Publications

Recent studies of J.H. Song et al. and S.Y. Yang et al. have been concentrated on mitigation measures against hydrogen risk. The authors have proposed installation of quenching meshes between compartments or around the essential equipment in order to contain hydrogen flames. Preliminary tests were conducted which demonstrated the possibility of flame extinction using metallic meshes of specific size.<br/>Considerable amount of numerical and theoretical work on flame quenching phenomenon has been performed in the second half of the last century and several techniques and models have been proposed to predict the quenching phenomenon of the laminar flame system. Most of these models appreciated the importance of heat loss to the surroundings as a primary cause of extinguishment in particular the heat transfer by conduction to the containing wall. The supporting simulations predict flame-quenching structure either between parallel plates (quenching distance) or inside a tube of a certain diameter (quenching diameter).<br/>In the present study the flame quenching is investigated assuming the laminar hydrogen flame propagating towards a quenching mesh using two-dimensional configuration and the earlier developed models. It is shown that due to a heat loss to a metallic grid the flame can be quenched numerically.

In searching for high gravimetric and volumetric density hydrogen storage systems it is inevitable that higher energy density materials will be used. In order to make safe and commercially acceptable condensed phase hydrogen storage systems it is important to understand quantitatively the hazards involved in using and handling these materials and to develop appropriate mitigation strategies to handle potential material exposure events. A crucial aspect of the development of risk identification and mitigation strategies is the development of rigorous environmental reactivity testing standards and procedures. This will allow for the identification of potential hazards and implementation of risk mitigation strategies. Modified testing procedures for shipping air and/or water sensitive materials as codified by the United Nations have been used to evaluate two potential hydrogen storage materials 2LiBH4·MgH2 and NH3BH3. The modified U.N. procedures include identification of self-reactive substances pyrophoric substances and gas-emitting substances with water contact. The results of these tests for air and water contact sensitivity will be compared to the pure material components where appropriate (e.g. LiBH4 and MgH2). The water contact tests are divided into two scenarios dependent on the hydride to water mole ratio and heat transport characteristics. Air contact tests were run to determine whether a substance will spontaneously react with air in a packed or dispersed form. Relative to 2LiBH4·MgH2 the chemical hydride NH3BH3 was observed to be less environmentally reactive.

Where does hydrogen fit into a global sustainable energy strategy for the 21st century as we face the enormous challenges of irreversible climate change and uncertain oil supply? This fundamental question is addressed by sketching a sustainable energy strategy that is based predominantly on renewable energy inputs and energy efficiency with hydrogen playing a crucial and substantial role. But this role is not an ex -distributed hydrogen production storage and distribution centres relying on local renewable energy sources and feedstocks would be created to avoid the need for an expensive long-distance hydrogen pipeline system. There would thus be complementary use of electricity and hydrogen as energy vectors. Importantly bulk hydrogen storage would provide the strategic energy reserve to guarantee national and global energy security in a world relying increasingly on renewable energy; and longer-term seasonal storage on electricity grids relying mainly on renewables. In the transport sector a 'horses for courses' approach is proposed in which hydrogen fuel cell vehicles would be used in road and rail vehicles requiring a range comparable to today's petrol and diesel vehicles and in coastal and international shipping while liquid hydrogen would probably have to be used in air transport. Plug-in battery electric vehicles would be reserved for shorter-trips. Energy-economic-environmental modelling is recommended as the next step to quantify the net benefits of the overall strategy outlined.

In socio-economics it is well known that the success of an innovation process not only depends upon the technological innovation itself or the improvement of economic and institutional system boundaries but also on the public acceptance of the innovation. The public acceptance can as seen with genetic engineering for agriculture be an obstacle for the development and introduction of a new and innovative idea. In respect to hydrogen technologies this means that the investigation compilation and communication of scientific risk assessments are not sufficient to enhance or generate public acceptance. Moreover psychological social and cultural aspects of risk perception have to be considered when introducing new technologies. Especially trust and familiarity play an important role for risk perception and thus public acceptance of new technologies.

It is important to understand and quantify the potential risk resulting from accidental environmental exposure of condensed phase hydrogen storage materials under differing environmental exposure scenarios. This paper describes a modelling and experimental study with the aim of predicting consequences of the accidental release of 2LiBH₄+MgH₂ from hydrogen storage systems. The methodology and results developed in this work are directly applicable to any solid hydride material and/or accident scenario using appropriate boundary conditions and empirical data.

The ability to predict hydride behaviour for hypothesized accident scenarios facilitates an assessment of the risk associated with the utilization of a particular hydride. To this end an idealized finite volume model was developed to represent the behaviour of dispersed hydride from a breached system. Semi-empirical thermodynamic calculations and substantiating calorimetric experiments were performed in order to quantify the energy released energy release rates and to quantify the reaction products resulting from water and air exposure of a lithium borohydride and magnesium hydride combination.

The hydrides LiBH₄ and MgH₂ were studied individually in the as-received form and in the 2:1 “destabilized” mixture. Liquid water hydrolysis reactions were performed in a Calvet calorimeter equipped with a mixing cell using neutral water. Water vapor and oxygen gas phase reactivity measurements were performed at varying relative humidities and temperatures by modifying the calorimeter and utilizing a gas circulating flow cell apparatus. The results of these calorimetric measurements were compared with standardized United Nations (UN) based test results for air and water reactivity and used to develop quantitative kinetic expressions for hydrolysis and air oxidation in these systems. Thermodynamic parameters obtained from these tests were then inputted into a computational fluid dynamics model to predict both the hydrogen generation rates and concentrations along with localized temperature distributions. The results of these numerical simulations can be used to predict ignition events and the resultant conclusions will be discussed.

This study investigated a pre-cooled turbojet engine for a Mach 5 class hypersonic transport aircraft. The engine was demonstrated under takeoff and Mach 2 flight conditions and a Mach 5 propulsion wind tunnel test is planned. The engine is composed of a pre-cooler a core engine and an afterburner. The engine was tested under simulated Mach 4 conditions using an air supply facility. High-temperature air under high pressure was supplied to the engine components through an airflow control valve and an orifice flow meter and liquid hydrogen was supplied to the pre-cooler and the core engine. The results confirmed that the starting sequence of the engine components was effective under simulated Mach 4 conditions using liquid hydrogen fuel. The pre-cooling effect caused no damage to the rotating parts of the core engine in the experiment.

A buoyant round vertical hydrogen jet is investigated using Large Eddy Simulations at low Mach number (M = 0.3). The influence of the transient concentration fields on the extent of the gas envelope with concentrations within the flammability limits is analyzed and their structure are characterized. The transient flammable region has a complex structure that extends up to 30% beyond the time-averaged flammable volume with high concentration pockets that persist sufficiently long for potential ignition. Safety envelopes devised on the basis of simplified time-averaged simulations would need to include a correction factor that accounts for transient incursions of high flammability concentrations.

The temperature of the hydrogen cylinder needs to be carefully controlled during fuelling process. The maximum temperature should be less than 85℃ according to the ISO draft code. If the fuelling period is reduced the maximum temperature should increase. In this study temperature change of a Type IV cylinder was measured during the hydrogen fuelling process up to 35 MPa. Fuelling period was 3 to 5 minutes. Twelve thermocouples were installed to measure inside gas temperature and seven were attached on the outside of the cylinder. An infrared camera was also used for measuring temperature distribution of outside of cylinder. The maximum gas temperature was higher than 85℃ inside of the cylinder. Significant temperature difference between the upper and lower part of the vessel was observed. Temperature near the plug and the valve was quickly increased and maintained higher than that of the other region. Temperature increases for the partial refuelling process were also discussed.

To advance hydrogen into the energy market it is necessary to consider risk assessment for scenarios that are complicated by accidental hydrogen release mixing with other combustible hydrocarbon fuels. The paper is aimed at examining the effect of mixing the hydrocarbon and inert gas into the hydrogen flame on the kinetic mechanisms the laminar burning velocity and the flame stability. The influences of hydrogen concentration on the flame burning velocity were determined for the hydrogen/propane (H2-C3H8) hydrogen/ethane (H2-C2H6) hydrogen/methane (H2-CH4) and hydrogen/carbon dioxide (H2-CO2) mixtures. Experimental tests were carried out to determine the lift-off blow-out and blowoff stability limits of H2 H2-C3H8 H2-C2H6 H2-CH4 and H2-CO2 jet flames in a 2 mm diameter burner. The kinetic mechanisms of hydrogen interacting with C3 C2 and C1 fuels is analysed using the kinetic mechanisms for hydrocarbon combustion.

The objectives of the presented experimental work were investigation of hydrogen release distribution and combustion modelling possible emergency situation at industry scale. Results of large scale experiments on distribution and combustion in an open and congested area are presented. The mass of hydrogen in experiments varied from 50g to 1000g with release rate from 180 to 220 g/s. Qualitative characteristics of high momentum hydrogen jet releases distribution and subsequent combustion were obtained. It is shown that obstacles slow down jet speed promote combustible mixture formation in a large volume and accelerate combustion process. The maximum overpressure in experiments with additional congested area reached ΔР = 0.4 atm. Using partial confinement of congested area turbulent combustion regime with the maximum overpressure more than 10 atm. was obtained.

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.

The lack of experimental data on hydrogen dispersion led to the experimental project DRIVE (Experimental Data for Hydrogen Automotive Risks Assessment for the validation of numerical tools and for the Edition of guidelines) that involves the CEA (French Atomic Energy Commission) the National Institute of Industrial Environment and Risks (INERIS) the French car manufacturer PSA PEUGEOT CITROËN and the Research Institute on Out of Equilibrium Phenomena (IRPHE). The CEA has developed an experimental setup named GARAGE in order to analyze the condition of formation of an explosive atmosphere in an enclosure. This is a full scale facility in which a real car can be parked. Hydrogen releases were simulated with helium which volume fraction was measured with mini-katharometers. These thermal conductivity probes allow spatial and time volume fraction variations measurements. We present experimental results on the dispersion of helium in the enclosure due to releases in a typical car. The tested parameters are the location of the source (engine bottom of the car storage) and the flow rate. Emphasis is put on the influence of these parameters on the time evolution of the volume fraction in the enclosure as well as on the vertical distribution of helium.

In the context of hydrogen production from biomass or organic waste with dark fermentation this study analysed 55 studies (339 experiments) in the literature looking for the effect of operating parameters on the process performance of dark fermentation. The effect of substrate concentration pH temperature and residence time on hydrogen yield productivity and content in the biogas was analysed. In addition a linear regression model was developed to also account for the effect of nature and pretreatment of the substrate inhibition of methanogenesis and continuous or batch operating mode. The analysis showed that the hydrogen yield was mainly affected by pH and residence time with the highest yields obtained for low pH and short residence time. High hydrogen productivity was favoured by high feed concentration short residence time and low pH. More modest was the effect on the hydrogen content. The mean values of hydrogen yield productivity and content were respectively 6.49% COD COD−1 135 mg L−1 d −1 51% v/v while 10% of the considered experiments obtained yield productivity and content of or higher than 15.55% COD COD−1 305.16 mg L−1 d −1 64% v/v. Overall this study provides insight into how to select the optimum operating conditions to obtain the desired hydrogen production.

Experimental data from vented explosion tests using lean hydrogen–air mixtures with concentrations from 12 to 19% vol. are presented. A 63.7-m3 chamber was used for the tests with a vent size of either 2.7 or 5.4 m2. The tests were focused on the effect of hydrogen concentration ignition location vent size and obstacles on the pressure development of a propagating flame in a vented enclosure. The dependence of the maximum pressure generated on the experimental parameters was analyzed. It was confirmed that the pressure maxima are caused by pressure transients controlled by the interplay of the maximum flame area the burning velocity and the overpressure generated outside of the chamber by an external explosion. A model proposed earlier to estimate the maximum pressure for each of the main pressure transients was evaluated for the various hydrogen concentrations. The effect of the Lewis number on the vented explosion overpressure is discussed.

Any technical installation need appropriate safety barriers installed to prevent or mitigate any adverse effects concerning people property and environment. In this context a safety barrier is a series of elements each consisting of a technical system or human action that implement a planned barrier function to prevent control or mitigate the propagation of a condition or event into an undesired condition or event. This is also important for new technologies as hydrogen refuelling stations being operated at very high pressures up to 900bar. In order to establish the needed barriers a hazard identification of the installation has to be carried out to identify the possible hazardous events. In this study this identification was done using the generic layout of a future large hydrogen refuelling station that has been developed by the EU NoE HySafe. This was based on experiences with smaller scale refuelling stations that has been in operation for several years e.g. being used in the former CUTE and ECTOS projects. Using this approach the object of the study is to support activities to further improve the safety performance of future larger refuelling stations. This will again help to inform the authorities and the public to achieve a proper public awareness and to support building up a realistic risk and safety perception of the safety on such future refuelling stations. In the second step the hazardous events that may take place and the barriers installed to stop hazards and their escalation are analysed also using in-house developed software to model the barriers and to quantify their performance. The paper will present an overview and discuss the state-of-the-art of the barriers established in the generic refuelling station.

In this paper the deflagration region and characteristics of the hydrogen flow which was generated by high-pressure hydrogen discharge from storage vessels were studied. A 3-D analytic model is established based on the species transfer model and the SST k −ω turbulence model. The established model is applied to the research of the flow characteristics of the hydrogen under-expanded jet under different filling pressures of 30 MPa 35 MPa and 40 MPa respectively. The evolution process of hydrogen combustible cloud is analyzed under the filling pressure of 30 MPa. It is revealed that a supersonic jet is formed after the high-pressure hydrogen discharge outlet In the vicinity of the Mach disk the hydrogen jet velocity and temperature reach the maximum values and the variation of filling pressure has little effect on the peak values of the hydrogen jet flow velocity and temperature during the considered pressure range. In the rear of the Mach disk the variation rates of the hydrogen flow velocity and temperature are in inversely proportional to the hydrogen filling pressure. At the preliminary stage the discharged hydrogen is apple-shaped which expands along the radial and then the axial growth rate of the hydrogen cloud increases with the passage of time.

To avoid failures due to hydrogen embrittlement it is important to know the amount of hydrogen absorbed by certain steel grades under service conditions. When a critical hydrogen content is reached the material properties begin to deteriorate. The hydrogen uptake and embrittlement of three different carbon steels (API 5CT L80 Type 1 P110 and 42CrMo4) was investigated in autoclave tests with hydrogen gas (H₂) at elevated pressure and in ambient pressure tests with hydrogen sulfide (H₂S). H₂ gas with a pressure of up to 100 bar resulted in an overall low but still detectable hydrogen absorption which did not cause any substantial hydrogen embrittlement in specimens under a constant load of 90% of the specified minimum yield strength (SMYS). The amount of hydrogen absorbed under conditions with H₂S was approximately one order of magnitude larger than under conditions with H₂ gas. The high hydrogen content led to failures of the 42CrMo4 and P110 specimens.

An efficient production of hydrogen from a mixture of methanol and water is possible in a spark discharge. In this discharge there is a synergistic effect of high-energy electrons and high temperature interactions which enables an efficient course of endothermic processes such as the production of hydrogen from methanol. The water to methanol molar ratio of 1:1 was kept constant during the study. While the discharge power and feed flow rate were varied from 15 to 55 W and from 0.25 to 2 mol/h respectively which corresponded to the residence time of the reactants in the plasma zone from 58 to 7 ms. The cooled gas mixture contained 56 to 60% of H2. Other gaseous products of the process were CO CO2 and a small amount of CH4. The maximum energy yield was 16.2 mol(H2)/kWh which represents 20% of the theoretical energy yield when the substrates are in a liquid phase.

The use of hydrogen as an energy carrier is a real perspective for Europe since a number of breakthroughs now enable to envision a deployment at the industrial scale. However some safety issues need to be further addressed but experimental data are still lacking especially about the explosion dynamics in realistic dimensions. A set of hydrogen-air vented explosions were thus performed in two medium scale chambers (1 m3 and 10 m3). Homogeneous mixtures were used (10% to 30% vol.). The explosion overpressure was measured inside the chamber and outside on the axis of the discharge from the vent. The incidence of the external explosion is clearly seen. All the results in this paper and the predictions from the standards differ greatly meaning that a significant effort is still required. It is the purpose of the French project DIMITRHY to help progressing.

This paper describes a series of numerical simulations with release and ignition of hydrogen. The objective of this work was to re-investigate the accidental explosion in an ammonia plant which happened in Norway in 1985 with modern CFD tools. The severe hydrogen-air explosion led to two fatalities and complete destruction of the factory building where the explosion occurred. A case history of the accident was presented at the 1.st ICHS in Pisa 2005.<br/>The numerical simulations have been performed with FLACS a commercial CFD simulation tool for gas dispersion and gas explosions. The code has in the recent years been validated in the area of hydrogen dispersion and explosions.<br/>The factory building was 100 m long 10 m wide and 7 m high. A blown-out gasket in a water pump led to release of hydrogen from a large reservoir storing gaseous hydrogen at 3.0 MPa. The accident report estimated a total mass of released hydrogen between 10 and 20 kg. The location of the faulty gasket is known but the direction of the accidental release is not well known and has been one of the topics of our investigations. Several simulations have been performed to investigate the mixing process of hydrogen-air clouds and the development of a flammable gas cloud inside the factory building resulting in a simulation matrix with dispersions in all axis directions. Simulations of ignition of the different gas clouds were carried out and resulting pressure examined. These results have been compared with the damages observed during the accident investigation.<br/>We have also performed FLACS simulations to study the effect of natural venting and level of congestion. The height of the longitudinal walls has been varied leading to different vent openings at floor level at the ceiling and a combination of the two. This was done to investigate the effects of congestion with regards to gas cloud formation.<br/>The base case simulation appears to be in good accordance to the observed damages from the accident. The simulations also show that the build up of the gas cloud strongly depends on the direction of the jet and degree of ventilation. The CFD study has given new insights to the accident and the results are a clear reminder of the importance of natural venting in hydrogen safety.

In 2003 the US Department of Energy (DOE) initiated a project to coordinate the development of a national template of hydrogen codes and standards for both vehicular and stationary applications. The process consisted of an initial evaluation to determine where there were gaps in the existing hydrogen codes and standards and the codes and standards required to fill these gaps. These codes and standards were to be developed by several Standards Development Organizations (SDOs). This effort to develop codes and standards has progressed from a position in 2003 when there were relatively few codes and standards that directly addressed hydrogen technology applications to the position at the end of 2008 where requirements to permit hydrogen technologies have been implemented in primary adopted codes- building and fire codes in hydrogen specific codes such as National Fire Protection Association (NFPA) 52 NFPA 55 and NFPA 853 and in many of the hydrogen specific component standards that are referenced primarily in the NFPA codes and standards. This paper describes the three levels of codes and standards that address hydrogen technologies for the built environment:<br/>Level 1. Primary adopted building and fire codes<br/>Level 2. Hydrogen specific codes and standards references in primary adopted code<br/>Level 3. Hydrogen specific component standards referenced in hydrogen specific codes<br/>This paper also describes the progress to date in populating these three levels with the required hydrogen codes and standards. The first two levels are essentially complete and are undergoing refinement and routine revision. Level 3 the hydrogen specific component standards is the furthest from having first edition documents that address requirements for a hydrogen system component.<br/>The DOE is focusing much of their codes and standards development efforts on these hydrogen specific component standards with the expectation that a first edition of most of these standards will be issued by 2010.

The integration of a hydrogen gas storage arrangement in vehicles has not been without its challenges. Gaseous state of hydrogen at ambient temperature combined with the fact that hydrogen is highly flammable results in the requirement of more robust high pressure storage systems that can meet modern safety standards. To develop these new safety standards and to properly predict the phenomena of hydrogen dispersion a better understanding of the resulting flow structures and flammable region from controlled and uncontrolled releases of hydrogen gas must be achieved. With the upper and lower explosive limits of hydrogen known the flammable envelope surrounding the site of a uncontrolled hydrogen release can be found from the concentration field. In this study the subsonic release of hydrogen was emulated using helium as a substitute working fluid. A sharp orifice round turbulent jet is used to emulate releases in which leak geometry is circular. Effects of buoyancy and crossflow were studied over a wide range of Froude numbers. The velocity fields of turbulent jets were characterized using particle image velocimetry (PIV). The mean and fluctuation velocity components were well quantified to show the effect of buoyancy due to the density difference between helium and the surrounding air. In the range of Froude numbers investigated (Fr = 1000 750 500 250 and 50) the increasing effects of buoyancy were seen to be proportional to the reduction of the Fr number. While buoyancy is experienced to have a negligible effect on centerline velocity fluctuations acceleration due to buoyancy in the other hand resulted in a slower decay of time-averaged axial velocity component along the centerline. The obtained results will serve as control reference values for further concentration measurement study and for computational fluid dynamics (CFD) validation.

A three-dimensional mathematical model of gaseous hydrogen deflagration in the enclosed space is developed. The process is described by the system of gas dynamics differential equations. Thermodynamic parameters of the mixture and its components are defined as functions of the local temperature and mixture composition. The concentration changes of the fuel and combustion products are determined using conservation laws taking into account rates of component disappearance and formation and turbulent diffusion. It is assumed that the chemical reaction takes place only in the volume where the fuel concentration is within the limits of inflammability. The mathematical model is validated during an intercomparison test to predict deflagration of a large-scale hydrogen-air mixture in open atmosphere. An algorithm of numerical solution based on the Godunov method is developed. A computer system of engineering analysis of gas-dynamic processes of hydrogen-air mixture formation and combustion in enclosed space with natural ventilation is created. It allows predicting the history of the changes of overpressure temperature concentrations of hydrogen and combustion products and other thermogasdynamic parameters of the mixture in space. This prognosis can be used to estimate dangerous zones of destruction and recommend some safety measures.

The development of a hydrogen-based economy is the perfect nexus between the need of discontinuing the use of fossil fuels (trying to mitigate climate change) the development of a system based on renewable energy (with the use of hydrogen allowing us to buffer the discontinuities produced in this generation) and the achievement of a local-based robust energy supply system. However extending the use of hydrogen as an energy vector must still overcome challenging issues with the key issues being related to its storage. Cryogenic or pressurized storage is relatively expensive technically complex and presents important safety concerns. As a promising alternative the use of organic hydrogen carriers has been suggested in recent years. The ideal carrier will be an organic compound with a low melting point and low viscosity with a significant number of unsaturated carbon–carbon bonds in addition to being easy to hydrogenate and dehydrogenate. These properties allow us to store and transport hydrogen in infrastructures designed for liquid fuels thus facilitating the replacement of fossil fuels by hydrogen

In this study the authors present a techno-economic assessment of on-site hydrogen refuelling stations (450 kg/day of H2 ) based on different hydrogen sources and production technologies. Green ammonia biogas and water have been considered as hydrogen sources while cracking autothermal reforming and electrolysis have been selected as the hydrogen production technologies. The electric energy requirements of the hydrogen refuelling stations (HRSs) are internally satisfied using the fuel cell technology as power units for ammonia and biogas-based configurations and the PV grid-connected power plant for the water-based one. The hydrogen purification where necessary is performed by means of a Palladium-based membrane unit. Finally the same hydrogen compression storage and distribution section are considered for all configurations. The sizing and the energy analysis of the proposed configurations have been carried out by simulation models adequately developed. Moreover the economic feasibility has been performed by applying the life cycle cost analysis. The ammonia-based configurations are the best solutions in terms of hydrogen production energy efficiency (>71% LHV) as well as from the economic point of view showing a levelized cost of hydrogen (LCOH) in the range of 6.28 EUR/kg to 6.89 EUR/kg a profitability index greater than 3.5 and a Discounted Pay Back Time less than five years.