United States

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.

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 (ESOI_e) 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 ESOI_eratio of 59 more favorable than the best battery technology available today (Li-ion ESOI_e= 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 ESOI_eratio and the high EROI of wind generation offset the low round-trip efficiency.

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.

One of the main benefits sought by including hydrogen in the alternative fuels mix is emissions reduction – eventually by 100%. However in the near term there is a very significant cost differential between fossil fuels and hydrogen. Hythane (a blend of hydrogen and natural gas) can act as a viable next step on the path to an ultimate hydrogen economy as a fuel blend consisting of 8−30 % hydrogen in methane can reduce emissions while not requiring significant changes in existing infrastructure. This work seeks to evaluate whether hythane may be safer than both hydrogen and methane under certain conditions. This is due to the fact hythane combines the positive safety properties of hydrogen (strong buoyancy high diffusivity) and methane (much lower flame speeds and narrower flammability limits as compared to hydrogen). For this purpose several different mixture compositions (e.g. 8 % 20 % and 30 % hydrogen) are considered. The evaluation of (a) dispersion characteristics (which are more positive than for methane) (b) combustion characteristics (which are closer to methane than hydrogen) and (c) Combined dispersion + explosion risk is performed. This risk is expected to be comparable to that of pure methane possibly lower in some situations and definitely lower than for pure hydrogen. The work is performed using the CFD software FLACS that has been well-validated for safety studies of both natural gas/methane and hydrogen systems. The first part of the work will involve validating the flame speeds and flammability limits predicted by FLACS against values available in literature. The next part of the work involves validating the overpressures predicted by the CFD tool for combustion of premixed mixtures of methane and hydrogen with air against available experimental data. In the end practical systems such as vehicular tunnels garages etc. is used to demonstrate positive safety benefits of hythane with comparisons to similar simulations for both hydrogen and methane.

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.

Improving efficiency of hydrogen cooling in cryogenic conditions is important for the wider applications of hydrogen energy systems. The approach investigated in this study is based on a Ranque-Hilsch vortex tube (RHVT) that generates temperature separation in a working fluid. The simplicity of RHVT is also a valuable characteristic for cryogenic systems. In the present work novel shapes of RHVT are computationally investigated with the goal to raise efficiency of the cooling process. Specifically a smooth transition is arranged between a vortex chamber where compressed gas is injected and the main tube with two exit ports at the tube ends. Flow simulations have been carried out using STAR-CCM+ software with the real-gas Redlich-Kwong model for hydrogen at temperatures near 70 K. It is determined that a vortex tube with a smooth transition of moderate size manifests about 7% improvement of the cooling efficiency when compared vortex tubes that use traditional vortex chambers with stepped transitions and a no-chamber setup with direct gas injection.

A technoeconomic analysis of photoelectrochemical (PEC) and photovoltaic-electrolytic (PV-E) solar-hydrogen production of 10 000 kg H₂ day⁻¹ (3.65 kilotons per year) was performed to assess the economics of each technology and to provide a basis for comparison between these technologies as well as within the broader energy landscape. Two PEC systems differentiated primarily by the extent of solar concentration (unconcentrated and 10× concentrated) and two PV-E systems differentiated by the degree of grid connectivity (unconnected and grid supplemented) were analyzed. In each case a base-case system that used established designs and materials was compared to prospective systems that might be envisioned and developed in the future with the goal of achieving substantially lower overall system costs. With identical overall plant efficiencies of 9.8% the unconcentrated PEC and non-grid connected PV-E system base-case capital expenses for the rated capacity of 3.65 kilotons H₂ per year were $205 MM ($293 per m² of solar collection area (m_S⁻²) $14.7 W_H2P⁻¹) and $260 MM ($371 mS−2 $18.8 W_H2P⁻¹) respectively. The untaxed plant-gate levelized costs for the hydrogen product (LCH) were $11.4 kg⁻¹ and $12.1 kg⁻¹ for the base-case PEC and PV-E systems respectively. The 10× concentrated PEC base-case system capital cost was $160 MM ($428 m_S−2 $11.5 WH₂P⁻¹) and for an efficiency of 20% the LCH was $9.2 kg−1. Likewise the grid supplemented base-case PV-E system capital cost was $66 MM ($441 _mS⁻² $11.5 W_H2P⁻¹) and with solar-to-hydrogen and grid electrolysis system efficiencies of 9.8% and 61% respectively the LCH was $6.1 kg⁻¹. As a benchmark a proton-exchange membrane (PEM) based grid-connected electrolysis system was analyzed. Assuming a system efficiency of 61% and a grid electricity cost of $0.07 kWh⁻¹ the LCH was $5.5 kg⁻¹. A sensitivity analysis indicated that relative to the base-case increases in the system efficiency could effect the greatest cost reductions for all systems due to the areal dependencies of many of the components. The balance-of-systems (BoS) costs were the largest factor in differentiating the PEC and PV-E systems. No single or combination of technical advancements based on currently demonstrated technology can provide sufficient cost reductions to allow solar hydrogen to directly compete on a levelized cost basis with hydrogen produced from fossil energy. Specifically a cost of CO₂ greater than ∼$800 (ton CO₂)−1 was estimated to be necessary for base-case PEC hydrogen to reach price parity with hydrogen derived from steam reforming of methane priced at $12 GJ⁻¹ ($1.39 (kg H₂)⁻¹). A comparison with low CO₂ and CO₂-neutral energy sources indicated that base-case PEC hydrogen is not currently cost-competitive with electrolysis using electricity supplied by nuclear power or from fossil-fuels in conjunction with carbon capture and storage. Solar electricity production and storage using either batteries or PEC hydrogen technologies are currently an order of magnitude greater in cost than electricity prices with no clear advantage to either battery or hydrogen storage as of yet. Significant advances in PEC technology performance and system cost reductions are necessary to enable cost-effective PEC-derived solar hydrogen for use in scalable grid-storage applications as well as for use as a chemical feedstock precursor to CO₂-neutral high energy-density transportation fuels. Hence such applications are an opportunity for foundational research to contribute to the development of disruptive approaches to solar fuels generation systems that can offer higher performance at much lower cost than is provided by current embodiments of solar fuels generators. Efforts to directly reduce CO₂ photoelectrochemically or electrochemically could potentially produce products with higher value than hydrogen but many as yet unmet challenges include catalytic efficiency and selectivity and CO₂ mass transport rates and feedstock cost. Major breakthroughs are required to obtain viable economic costs for solar hydrogen production but the barriers to achieve cost-competitiveness with existing large-scale thermochemical processes for CO₂ reduction are even greater.

Hydrogen jet flames resulting from ignition of unintended releases can be extensive in length and pose significant radiation and impingement hazards. Depending on the leak diameter and source pressure the resulting consequence distances can be unacceptably large. One possible mitigation strategy to reduce exposure to jet flames is to incorporate barriers around hydrogen storage and delivery equipment. An experimental and modeling program has been performed at Sandia National Laboratories to better characterize the effectiveness of barrier walls to reduce hazards. This paper describes the experimental and modeling program and presents results obtained for various barrier configurations. The experimental measurements include flame deflection using standard and infrared video and high-speed movies (500 fps) to study initial flame propagation from the ignition source. Measurements of the ignition overpressure wall deflection radiative heat flux and wall and gas temperature were also made at strategic locations. The modeling effort includes three-dimensional calculations of jet flame deflection by the barriers computations of the thermal radiation field around barriers predicted overpressure from ignition and the computation of the concentration field from deflected unignited hydrogen releases. The various barrier designs are evaluated in terms of their mitigation effectiveness for the associated hazards present. The results show that barrier walls are effective at deflecting jet flames in a desired direction and can help attenuate the effects of ignition overpressure and flame radiative heat flux.

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.

We have modelled sudden hydrogen expansion from a cryogenic pressure vessel. This model considers real gas equations of state single and two-phase flow and the specific “vessel within vessel” geometry of cryogenic vessels. The model can solve sudden hydrogen expansion for initial pressures up to 1210 bar and for initial temperatures ranging from 27 to 400 K. For practical reasons our study focuses on hydrogen release from 345 bar with temperatures between 62 K and 300 K. The pressure vessel internal volume is 151 L. The results indicate that cryogenic pressure vessels may offer a safety advantage with respect to compressed hydrogen vessels because i) the vacuum jacket protects the pressure vessel from environmental damage ii) hydrogen when released discharges first into an intermediate chamber before reaching the outside environment and iii) working temperature is typically much lower and thus the hydrogen has less energy. Results indicate that key expansion parameters such as pressure rate of energy release and thrust are all considerably lower for a cryogenic vessel within vessel geometry as compared to ambient temperature compressed gas vessels. Future work will focus on taking advantage of these favourable conditions to attempt fail-safe cryogenic vessel designs that do not harm people or property even after catastrophic failure of the inner pressure vessel.