France
HySafe European Network of Excellence on Hydrogen Safety
Sep 2005
Publication
Introduction and commercialisation of hydrogen as an energy carrier of the future make great demands on all aspects of safety. Safety is a critical issue for innovations as it influences the economic attractiveness and public acceptance of any new idea or product. However research and safety expertise related to hydrogen is quite fragmented in Europe. The vision of a significant increased use of hydrogen as an energy carrier in Europe could not go ahead without strengthening and merging this expertise. This was the reason for the European Commission to support the launch on the first of March 2004 of a so-called Network of Excellence (NoE) on hydrogen safety: HySafe.
Testing Safety of Hydrogen Components
Sep 2007
Publication
Hydrogen as a new and ecologic energy source is tempting though it creates the challenge of ensuring the safe use of hydrogen for all future consumers. Making sure that a hydrogen vehicle can be simply and safely used by anyone while performing as expected requires that the car be light with built-in safety features. This is achieved by combining high pressure composite cylinders with strict test procedures. Composite cylinders of up to 150 L operated to a maximum of 700 bar are required for vehicle applications. Air Liquide has developed test benches to hydraulically cycle such cylinders at 1400 bar and up to 3500 bar for burst tests. These tests are performed under controlled temperature conditions at ambient and extreme temperatures in order to simulate cylinder aging. Components in gas service such as valves hoses and other pressure devices are tested up to 1400 bars with hydrogen to simulate actual usage conditions. Hydrogen is used as a testing gas instead of nitrogen which is commonly used for such tests because hydrogen interacts with materials (e.g. hydrogen embrittlement) and because hydrogen has a special thermodynamic behaviour ( pressure drop velocity heat exchange…)
Impact of Hydrogen Admixture on Combustion Processes – Part I: Theory
Jun 2020
Publication
Climate change is one of today’s most pressing global challenges. Since the emission of greenhouse gases is often closely related to the use and supply of energy the goal to avoid emissions requires a fundamental restructuring of the energy system including all parts of the technology chains from production to end-use. Natural gas is today one of the most important primary energy sources in Europe with utilization ranging from power generation and industry to appliances in the residential and commercial sector as well as mobility. As natural gas is a fossil fuel gas utilization is thus responsible for significant emissions of carbon dioxide (CO2 ) a greenhouse gas. However the transformation of the gas sector with its broad variety of technologies and end-use applications is a challenge as a fuel switch is related to changing physical properties. Today the residential and commercial sector is the biggest end user sector for natural gas in the EU both in terms of consumption and in the number of installed appliances. Natural gas is used to provide space heating as well as hot water and is used in cooking and catering appliances with in total about 200 million gas-fired residential and commercial end user appliances installed. More than 40 % of the EU gas consumption is accounted for by the residential and commercial sector. The most promising substitutes for natural gas are biogases and hydrogen. The carbon-free fuel gas hydrogen may be produced e.g. from water and renewable electricity; therefore it can be produced with a greatly lowered carbon footprint and on a very large scale. As a gaseous fuel it can be transported stored and utilised in all end-use sectors that are served by natural gas today: Power plants industry commercial appliances households and mobility. Technologies and materials however need to be suitable for the new fuel. The injection of hydrogen into existing gas distribution for example will impact all gas-using equipment in the grids since these devices are designed and optimized to operate safely efficiently and with low pollutant emissions with natural gas as fuel. The THyGA project1 focusses on all technical aspects and the regulatory framework concerning the potential operation of domestic and commercial end user appliances with hydrogen / natural gas blends. The THyGA deliverables start with theoretical background from material science (D2.4) and combustion theory (this report) and extend to the project’s experimental campaign on hydrogen tolerance tests as well as reports on the status quo and potential future developments on rules and standards as well as mitigation strategies for coping with high levels of hydrogen admixture. By this approach the project aims at investigating which levels of hydrogen blending impact the various appliance technologies to which extent and to identify the regime in which a safe efficient and low-polluting operation is possible. As this is in many ways a question of combustion this report focuses on theoretical considerations about the impact of hydrogen admixture on combustion processes. The effects of hydrogen admixture on main gas quality properties as well as combustion temperatures laminar combustion velocities pollutant formation (CO NOx) safety-related aspects and the impact of combustion control are discussed. This overview provides a basis for subsequent steps of the project e.g. for establishing the testing program. A profound understanding of the impact on hydrogen on natural gas combustion is also essential for the development of mitigation strategies to reduce potential negative consequences of hydrogen admixture on appliances.
This is part one. Part two of this project can be found at this link
This is part one. Part two of this project can be found at this link
Modelling of H2 Dispersion and Combustion Phenomena Using CFD Codes
Sep 2005
Publication
Computational Fluid Dynamics codes are increasingly being considered for safety assessment demonstrations in many industrial fields as tools to model accidental phenomena and to design mitigation (risk reducing) systems. Thus they naturally complement experimental programmes which may be expensive to run or difficult to set up. However to trust numerical simulations the validity of the codes must be firmly established and a certain number of error sources (user effect modelling errors discretization errors etc) reduced to the minimum. Code validation and establishment of “best practice guidelines” in the application of simulation tools to hydrogen safety assessment are some of the objectives pursued by the HYSAFE Network of Excellence. This paper will contribute to these goals by describing some of the validation efforts that CEA is making in the areas of release dispersion combustion and mitigation thereby proposing the outline of a validation matrix for hydrogen safety problems.
Vented Explosion of Hydrogen/Air Mixtures: Influence of Vent Cover and Stratification
Sep 2017
Publication
Explosion venting is a prevention/mitigation solution widely used in the process industry to protect indoor equipment or buildings from excessive internal pressure caused by an accidental explosion. Vented explosions are widely investigated in the literature for various geometries hydrogen/air concentrations ignition positions initial turbulence etc. In real situations the vents are normally covered by a vent panel. In the case of an indoor leakage the hydrogen/air cloud will be stratified rather than homogeneous. Nowadays there is a lack in understanding about the vented explosion of stratified clouds and about the influence of vent cover inertia on the internal overpressure. This paper aims at shedding light on these aspects by means of experimental investigation of vented hydrogen/air deflagration using an experimental facility of 1m3 and via numerical simulations using the computational fluid dynamics (CFD) code FLACS
Highly Resolve Large Eddy Simulations of a Transitional Air-helium Buoyant Jet in a Two Vented Enclosure: Validation Against Particle Image Velocimetry Experiments
Sep 2017
Publication
The article deals with LES simulations of an air-helium buoyant jet in a two vented enclosure and their validation against particle image velocimetry experiments. The main objective is to test the ability of LES models to simulate such scenarios. These types of scenarios are of first interest considering safety studies for new hydrogen systems. Three main challenges are identified. The two first are the ability of the LES model to account for a rapid laminar-to-turbulence transition mainly due to the buoyancy accelerations and the Rayleigh-Taylor instabilities that can develop due to sharp density gradients. The third one is the outlet boundary conditions to be imposed on the vent surfaces. The influence of the classical pressure boundary condition is studied by comparing the simulations results when an exterior region is added in the simulations. The comparisons against particle image velocimetry experiments show that the use of an exterior domain gives more accurate results than the classical pressure boundary condition. This result and the description of the phenomena involved are the main outlets of the article.
Failure of PEM Water Electrolysis Cells: Case Study Involving Anode Dissolution and Membrane Thinning
Sep 2013
Publication
Polymer electrolyte membrane (PEM) water electrolysis is an efficient and environmental friendly method that can be used for the production of molecular hydrogen of electrolytic grade using zero-carbon power sources such as renewable and nuclear. However market applications are asking for cost reduction and performances improvement. This can be achieved by increasing operating current density and lifetime of operation. Concerning performance safety reliability and durability issues the membrane-electrode assembly (MEA) is the weakest cell component. Most performance losses and most accidents occurring during PEM water electrolysis are usually due to the MEA. The purpose of this communication is to report on some specific degradation mechanisms that have been identified as a potential source of performance loss and membrane failure. An accelerated degradation test has been performed on a MEA by applying galvanostatic pulses. Platinum has been used as electrocatalyst at both anode and cathode in order to accelerate degradation rate by maintaining higher cell voltage and higher anodic potential that otherwise would have occurred if conventional Ir/IrOx catalysts had been used. Experimental evidence of degradation mechanisms have been obtained by post-mortem analysis of the MEA using microscopy and chemical analysis. Details of these degradation processes are presented and discussed.
Quantifying the Hydrogen Embrittlement of Pipeline Steels for Safety Considerations
Sep 2011
Publication
In a near future with an increasing use of hydrogen as an energy vector gaseous hydrogen transport as well as high capacity storage may imply the use of high strength steel pipelines for economical reasons. However such materials are well known to be sensitive to hydrogen embrittlement (HE). For safety reasons it is thus necessary to improve and clarify the means of quantifying embrittlement. The present paper exposes the changes in mechanical properties of a grade API X80 steel through numerous mechanical tests i.e. tensile tests disk pressure test fracture toughness and fatigue crack growth measurements WOL tests performed either in neutral atmosphere or in high-pressure of hydrogen gas. The observed results are then discussed in front of safety considerations for the redaction of standards for the qualification of materials dedicating to hydrogen transport.
Threshold Stress Intensity Factor for Hydrogen Assisted Cracking of Cr-Mo Steel Used as Stationary Storage Buffer of a Hydrogen Refueling Station
Oct 2015
Publication
In order to determine appropriate value for threshold stress intensity factor for hydrogen-assisted cracking (KIH) constant-displacement and rising-load tests were conducted in high-pressure hydrogen gas for JIS-SCM435 low alloy steel (Cr-Mo steel) used as stationary storage buffer of a hydrogen refuelling station with 0.2% proof strength and ultimate tensile strength equal to 772 MPa and 948 MPa respectively. Thresholds for crack arrest under constant displacement and for crack initiation under rising load were identified. The crack arrest threshold under constant displacement was 44.3 MPa m1/2 to 44.5 MPa m1/2 when small-scale yielding and plane-strain criteria were satisfied and the crack initiation threshold under rising load was 33.1 MPa m1/2 to 41.1 MPa m1/2 in 115 MPa hydrogen gas. The crack arrest threshold was roughly equivalent to the crack initiation threshold although the crack initiation threshold showed slightly more conservative values. It was considered that both test methods could be suitable to determine appropriate value for KIH for this material.
Hydrogen Safety Aspects Related to High Pressure - PEM Water Electrolysis
Sep 2007
Publication
Polymer electrolyte membrane (PEM) water electrolysis has demonstrated its potentialities in terms of cell efficiency (energy consumption ≈ 4.0-4.2 kW/Nm3 H2) and gas purity (> 99.99% H2). Current research activities are aimed at increasing operating pressure up to several hundred bars for direct storage of hydrogen in pressurized vessels. Compared to atmospheric pressure electrolysis high-pressure operation yields additional problems especially with regard to safety considerations. In particular the rate of gases (H2 and O2) cross-permeation across the membrane and their water solubility both increase with pressure. As a result gas purity is affected in both anodic and cathodic circuits and this can lead to the formation of explosive gas mixtures. To prevent such risks two different solutions reported in this communication have been investigated. First the chemical modification of the solid polymer electrolyte in order to reduce cross-permeation phenomena. Second the use of catalytic H2/O2 recombiners to maintain H2 levels in O2 and O2 levels in H2 at values compatible with safety requirements.
Engineering Safety in Hydrogen-Energy Applications
Oct 2015
Publication
Since a few years hydrogen appears as a practical energy vector and some hydrogen applications are already on the market. However these applications are still considered dangerous hazardous events like explosion could occur and some accidents like the Hindenburg disaster are still in the mind. Objectively hydrogen ignites easily and explodes violently. Safety engineering has to be particularly strong and demonstrative; a method of precise identification of accidental scenarios (“probabilities”; “severity”) is developed in this article. This method derived from ARAMIS method permits to identify and to estimate the most relevant safety barriers and therefore helps future users choose appropriate safety strategies.
Estimation of an Allowable Hydrogen Permeation Rate From Road Vehicle Compressed Gaseous H2 Storage Systems In Typical Garages, Part 2: CFC Dispersion Calculations Using the ADREA-HF Code and Experimental Validation Using Helium Tests at the Garage Facility
Sep 2009
Publication
The time and space evolution of the distribution of hydrogen in confined settings was investigated computationally and experimentally for permeation from typical compressed gaseous hydrogen storage systems for buses or cars. The work was performed within the framework of the InsHyde internal project of the HySafe NoE funded by EC. The main goal was to examine whether hydrogen is distributed homogeneously within a garage like facility or whether stratified conditions are developed under certain conditions. The nominal hydrogen flow rate considered was 1.087 NL/min based on the then current SAE standard for composite hydrogen containers with a non-metallic liner (type 4) at simulated end of life and maximum material temperature in a bus facility with a volume of 681m3. The release was assumed to be directed upwards from a 0.15m diameter hole located at the middle part of the bus cylinders casing. Ventilation rates up to 0.03 ACH were considered. Simulated time periods extended up to 20 days. The CFD simulations performed with the ADREA-HF code showed that fully homogeneous conditions exist for low ventilation rates while stratified conditions prevail for higher ventilation rates. Regarding flow structure it was found that the vertical concentration profiles can be considered as the superposition of the concentration at the floor (driven by laminar diffusion) plus a concentration difference between floor and ceiling (driven by buoyancy forces). In all cases considered this concentration difference was found to be less than 0.5%. The dispersion experiments were performed at the GARAGE facility using Helium. Comparison between CFD simulations and experiments showed that the predicted concentrations were in good agreement with the experimental data. Finally simulations were performed using two integral models: the fully homogeneous model and the two-layer model proposed by Lowesmith et al. (ICHS-2 2007) and the results were compared both against CFD and the experimental data.
Comparative Study of Regulations, Codes and Standards and Practices on Hydrogen Fuelling Stations
Oct 2015
Publication
This work deals with a comparative study of regulations codes and standards for hydrogen fuelling station dedicated for light duty land vehicles in the following countries: United States (California) United Kingdom Italy Germany Canada Sweden Norway Denmark and Spain.<br/>The following technical components of a hydrogen fuelling station are included in the scope of the study: the hydrogen storage systems (cryogenic or compressed gases) and buffer storage the compressor stations the high pressure buffer storage the cooling systems for hydrogen the dispensing equipments and the dispensing area. The hydride storage the pipelines on site production and the hydrogen vehicle have been excluded.<br/>The analysis performed in September 2014 in a report from INERIS DRA-14-141532-06227C BENCHMARK STATIONS-SERVICE HYDROGENE is based on documents collected by bibliographic review and information obtained through a questionnaire sent to authorities and IA HySafe members in the above mentioned countries.<br/>This paper gives a synthesis of the regulations and on permitting process in the different studied countries (including the new European Directive on the deployment of alternative fuels infrastructure in Europe) it develops the required safety barriers in the different parts of a fuelling station and specially for the dispensing area gives an overview of the different approaches for safety distances and processes to obtain licences to operate.
Hydrogen Storage: Recent Improvements and Industrial Prospective
Oct 2015
Publication
Efficient storage of hydrogen is crucial for the success of hydrogen energy markets (early markets as well as transportation market). Hydrogen can be stored either as a compressed gas a refrigerated liquefied gas a cryo-compressed gas or in hydrides. This paper gives an overview of hydrogen storage technologies and details the specific issues and constraints related to the materials behaviour in hydrogen and conditions representative of hydrogen energy uses. It is indeed essential for the development of applications requiring long-term performance to have good understanding of long-term behaviour of the materials of the storage device and its components under operational loads.
Explosion and Fire Risk Analyses of Maritime Fuel Cell Rooms with Hydrogen
Sep 2017
Publication
A methodology for explosion and fire risk analyses in enclosed rooms is presented. The objectives of this analysis are to accurately predict the risks associated with hydrogen leaks in maritime applications and to use the approach to provide decision support regarding design and risk-prevention and risk mitigating measures. The methodology uses CFD tools and simpler consequence models for ventilation dispersion and explosion scenarios as well as updated frequency for leaks and ignition. Risk is then efficiently calculated with a Monte Carlo routine capturing the transient behavior of the leak. This makes it possible to efficiently obtain effects of sensitivities and design options maintaining safety and reducing costs.
Comparison of Two Simplified Models Predictions with Experimental Measurements for Gas Release Within an Enclosure
Sep 2009
Publication
In this work the validity of simplified mathematical models for predicting dispersion of turbulent buoyant jet or plume within a confined volume is evaluated. In the framework of the HYSAFE Network of Excellence CEA performed experimental tests in a full-scale Garage facility in order to reproduce accidental gas leakages into an unventilated residential garage. The effects of release velocities diameters durations mass flow rates and flow regimes on the vertical distribution of the gas concentration are investigated. Experimental data confirm the formation for the release conditions of an almost well-mixed upper layer and a stratified lower layer. The comparison of the measurements and the model predictions shows that a good agreement is obtained for a relatively long-time gas discharge for jet like or plume like flow behaviour.
Study of Potential Leakage on Several Stressed Fittings for Hydrogen Pressures Up To 700 Bar
Sep 2011
Publication
In order to improve risk analyses and influence the design of the future H2 systems an experimental study on “real” leaks qualification and quantification was performed. In H2 energy applications fittings appeared as a significant leakage potential and subsequently explosion and flame hazards. Thus as a part of the “Horizon Hydrogène Energie” French program four kinds of commercial fittings usually employed on H2 systems were tested thanks to a new high pressure test bench – designed setup and operated by INERIS – allowing experiments to be led for H2 pressures until 700 bar. The fittings underwent defined stresses representative of H2 systems lifetime and beyond. The associated leaks – when existing – are characterized in terms of flow rate.
Processes of the Formation of Large Unconfined Clouds Following a Massive Spillage of Liquid Hydrogen on the Ground
Sep 2007
Publication
Because of hydrogen low volumetric energy content under its gaseous form transport and storage of liquid hydrogen will certainly play a major role in any future hydrogen economy. One of the obstacles to the expected development use of hydrogen is the poor state of knowledge on explosion risks in the event of an extensive spillage. INERIS set up a large-scale experiment to study the mechanisms of the formation of the gas cloud resulting from such a spillage and the associated mixing process and turbulence effects. Dispersion tests have been performed with cryogenic helium presenting similar dispersion characteristics than liquid hydrogen (buoyancy). Flowrates up to 3 kg/s have been investigated and the instrumentation allowed the observation and quantification of bouyancy effects including internal turbulence. Those results constitute an originals et of data which can be used as a basis for the development of dispersion software and reinterpretation of other existing databases ([10 11])
Non-combustion Related Impact of Hydrogen Admixture - Material Compatibility
Jun 2020
Publication
The present document is part of a larger literature survey of this WP aiming to establish the current status of gas utilisation technologies in order to determine the impact of hydrogen (H2) admixture on natural gas (NG) appliances. This part focuses on the non-combustion related aspects of injecting hydrogen in the gas distribution networks within buildings including hydrogen embrittlement of metallic materials chemical compatibility and leakage issues. In the particular conditions of adding natural gas and hydrogen (NG / H2) mixture into a gas distribution network hydrogen is likely to reduce the mechanical properties of metallic components. This is known as hydrogen embrittlement (HE) (Birnbaum 1979). This type of damage takes place once a critical level of stress / strain and hydrogen content coexist in a susceptible microstructure. Currently four mechanisms were identified and will be discussed in detail. The way those mechanisms act independently or together is strongly dependent on the material the hydrogen charging procedure and the mechanical loading type. The main metallic materials used in gas appliances and gas distribution networks are: carbon steels stainless steels copper brass and aluminium alloys (Thibaut 2020). The presented results showed that low alloy steels are the most susceptible materials to hydrogen embrittlement followed by stainless steels aluminium copper and brass alloys. However the relative pressures of the operating conditions of gas distribution network in buildings are low i.e. between 30 to 50 mbar. At those low hydrogen partial pressures it is assumed that a gas mixture composed of NG and up to 50% H2 should not be problematic in terms of HE for any of the metallic materials used in gas distribution network unless high mechanical stress / strain and high stress concentrations are applied. The chemical compatibility of hydrogen with other materials and specifically polyethylene (PE) which is a reference material for the gas industry is also discussed. PE was found to have no corrosion issues and no deterioration or ageing was observed after long term testing in hydrogen gas. The last non-combustion concern related to the introduction of hydrogen in natural gas distribution network is the propensity of hydrogen toward leakage. Indeed the physical properties of hydrogen are different from other gases such as methane or propane and it was observed that hydrogen leaks 2.5 times quicker than methane. This bibliographical report on material deterioration chemical compatibility and leakage concerns coming with the introduction of NG / H2 mixture in the gas distribution network sets the basis for the upcoming experimental work where the tightness of gas distribution network components will be investigated (Task 3.2.3 WP3). In addition tightness of typical components that connect end-user appliances to the local distribution line shall be evaluated as well.
Assessing the Durability and Integrity of Natural Gas Infrastructures for Transporting and Distributing Mixtures of Hydrogen and Natural Gas
Sep 2005
Publication
Extensive infrastructure exists for the transport of natural gas and it is an obvious step to assess its use for the movement of hydrogen. The Naturalhy project’s objective is to prepare the European natural gas industry for the introduction of hydrogen by assessing the capability of the natural gas infrastructure to accept mixtures of hydrogen and natural gas. This paper presents the ongoing work within both Durability and Integrity Work Packages of the Naturalhy project. This work covers a gap in knowledge on risk assessment required for delivering H2+natural gas blends by means of the existing natural gas grids in safe operation.<br/>Experiments involving several parts of the existing infrastructure will be described that are being carried out to re-examine the major risks previously studied for natural gas including: effect of H2 on failure behaviour and corrosion of transmission pipes and their burst resistance (link to the Work Package Safety) on permeability and ageing of distribution pipes on reliability and ageing of domestic gas meters tightness to H2 of domestic appliances and their connexions. The information will be integrated into existing Durability assessment methodologies originally developed for natural gas.<br/>An Integrity Management Tool will be developed taking account of the effect of hydrogen on the materials properties. The tool should enable a cost effective selection of appropriate measures to control the structural integrity and maintaining equipment. The main measures considered are monitoring non destructive examination (pigging and non pigging) and repair strategies. The tool will cover a number of parameters e.g.: percentage of hydrogen in the gas mixture material of construction operating conditions and condition of cathodic protection. Thus the Integrity Management Tool will yield an inspection and maintenance plan based on the specific circumstances.
Massive H2 Production With Nuclear Heating, Safety Approach For Coupling A VHTR With An Iodine Sulfur Process Cycle
Sep 2005
Publication
In the frame of a sustainable development investigations dealing with massive Hydrogen production by means of nuclear heating are carried out at CEA. For nuclear safety thermodynamic efficiency and waste minimization purposes the technological solution privileged is the coupling of a gas cooled Very High Temperature Reactor (VHTR) with a plant producing Hydrogen from an Iodine/Sulfur (I/S) thermochemical cycle. Each of the aforementioned facilities presents different risks resulting from the operation of a nuclear reactor (VHTR) and from a chemical plant including Hydrogen other flammable and/or explosible substances as well as toxic ones. Due to these various risks the safety approach is an important concern. Therefore this paper deals with the preliminary CEA investigations on the safety issues devoted to the whole plant focusing on the safety questions related to the coupling between the nuclear reactor and the Hydrogen production facility. Actually the H2 production process and the energy distribution network between the plants are currently at a preliminary design stage. A general safety approach is proposed based on a Defence In Depth (DID) principle permitting to analyze all the system configurations successively in normal incidental and accidental expected operating conditions. More precisely the dynamic answer of an installation to a perturbation affecting the other one during the previous conditions as well as the potential aggressions of the chemical plant towards the nuclear reactor have to be considered. The methodology presented in this paper is intended to help the designer to take into account the coupling safety constraints and to provide some recommendations on the global architecture of both plants especially on their coupling system. As a result the design of a VHTR combined to a H2 production process will require an iterative process between design and safety requirements.
Validation and Recommendations for CFD and Engineering Modeling of Hydrogen Vented Explosions: Effects of Concentration, Stratification, Obstruction and Vent Area
Oct 2015
Publication
Explosion venting is commonly used in the process industry as a prevention solution to protect equipment or buildings against excessive internal pressure caused by an explosion. This article is dedicated to the validation of FLACS CFD code for the modelling of vented explosions. Analytical engineering models fail when complex cases are considered for instance in the presence of obstacles or H2 stratified mixtures. CFD is an alternative solution but has to be carefully validated. In this study FLACS simulations are compared to published experimental results and recommendations are suggested for their application.
On the Use of Hydrogen in Confined Spaces: Results from the Internal Project InsHyde
Sep 2009
Publication
Alexandros G. Venetsanos,
Paul Adams,
Inaki Azkarate,
A. Bengaouer,
Marco Carcassi,
Angunn Engebø,
E. Gallego,
Olav Roald Hansen,
Stuart J. Hawksworth,
Thomas Jordan,
Armin Keßler,
Sanjay Kumar,
Vladimir V. Molkov,
Sandra Nilsen,
Ernst Arndt Reinecke,
M. Stöcklin,
Ulrich Schmidtchen,
Andrzej Teodorczyk,
D. Tigreat,
N. H. A. Versloot and
L. Boon-Brett
The paper presents an overview of the main achievements of the internal project InsHyde of the HySafe NoE. The scope of InsHyde was to investigate realistic small-medium indoor hydrogen leaks and provide recommendations for the safe use/storage of indoor hydrogen systems. Additionally InsHyde served to integrate proposals from HySafe work packages and existing external research projects towards a common effort. Following a state of the art review InsHyde activities expanded into experimental and simulation work. Dispersion experiments were performed using hydrogen and helium at the INERIS gallery facility to evaluate short and long term dispersion patterns in garage like settings. A new facility (GARAGE) was built at CEA and dispersion experiments were performed there using helium to evaluate hydrogen dispersion under highly controlled conditions. In parallel combustion experiments were performed by FZK to evaluate the maximum amount of hydrogen that could be safely ignited indoors. The combustion experiments were extended later on by KI at their test site by considering the ignition of larger amounts of hydrogen in obstructed environments outdoors. An evaluation of the performance of commercial hydrogen detectors as well as inter-lab calibration work was jointly performed by JRC INERIS and BAM. Simulation work was as intensive as the experimental work with participation from most of the partners. It included pre-test simulations validation of the available CFD codes against previously performed experiments with significant CFD code inter-comparisons as well as CFD application to investigate specific realistic scenarios. Additionally an evaluation of permeation issues was performed by VOLVO CEA NCSRD and UU by combining theoretical computational and experimental approaches with the results being presented to key automotive regulations and standards groups. Finally the InsHyde project concluded with a public document providing initial guidance on the use of hydrogen in confined spaces.
An Intercomparison Exercise on the Capabilities of CFD Models to Predict Distribution and Mixing of H2 in a Closed Vessel.
Sep 2005
Publication
This paper presents a compilation and discussion of the results supplied by HySafe partners participating in the Standard Benchmark Exercise Problem (SBEP) V1 which is based on an experiment on hydrogen release mixing and distribution inside a vessel. Each partner has his own point of view of the problem and uses a different approach to the solution. The main characteristics of the models employed for the calculations are compared. The comparison between results together with the experimental data when available is made. Relative deviations of each model from the experimental values are also included. Explanations and interpretations of the results are presented together with some useful conclusions for future work.
An Inter-Comparison Exercise on the Capabilities of CFD Models to Predict the Short and Long Term Distribution and Mixing of Hydrogen in a Garage
Sep 2007
Publication
Alexandros G. Venetsanos,
E. Papanikolaou,
J. García,
Olav Roald Hansen,
Matthias Heitsch,
Asmund Huser,
Wilfried Jahn,
Jean-Marc Lacome,
Thomas Jordan,
H. S. Ledin,
Dmitry Makarov,
Prankul Middha,
Etienne Studer,
Andrei V. Tchouvelev,
Franck Verbecke,
M. M. Voort,
Andrzej Teodorczyk and
M. A. Delichatsios
The paper presents the results of the CFD inter-comparison exercise SBEP-V3 performed within the activity InsHyde internal project of the HYSAFE network of excellence in the framework of evaluating the capability of various CFD tools and modelling approaches in predicting the physical phenomena associated to the short and long term mixing and distribution of hydrogen releases in confined spaces. The experiment simulated was INERIS-TEST-6C performed within the InsHyde project by INERIS consisting of a 1 g/s vertical hydrogen release for 240 s from an orifice of 20 mm diameter into a rectangular room (garage) of dimensions 3.78x7.2x2.88 m in width length and height respectively. Two small openings at the front and bottom side of the room assured constant pressure conditions. During the test hydrogen concentration time histories were measured at 12 positions in the room for a period up to 5160 s after the end of release covering both the release and the subsequent diffusion phases. The benchmark was organized in two phases. The first phase consisted of blind simulations performed prior to the execution of the tests. The second phase consisted of post calculations performed after the tests were concluded and the experimental results made available. The participation in the benchmark was high: 12 different organizations (2 non-HYSAFE partners) 10 different CFD codes and 8 different turbulence models. Large variation in predicted results was found in the first phase of the benchmark between the various modelling approaches. This was attributed mainly to differences in turbulence models and numerical accuracy options (time/space resolution and discretization schemes). During the second phase of the benchmark the variation between predicted results was reduced.
On Numerical Simulation of Liquefied and Gaseous Hydrogen Releases at Large Scales
Sep 2005
Publication
The large eddy simulation (LES) model developed at the University of Ulster has been applied to simulate releases of 5.11 m3 liquefied hydrogen (LH2) in open atmosphere and gaseous hydrogen (GH2) in 20-m3 closed vessel. The simulations of a spill of liquefied hydrogen confirmed the advantage of LES application to reproduce experimentally observed eddy structure of hydrogen-air cloud. The inclination angle of simulated cloud is close to experimentally reported 300. The processes of two phase hydrogen release and heat transfer were simplified by inflow of gaseous hydrogen with temperature 20 K equal to boiling point. It is shown that difference in inflow conditions geometry and grid resolution affects simulation results. It is suggested that phenomenon of air condensationevaporation in the cloud in temperature range 20-90 K should be accounted for in future. The simulations reproduced well experimental data on GH2 release and transport in 20-m3 vessel during 250 min including a phenomenon of hydrogen concentration growth at the bottom of the vessel. Higher experimental hydrogen concentration at the bottom is assumed to be due to non-uniformity of temperature of vessel walls generating additional convection. The comparison of convective and diffusion terms in Navie-Stokes equations has revealed that a value of convective term is more than order of magnitude prevail over a value of turbulent diffusion term. It is assumed that the hydrogen transport to the bottom of the vessel is driven by the remaining chaotic flow velocities superimposed on stratified hydrogen concentration field. Further experiments and simulations with higher accuracy have to be performed to confirm this phenomenon. It has been demonstrated that hydrogen-air mixture became stratified in about 1 min after release was completed. However one-dimensional models are seen not capable to reproduce slow transport of hydrogen during long period of time characteristic for scenarios such as leakage in a garage.
Numerical Study of the Near-field of Highly Under-expanded Turbulent Gas Jets
Sep 2011
Publication
For safety issues related to the storage of hydrogen under high pressure it is necessary to determine how the gas is released in the case of failure. In particular there exist limited quantitative information on the near-field properties of the gas jets which are important for establishing proper decay laws in the far-field. This paper reports recent CFD results for air and helium obtained in the near-field of the highly under-expanded jets. The gas jets are released from a 30-bar tank with the same opening (orifice). The Reynolds number based on the diameter of the orifice and corresponding gas conditions at the exit was well beyond 106 . The 3D Compressible Multi-Component Navier-Stokes equations were solved directly without relying on the compressibility-corrected turbulence models. The numerical model was initially tested on a one-component (air-air) case where a few aerospace-driven data sets are available for validation. The shock geometry is characterized through the Mach disk position and diameter. These are compared to the results known from the literature and to the scaling laws developed based on the dimensional analysis. In the second two-component (helium-air) jet scenario the density field was validated and examined together with other fields in the attempt to suggest potential initial conditions for the forthcoming far-field simulations.
Batteries and Hydrogen Technology: Keys for a Clean Energy Future
May 2020
Publication
As governments focus on dealing with the Covid-19 health emergency they are increasingly turning their attention to the impact of shutting down their economies and how to revive them quickly through stimulus measures. Economic recovery packages offer a unique opportunity to create jobs while supporting clean energy transitions around the world.
Energy efficiency and renewable energy like wind and solar PV – the cornerstones of any clean energy transition – are good places to start. Those industries employ millions of people across their value chains and offer environmentally sustainable ways to create jobs and help revitalise the global economy.
But more than just renewables and efficiency will be required to put the world on track to meet climate goals and other sustainability objectives. IEA analysis has repeatedly shown that a broad portfolio of clean energy technologies will be needed to decarbonise all parts of the economy. Batteries and hydrogen-producing electrolysers stand out as two important technologies thanks to their ability to convert electricity into chemical energy and vice versa. This is why they also deserve a place in any economic stimulus packages being discussed today.
Link to Document on IEA Website
Energy efficiency and renewable energy like wind and solar PV – the cornerstones of any clean energy transition – are good places to start. Those industries employ millions of people across their value chains and offer environmentally sustainable ways to create jobs and help revitalise the global economy.
But more than just renewables and efficiency will be required to put the world on track to meet climate goals and other sustainability objectives. IEA analysis has repeatedly shown that a broad portfolio of clean energy technologies will be needed to decarbonise all parts of the economy. Batteries and hydrogen-producing electrolysers stand out as two important technologies thanks to their ability to convert electricity into chemical energy and vice versa. This is why they also deserve a place in any economic stimulus packages being discussed today.
Link to Document on IEA Website
Fuel Cell Electric Vehicles—A Brief Review of Current Topologies and Energy Management Strategies
Jan 2021
Publication
With the development of technologies in recent decades and the imposition of international standards to reduce greenhouse gas emissions car manufacturers have turned their attention to new technologies related to electric/hybrid vehicles and electric fuel cell vehicles. This paper focuses on electric fuel cell vehicles which optimally combine the fuel cell system with hybrid energy storage systems represented by batteries and ultracapacitors to meet the dynamic power demand required by the electric motor and auxiliary systems. This paper compares the latest proposed topologies for fuel cell electric vehicles and reveals the new technologies and DC/DC converters involved to generate up-to-date information for researchers and developers interested in this specialized field. From a software point of view the latest energy management strategies are analyzed and compared with the reference strategies taking into account performance indicators such as energy efficiency hydrogen consumption and degradation of the subsystems involved which is the main challenge for car developers. The advantages and disadvantages of three types of strategies (rule-based strategies optimization-based strategies and learning-based strategies) are discussed. Thus future software developers can focus on new control algorithms in the area of artificial intelligence developed to meet the challenges posed by new technologies for autonomous vehicles.
Worst Case Scenario for Delayed Explosion of Hydrogen Jets at a High Pressure: Ignition Position
Sep 2021
Publication
Delayed explosion of free field hydrogen releases at a high pressure is subject of multiple investigation performed by various authors in the past years. These studied considered various parameters such as pressures flow rates etc. and their influence on the resulting overpressure. However the influence of the ignition position on the maximum overpressure was not fully explored. Current investigation addressed by computational fluid dynamics (CFD) simulations and experimental measurement fills this gap. This work demonstrates that the ignition positions corresponding to 55%-65% of H2/air mixture give the maximum overpressure. This observation initially observed numerically and afterword confirmed experimentally. A simple model is also suggested.
Using Additives to Control the Decomposition Temperature of Sodium Borohydride
May 2020
Publication
Hydrogen (H2) shows great promise as zero-carbon emission fuel but there are several challenges to overcome in regards to storage and transportation to make it a more universal energy solution. Gaseous hydrogen requires high pressures and large volume tanks while storage of liquid hydrogen requires cryogenic temperatures; neither option is ideal due to cost and the hazards involved. Storage in the solid state presents an attractive alternative and can meet the U.S. Department of Energy (DOE) constraints to find materials containing > 7 % H2 (gravimetric weight) with a maximum H2 release under 125 °C.
While there are many candidate hydrogen storage materials the vast majority are metal hydrides. Of the hydrides this review focuses solely on sodium borohydride (NaBH4) which is often not covered in other hydride reviews. However as it contains 10.6% (by weight) H2 that can release at 133 ± 3 JK−1mol−1 this inexpensive material has received renewed attention. NaBH4 should decompose to H2g) Na(s) and B(s) and could be recycled into its original form. Unfortunately metal to ligand charge transfer in NaBH4 induces high thermodynamic stability creating a high decomposition temperature of 530 °C. In an effort make H2 more accessible at lower temperatures researchers have incorporated additives to destabilize the structure.
This review highlights metal additives that have successfully reduced the decomposition temperature of NaBH4 with temperatures ranging from 522 °C (titanium (IV) fluoride) to 379 °C (niobium (V) fluoride). We describe synthetic methods employed chemical pathways taken and the challenges of boron derivative formation on H2 cycling. Though no trends can be found across all additives it is our hope that compiling the data here will enable researchers to gain a better understanding of the additives’ influence and to determine how a new system might be designed to make NaBH4 a more viable H2 fuel source.
While there are many candidate hydrogen storage materials the vast majority are metal hydrides. Of the hydrides this review focuses solely on sodium borohydride (NaBH4) which is often not covered in other hydride reviews. However as it contains 10.6% (by weight) H2 that can release at 133 ± 3 JK−1mol−1 this inexpensive material has received renewed attention. NaBH4 should decompose to H2g) Na(s) and B(s) and could be recycled into its original form. Unfortunately metal to ligand charge transfer in NaBH4 induces high thermodynamic stability creating a high decomposition temperature of 530 °C. In an effort make H2 more accessible at lower temperatures researchers have incorporated additives to destabilize the structure.
This review highlights metal additives that have successfully reduced the decomposition temperature of NaBH4 with temperatures ranging from 522 °C (titanium (IV) fluoride) to 379 °C (niobium (V) fluoride). We describe synthetic methods employed chemical pathways taken and the challenges of boron derivative formation on H2 cycling. Though no trends can be found across all additives it is our hope that compiling the data here will enable researchers to gain a better understanding of the additives’ influence and to determine how a new system might be designed to make NaBH4 a more viable H2 fuel source.
Hydrogen Fuel Cell Road Vehicles and Their Infrastructure: An Option Towards an Environmentally Friendly Energy Transition
Nov 2020
Publication
The latest pre-production vehicles on the market show that the major technical challenges posed by integrating a fuel cell system (FCS) within a vehicle—compactness safety autonomy reliability cold starting—have been met. Regarding the ongoing maturity of fuel cell systems dedicated to road transport the present article examines the advances still needed to move from a functional but niche product to a mainstream consumer product. It seeks to address difficulties not covered by more traditional innovation approaches. At least in long-distance heavy-duty vehicles fuel cell vehicles (FCVs) are going to play a key role in the path to zero-emissions in one or two decades. Hence the present study also addresses the structuring elements of the complete chain: the latter includes the production storage and distribution of hydrogen. Green hydrogen appears to be one of the potential uses of renewable energies. The greener the electricity is the greater the advantage for hydrogen since it permits to economically store large energy quantities on seasonal rhythms. Moreover natural hydrogen might also become an economic reality pushing the fuel cell vehicle to be a competitive and environmentally friendly alternative to the battery electric vehicle. Based on its own functional benefits for on board systems hydrogen in combination with the fuel cell will achieve a large-scale use of hydrogen in road transport as soon as renewable energies become more widespread. Its market will expand from large driving range and heavy load vehicles
Building an Optimal Hydrogen Transportation System for Mobility, Focus on Minimizing the Cost of Transportation via Truck
Jan 2018
Publication
The approach developed aims to identify the methodology that will be used to deliver the minimum cost for hydrogen infrastructure deployment using a mono-objective linear optimisation. It focuses on minimizing both capital and operation costs of the hydrogen transportation based on transportation via truck which represents the main focus of this paper and a cost-minimal pipeline system in the case of France and Germany. The paper explains the mathematical model describing the link between the hydrogen production via electrolysers and the distribution for mobility needs. The main parameters and the assumed scenario framework are explained. Subsequently the transportation of hydrogen via truck using different states of aggregation is analysed as well as the transformation and storage of hydrogen. This is used finally to build a linear programming aiming to minimize the sum of costs of hydrogen transportation between the different nodes and transformation/storage within the nodes.
Some Fundamental Combustion Properties of "Cryogenic" Premixed Hydrogen Air Flames
Sep 2021
Publication
Because of the emergence of the U.E. “green deal” and because of the significant implication of national and regional authorities throughout Europe the “hydrogen” economy is emerging. And with it numerous questions and experimentations. One of them perhaps a key point is the storage and transport of hydrogen. Liquid hydrogen in cryogenic conditions is a possibility already used in the space industry but under a lot of constrains. What may be acceptable in a well-controlled and restrained domain may not be realistic in a wider application closer to the public. Safety should be ensured and there is a need for a better knowledge of the flammable and ignition properties of the “cold” hydrogen mixtures following a cryogenic spillage for instance to select adequate ATEX equipment. The purpose of PRESLHY project [4] is to investigate the ignition fire and explosion characteristics of cryogenic hydrogen spillages and to propose safety engineering methods. The present work is part of it and addresses the measurement of the laminar burning velocity (Sl) flammability limits (FL) minimum ignition energy (MIE)… of hydrogen air mixtures at atmospheric pressure but down to -150°C. To do this a special burner was designed with details given inside this paper together with the experimental results. It is found that the FL domain is reduced when the temperature drops that MIE increases slightly and Sl decreases.
Prospecting Stress Formed by Hydrogen or Isotope Diffused in Palladium Alloy Cathode
Oct 2018
Publication
The objective of this project is to take into account the mechanical constraints formed by diffusion of hydrogen or tritium in watertight palladium alloy cathode. To know the origin of these it was necessary to discriminating the damaging effects encountered. Effectively hydrogen and isotope induce deformation embrittlement stress corrosion cracking and cathodic corrosion in different regions of cathode. Palladium can be alloyed with silver or yttrium to favourably increase diffusion and reduce these constraints. Effects of electrochemical factors temperature cathode structure adsorbed transient complex of palladium and porous material support are given to estimate and to limit possible damage.
Challenges and Important Considerations When Benchmarking Single-cell Alkaline Electrolyzers
Nov 2021
Publication
This study outlines an approach to identifying the difficulties associated with the bench-marking of alkaline single cells under real electrolyzer conditions. A challenging task in the testing and comparison of different catalysts is obtaining reliable and meaningful benchmarks for these conditions. Negative effects on reproducibility were observed due to the reduction in conditioning time. On the anode side a stable passivation layer of NiO can be formed by annealing of the Ni foams which is even stable during long-term operation. Electrical contact resistance and impedance measurements showed that most of the contact resistance derived from the annealed Ni foam. Additionally analysis of various overvoltages indicated that most of the total overvoltage comes from the anode and cathode activation overpotential. Different morphologies of the substrate material exhibited an influence on the performance of the alkaline single cell based on an increase in the ohmic resistance.
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.
Global Energy Review 2020- The Impacts of the Covid-19 Crisis on Global Energy Demand and CO2 Emissions
Apr 2020
Publication
In response to the exceptional circumstances stemming from the coronavirus pandemic the annual IEA Global Energy Review has expanded its coverage to include real-time analysis of developments to date in 2020 and possible directions for the rest of the year. In addition to reviewing 2019 energy and CO2 emissions data by fuel and country for this section of the Global Energy Review we have tracked energy use by country and fuel over the past three months and in some cases – such as electricity – in real time. Some tracking will continue on a weekly basis. The uncertainty surrounding public health the economy and hence energy over the rest of 2020 is unprecedented. This analysis therefore not only charts a possible path for energy use and CO2 emissions in 2020 but also highlights the many factors that could lead to differing outcomes. We draw key lessons on how to navigate this once-in-a-century crisis.
Link to Document on IEA websitte
Link to Document on IEA websitte
Statistics, Lessons Learned and Recommendations from Analysis of HIAD 2.0 Database
Mar 2022
Publication
The manuscript firstly describes the data collection and validation process for the European Hydrogen Incidents and Accidents Database (HIAD 2.0) a public repository tool collecting systematic data on hydrogen-related incidents and near-misses. This is followed by an overview of HIAD 2.0 which currently contains 706 events. Subsequently the approaches and procedures followed by the authors to derive lessons learned and formulate recommendations from the events are described. The lessons learned have been divided into four categories including system design; system manufacturing installation and modification; human factors and emergency response. An overarching lesson learned is that minor events which occurred simultaneously could still result in serious consequences echoing James Reason's Swiss Cheese theory. Recommendations were formulated in relation to the established safety principles adapted for hydrogen by the European Hydrogen Safety Panel considering operational modes industrial sectors and human factors. This work provide an important contribution to the safety of systems involving hydrogen benefitting technical safety engineers emergency responders and emergency services. The lesson learned and the discussion derived from the statistics can also be used in training and risk assessment studies being of equal importance to promote and assist the development of sound safety culture in organisations.
Influence of Doping Element in Distributed Hydrogen Optical Fiber Densors with Brillouin Scattering
Sep 2013
Publication
Distributed hydrogen optical fiber sensor with Brillouin scattering is an innovative solution to measure hydrogen in harsh environment as nuclear industry. Glass composition is the key point to enhance the sensing parameter of the fiber in the target application. Several optical fiber with different doping element were used for measuring hydrogen saturation. Permeability of optical plays a major role to the kinetic of hydrogen diffusion. Fluorine doped fiber increase the sorption and the desorption of hydrogen.
Experimental Determination of Minimum Ignition Current (MIC) for Hydrogen & Methane Mixtures for the Determination of the Explosion Group Corresponding to IEC 60079-20-1
Sep 2017
Publication
Power to gas could get an important issue in future permitting the valorisation of green electric excess energy by producing hydrogen mixing it with natural gas (NG) and use the NG grid as temporary storage. NG grid stakeholders expect that blends up to 20% seem to be a realistic scenario. The knowledge of the explosion group for these hydrogen/NG (H2NG) mixtures is a necessary information for the choice of equipment and protective systems intended for the use in potentially explosive atmospheres of these mixtures. Therefore we determined experimentally the minimum ignition current (MIC) the MIC ratios referenced on MIC of pure methane corresponding to IEC 60079-20-1 standard. The results are compared to those obtained by maximum experimental safe gap (MESG) the second standardized method. The tested gas mixtures started from 2 vol.% volume admixture in methane rising in 2% steps up to 20 vol.% of hydrogen. The interpretation of these results could conduct to consider methane/hydrogen mixtures containing more than 14 vol.% of hydrogen as Group IIB gases.
An Analysis of the Experiments Carried Out by HSL in the HyIndoor European Project Studying Accumulation of Hydrogen Released into a Semi-confined Enclosure
Oct 2015
Publication
Experimental work on hydrogen releases consequences in a 31-m3 semi-confined enclosure was performed in the framework of the collaborative European Hyindoor project. Natural ventilation effectiveness on hydrogen build-up limitation in a confined area was studied for several configurations of ventilation openings and of release conditions in real environmental conditions [1]; influence of wind on gas build-up was observed as well. This paper proposes a critical analysis of these experiments carried out by HSL and compares results with analytical approaches available in open scientific literature. The validity of these models in presence of wind was broached.
An Inter-comparison Exercise on Engineering Models Capabilities to Simulate Hydrogen Vented Explosions
Sep 2013
Publication
A benchmark exercise on vented explosion engineering model was carried out against the maximum overpressures (one or two peaks) of published experiments. The models evaluated are Bauwens et al. (2012-1 and 2012-2) [4 7] models Molkov Vent Sizing Technology 1999 2001 and 2008 models [12 13 6]. The experiments in consideration are Pasman et al. experiments (1974) (30% H2 - 1m3) [1] Bauwens et al. (2012) experiments (64m3) [4] Daubech et al. (2011) experiments (10 to 30% H2 - 1 and 10 m3) [2] and Daubech et al. (2013) [5] experiments (4 m3 – H2 10 to 30%). On this basis recommendations and limits of use of these models are proposed.
Feasibility of Hydrogen Detection by the Use of Uncoated Silicon Microcantilever-based Sensors
Sep 2013
Publication
Hydrogen is a key parameter to monitor radioactive disposal facility such as the envisioned French geological repository for nuclear wastes. The use of microcantilevers as chemical sensors usually involves a sensitive layer whose purpose is to selectively sorb the analyte of interest. The sorbed substance can then be detected by monitoring either the resonant frequency shift (dynamic mode) or the quasi-static deflection (static mode). The objective of this paper is to demonstrate the feasibility of eliminating the need for the sensitive layer in the dynamic mode thereby increasing the long-term reliability. The microcantilever resonant frequency allows probing the mechanical properties (mass density and viscosity) of the surrounding fluid and thus to determine the concentration of a species in a binary gaseous. Promising preliminary work has allowed detecting concentration of 200 ppm of hydrogen in air with non-optimized geometry of silicon microcantilever with integrated actuation and read-out.
Development of a Model Evaluation Protocol for CFD Analysis of Hydrogen Safety Issues – The SUSANA Project
Oct 2015
Publication
The “SUpport to SAfety aNAlysis of Hydrogen and Fuel Cell Technologies (SUSANA)” project aims to support stakeholders using Computational Fluid Dynamics (CFD) for safety engineering design and assessment of FCH systems and infrastructure through the development of a model evaluation protocol. The protocol covers all aspects of safety assessment modelling using CFD from release through dispersion to combustion (self-ignition fires deflagrations detonations and Deflagration to Detonation Transition - DDT) and not only aims to enable users to evaluate models but to inform them of the state of the art and best practices in numerical modelling. The paper gives an overview of the SUSANA project including the main stages of the model evaluation protocol and some results from the on-going benchmarking activities.
Effects of Oxidants on Hydrogen Spontaneous Ignition: Experiments and Modelling
Sep 2017
Publication
Experiments were performed on the influence of oxidants (air pure oxygen O2 and pure nitrous oxide N2O at atmospheric pressure) in the straight expansion tube after the burst disk on the hydrogen spontaneous ignition. The lowest pressure at which the spontaneous ignition is observed has been researched for a 4 mm diameter tube with a length of 10 cm for the two oxidant gases. The ignition phenomenon is observed with a high speed camera and the external overpressures are measured. Numerical simulations have also been conducted with the high resolution CFD approach detailed chemistry formerly developed by Wen and co-workers. Comparison is made between the predictions and the experimental data.
Prevention of Hydrogen Accumulation Inside the Vacuum Vessel Pressure Suppression System of the ITER Facility by Means of Passive Auto-catalytic Recombiners
Sep 2017
Publication
Hydrogen safety is a relevant topic for both nuclear fission and fusion power plants. Hydrogen generated in the course of a severe accident may endanger the integrity of safety barriers and may result in radioactive releases. In the case of the ITER fusion facility accident scenarios with water ingress consider the release of hydrogen into the suppression tank (ST) of the vacuum vessel pressure suppression system (VVPSS). Under the assumption of additional air ingress the formation of flammable gas mixtures may lead to explosions and safety component failure.<br/>The installation of passive auto-catalytic recombiners (PARs) inside the ST which are presently used as safety devices inside the containments of nuclear fission reactors is one option under consideration to mitigate such a scenario. PARs convert hydrogen into water vapor by means of passive mechanisms and have been qualified for operation under the conditions of a nuclear power plant accident since the 1990s.<br/>In order to support on-going hydrogen safety considerations simulations of accident scenarios using the CFD code ANSYS-CFX are foreseen. In this context the in-house code REKO-DIREKT is coupled to CFX to simulate PAR operation. However the operational boundary conditions for hydrogen recombination (e.g. temperature pressure gas mixture) of a fusion reactor scenario differ significantly from those of a fission reactor. In order to enhance the code towards realistic PAR operation a series of experiments has been performed in the REKO-4 facility with specific focus on ITER conditions. These specifically include operation under sub-atmospheric pressure (0.2–1.0 bar) gas compositions ranging from lean to rich H2/O2 mixtures and superposed flow conditions.<br/>The paper gives an overview of the experimental program presents results achieved and gives an outlook on the modelling approach towards accident scenario simulation.
European Hydrogen Safety Training Programme for First Responders: Hyresponse Outcomes and Perspectives
Sep 2017
Publication
The paper presents the outcomes of the HyResponse project i.e. the European Hydrogen Safety Training Programme for first responders. The threefold training is described: the content of the educational training is presented the operational training platform and its mock-up real scale transport and hydrogen stationary installations are detailed and the innovative virtual tools and training exercises are highlighted. The paper underlines the outcomes the three pilot sessions as well as the Emergency Response Guide available on the HyResponse’s public website. The next steps for widespread dissemination into the community are discussed.
Delayed Explosion of Hydrogen High Pressure Jets in a Highly Obstructed Geometry
Sep 2017
Publication
Delayed explosions of accidental high pressure hydrogen releases are an important risk scenario in safety studies of production plants transportation pipelines and fuel cell vehicles charging stations. Such explosions were widely explored in multiple experimental and numerical investigations. Explosion of high pressure releases in highly obstructed geometries with high blockage ratio is a much more complicated phenomenon. This paper is dedicated to the experimental investigation of the influence of obstacles on a delayed deflagration of hydrogen jets. The computational fluid dynamics (CFD) code FLACS is used to reproduce experimental data. In the current study the computed overpressure signals are compared to the experimentally measured ones at different monitoring points. Simulations are in close agreement with experimental results and can be used to predict overpressure where experimental pressure detectors were saturated. For homogenous stationary clouds a new approach of equivalent mixture of H2/air (~16.5%) to stoichiometric mixture of CH4/air is suggested. This approach is validated versus experimental data from the literature in terms of overpressure maxima. A parametric study is performed using FLACS for various concentrations in the same geometry in order to identify a possible transition from deflagration to detonation.
Sample Scale Testing Method to Prevent Collapse of Plastic Liners in Composite Pressure Vessels
Sep 2017
Publication
Type IV pressure vessels are commonly used for hydrogen on-board stationary or bulk storages. When pressurised hydrogen permeates through the materials and solves into them. Emptying then leads to a difference of pressure at the interface between composite and liner possibly leading to a permanent deformation of the plastic liner called “collapse” or “buckling”. This phenomenon has been studied through French funded project Colline allowing to better understand its initiation and long-term effects. This paper presents the methodology followed using permeation tests hydrogen decompression tests on samples and gas diffusion calculation in order to determine safe operating conditions such as maximum flow rate or residual pressure level.
Hydrogen-air Vented Explosions- New Experimental Data
Sep 2013
Publication
The use of hydrogen as an energy carrier is a real perspective in Europe since a number of breakthroughs obtained in the last decades open the possibility to envision a deployment at the industrial scale if safety issues are duly accounted. However on this particular aspects experimental data are still lacking especially about the explosion dynamics in realistic dimensions. The purpose of this paper is to provide a set of totally new and well instrumented hydrogen - air vented explosions. Experiments were performed in a large explosion chamber within the scope of the DIMITRHY project (sponsored by the National French Agency for Research). The 4 m3 rectangular experimental chamber (2 m height 2 m width and 1 m depth) is equipped with transparent walls and is vented (0.25 and 0.5 m2 square vents).. Six pressure gauges were used to measure the overpressure evolution inside and outside the chamber. Six concentration gauges were used to control the hydrogen repartition in the vessel. The hydrogen-air cloud was seeded with micro particles of ammonium chloride to see the propagation of the flame the movement of the cloud inside and outside the chamber. The incidence of reactivity vent size ignition position and non homogenous repartition of hydrogen received a particular attention.
Fire Tests Carried Out in FCH JU FIRECOMP Project, Recommendations and Application to Safety of Gas Storage Systems
Sep 2017
Publication
In the event of a fire composite pressure vessels behave very differently from metallic ones: the material is degraded potentially leading to a burst without significant pressure increase. Hence such objects are when necessary protected from fire by using thermally-activated devices (TPRD) and standards require testing cylinder and TPRD together. The pre-normative research project FireComp aimed at understanding better the conditions which may lead to burst through testing and simulation and proposed an alternative way of assessing the fire performance of composite cylinders. This approach is currently used by Air Liquide for the safety of composite bundles carrying large amounts of hydrogen gas.
Fast Synthesis of TiNi by Mechanical Alloying and its Hydrogenation Properties
Mar 2019
Publication
Mechanical alloying is widely used for the synthesis of hydrogen storage materials. However amorphization and contamination triggered by long-time milling are serious drawbacks for obtaining efficient hydrogen storage. In this work short-time ball milling synthesis is explored for a representative hydride forming compound: TiNi. Through structural morphological and chemical characterizations we evidence that formation of TiNi is complete in only 20 min with minor Fe contamination (0.2 wt%). Cross-sectional analysis of powder stuck on milling balls reveals that alloy formation occurs through the interdiffusion between thin layers of co-laminated pure elements. Hydrogenation thermodynamics and kinetics of short-time mechanically alloyed TiNi are similar to those of coarse-grained compounds obtained by classical high-temperature melting. Mechanical alloying is a suitable method for fast and energy-efficient synthesis of intermetallic compounds such as TiNi.
Isotopic Tracing of Hydrogen Transport and Trapping in Nuclear Materials
Jun 2017
Publication
Some illustrations of the use of deuterium or tritium for isotopic tracing of hydrogen absorption transport and trapping in nuclear materials are presented. Isotopic tracing of hydrogen has been shown to be successful for the determination of the boundaries conditions for hydrogen desorption or absorption in a material exposed to a hydrogen source. Also the unique capabilities of isotopic tracing and related techniques to characterize H interactions with point defects and dislocations acting as moving traps has been demonstrated. Such transport mechanisms are considered to play a major role in some stress corrosion cracking and hydrogen embrittlement mechanisms.
Link to document download on Royal Society Website
Link to document download on Royal Society Website
Comparisons of Helium and Hydrogen Releases in 1 M3 and 2 M3 Two Vents Enclosures: Concentration Measurements at Different Flow Rates and for Two Diameters of Injection Nozzle
Oct 2015
Publication
This work presents a parametric study on the similitude between hydrogen and helium distribution when released in the air by a source located inside of a naturally ventilated enclosure with two vents. Several configurations were experimentally addressed in order to improve knowledge on dispersion. Parameters were chosen to mimic operating conditions of hydrogen energy systems. Thus the varying parameters of the study were mainly the source diameter the releasing flow rate the volume and the geometry of the enclosure. Two different experimental set-ups were used in order to vary the enclosure's height between 1 and 2 m. Experimental results obtained with helium and hydrogen were compared at equivalent flow rates determined with existing similitude laws. It appears for the plume release case that helium can suitably be used for predicting hydrogen dispersion in these operating designs. On the other hand – when the flow turns into a jet – non negligible differences between hydrogen and helium dispersion appear. In this case helium – used as a direct substitute to hydrogen – will over predict concentrations we would get with hydrogen. Therefore helium concentration read-outs should be converted to obtain correct predictions for hydrogen. However such a converting law is not available yet.
Calibration of Hydrogen Coriolis Flow Meters Using Nitrogen and Air and Investigation of the Influence of Temperature on Measurement Accuracy
Feb 2021
Publication
The performance of four Coriolis flow meters designed for use in hydrogen refuelling stations was evaluated with air and nitrogen by three members of the MetroHyVe JRP consortium; NEL METAS and CESAME EXADEBIT.<br/>A wide range of conditions were tested overall with gas flow rates ranging from (0.05–2) kg/min and pressures ranging from (20–86) bar. The majority of tests were conducted at nominal pressures of either 20 bar or 40 bar in order to match the density of hydrogen at 350 bar and 20 °C or 700 bar and −40 °C. For the conditions tested pressure did not have a noticeable influence on meter performance.<br/>When the flow meters were operated at ambient temperatures and within the manufacturer's recommended flow rate ranges errors were generally within ±1%. Errors within ±0.5% were achievable for the medium to high flow rates.<br/>The influence of temperature on meter performance was also studied with testing under both stable and transient conditions and temperatures as low as −40 °C.<br/>When the tested flow meters were allowed sufficient time to reach thermal equilibrium with the incoming gas temperature effects were limited. The magnitude and spread of errors increased but errors within ±2% were achievable at moderate to high flow rates. Conversely errors as high as 15% were observed in tests where logging began before temperatures stabilised and there was a large difference in temperature between the flow meter and the incoming gas.<br/>One of the flow meters tested with nitrogen was later installed in a hydrogen refuelling station and tested against the METAS Hydrogen Field Test Standard (HFTS). Under these conditions errors ranged from 0.47% to 0.91%. Testing with nitrogen at the same flow rates yielded errors of −0.61% to −0.82%.
Test Campaign on Existing HRS & Dissemination of Results
Apr 2019
Publication
This document is the final deliverable of Tasks 2 & 3 of the tender N° FCH / OP / CONTRACT 196: “Development of a Metering Protocol for Hydrogen Refuelling Stations”. In Task 2 a test campaign was organized on several HRS in Europe to apply the testing protocol defined in Task 1. This protocol requires mainly to perform different accuracy tests in order to determine the error of the complete measuring system (i.e. from the mass flow meter to the nozzle) in real fueling conditions. Seven HRS have been selected to fulfill the requirements specified in the tender. Tests results obtained are presented in this deliverable and conclusions are proposed to explain the errors observed. In the frame of Task 3 results and conclusions have been widely presented to additional Metrology Institutes than those involved in Task 1 in order to get their adhesion on the testing proposed protocol. All the work performed in Tasks 2 & 3 and associated outcomes / conclusions are reported here.
Towards Non-Mechanical Hybrid Hydrogen Compression for Decentralized Hydrogen Facilities
Jun 2020
Publication
The cost of the hydrogen value chain needs to be reduced to allow the widespread development of hydrogen applications. Mechanical compressors widely used for compressing hydrogen to date account for more than 50% of the CAPEX (capital expenditure) in a hydrogen refuelling station. Moreover mechanical compressors have several disadvantages such as the presence of many moving parts hydrogen embrittlement and high consumption of energy. Non-mechanical hydrogen compressors have proven to be a valid alternative to mechanical compressors. Among these electrochemical compressors allow isothermal and therefore highly efficient compression of hydrogen. On the other hand adsorption-desorption compressors allow hydrogen to be compressed through cooling/heating cycles using highly microporous materials as hydrogen adsorbents. A non-mechanical hybrid hydrogen compressor consisting of a first electrochemical stage followed by a second stage driven by adsorption-desorption of hydrogen on activated carbons allows hydrogen to be produced at 70 MPa a value currently required for the development of hydrogen automotive applications. This system has several advantages over mechanical compressors such as the absence of moving parts and high compactness. Its use in decentralized hydrogen facilities such as hydrogen refuelling stations can be considered
Probability of Occurrence of ISO 14687-2 Contaminants in Hydrogen: Principles and Examples from Steam Methane Reforming and Electrolysis (Water and Chlor-alkali) Production Processes Model
Apr 2018
Publication
According to European Directive 2014/94/EU hydrogen providers have the responsibility to prove that their hydrogen is of suitable quality for fuel cell vehicles. Contaminants may originate from hydrogen production transportation refuelling station or maintenance operation. This study investigated the probability of presence of the 13 gaseous contaminants (ISO 14687-2) in hydrogen on 3 production processes: steam methane reforming (SMR) process with pressure swing adsorption (PSA) chlor-alkali membrane electrolysis process and water proton exchange membrane electrolysis process with temperature swing adsorption. The rationale behind the probability of contaminant presence according to process knowledge and existing barriers is highlighted. No contaminant was identified as possible or frequent for the three production processes except oxygen (frequent for chlor-alkali membrane process) carbon monoxide (frequent) and nitrogen (possible) for SMR with PSA. Based on it a hydrogen quality assurance plan following ISO 19880-8 can be devised to support hydrogen providers in monitoring the relevant contaminants.
Numerical and Experimental Investigation of H2-air and H2-O2 Detonation Parameters in a 9 m Long Tube, Introduction of a New Detonation Model
Sep 2017
Publication
Experimental and numerical investigation of hydrogen-air and hydrogen-oxygen detonation parameters was performed. A new detonation model was introduced and validated against the experimental data. Experimental set-up consisted of 9 m long tube with 0.17 m in diameter where pressure was measured with piezoelectric transducers located along the channel. Numerical simulations were performed within OpenFoam code based on progress variable equation where the detonative source term accounts for autoignition effects. Autoignition delay times were computed at a simulation run-time with the use of a multivariate regression model where independent variables were: pressure temperature and fuel concentration. The dependent variable was the autoignition delay time. Range of the analyzed gaseous mixture composition varied between 20% and 50% of hydrogen-air and 50%–66% of hydrogen in oxygen. Simulations were performed using LES one-equation eddy viscosity turbulence model in 2D and 3D. Calculations were validated against experimental data.
Hydrogen Dispersion in a Closed Environment
Sep 2017
Publication
The highly combustible nature of hydrogen poses a great hazard creating a number of problems with its safety and handling. As a part of safety studies related to the use of hydrogen in a confined environment it is extremely important to have a good knowledge of the dispersion mechanism.<br/>The present work investigates the concentration field and flammability envelope from a small scale leak. The hydrogen is released into a 0.47 m × 0.33 m x 0.20 m enclosure designed as a 1/15 – scale model of a room in a nuclear facility. The performed tests evaluates the influence of the initial conditions at the leakage source on the dispersion and mixing characteristics in a confined environment. The role of the leak location and the presence of obstacles are also analyzed. Throughout the test during the release and the subsequent dispersion phase temporal profiles of hydrogen concentration are measured using thermal conductivity gauges within the enclosure. In addition the BOS (Background Oriented Schlieren) technique is used to visualise the cloud evolution inside the enclosure. These instruments allow the observation and quantification of the stratification effects.
Hot Surface Ignition in Flowing Streams of Hydrogen-Air Mixtures
Sep 2019
Publication
A set of original experiments is presented covering the topic of hydrogen-air mixture ignition by a hot surface. The hot surface is a 30 mm long/10 mm diameter heated coil which temperature is controlled by IR techniques. The coil is placed into the flowing stream of hydrogen air mixtures. The variable parameters are the composition of the flammable atmosphere (4 to 75% H2 v/v) the flow speed (from 0.5 m/s to 30 m/s) and its temperature (from -110°C to ambient). The experimental techniques and results are presented and a tentative interpretation is proposed based on ignition theories and highspeed video recordings. It is shown that the ignition temperature (600°C) is insensitive to flowing conditions which is a very unexpected result.
Development of a Realistic Hydrogen Flammable Atmosphere Inside a 4-m3 Enclosure
Sep 2017
Publication
To define a strategy of mitigation for containerized hydrogen systems (fuel cells for example) against explosion the main characteristics of flammable atmosphere (size concentration turbulence…) shall be well-known. This article presents an experimental study on accidental hydrogen releases and dispersion into an enclosure of 4 m3 (2 m x 2 m x 1 m). Different release points are studied: two circular releases of 1 and 3 mm and a system to create ring-shaped releases. The releases are operated with a pressure between 10 and 40 bars in order to be close to the process conditions. Different positions of the release inside the enclosure i.e. centred on the floor or along a wall are also studied. A specific effort is made to characterize the turbulence in the enclosure during the releases. The objectives of the experimental study are to understand and quantify the mechanisms of formation of the explosive atmosphere taking into account the geometry and position of the release point and the confinement. Those experimental data are analyzed and compared with existing models and could bring some new elements to improve them.
Syngas Explosion Reactivity in Steam Methane Reforming Process
Sep 2013
Publication
During the synthesis of hydrogen by methane steam reforming mixtures composed of H2 CH4 CO and CO2 are produced in the process. In this work the explosion reactivity of these mixtures on the basis of detonation cell size and laminar flame speed is calculated using a reactant assimilation simplification and a kinetic approach. The detonation cells width are calculated using the Cell_CH Kurchatov institute method and the laminar flame velocities are calculated with Chemkin Premix using different detailed chemical kinetic mechanisms. These calculations are used to define if these mixtures could be considered having a medium or a high reactivity for risk assessment in case of leak in the hydrogen plants.
Evaluation of the Performance Degradation of a Metal Hydride Tank in a Real Fuel Cell Electric Vehicle
May 2022
Publication
In a fuel cell electric vehicle (FCEV) powered by a metal hydride tank the performance of the tank is an indicator of the overall health status which is used to predict its behaviour and make appropriate energy management decisions. The aim of this paper is to investigate how to evaluate the effects of charge/discharge cycles on the performance of a commercial automotive metal hydride hydrogen storage system applied to a real FCEV. For this purpose a mathematical model is proposed based on uncertain physical parameters that are identified using the stochastic particle swarm optimisation (PSO) algorithm combined with experimental measurements. The variation of these parameters allows an assessment of the degradation level of the tank’s performance on both the quantitative and qualitative aspects. Simulated results derived from the proposed model and experimental measurements were in good agreement with a maximum relative error of less than 2%. The validated model was used to establish the correlations between the observed degradations in a hydride tank recovered from a real FCEV. The results obtained show that it is possible to predict tank degradations by developing laws of variation of these parameters as a function of the real conditions of the use of the FCEV (number of charging/discharging cycles pressures mass flow rates temperatures).
The Role of Critical Minerals in Clean Energy Transitions
May 2021
Publication
Minerals are essential components in many of today’s rapidly growing clean energy technologies – from wind turbines and electricity networks to electric vehicles. Demand for these minerals will grow quickly as clean energy transitions gather pace. This new World Energy Outlook Special Report provides the most comprehensive analysis to date of the complex links between these minerals and the prospects for a secure rapid transformation of the energy sector.
Alongside a wealth of detail on mineral demand prospects under different technology and policy assumptions it examines whether today’s mineral investments can meet the needs of a swiftly changing energy sector. It considers the task ahead to promote responsible and sustainable development of mineral resources and offers vital insights for policy makers including six key IEA recommendations for a new comprehensive approach to mineral security."
Link to International Energy Agency website
Alongside a wealth of detail on mineral demand prospects under different technology and policy assumptions it examines whether today’s mineral investments can meet the needs of a swiftly changing energy sector. It considers the task ahead to promote responsible and sustainable development of mineral resources and offers vital insights for policy makers including six key IEA recommendations for a new comprehensive approach to mineral security."
Link to International Energy Agency website
Hydrogen Storage in Pure and Boron-Substituted Nanoporous Carbons—Numerical and Experimental Perspective
Aug 2021
Publication
Nanoporous carbons remain the most promising candidates for effective hydrogen storage by physisorption in currently foreseen hydrogen-based scenarios of the world’s energy future. An optimal sorbent meeting the current technological requirement has not been developed yet. Here we first review the storage limitations of currently available nanoporous carbons then we discuss possible ways to improve their storage performance. We focus on two fundamental parameters determining the storage (the surface accessible for adsorption and hydrogen adsorption energy). We define numerically the values nanoporous carbons have to show to satisfy mobile application requirements at pressures lower than 120 bar. Possible necessary modifications of the topology and chemical compositions of carbon nanostructures are proposed and discussed. We indicate that pore wall fragmentation (nano-size graphene scaffolds) is a partial solution only and chemical modifications of the carbon pore walls are required. The positive effects (and their limits) of the carbon substitutions by B and Be atoms are described. The experimental ‘proof of concept’ of the proposed strategies is also presented. We show that boron substituted nanoporous carbons prepared by a simple arc-discharge technique show a hydrogen adsorption energy twice as high as their pure carbon analogs. These preliminary results justify the continuation of the joint experimental and numerical research effort in this field.
Global Hydrogen Review 2021
Oct 2021
Publication
The Global Hydrogen Review is a new annual publication by the International Energy Agency to track progress in hydrogen production and demand as well as in other critical areas such as policy regulation investments innovation and infrastructure development.
The report is an output of the Clean Energy Ministerial Hydrogen Initiative (CEM H2I) and is intended to inform energy sector stakeholders on the status and future prospects of hydrogen while serving as an input to the discussions at the Hydrogen Energy Ministerial Meeting (HEM) organised by Japan. It examines what international progress on hydrogen is needed to help address climate change – and compares real-world developments with the stated ambitions of government and industry and with key actions under the Global Action Agenda launched at the HEM in 2019.
Focusing on hydrogen’s usefulness for meeting climate goals this Review aims to help decision makers fine-tune strategies to attract investment and facilitate deployment of hydrogen technologies while also creating demand for hydrogen and hydrogen-based fuels.
Link to International Energy Agency website
The report is an output of the Clean Energy Ministerial Hydrogen Initiative (CEM H2I) and is intended to inform energy sector stakeholders on the status and future prospects of hydrogen while serving as an input to the discussions at the Hydrogen Energy Ministerial Meeting (HEM) organised by Japan. It examines what international progress on hydrogen is needed to help address climate change – and compares real-world developments with the stated ambitions of government and industry and with key actions under the Global Action Agenda launched at the HEM in 2019.
Focusing on hydrogen’s usefulness for meeting climate goals this Review aims to help decision makers fine-tune strategies to attract investment and facilitate deployment of hydrogen technologies while also creating demand for hydrogen and hydrogen-based fuels.
Link to International Energy Agency website
Intermetallic Compounds Synthesized by Mechanical Alloying for Solid-State Hydrogen Storage: A Review
Sep 2021
Publication
Hydrogen energy is a very attractive option in dealing with the existing energy crisis. For the development of a hydrogen energy economy hydrogen storage technology must be improved to over the storage limitations. Compared with traditional hydrogen storage technology the prospect of hydrogen storage materials is broader. Among all types of hydrogen storage materials solid hydrogen storage materials are most promising and have the most safety security. Solid hydrogen storage materials include high surface area physical adsorption materials and interstitial and non-interstitial hydrides. Among them interstitial hydrides also called intermetallic hydrides are hydrides formed by transition metals or their alloys. The main alloy types are A2B AB AB2 AB3 A2B7 AB5 and BCC. A is a hydride that easily forms metal (such as Ti V Zr and Y) while B is a non-hydride forming metal (such as Cr Mn and Fe). The development of intermetallic compounds as hydrogen storage materials is very attractive because their volumetric capacity is much higher (80–160 kgH2m−3 ) than the gaseous storage method and the liquid storage method in a cryogenic tank (40 and 71 kgH2m−3 ). Additionally for hydrogen absorption and desorption reactions the environmental requirements are lower than that of physical adsorption materials (ultra-low temperature) and the simplicity of the procedure is higher than that of non-interstitial hydrogen storage materials (multiple steps and a complex catalyst). In addition there are abundant raw materials and diverse ingredients. For the synthesis and optimization of intermetallic compounds in addition to traditional melting methods mechanical alloying is a very important synthesis method which has a unique synthesis mechanism and advantages. This review focuses on the application of mechanical alloying methods in the field of solid hydrogen storage materials.
Technologies and Policies to Decarbonize Global Industry: Review and Assessment of Mitigation Drivers Through 2070
Mar 2020
Publication
Jeffrey Rissman,
Chris Bataille,
Eric Masanet,
Nate Aden,
William R. Morrow III,
Nan Zhou,
Neal Elliott,
Rebecca Dell,
Niko Heeren,
Brigitta Huckestein,
Joe Cresko,
Sabbie A. Miller,
Joyashree Roy,
Paul Fennell,
Betty Cremmins,
Thomas Koch Blank,
David Hone,
Ellen D. Williams,
Stephane de la Rue du Can,
Bill Sisson,
Mike Williams,
John Katzenberger,
Dallas Burtraw,
Girish Sethi,
He Ping,
David Danielson,
Hongyou Lu,
Tom Lorber,
Jens Dinkel and
Jonas Helseth
Fully decarbonizing global industry is essential to achieving climate stabilization and reaching net zero greenhouse gas emissions by 2050–2070 is necessary to limit global warming to 2 °C. This paper assembles and evaluates technical and policy interventions both on the supply side and on the demand side. It identifies measures that employed together can achieve net zero industrial emissions in the required timeframe. Key supply-side technologies include energy efficiency (especially at the system level) carbon capture electrification and zero-carbon hydrogen as a heat source and chemical feedstock. There are also promising technologies specific to each of the three top-emitting industries: cement iron & steel and chemicals & plastics. These include cement admixtures and alternative chemistries several technological routes for zero-carbon steelmaking and novel chemical catalysts and separation technologies. Crucial demand-side approaches include material-efficient design reductions in material waste substituting low-carbon for high-carbon materials and circular economy interventions (such as improving product longevity reusability ease of refurbishment and recyclability). Strategic well-designed policy can accelerate innovation and provide incentives for technology deployment. High-value policies include carbon pricing with border adjustments or other price signals; robust government support for research development and deployment; and energy efficiency or emissions standards. These core policies should be supported by labeling and government procurement of low-carbon products data collection and disclosure requirements and recycling incentives. In implementing these policies care must be taken to ensure a just transition for displaced workers and affected communities. Similarly decarbonization must complement the human and economic development of low- and middle-income countries.
Techno-Economic Assessment of Natural Gas Pyrolysis in Molten Salts
Jan 2022
Publication
Steam methane reforming with CO2 capture (blue hydrogen) and water electrolysis based on renewable electricity (green hydrogen) are commonly assumed to be the main supply options in a future hydrogen economy. However another promising method is emerging in the form of natural gas pyrolysis (turquoise hydrogen) with pure carbon as a valuable by-product. To better understand the potential of turquoise hydrogen this study presents a techno-economic assessment of a molten salt pyrolysis process. Results show that moderate reactor pressures around 12 bar are optimal and that reactor size must be limited by accepting reactor performance well below the thermodynamic equilibrium. Despite this challenge stemming from slow reaction rates the simplicity of the molten salt pyrolysis process delivers high efficiencies and promising economics. In the long-term carbon could be produced for 200–300 €/ton granting access to high-volume markets in the metallurgical and chemical process industries. Such a scenario makes turquoise hydrogen a promising alternative to blue hydrogen in regions with public resistance to CO2 transport and storage. In the medium-term expensive first-of-a-kind plants could produce carbon around 400 €/ton if hydrogen prices are set by conventional blue hydrogen production. Pure carbon at this cost level can access smaller high-value markets such as carbon anodes and graphite ensuring profitable operation even for first movers. In conclusion the economic potential of molten salt pyrolysis is high and further demonstration and scale-up efforts are strongly recommended.
Hydrogen Energy Systems: A Critical Review of Technologies, Applications, Trends and Challenges
May 2021
Publication
The global energy transition towards a carbon neutral society requires a profound transformation of electricity generation and consumption as well as of electric power systems. Hydrogen has an important potential to accelerate the process of scaling up clean and renewable energy however its integration in power systems remains little studied. This paper reviews the current progress and outlook of hydrogen technologies and their application in power systems for hydrogen production re-electrification and storage. The characteristics of electrolysers and fuel cells are demonstrated with experimental data and the deployments of hydrogen for energy storage power-to-gas co- and tri-generation and transportation are investigated using examples from worldwide projects. The current techno-economic status of these technologies and applications is presented in which cost efficiency and durability are identified as the main critical aspects. This is also confirmed by the results of a statistical analysis of the literature. Finally conclusions show that continuous efforts on performance improvements scale ramp-up technical prospects and political support are required to enable a cost-competitive hydrogen economy.
Numerical Simulations of Atmospheric Dispersion of Large-scale Liquid Hydrogen Releases
Sep 2021
Publication
Numerical simulations have been conducted for LH2 massive releases and the subsequent atmospheric dispersion using an in-house modified version of the open source computational fluid dynamics (CFD) code OpenFOAM. A conjugate heat transfer model has been added for heat transfer between the released LH2 and the ground. Appropriate interface boundary conditions are applied to ensure the continuities of temperature and heat fluxes. The significant temperature difference between the cryogenic hydrogen and the ground means that the released LH2 will instantly enter in a boiling state resulting in a hydrogen- air gaseous cloud which will initially behave like a dense gas. Numerical predictions have been conducted for the subsequent atmospheric dispersion of the vaporized LH2 for a series of release scenarios - with and without retention pits - to limit the horizontal spread of the LH2 on the ground. The considered cases included the instantaneous release of 1 10 and 50 tons of LH2 under neutral (D) and stable (F) weather conditions. More specifically 3F and 5D conditions were simulated with the former representing stable weather conditions under wind speed of 3 m/s at 10 m above the ground and the later corresponding to neutral weather conditions under 5 m/s wind speed (10 m above the ground). Specific numerical tests have also been conducted for selected scenarios under different ambient temperatures from 233 up to 313 K. According to the current study although the retention pit can extend the dispersion time it can significantly reduce the extent of hazards due to much smaller cloud size within both the flammability and explosion limits. While the former has negative impact on safety the later is beneficial. The use of retention pit should hence be considered with caution in practical applications.
Life Cycle Assessments on Battery Electric Vehicles and Electrolytic Hydrogen: The Need for Calculation Rules and Better Databases on Electricity
May 2021
Publication
LCAs of electric cars and electrolytic hydrogen production are governed by the consumption of electricity. Therefore LCA benchmarking is prone to choices on electricity data. There are four issues: (1) leading Life Cycle Impact (LCI) databases suffer from inconvenient uncertainties and inaccuracies (2) electricity mix in countries is rapidly changing year after year (3) the electricity mix is strongly fluctuating on an hourly and daily basis which requires time-based allocation approaches and (4) how to deal with nuclear power in benchmarking. This analysis shows that: (a) the differences of the GHG emissions of the country production mix in leading databases are rather high (30%) (b) in LCA a distinction must be made between bundled and unbundled registered electricity certificates (RECs) and guarantees of origin (GOs); the residual mix should not be applied in LCA because of its huge inaccuracy (c) time-based allocation rules for renewables are required to cope with periods of overproduction (d) benchmarking of electricity is highly affected by the choice of midpoints and/or endpoint systems and (e) there is an urgent need for a new LCI database based on measured emission data continuously kept up-to-date transparent and open access.
Improved Hydrogen-Production-Based Power Management Control of a Wind Turbine Conversion System Coupled with Multistack Proton Exchange Membrane Electrolyzers
Mar 2020
Publication
This paper deals with two main issues regarding the specific energy consumption in an electrolyzer (i.e. the Faraday efficiency and the converter topology). The first aspect is addressed using a multistack configuration of proton exchange membrane (PEM) electrolyzers supplied by a wind turbine conversion system (WTCS). This approach is based on the modeling of the wind turbine and the electrolyzers. The WTCS and the electrolyzers are interfaced through a stacked interleaved DC–DC buck converter (SIBC) due to its benefits for this application in terms of the output current ripple and reliability. This converter is controlled so that it can offer dynamic behavior that is faster than the wind turbine avoiding overvoltage during transients which could damage the PEM electrolyzers. The SIBC is designed to be connected in array configuration (i.e. parallel architecture) so that each converter operates at its maximum efficiency. To assess the performance of the power management strategy experimental tests were carried out. The reported results demonstrate the correct behavior of the system during transient operation.
An Evaluation of Turbocharging and Supercharging Options for High-Efficiency Fuel Cell Electric Vehicles
Dec 2018
Publication
Mass-produced off-the-shelf automotive air compressors cannot be directly used for boosting a fuel cell vehicle (FCV) application in the same way that they are used in internal combustion engines since the requirements are different. These include a high pressure ratio a low mass flow rate a high efficiency requirement and a compact size. From the established fuel cell types the most promising for application in passenger cars or light commercial vehicle applications is the proton exchange membrane fuel cell (PEMFC) operating at around 80 ◦C. In this case an electric-assisted turbocharger (E-turbocharger) and electric supercharger (single or two-stage) are more suitable than screw and scroll compressors. In order to determine which type of these boosting options is the most suitable for FCV application and assess their individual merits a co-simulation of FCV powertrains between GT-SUITE and MATLAB/SIMULINK is realised to compare vehicle performance on the Worldwide Harmonised Light Vehicle Test Procedure (WLTP) driving cycle. The results showed that the vehicle equipped with an E-turbocharger had higher performance than the vehicle equipped with a two-stage compressor in the aspects of electric system efficiency (+1.6%) and driving range (+3.7%); however for the same maximal output power the vehicle’s stack was 12.5% heavier and larger. Then due to the existence of the turbine the E-turbocharger led to higher performance than the single-stage compressor for the same stack size. The solid oxide fuel cell is also promising for transportation application especially for a use as range extender. The results show that a 24-kWh electric vehicle can increase its driving range by 252% due to a 5 kW solid oxide fuel cell (SOFC) stack and a gas turbine recovery system. The WLTP driving range depends on the charge cycle but with a pure hydrogen tank of 6.2 kg the vehicle can reach more than 600 km.
Use of Hydrogen in Off-Grid Locations, a Techno-Economic Assessment
Nov 2018
Publication
Diesel generators are currently used as an off-grid solution for backup power but this causes CO2 and GHG emissions noise emissions and the negative effects of the volatile diesel market influencing operating costs. Green hydrogen production by means of water electrolysis has been proposed as a feasible solution to fill the gaps between demand and production the main handicaps of using exclusively renewable energy in isolated applications. This manuscript presents a business case of an off-grid hydrogen production by electrolysis applied to the electrification of isolated sites. This study is part of the European Ely4off project (n◦ 700359). Under certain techno-economic hypothesis four different system configurations supplied exclusively by photovoltaic are compared to find the optimal Levelized Cost of Electricity (LCoE): photovoltaic-batteries photovoltaic-hydrogen-batteries photovoltaic-diesel generator and diesel generator; the influence of the location and the impact of different consumptions profiles is explored. Several simulations developed through specific modeling software are carried out and discussed. The main finding is that diesel-based systems still allow lower costs than any other solution although hydrogen-based solutions can compete with other technologies under certain conditions.
Optimization of Hydrogen Cost and Transport Technology in France and Germany for Various Production and Demand Scenarios
Jan 2021
Publication
Green hydrogen for mobility represents an alternative to conventional fuel to decarbonize the transportation sector. Nevertheless the thermodynamic properties make the transport and the storage of this energy carrier at standard conditions inefficient. Therefore this study deploys a georeferenced optimal transport infrastructure for four base case scenarios in France and Germany that differs by production distribution based on wind power potential and demand capacities for the mobility sector at different penetration shares for 2030 and 2050. The restrained transport network to the road infrastructure allows focusing on the optimum combination of trucks operating at different states of aggregations and storage technologies and its impact on the annual cost and hydrogen flow using linear programming. Furthermore four other scenarios with production cost investigate the impact of upstream supply chain cost and eight scenarios with daily transport and storage optimization analyse the modeling method sensitivity. The results show that compressed hydrogen gas at a high presser level around 500 bar was on average a better option. However at an early stage of hydrogen fuel penetration substituting compressed gas at low to medium pressure levels by liquid organic hydrogen carrier minimizes the transport and storage costs. Finally in France hydrogen production matches population distribution in contrast to Germany which suffers from supply and demand disparity.
Overview on Hydrogen Risk Research and Development Activities: Methodology and Open Issues
Jan 2015
Publication
During the course of a severe accident in a light water nuclear reactor large amounts of hydrogen can be generated and released into the containment during reactor core degradation. Additional burnable gases [hydrogen (H2) and carbon monoxide (CO)] may be released into the containment in the corium/concrete interaction. This could subsequently raise a combustion hazard. As the Fukushima accidents revealed hydrogen combustion can cause high pressure spikes that could challenge the reactor buildings and lead to failure of the surrounding buildings. To prevent the gas explosion hazard most mitigation strategies adopted by European countries are based on the implementation of passive autocatalytic recombiners (PARs). Studies of representative accident sequences indicate that despite the installation of PARs it is difficult to prevent at all times and locations the formation of a combustible mixture that potentially leads to local flame acceleration. Complementary research and development (R&D) projects were recently launched to understand better the phenomena associated with the combustion hazard and to address the issues highlighted after the Fukushima Daiichi events such as explosion hazard in the venting system and the potential flammable mixture migration into spaces beyond the primary containment. The expected results will be used to improve the modeling tools and methodology for hydrogen risk assessment and severe accident management guidelines. The present paper aims to present the methodology adopted by Institut de Radioprotection et de Suˆ rete Nucleaire to assess hydrogen risk in nuclear power plants in particular French nuclear power plants the open issues and the ongoing R&D programs related to hydrogen distribution mitigation and combustion.
The Impact of Hydrogen on Mechanical Properties; A New In Situ Nanoindentation Testing Method
Feb 2019
Publication
We have designed a new method for electrochemical hydrogen charging which allows us to charge very thin coarse-grained specimens from the bottom and perform nanomechanical testing on the top. As the average grain diameter is larger than the thickness of the sample this setup allows us to efficiently evaluate the mechanical properties of multiple single crystals with similar electrochemical conditions. Another important advantage is that the top surface is not affected by corrosion by the electrolyte. The nanoindentation results show that hydrogen reduces the activation energy for homogenous dislocation nucleation by approximately 15–20% in a (001) grain. The elastic modulus also was observed to be reduced by the same amount. The hardness increased by approximately 4% as determined by load-displacement curves and residual imprint analysis.
Experimental Challenges in Studying Hydrogen Absorption in Ultrasmall Metal Nanoparticles
Jun 2016
Publication
Recent advances on synthesis characterization and hydrogen absorption properties of ultrasmall metal nanoparticles (defined here as objects with average size ≤3 nm) are briefly reviewed in the first part of this work. The experimental challenges encountered in performing accurate measurements of hydrogen absorption in Mg- and noble metal-based ultrasmall nanoparticles are addressed. The second part of this work reports original results obtained for ultrasmall bulk-immiscible Pd–Rh nanoparticles. Carbon-supported Pd–Rh nanoalloys in the whole binary chemical composition range have been successfully prepared by liquid impregnation method followed by reduction at 300°C. EXAFS investigations suggested that the local structure of these nanoalloys is partially segregated into Rh-rich core and Pd-rich surface coexisting within the same nanoparticles. Downsizing to ultrasmall dimensions completely suppresses the hydride formation in Pd-rich nanoalloys at ambient conditions contrary to bulk and larger nanosized (5–6 nm) counterparts. The ultrasmall Pd90Rh10 nanoalloy can absorb hydrogen-forming solid solutions under these conditions as suggested by in situ X-ray diffraction (XRD). Apart from this composition common laboratory techniques such as in situ XRD DSC and PCI failed to clarify the hydrogen interaction mechanism: either adsorption on developed surfaces or both adsorption and absorption with formation of solid solutions. Concluding insights were brought by in situ EXAFS experiments at synchrotron: ultrasmall Pd75Rh25 and Pd50Rh50 nanoalloys absorb hydrogen-forming solid solutions at ambient conditions. Moreover the hydrogen solubility in these solid solutions is higher with increasing Pd content and this trend can be understood in terms of hydrogen preferential occupation in the Pd-rich regions as suggested by in situ EXAFS. The Rh-rich nanoalloys (Pd25Rh75 and Pd10Rh90) only adsorb hydrogen on the developed surface of ultrasmall nanoparticles. In summary in situ characterization techniques carried out at large-scale facilities are unique and powerful tools for in-depth investigation of hydrogen interaction with ultrasmall nanoparticles at local level.
Role of Hydrogen-Charging on Nucleation and Growth of Ductile Damage in Austenitic Stainless Steels
May 2019
Publication
Hydrogen energy is a possible solution for storage in the future. The resistance of packaging materials such as stainless steels has to be guaranteed for a possible use of these materials as containers for highly pressurized hydrogen. The effect of hydrogen charging on the nucleation and growth of microdamage in two different austenitic stainless steels AISI316 and AISI316L was studied using in situ tensile tests in synchrotron X-ray tomography. Information about damage nucleation void growth and void shape were obtained. AISI316 was found to be more sensitive to hydrogen compared to AISI316L in terms of ductility loss. It was measured that void nucleation and growth are not affected by hydrogen charging. The effect of hydrogen was however found to change the morphology of nucleated voids from spherical cavities to micro-cracks being oriented perpendicular to the tensile axis.
Energy Transition in France
May 2022
Publication
To address the climate emergency France is committed to achieving carbon neutrality by 2050. It plans to significantly increase the contribution of renewable energy in its energy mix. The share of renewable energy in its electricity production which amounts to 25.5% in 2020 should reach at least 40% in 2030. This growth poses several new challenges that require policy makers and regulators to act on the technological changes and expanding need for flexibility in power systems. This document presents the main strategies and projects developed in France as well as various recommendations to accompany and support its energy transition policy.
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.
Validation of Selected Optical Methods for Assessing Polyethylene (PE) Liners Used in High Pressure Vessels for Hydrogen Storage
Jun 2021
Publication
A polyethylene (PE) liner is the basic element in high-pressure type 4 composite vessels designed for hydrogen or compressed natural gas (CNG) storage systems. Liner defects may result in the elimination of the whole vessel from use which is very expensive both at the manufacturing and exploitation stage. The goal is therefore the development of efficient non-destructive testing (NDT) methods to test a liner immediately after its manufacturing before applying a composite reinforcement. It should be noted that the current regulations codes and standards (RC&S) do not specify liner testing methods after manufacturing. It was considered especially important to find a way of locating and assessing the size of air bubbles and inclusions and the field of deformations in liner walls. It was also expected that these methods would be easily applicable to mass-produced liners. The paper proposes the use of three optical methods namely visual inspection digital image correlation (DIC) and optical fiber sensing based on Bragg gratings (FBG). Deformation measurements are validated with finite element analysis (FEA). The tested object was a prototype of a hydrogen liner for high-pressure storage (700 bar). The mentioned optical methods were used to identify defects and measure deformations.
Autonomous Hydrogen Production for Proton Exchange Membrane Fuel Cells PEMFC
Apr 2020
Publication
This paper focuses on hydrogen production for green mobility applications (other applications are currently under investigation). Firstly a brief state of the art of hydrogen generation by hydrolysis with magnesium is shown. The hydrolysis performance of Magnesium powder ball–milled along with different additives (graphite and transition metals TM = Ni Fe and Al) is taken for comparison. The best performance was observed with Mg–10 wt.% g mixtures (95% of theoretical hydrogen generation yield in about 3 min). An efficient solution to control this hydrolysis reaction is proposed to produce hydrogen on demand and to feed a PEM fuel cell. Tests on a bench fitted with a 100 W Proton Exchange Membrane (PEM) fuel cell have demonstrated the technological potential of this solution for electric assistance applications in the field of light mobility.
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.
High-Purity and Clean Syngas and Hydrogen Production From Two-Step CH4 Reforming and H2O Splitting Through Isothermal Ceria Redox Cycle Using Concentrated Sunlight
Jul 2020
Publication
The thermochemical conversion of methane (CH4) and water (H2O) to syngas and hydrogen via chemical looping using concentrated sunlight as a sustainable source of process heat attracts considerable attention. It is likewise a means of storing intermittent solar energy into chemical fuels. In this study solar chemical looping reforming of CH4 and H2O splitting over non-stoichiometric ceria (CeO2/CeO2−δ) redox cycle were experimentally investigated in a volumetric solar reactor prototype. The cycle consists of (i) the endothermic partial oxidation of CH4 and the simultaneous reduction of ceria and (ii) the subsequent exothermic splitting of H2O and the simultaneous oxidation of the reduced ceria under isothermal operation at ~1000°C enabling the elimination of sensible heat losses as compared to non-isothermal thermochemical cycles. Ceria-based reticulated porous ceramics with different sintering temperatures (1000 and 1400°C) were employed as oxygen carriers and tested with different methane flow rates (0.1–0.4 NL/min) and methane concentrations (50 and 100%). The impacts of operating conditions on the foam-averaged oxygen non-stoichiometry (reduction extent δ) syngas yield methane conversion solar-to-fuel energy conversion efficiency as well as the effects of transient solar conditions were demonstrated and emphasized. As a result clean syngas was successfully produced with H2/CO ratios approaching 2 during the first reduction step while high-purity H2 was subsequently generated during the oxidation step. Increasing methane flow rate and CH4 concentration promoted syngas yields up to 8.51 mmol/gCeO2 and δ up to 0.38 at the expense of enhanced methane cracking reaction and reduced CH4 conversion. Solar-to-fuel energy conversion efficiency namely the ratio of the calorific value of produced syngas to the total energy input (solar power and calorific value of converted methane) and CH4 conversion were achieved in the range of 2.9–5.6% and 40.1–68.5% respectively.
Interaction of Hydrogen with the Bulk, Surface and Subsurface of Crystalline RuO2 from First Principles
Feb 2021
Publication
Hydrogen and its interaction with metal oxide surfaces is of major importance for a wide range of research and applied fields spanning from catalysis energy storage microelectronics to metallurgy. This paper reviews state of the art of first principles calculations on the well-known ruthenium oxide (RuO2) surface in its (110) orientation and its interaction with hydrogen. In addition to it the paper also fills gaps in knowledge with new calculations and results on the (001) surface. Bulk and surface interactions are thoroughly reviewed. This includes systematic analysis of adsorption sites local agglomeration propensity of hydrogen and migration pathways in which literature data and their potential deviations are explained. We notably discuss novel results on propensity for agglomeration of hydrogen within bulk channels [001] oriented in which the proton-like behavior of adsorbed hydrogen hinders further agglomeration in adjacent channels. The paper brings new insights into the migration pathways on the surface and in bulk both exhibiting preferential diffusion paths along the [001] direction. The paper finally investigates the subsurface region. We show that while the subsurface has more stable sites for adsorption compared to bulk its accessibility from the surface shows prohibitive activation barriers inhibiting penetration into subsurface and bulk. We further calculate and discuss adsorption and penetration processes on the alternative RuO2 (001) surface.
Morphological, Structural and Hydrogen Storage Properties of LaCrO3 Perovskite-Type Oxides
Feb 2022
Publication
Recently perovskite-type oxides have attracted researchers as new materials for solid hydrogen storage. This paper presents the performances of perovskite-type oxide LaCrO3 dedicated for hydrogen solid storage using both numerical and experimental methods. Ab initio calculations have been used here with the aim to investigate the electronic mechanical and elastic properties of LaCrO3Hx (x = 0 6) for hydrogen storage applications. Cell parameters crystal structures and mechanical properties are determined. Additionally the cohesive energy indicates the stability of the hydride. Furthermore the mechanical properties showed that both compounds (before and after hydrogenation) are stable. The microstructure and storage capacity at different temperatures of these compounds have been studied. We have shown that storage capacities are around 4 wt%. The properties obtained from this type of hydride showed that it can be used for future applications. XRD analysis was conducted in order to study the structural properties of the compound. Besides morphological thermogravimetric analysis was also conducted on the perovskite-type oxide. Finally a comparison of these materials with other hydrides used for hydrogen storage was carried out.
Main Hydrogen Production Processes: An Overview
May 2021
Publication
Due to its characteristics hydrogen is considered the energy carrier of the future. Its use as a fuel generates reduced pollution as if burned it almost exclusively produces water vapor. Hydrogen can be produced from numerous sources both of fossil and renewable origin and with as many production processes which can use renewable or non-renewable energy sources. To achieve carbon neutrality the sources must necessarily be renewable and the production processes themselves must use renewable energy sources. In this review article the main characteristics of the most used hydrogen production methods are summarized mainly focusing on renewable feedstocks furthermore a series of relevant articles published in the last year are reviewed. The production methods are grouped according to the type of energy they use; and at the end of each section the strengths and limitations of the processes are highlighted. The conclusions compare the main characteristics of the production processes studied and contextualize their possible use.
Effects of Hydrogen Addition on Design, Maintenance and Surveillance of Gas Networks
Jul 2021
Publication
Hydrogen when is blended with natural gas over time degrades the materials used for pipe transport. Degradation is dependent on the proportion of hydrogen added to the natural gas. The assessment is made according to hydrogen permeation risk to the integrity of structures adaptation of surveillance and maintenance of equipment. The paper gives a survey of HE and its consequence on the design and maintenance. It is presented in a logical sequence: the design before use; the hydrogen embrittlement (HE) effects on Maximum Allowable Operating Pressure (MAOP); maintenance and surveillance during use of smooth and damaged pipes; and particularly for crack-like defects corrosion defects and dents.
Risk Assessment of a Gaseous Hydrogen Fueling Station (GHFs)
Sep 2021
Publication
Promoted by national and European investment plans promoting the use of hydrogen as energy carrier the number of Gaseous Hydrogen Fueling Station (or GHFS) has been growing up quite significantly over the past years. Considering the new possible hazards and the related accidents induced by these installations like seen in 2019 in Norway this paper presents a risk assessment of a typical GHFS using the same methodology as the one required in France by the authorities for Seveso facilities. The fact that a hydrogen fueling station could be used by a public not particularly trained to handle hydrogen underlines the importance of this risk assessment. In this article typical components related to GHFS (dispenser high pressure storage compressor low pressure storage) are listed and the hazard potentials linked to these components and the substances involved are identified. Based on these elements and an accidentology a risk analysis has been conducted in order to identify all accidental situations that could occur. The workflow included a detailed risk assessment consisting in modeling the thermal and explosion effects of all hazardous phenomena and in assessing the probability of occurrence for these scenarios. Regarding possible mitigation measures the study was based on an international benchmark for codes and standards made for GFHS. These preliminary outcomes of this study may be useful for any designer and/or owner of a GFHS.
Blowout Prediction on a Salt Cavern Selected for a Hydrogen Storage Pilot
Oct 2022
Publication
To prevent climate change Europe and the world must shift to low-carbon and renewable energies. Hydrogen as an energy vector provides viable solutions for replacing polluting and carbon-emitting fossil fuels. Gaseous hydrogen can be stored underground and coupled with existing natural gas pipe networks. Salt cavern storage is the best suited technology to meet the challenges of new energy systems. Hydrogen storage caverns are currently operated in the UK and Texas. A preliminary risk analysis dedicated to underground hydrogen salt caverns highlighted the importance of containment losses (leaks) and the formation of gas clouds following blowouts whose ignition may generate dangerous phenomena such as jet fires unconfined vapor cloud explosions (UVCEs) or flashfires. A blowout is not a frequent accident in gas storage caverns. A safety valve is often set at a 30 m depth below ground level; it is automatically triggered following a pressure drop at the wellhead. Nevertheless a blowout remains to be one of the significant accidental scenarios likely to occur during hydrogen underground storage in salt caverns. In this paper we present modelling the subterraneous and aerial parts of a blowout on an EZ53 salt cavern fully filled with hydrogen.
Circular Economy for the Energy System as a Leverage for Low-carbon Transition: Long-Ter, Analysis of the Case of the South-East Region of France
Mar 2024
Publication
The circular economy is a decisive strategy for reconciling economic development and the environment. In France the CE was introduced into the law in 2015 with the objective of closing the loop. The legislation also delegates energy policy towards the French regions by granting them the jurisdiction to directly plan the energy–climate issues on their territory and to develop local energy resources. Thereby the SUD PACA region has redefined its objectives and targeted carbon neutrality and the transition to a CE by 2050. To study this transition we developed a TIMESPACA optimization model. The results show that following a CE perspective to develop a local energy system could contribute to reducing CO2 emissions by 50% in final energy consumption and reaching almost free electricity production. To obtain greater reductions the development of the regional energy systems should follow a careful policy design favoring the transition to low energy-consuming behavior and the strategical allocation of resources across the different sectors. Biomethane should be allocated to the buildings and industrial sector while hydrogen should be deployed for buses and freight transport vehicles.
Methane Cracking for Hydrogen Production: A Review of Catalytic and Molten Media Pyrolysis
May 2022
Publication
Currently hydrogen is mainly generated by steam methane reforming with significant CO2 emissions thus exacerbating the greenhouse effect. This environmental concern promotes methane cracking which represents one of the most promising alternatives for hydrogen production with theoretical zero CO/CO2 emissions. Methane cracking has been intensively investigated using metallic and carbonaceous catalysts. Recently research has focused on methane pyrolysis in molten metals/salts to prevent both reactor coking and rapid catalyst deactivation frequently encountered in conventional pyrolysis. Another expected advantage is the heat transfer improvement due to the high heat capacity of molten media. Apart from the reaction itself that produces hydrogen and solid carbon the energy source used in this endothermic process can also contribute to reducing environmental impacts. While most researchers used nonrenewable sources based on fossil fuel combustion or electrical heating concentrated solar energy has not been thoroughly investigated to date for pyrolysis in molten media. However it could be a promising innovative pathway to further improve hydrogen production sustainability from methane cracking. After recalling the basics of conventional catalytic methane cracking and the developed solar cracking reactors this review delves into the most significant results of the state-of-the-art methane pyrolysis in melts (molten metals and salts) to show the advantages and the perspectives of this new path as well as the carbon products’ characteristics and the main factors governing methane conversion.
Hydrogen Fuel Quality from Two Main Production Processes: Steam Methane Reforming and Proton Exchange Membrane Water Electrolysis
Oct 2019
Publication
Thomas Bacquart,
Karine Arrhenius,
Stefan Persijn,
Andrés Rojo,
Fabien Auprêtre,
Bruno Gozlan,
Abigail Morris,
Andreas Fischer,
Arul Murugan,
Sam Bartlett,
Niamh Moore,
Guillaume Doucet,
François Laridant,
Eric Gernot,
Teresa E. Fernandez,
Concepcion Gomez,
Martine Carré,
Guy De Reals and
Frédérique Haloua
The absence of contaminants in the hydrogen delivered at the hydrogen refuelling station is critical to ensure the length life of FCEV. Hydrogen quality has to be ensured according to the two international standards ISO 14687–2:2012 and ISO/DIS 19880-8. Amount fraction of contaminants from the two hydrogen production processes steam methane reforming and PEM water electrolyser is not clearly documented. Twenty five different hydrogen samples were taken and analysed for all contaminants listed in ISO 14687-2. The first results of hydrogen quality from production processes: PEM water electrolysis with TSA and SMR with PSA are presented. The results on more than 16 different plants or occasions demonstrated that in all cases the 13 compounds listed in ISO 14687 were below the threshold of the international standards. Several contaminated hydrogen samples demonstrated the needs for validated and standardised sampling system and procedure. The results validated the probability of contaminants presence proposed in ISO/DIS 19880-8. It will support the implementation of ISO/ DIS 19880-8 and the development of hydrogen quality control monitoring plan. It is recommended to extend the study to other production method (i.e. alkaline electrolysis) the HRS supply chain (i.e. compressor) to support the technology growth.
Investigation of an Intensified Thermo-Chemical Experimental Set-Up for Hydrogen Production from Biomass: Gasification Process Integrated to a Portable Purification System—Part II
Jun 2022
Publication
Biomass gasification is a versatile thermochemical process that can be used for direct energy applications and the production of advanced liquid and gaseous energy carriers. In the present work the results are presented concerning the H2 production at a high purity grade from biomass feedstocks via steam/oxygen gasification. The data demonstrating such a process chain were collected at an innovative gasification prototype plant coupled to a portable purification system (PPS). The overall integration was designed for gas conditioning and purification to hydrogen. By using almond shells as the biomass feedstock from a product gas with an average and stable composition of 40%-v H2 21%-v CO 35%-v CO2 2.5%-v CH4 the PPS unit provided a hydrogen stream with a final concentration of 99.99%-v and a gas yield of 66.4%.
THyGA - Tightness Testing of Gas Distribution Components in 40%H2+60%CH4
Aug 2022
Publication
The present work is concerned with the evaluation of the tightness of the components located on domestic and commercial gas lines from the gas meter to the end user appliance in presence of a mixture 40%H2+60%CH4 at 35 mbar. The components were taken from installations being used currently in Germany Denmark Belgium and France. The current standard methods to evaluate natural gas distribution tightness propose testing duration of several minutes. In this work the components tightness was first evaluated using such standard methods before carrying out tests on longer period of time and evaluate the potential influence of time and the results were compared to admissible leakage rates for natural gas in distribution network and in appliances.
Renewable Hydrogen Production Processes for the Off-Gas Valorization in Integrated Steelworks through Hydrogen Intensified Methane and Methanol Syntheses
Nov 2020
Publication
Within integrated steelmaking industries significant research efforts are devoted to the efficient use of resources and the reduction of CO2 emissions. Integrated steelworks consume a considerable quantity of raw materials and produce a high amount of by-products such as off-gases currently used for the internal production of heat steam or electricity. These off-gases can be further valorized as feedstock for methane and methanol syntheses but their hydrogen content is often inadequate to reach high conversions in synthesis processes. The addition of hydrogen is fundamental and a suitable hydrogen production process must be selected to obtain advantages in process economy and sustainability. This paper presents a comparative analysis of different hydrogen production processes from renewable energy namely polymer electrolyte membrane electrolysis solid oxide electrolyze cell electrolysis and biomass gasification. Aspen Plus® V11-based models were developed and simulations were conducted for sensitivity analyses to acquire useful information related to the process behavior. Advantages and disadvantages for each considered process were highlighted. In addition the integration of the analyzed hydrogen production methods with methane and methanol syntheses is analyzed through further Aspen Plus®-based simulations. The pros and cons of the different hydrogen production options coupled with methane and methanol syntheses included in steelmaking industries are analyzed
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