United States
Very Low-cost Visual and Wireless Sensors for Effective Hydrogen Gas Leak Detection
Sep 2013
Publication
Element One Inc. Boulder CO is developing novel hydrogen gas leak indicators to improve the safety and maintenance operations of hydrogen production and chemical processing facilities and hydrogen fueling stations. These technologies can be used to make visual gas leak indicators such as paints decals and conformal plastic films as well as RF sensors for wireless networks. The primary advantage of the Element One hydrogen gas indicators is their low cost and easy deployment which allows them to be used ubiquitously at each and every potential hydrogen leak site. They have the potential to convert safety problems into routine maintenance problems thereby improving overall safety and decreasing operational costs.
Spin Pinning Effect to Reconstructed Oxyhydroxide Layer on Ferromagnetic Oxides for Enhanced Water Oxidation
Jun 2021
Publication
Producing hydrogen by water electrolysis suffers from the kinetic barriers in the oxygen evolution reaction (OER) that limits the overall efficiency. With spin-dependent kinetics in OER to manipulate the spin ordering of ferromagnetic OER catalysts (e.g. by magnetization) can reduce the kinetic barrier. However most active OER catalysts are not ferromagnetic which makes the spin manipulation challenging. In this work we report a strategy with spin pinning effect to make the spins in paramagnetic oxyhydroxides more aligned for higher intrinsic OER activity. The spin pinning effect is established in oxideFM/oxyhydroxide interface which is realized by a controlled surface reconstruction of ferromagnetic oxides. Under spin pinning simple magnetization further increases the spin alignment and thus the OER activity which validates the spin effect in rate-limiting OER step. The spin polarization in OER highly relies on oxyl radicals (O∙) created by 1st dehydrogenation to reduce the barrier for subsequent O-O coupling.
A New Design Concept for Prevention of Hydrogen-induced Mechanical Degradation: Viewpoints of Metastability and High Entropy
Dec 2018
Publication
‟How crack growth is prevented” is key to improve both fatigue and monotonic fracture resistances under an influence of hydrogen. Specifically the key points for the crack growth resistance are hydrogen diffusivity and local ductility. For instance type 304 austenitic steels show high hydrogen embrittlement susceptibility because of the high hydrogen diffusivity of bcc (α´) martensite. In contrast metastability in specific austenitic steels enables fcc (γ) to hcp (ε) martensitic transformation which decreases hydrogen diffusivity and increases strength simultaneously. As a result even if hydrogen-assisted cracking occurs during monotonic tensile deformation the ε-martensite acts to arrest micro-damage evolution when the amount of ε-martensite is limited. Thus the formation of ε-martensite can decrease hydrogen embrittlement susceptibility in austenitic steels. However a considerable amount of ε-martensite is required when we attempt to have drastic improvements of work hardening capability and strength level with respect to transformation-induced plasticity effect. Since the hcp structure contains a less number of slip systems than fcc and bcc the less stress accommodation capacity often causes brittle-like failure when the ε-martensite fraction is large. Therefore ductility of ε-martensite is another key when we maximize the positive effect of ε-martensitic transformation. In fact ε-martensite in a high entropy alloy was recently found to be extraordinary ductile. Consequently the metastable high entropy alloys showed low fatigue crack growth rates in a hydrogen atmosphere compared with conventional metastable austenitic steels with α´-martensitic transformation. We here present effects of metastability to ε-phase and configurational entropy on hydrogen-induced mechanical degradation including monotonic tension properties and fatigue crack growth resistance.
Reversible Hydrogen Storage Using Nanocomposites
Jul 2020
Publication
In the field of energy storage recently investigated nanocomposites show promise in terms of high hydrogen uptake and release with enhancement in the reaction kinetics. Among several carbonaceous nanovariants like carbon nanotubes (CNTs) fullerenes and graphitic nanofibers reveal reversible hydrogen sorption characteristics at 77 K due to their van der Waals interaction. The spillover mechanism combining Pd nanoparticles on the host metal-organic framework (MOF) show room temperature uptake of hydrogen. Metal or complex hydrides either in the nanocomposite form and its subset nanocatalyst dispersed alloy phases illustrate the concept of nanoengineering and nanoconfinement of particles with tailor-made properties for reversible hydrogen storage. Another class of materials comprising polymeric nanostructures such as conducting polyaniline and their functionalized nanocomposites are versatile hydrogen storage materials because of their unique size high specific surface-area pore-volume and bulk properties. The salient features of nanocomposite materials for reversible hydrogen storage are reviewed and discussed.
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.
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.
Great Expectations: Asia, Australia and Europe Leading Emerging Green Hydrogen Economy, but Project Delays Likely
Aug 2020
Publication
In July 2020 the European Union unveiled its new Hydrogen Strategy a visionary plan to accelerate the adoption of green hydrogen to meet the EU’s net-zero emissions goal by 2050. Combined with smaller-scale plans in South Korea and Japan IEEFA believes this could form the beginnings of a global green hydrogen economy.
Green hydrogen produced exclusively with renewable energy has been acclaimed for decades but ever lower solar electricity costs mean this time really is different.
We expect the EU’s initiative to find strong support as the proposed investment of €430bn by 2030 places it in pole position to develop a world-class green energy manufacturing industry and provides a vital bridge for energy transition by repurposing existing ‘natural’ gas pipelines and fossil-fuel dependent ports.
In the past year numerous green hydrogen projects have been proposed primarily in Asia Europe Australia.
We estimate there are 50 viable projects globally announced in the past year with a total hydrogen production capacity of 4 million tons per annum and renewable power capacity of 50 gigawatts (GW) requiring capex of US$75bn.
The paper can be download on the IEEFA website
Green hydrogen produced exclusively with renewable energy has been acclaimed for decades but ever lower solar electricity costs mean this time really is different.
We expect the EU’s initiative to find strong support as the proposed investment of €430bn by 2030 places it in pole position to develop a world-class green energy manufacturing industry and provides a vital bridge for energy transition by repurposing existing ‘natural’ gas pipelines and fossil-fuel dependent ports.
In the past year numerous green hydrogen projects have been proposed primarily in Asia Europe Australia.
We estimate there are 50 viable projects globally announced in the past year with a total hydrogen production capacity of 4 million tons per annum and renewable power capacity of 50 gigawatts (GW) requiring capex of US$75bn.
The paper can be download on the IEEFA website
Cross-regional Drivers for CCUS Deployment
Jul 2020
Publication
CO2 capture utilization and storage (CCUS) is recognized as a uniquely important option in global efforts to control anthropogenic greenhouse-gas (GHG) emissions. Despite significant progress globally in advancing the maturity of the various component technologies and their assembly into full-chain demonstrations a gap remains on the path to widespread deployment in many countries. In this paper we focus on the importance of business models adapted to the unique technical features and sociopolitical drivers in different regions as a necessary component of commercial scale-up and how lessons might be shared across borders. We identify three archetypes for CCUS development—resource recovery green growth and low-carbon grids—each with different near-term issues that if addressed will enhance the prospect of successful commercial deployment. These archetypes provide a framing mechanism that can help to translate experience in one region or context to other locations by clarifying the most important technical issues and policy requirements. Going forward the archetype framework also provides guidance on how different regions can converge on the most effective use of CCUS as part of global deep-decarbonization efforts over the long term.
Study of the Microstructural and First Hydrogenation Properties of TiFe Alloy with Zr, Mn and V as Additives
Jul 2021
Publication
In this paper we report the effect of adding Zr + V or Zr + V + Mn to TiFe alloy on microstructure and hydrogen storage properties. The addition of only V was not enough to produce a minimum amount of secondary phase and therefore the first hydrogenation at room temperature under a hydrogen pressure of 20 bars was impossible. When 2 wt.% Zr + 2 wt.% V or 2 wt.% Zr + 2 wt.% V + 2 wt.% Mn is added to TiFe the alloy shows a finely distributed Ti2Fe-like secondary phase. These alloys presented a fast first hydrogenation and a high capacity. The rate-limiting step was found to be 3D growth diffusion controlled with decreasing interface velocity. This is consistent with the hypothesis that the fast reaction is likely to be the presence of Ti2Fe-like secondary phases that act as a gateway for hydrogen.
Measurement of Fatigue Crack Growth Rates for Steels in Hydrogen Containment Components
Sep 2009
Publication
The objective of this work was to enable the safe design of hydrogen pressure vessels by measuring the fatigue crack growth rates of ASME code-qualified steels in high-pressure hydrogen gas. While a design framework has recently been established for high-pressure hydrogen vessels a material property database does not exist to support the design calculations. This study addresses such voids in the database by measuring the fatigue crack growth rates of three different heats of ASME SA-372 Grade J steel in 100 MPa hydrogen gas. Results showed that the fatigue crack growth rates were similar for all three steel heats although the highest-strength steel appeared to exhibit the highest growth rates. Hydrogen accelerated the fatigue crack growth rates of the steels by as much as two orders of magnitude relative to anticipated crack growth rates in inert environments. Despite such dramatic effects of hydrogen on the fatigue crack growth rates measurement of these properties enables reliable definition of the design life of steel hydrogen containment vessels.
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.
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.
For a Successful Arrival of the Hydrogen Economy Improve Now the Confidence Level of Risk Assessments
Sep 2009
Publication
For large-scale distribution and use of energy carriers classified as hazardous material in many countries as a method to assist land use planning to grant licenses to design a safe installation and to operate it safely some form of risk analysis and assessment is applied. Despite many years of experience the methods have still their weaknesses even the most elaborated ones as e.g. shown by the large spread in results when different teams perform an analysis on a same plant as was done in EU projects. Because a fuel as hydrogen with its different properties will come new in the daily use of many people incidents may happen and risks will be discussed. HySafe and other groups take good preparatory action in this respect and work in the right direction as appears from various documents produced. However already a superficial examination of the results so far tells that further cooperative work is indispensable. To avoid criticism skepticism and frustration not only the positive findings should be described and general features of the methods but the community has also to give strong guidance with regard to the uncertainties. Scenario development appears to be very dependent on insight and experience of an individual analyst leak and ignition probability may vary over a wide range of values Computational Fluid Dynamics or CFD models may lead to very different result. The Standard Benchmark Exercise Problems SBEPs are a good start but shall produce guidelines or recommendations for CFD use or even perhaps certification of models. Where feasible narrowing of possible details of scenarios to the more probable ones taking into account historical incident data and schematizing in bowties more explicit use of confidence intervals on e.g. failure rates and ignition probability estimates will help. Further knowledge gaps should be defined.
Using Hydrogen Safety Best Practices and Learning From Safety Events
Sep 2009
Publication
A best practice is a technique or methodology that has reliably led to a desired result. A wealth of experience regarding the safe use and handling of hydrogen exists as a result of an extensive history in a wide variety of industrial and aerospace settings. Hydrogen Safety Best Practices (www.h2bestpractices.org) captures this vast knowledge base and makes it publicly available to those working with hydrogen and related systems including those just starting to work with hydrogen. This online manual is organized under a number of hierarchical technical content categories. References including publications and other online links that deal with the safety aspects of hydrogen are compiled for easy access. This paper discusses the development of Hydrogen Safety Best Practices as a safety knowledge tool the nature of its technical content and the steps taken to enhance its value and usefulness. Specific safety event examples are provided to illustrate the link between technical content in the online best practices manual and a companion safety knowledge tool Hydrogen Incident Reporting and Lessons Learned (www.h2incidents.org) which encourages the sharing of lessons learned and other safety event information.
Risk-Informed Separation Distances For Hydrogen Refuelling Stations
Sep 2007
Publication
The development of an infrastructure for the future hydrogen economy will require the simultaneous development of a set of codes and standards. As part of the U.S. Department of Energy Hydrogen Fuel Cells & Infrastructure Technologies Program Sandia National Laboratories is developing the technical basis for assessing the safety of hydrogen-based systems for use in the development/modification of relevant codes and standards. This work includes experimentation and modelling to understand the fluid mechanics and dispersion of hydrogen for different release scenarios including investigations of hydrogen combustion and subsequent heat transfer from hydrogen flames. The resulting technical information is incorporated into engineering models that are used for assessment of different hydrogen release scenarios and for input into quantitative risk assessments (QRA) of hydrogen facilities. The QRAs are used to identify and quantify scenarios for the unintended release of hydrogen and to identify the significant risk contributors at different types of hydrogen facilities. The results of the QRAs are one input into a risk-informed codes and standards development process that can also include other considerations by the code and standard developers. This paper describes an application of QRA methods to help establish one key code requirement: the minimum separation distances between a hydrogen refuelling station and other facilities and the public at large. An example application of the risk-informed approach has been performed to illustrate its utility and to identify key parameters that can influence the resulting selection of separation distances. Important parameters that were identified include the selected consequence measures and risk criteria facility operating parameters (e.g. pressure and volume) and the availability of mitigation features (e.g. automatic leak detection and isolation). The results also indicate the sensitivity of the results to key modelling assumptions and the component leakage rates used in the QRA models.
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.
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
Wide Area and Distributed Hydrogen Sensors
Sep 2009
Publication
Recent advances in optical sensors show promise for the development of new wide area monitoring and distributed optical network hydrogen detection systems. Optical hydrogen sensing technologies reviewed here are: 1) open path Raman scattering systems 2) back scattering from chemically treated solid polymer matrix optical fiber sensor cladding; and 3) schlieren and shearing interferometry imaging. Ultrasonic sensors for hydrogen release detection are also reviewed. The development status of these technologies and their demonstrated results in sensor path length low hydrogen concentration detection ability and response times are described and compared to the corresponding status of hydrogen spot sensor network technologies.
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.
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