United States

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.

Performing research in the interest of providing relevant safety requirements is a valuable and essential endeavor but translating research results into enforceable requirements adopted into codes and standards a process sometimes referred to as codification can be a separate and challenging task. This paper discusses the process utilized to successfully translate research results related to bulk gaseous hydrogen storage separation (or stand-off) distances into code requirements in NFPA 55:Storage Use and Handling of Compressed Gases and Cryogenic Fluids in Portable and StationaryContainers Cylinders and Tanks and NFPA 2: Hydrogen Technologies. The process utilized can besummarized as follows: First the technical committees for the documents to be revised were engaged to confirm that the codification process was endorsed by the committee. Then a sub-committee referred to as a task group was formed. A chair must be elected or appointed. The chair should be a generalist with code enforcement or application experience. The task group was populated with several voting members of each technical committee. By having voting members as part of the task group the group becomes empowered and uniquely different from any other code proposal generating body. The task group was also populated with technical experts as needed but primarily the experts needed are the researchers involved. Once properly populated and empowered the task group must actively engage its members. The researchers must educate the code makers on the methods and limitations of their work and the code makers must take the research results and fill the gaps as needed to build consensus and create enforceable code language and generate a code change proposal that will be accepted. While this process seems simple there are pitfalls along the way that can impede or nullify the desired end result – changes to codes and standards. A few of these pitfalls include: wrong task group membership task group not empowered task group not supported in-person meetings not possible consensus not achieved. This paper focuses on the process used and how pitfalls can be avoided for future efforts.

The 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.

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.

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.

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.

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.

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.

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.

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.