porous polymers;
(c) H2 storage in different classes of highly porous organic polymers;
(d) characterization of microporosity in these polymers; and
(e) future developments for highly porous organic polymers for H2 fuel storage. These topics will provide an introductory overview of highly porous organic polymers in H2 fuel storage.
Biomass Derived Porous Nitrogen Doped Carbon for Electrochemical Devices
Mar 2017
Publication
Biomass derived porous nanostructured nitrogen doped carbon (PNC) has been extensively investigated as the electrode material for electrochemical catalytic reactions and rechargeable batteries. Biomass with and without containing nitrogen could be designed and optimized to prepare PNC via hydrothermal carbonization pyrolysis and other methods. The presence of nitrogen in carbon can provide more active sites for ion absorption improve the electronic conductivity increase the bonding between carbon and sulfur and enhance the electrochemical catalytic reaction. The synthetic methods of natural biomass derived PNC heteroatomic co- or tri-doping into biomass derived carbon and the application of biomass derived PNC in rechargeable Li/Na batteries high energy density Li–S batteries supercapacitors metal-air batteries and electrochemical catalytic reaction (oxygen reduction and evolution reactions hydrogen evolution reaction) are summarized and discussed in this review. Biomass derived PNCs deliver high performance electrochemical storage properties for rechargeable batteries/supercapacitors and superior electrochemical catalytic performance toward hydrogen evolution oxygen reduction and evolution as promising electrodes for electrochemical devices including battery technologies fuel cell and electrolyzer.
Advanced Hydrogen and CO2 Capture Technology for Sour Syngas
Apr 2011
Publication
A key challenge for future clean power or hydrogen projects via gasification is the need to reduce the overall cost while achieving significant levels of CO2 capture. The current state of the art technology for capturing CO2 from sour syngas uses a physical solvent absorption process (acid gas removal–AGR) such as Selexol™ or Rectisol® to selectively separate H2S and CO2 from the H2. These two processes are expensive and require significant utility consumption during operation which only escalates with increasing levels of CO2 capture. Importantly Air Products has developed an alternative option that can achieve a higher level of CO2 capture than the conventional technologies at significantly lower capital and operating costs. Overall the system is expected to reduce the cost of CO2 capture by over 25%.<br/>Air Products developed this novel technology by leveraging years of experience in the design and operation of H2 pressure swing adsorption (PSA) systems in its numerous steam methane reformers. Commercial PSAs typically operate on clean syngas and thus need an upstream AGR unit to operate in a gasification process. Air Products recognized that a H2 PSA technology adapted to handle sour feedgas (Sour PSA) would enable a new and enhanced improvement to a gasification system. The complete Air Products CO2 Capture technology (CCT) for sour syngas consists of a Sour PSA unit followed by a low-BTU sour oxycombustion unit and finally a CO2 purification / compression system.
Validation of Leading Point Concept in RANS Simulations of Highly Turbulent Lean Syngas-air Flames with Well-pronounced Diffusional-thermal Effects
Jan 2021
Publication
While significant increase in turbulent burning rate in lean premixed flames of hydrogen or hydrogen-containing fuel blends is well documented in various experiments and can be explained by highlighting local diffusional-thermal effects capabilities of the vast majority of available models of turbulent combustion for predicting this increase have not yet been documented in numerical simulations. To fill this knowledge gap a well-validated Turbulent Flame Closure (TFC) model of the influence of turbulence on premixed combustion which however does not address the diffusional-thermal effects is combined with the leading point concept which highlights strongly perturbed leading flame kernels whose local structure and burning rate are significantly affected by the diffusional-thermal effects. More specifically within the framework of the leading point concept local consumption velocity is computed in extremely strained laminar flames by adopting detailed combustion chemistry and subsequently the computed velocity is used as an input parameter of the TFC model. The combined model is tested in RANS simulations of highly turbulent lean syngas-air flames that were experimentally investigated at Georgia Tech. The tests are performed for four different values of the inlet rms turbulent velocities different turbulence length scales normal and elevated (up to 10 atm) pressures various H2/CO ratios ranging from 30/70 to 90/10 and various equivalence ratios ranging from 0.40 to 0.80. All in all the performed 33 tests indicate that the studied combination of the leading point concept and the TFC model can predict well-pronounced diffusional-thermal effects in lean highly turbulent syngas-air flames with these results being obtained using the same value of a single constant of the combined model in all cases. In particular the model well predicts a significant increase in the bulk turbulent consumption velocity when increasing the H2/CO ratio but retaining the same value of the laminar flame speed.
Metal Hydride Hydrogen Compressors
Feb 2014
Publication
Metal hydride (MH) thermal sorption compression is an efficient and reliable method allowing a conversion of energy from heat into a compressed hydrogen gas. The most important component of such a thermal engine – the metal hydride material itself – should possess several material features in order to achieve an efficient performance in the hydrogen compression. Apart from the hydrogen storage characteristics important for every solid H storage material (e.g. gravimetric and volumetric efficiency of H storage hydrogen sorption kinetics and effective thermal conductivity) the thermodynamics of the metal–hydrogen systems is of primary importance resulting in a temperature dependence of the absorption/desorption pressures). Several specific features should be optimised to govern the performance of the MH-compressors including synchronisation of the pressure plateaus for multi-stage compressors reduction of slope of the isotherms and hysteresis increase of cycling stability and life time together with challenges in system design associated with volume expansion of the metal matrix during the hydrogenation.<br/>The present review summarises numerous papers and patent literature dealing with MH hydrogen compression technology. The review considers (a) fundamental aspects of materials development with a focus on structure and phase equilibria in the metal–hydrogen systems suitable for the hydrogen compression; and (b) applied aspects including their consideration from the applied thermodynamic viewpoint system design features and performances of the metal hydride compressors and major applications.
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