Safety

From 2006 to 2009 INERIS alongside with CEA PSA PEUGEOT CITROËN and IRPHE were involved in a project called DRIVE. Its objective was to provide data on the whole reaction chain leading to a hydrogen hazard onboard a vehicle. Out of the three types of leakage identified by the consortium (permeation chronic and accidental) the chronic leakage taking place within the engine was judged to be more problematic since it can feature a high probability of occurrence and a significant release flow rate (up to 100 NL/min). Ignition tests carried out within a real and dummy engine compartment showed that pressure effects due to an explosion will be relatively modest provided that the averaged hydrogen concentration in this area is limited to 10% vol/vol which would correspond to a maximum release flow of 10 NL/min. This maximum concentration could be used as a threshold value for detection or as a target while designing the vehicle. Jet fire experiments were also conducted in the frame of the DRIVE project. It was found that pressure-relief devices (PRDs) might be unsuited to protect humans from the explosion of a tank caused by a bonfire. Other solutions are proposed in this paper.

In order to simulate an accidental hydrogen release from the low pressure pipe system of a hydrogen vehicle a systematic study on the nature of transient hydrogen jets into air and their combustion behaviour was performed at the FZK hydrogen test site HYKA. Horizontal unsteady hydrogen jets with an amount of hydrogen up to 60 STP dm3 and initial pressures of 5 and 16 bar have been investigated. The hydrogen jets were ignited with different ignition times and positions. The experiments provide new experimental data on pressure loads and heat releases resulting from the deflagration of hydrogen-air clouds formed by unsteady turbulent hydrogen jets released into a free environment. It is shown that the maximum pressure loads occur for ignition in a narrow position and time window. The possible hazard potential arising from an ignited free transient hydrogen jet is described.

This paper discusses the results of computational fluid dynamics (CFD) modelling of hydrogen releases and dispersion outdoors during venting of hydrogen storage in real environment and geometry of a hydrogen refuelling or energy station for a given flow rate and dimensions of vent stack. The PHOENICS CFD software package was used to solve the continuity momentum and concentration equations with the appropriate boundary conditions buoyancy model and turbulence models. Also thermal effects resulting from potential ignition of flammable hydrogen clouds were assessed using TNO “Yellow Book” recommended approaches. The obtained results were then applied to determine appropriate clearance distances for venting of hydrogen storage for contribution to code development and station design considerations. CFD modelling of hydrogen concentrations and TNO-based modelling of thermal effects have proven to be reliable effective and relatively inexpensive tools to evaluate the effects of hydrogen releases.

Hydrogen jet flames resulting from ignition of unintended releases can be extensive in length and pose significant radiation and impingement hazards. One possible mitigation strategy to reduce exposure to jet flames is to incorporate barriers around hydrogen storage and delivery equipment. While reducing the extent of unacceptable consequences the walls may introduce other hazards if not properly configured. This paper describes experiments carried out to characterize the effectiveness of different barrier wall configurations at reducing the hazards created by jet fires. The hazards that are evaluated are the generation of overpressure during ignition the thermal radiation produced by the jet flame and the effectiveness of the wall at deflecting the flame.<br/>The tests were conducted against a vertical wall (1-wall configuration) and two “3-wall” configurations that consisted of the same vertical wall with two side walls of the same dimensions angled at 135° and 90°. The hydrogen jet impinged on the center of the central wall in all cases. In terms of reducing the radiation heat flux behind the wall the 1-wall configuration performed best followed by the 3-wall 135° configuration and the 3-wall 90°. The reduced shielding efficiency of the three-wall configurations was probably due to the additional confinement created by the side walls that limited the escape of hot gases to the sides of the wall and forced the hot gases to travel over the top of the wall.<br/>The 3-wall barrier with 135° side walls exhibited the best overall performance. Overpressures produced on the release side of the wall were similar to those produced in the 1-wall configuration. The attenuation of overpressure and impulse behind the wall was comparable to that of the three-wall configuration with 90° side walls. The 3-wall 135° configuration’s ability to shield the back side of the wall from the heat flux emitted from the jet flame was comparable to the 1-wall and better than the 3-wall 90° configuration. The ratio of peak overpressure (from in front of the wall and from behind the wall) showed that the 3-wall 135° configuration and the 3-wall 90° configuration had a similar effectiveness. In terms of the pressure mitigation the 3-wall configurations performed significantly better than the 1-wall configuration

Clarification of questions of safety represents a decisive contribution to the successful introduction of vehicles fuelled by hydrogen. At the moment the safety of hydrogen is being discussed and investigated by various bodies. The primary focus is on fuel-cell vehicles with hydrogen stored in gaseous form. This paper looks at the safety of hydrogen-fuelled vehicles with an internal combustion engine and liquefied hydrogen storage. The safety concept of BMW’s hydrogen vehicles is described and the specific aspects of the propulsion and storage concepts discussed. The main discussion emphasis is on the utilization of boil-off parking of the vehicles in an enclosed space and their crash behaviour. Theoretical safety observations are complemented by the latest experimental and test results. Finally reference is made to the topic-areas in the field of hydrogen safety in which cooperative research work could make a valuable contribution to the future of the hydrogen-powered vehicle.

In the course towards a safe future hydrogen based society one of the tasks to be considered is the investigation of the conditions under which the use or storage of hydrogen systems inside buildings becomes too dangerous to be accepted. One of the relevant scenarios which is expected to have a relatively high risk is a slow (and long lasting) hydrogen release from a vehicle stored in a closed private garage without any forced ventilation i.e. only with natural ventilation. This scenario has been earlier investigated experimentally (by M. Swain) using He (helium) to simulate the hydrogen behavior. In the present work the CFD code ADREA-HF is used to simulate three of the abovementioned experiments using the standard k-  turbulence model. For each case modeled the predicted concentration (by vol.) time series are compared against the experimental at the given sensor locations. In addition the structure of the flow is investigated by presenting the helium concentration field.

In this paper a vertical turbulent round jet of helium was studied numerically using the PHOENICS software package. The flow was assumed to be steady incompressible and turbulent. The jet discharge Froude number was 14000 and the turbulent Schmidt number was 0.7. The incompressible Reynolds average Navier-Stokes equations and helium transport equation expressed in 2-D axisymmetric domain were applied to model the underlying helium release. The k-e RNG turbulence model was used for the calculations of the corresponding turbulent viscosity diffusivity velocity and concentration fields in the domain. The simulation results are compared with the experimental measurements from the earlier published studies on helium jets in non-buoyant jet region (NBJ) intermediate region (I) and buoyant plume region (BP). The numerical results show that the radial profiles of mean velocity and mean concentration are consistent with the empirical data scaled by the effective diameter and density-ratio dependence. The mean velocity and concentration fields along the axis of the jet agree with the decay laws correlated from the previous experiments. The discrepancy between the numerical and experimental data is within 10% proving that the current CFD model for gas release and dispersion is robust accurate and reliable and that the CFD technique can be used as an alternative to the experiments with similar helium jets. The authors believe that the current CFD model is well validated through this study and can be further extended to predict similar hydrogen releases and dispersion if the model is properly applied with hydrogen properties.

Wet dust removal systems used to control dust in the polishing or grinding process of Mg alloy products are frequently associated with potential hydrogen explosion caused by magnesium-water reaction. For purpose of avoiding hydrogen explosion risks we try to use a combination of chitosan (CS) and sodium phosphate (SP) to inhibit the hydrogen evolution reaction between magnesium alloy waste dust and water. The hydrogen evolution curves and chemical kinetics modeling for ten different mixing ratios demonstrate that 0.4% wt CS + 0.1% wt SP yields the best inhibition efficiency with hydrogen generation rate of almost zero. SEM and EDS analyses indicate that this composite inhibitor can create a uniform smooth tight protective film over the surface of the alloy dust particles. FTIR and XRD analysis of the chemical composition of the surface film show that this protective film contains CS and SP chemically adsorbed on the surface of ZK60 but no detectable Mg(OH)2 suggesting that magnesium-water reaction was totally blocked. Our new method offers a thorough solution to hydrogen explosion by inhibiting the hydrogen generation of magnesium alloy waste dust in a wet dust removal system.

Abatement of greenhouse gas emissions and diversification of energy sources will probably lead to an economy based on hydrogen. In order to evaluate safety conditions during transport and distribution experimental data is needed on the detonation of Hydrogen/Natural gas blend mixtures. The aim of this study is to constitute detonation and deflagration to detonation transition (DDT) database of H2/CH4-air mixtures. More precisely the detonability of such mixtures is evaluated by the detonation cell size and the DDT run up distance measurements. Large experimental conditions are investigated (i) various equivalence ratios from 0.6 to 3 (ii) various H2 molar fraction x ( ( )2 2 4x H H CH= + ) from 0.5 to 1 (iii) different initial pressure P0 from 0.2 to 2 bar at fixed ambient temperature T0=293 K. Detonation pressures P velocities D and cell sizes ? were measured in two smooth tubes with different i.d. d (52 and 106 mm). For DDT data minimum DDT run up distances LDDT were determined in the d=52 mm tube containing a 2.8 m long Schelkin spiral with a blockage ratio BR = 0.5 and a pitch equal to the diameter. Measured detonation velocities D are very close to the Chapman Jouguet values (DCJ). Concerning the effect of detonation cell size ? follows a classical U shaped- curve with a minimum close to =1 and concerning the effect of x ? decreases when x increases. The ratio ik L?= obtained from different chemical kinetics (Li being the ZND induction length) is well approximated by the value 40 in the range 0.5 < x < 0.9 and 50 for x 0.9. Minimum DDT run up distance LDDT varies from 0.36 to 1.1m when x varies from 1 to 0.8. The results show that LDDT obeys the linear law LDDT ~ 30-40? previously validated in H2/Air mixtures. Adding Hydrogen in Natural Gas promotes the detonability of the mixtures and for x 0.65 these mixtures are considered more sensitive than common heavy Alkane-Air mixtures.

This paper discusses the preliminary results of the Risk Management subtask efforts within the International Energy Agency (IEA) Hydrogen Implementing Agreement (HIA) Task 19 on Hydrogen Safety to develop uniform harm criteria for use in the Quantitative Risk Assessments (QRAs) of hydrogen facilities. The IEA HIA Task 19 efforts are focused on developing guidelines and criteria for performing QRAs of hydrogen facilities. The performance of QRAs requires that the level of harm that is represented in the risk evaluation be established using deterministic models. The level of harm is a function of the type and level of hazard. The principle hazard associated with hydrogen facilities is uncontrolled accumulation of hydrogen in (semi) confined spaces and consecutive ignition. Another significant hazard is combustion of accidentally released hydrogen gas or liquid which may or may not happen instantaneously. The primary consequences from fire hazards consist of personnel injuries or fatalities or facility and equipment damage due to high air temperatures radiant heat fluxes or direct contact with hydrogen flames. The possible consequences of explosions on humans and structures or equipment include blast wave overpressure effects impact from fragments generated by the explosion the collapse of buildings and the heat effects from subsequent fire balls. A harm criterion is used to translate the consequences of an accident evaluated from deterministic models to a probability of harm to people structures or components. Different methods can be used to establish harm criteria including the use of threshold consequence levels and continuous functions that relate the level of a hazard to a probability of damage. This paper presents a survey of harm criteria that can be utilized in QRAs and makes recommendations on the criteria that should be utilized for hydrogen-related hazards.

A series of experiments are described in which helium was released at a constant rate into a 1.5 m × 1.5 m × 0.75 m enclosure designed as a ¼-scale model of a two car garage. The purpose was to provide reference data sets for testing and validating computational fluid dynamics (CFD) models and to experimentally characterize the effects of a number of variables on the mixing behaviour within an enclosure and the exchange of helium with the surroundings. Helium was used as a surrogate for hydrogen and the total volume released was scaled as the amount that would be released by a typical hydrogen fuelled automobile with a full tank. Temporal profiles of helium were measured at seven vertical locations within the enclosure during and following one hour and four hour releases. Idealized vents in one wall sized to provide air exchange rates typical of actual garages were used. The effects of vent size number and location were investigated using three different vent combinations. The dependence on leak location was considered by releasing helium from three different points within the enclosure. It is shown that the National Institute of Standards and Technology (NIST) CFD code Fire Dynamics Simulator (FDS) provides time resolved predictions for helium concentrations that agree well with the experimental measurements.

Computational fluid dynamics is used to simulate the release of high pressure Hydrogen from a reservoir with an exit of increasing diameter. Abel-Noble real gas equation of state is used to accurately simulate this high pressure release. Parallel processing based on Message Passing Interface for domain decomposition is employed to decrease the solution time. The release exit boundary is increased in time to simulate a scenario when the exit area increases during the release. All nodes and elements are moved accordingly at each time step to maintain the quality of the mesh. Different speeds of increasing diameter are investigated to see the impact on this unsteady flow.

High resolution numerical simulations used to study the mechanism of deflagration-to-detonation transition (DDT). The computations solved two-dimensional time-dependent reactive Navier-Stokes equations including the effects of compressibility molecular diffusion thermal conduction viscosity and detailed chemical kinetics for the reactive species with subsequent chain branching production of radicals and energy release. It is shown that from the beginning the flame accelerates exponentially producing shock waves far ahead. On the next stage the flame acceleration decreases and the shocks are formed close ahead of the flame front. The final stage is the actual transition to detonation. During the second stage a compressed unreacted mixture of increased density enters the flame producing a high pressure pulse which enhances reaction rate and the heat release in the reaction zone with a positive feedback coupling between the pressure pulse and the reaction rate. As a result the peak of the pressure pulse grows exponentially steepens into a strong shock which is coupled with the reaction zone forming the overdriven detonation. This new mechanism of DDT is different from the Zel’dovich’s gradient mechanism. The temperature gradients which appear in the form of hot spots and the like are not suitable to initiate detonation.

The effect of vertical surface on the extent of high pressure unignited jets of both hydrogen and methane is studied using computer fluid dynamics simulations performed with FLACS Hydrogen. Results for constant flow rate through a 6.35 mm round leak orifice from 100 barg 250 barg 400 barg 550 barg and 700 barg compressed gas systems are presented for vertical jets. To quantify the effect of the surface on the jet the jet exit is positioned at various distances from the surface ranging from 0.029 m to 12 m. Free jets simulations are performed for comparison purposes.

Because of air quality problems the problem of CO2 related greenhouse gas emissions and shortage of fossil fuels many vehicles with gaseous fuels (CNG biogas hydrogen etc.) are under research and development. Such vehicles have to prove that as well as their exhaust emissions their overall system emissions (including running loss) remain below certain safety limits before they can be used in practice. This paper presents a cost-effective way of monitoring such system emissions from hydrogen or other gaseous fuel powered vehicles within an air-conditioned chassis dynamometer test cell as commonly used for low ambient emission tests on gasoline vehicles. The only additional equipment needed is a low-concentration sensor for the gas of interest (e.g hydrogen). The method is based on concentration measurements and a dynamic mass balance model. This method is based on the fact that atoms cannot vanish. Applied to a room containing a gas mixture this means that the change of mass of a gaseous matter (called gas G subsequently) inside the chamber is the difference of all mass of G flowing into the chamber and all mass of G flowing out of the chamber. This assumes that no chemical reactions of the gas in mind with other matter take place. By measuring the flow rates and concentrations of ventilation-in flow and ventilation-out flow as well as room concentration the emissions of G of a source i.e. the vehicle to be tested can be calculated. These concentrations need to be measured as functions of time to be able to give values of emissions per time unit. It is shown by a real experiment that very low emissions can be recorded. Additionally error bounds and sensitivities on different parameters such as air exchange ratio are quantified.

The present work is concerned with numerical simulations of large scale hydrogen detonations. Euler equations have been solved along with a single step reaction for the chemistry. Total variation diminishing (TVD) numerical schemes are used for shock capturing. The equations are solved in parallel in a decomposed domain. Predictions were firstly conducted with a small domain to ensure that the reaction scheme has been properly tuned to capture the correct detonation pressure and velocity. On this basis simulations were set up for the detonation tests carried out at the RUT tunnel facilities in Russia. This is one of the standard benchmark test cases selected for HYSAFE [1]. Comparison is made between the predictions and measurements. Reasonably good agreement has been obtained on pressure decay and the propagation speed of detonation. Further simulations were then conducted for a hypothetical hydrogen-air cloud in the open to assess the impulse as well as overpressure. The effects of cloud height width were investigated in the safety context.

Buoyant round vertical jet had been investigated using Large Eddy Simulations at low Mach number. For the purpose of comparison with in-house experimental data in the present work helium has been used as a substitute for hydrogen. The influence of the transient concentration fields on the volume of gas with concentration within flammability limits has been investigated and their evolution and relation with average fields ad been characterized. Transient concentration fields created during initial jet development had been considered. Numerical results have been compared with in-house experiments and data published in the literature.

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.

The possibility of using a risk based approach for the safe installation and siting of stationary fuel cell systems depends upon the availability of normative data and guidance on potential hazards and the probabilities of their occurrence. Such guidance data is readily available for most common hydrocarbon fuels. For hydrogen however data is still required on the hazards associated with different release scenarios. This data can then be related to the probability of different types of scenarios from historical fault data to allow safety distances to be defined and controlled using different techniques. Some data on releases has started to appear but this data generally relates to hydrogen vehicle refuelling systems that are designed for larger throughput higher pressures and the general use of larger pipe diameters than are likely to be used for small fuel cell systems.

As Europe is gradually moving towards a hydrogen based society it has been acknowledged that adding certain amount of hydrogen as a clean energy carrier to the existing natural gas pipeline will help reduce the CO2 emissions which contribute to the greenhouse effect. On the other hand hydrogen has been demonstrated to be able to change the behaviour of the pipeline steel such as lower toughness and faster crack growth due to hydrogen embrittlement. Therefore it is necessary that the risks associated with the failure of the pipeline carrying mixtures of natural gas and hydrogen be assessed.<br/>The study reported in this paper is part of European NATURALHY project whose aim is to investigate the possibility of using the existing natural gas transmission pipelines to convey natural gas/hydrogen mixtures. According to the EGIG database the most common cause of failure for the existing natural gas pipelines is third party damage which mainly refers to a gouge a dent/gouge combination of known geometry. Among third party damage failures 90% are the result of immediate failure i.e. leakage or rupture of the pipeline and only 10% of them are the result of delayed failure. While its not expected that hydrogen will impact the immediate failure it could increase the vulnerability of the pipe to delayed failure through the initiation or activation of crack like defects.<br/>This paper will present a methodology to predict the probability of increased failures and describe a software tool that has been developed to perform the calculations.

A benchmarking exercise on quantitative risk assessment (QRA) methodologies has been conducted within the project HyQRA under the framework of the European Network of Excellence (NoE) HySafe. The aim of the exercise was basically twofold: (i) to identify the differences and similarities in approaches in a QRA and their results for a hydrogen installation between nine participating partners representing a broad spectrum of background in QRA culture and history and (ii) to identify knowledge gaps in the various steps and parameters underlying the risk quantification. In the first step a reference case was defined: a virtual hydrogen refuelling station (HRS) in virtual surroundings comprising housing school shops and other vulnerable objects. All partners were requested to conduct a QRA according to their usual approach and experience. Basically participants were free to define representative release cases to apply models and frequency assessments according their own methodology and to present risk according to their usual format. To enable inter-comparison a required set of results data was prescribed like distances to specific thermal radiation levels from fires and distances to specific overpressure levels. Moreover complete documentation of assumptions base data and references was to be reported. It was not surprising that a wide range of results was obtained both in the applied approaches as well as in the quantitative outcomes and conclusions. This made it difficult to identify exactly which assumptions and parameters were responsible for the differences in results as the paper will show. A second phase was defined in which the QRA was determined by a more limited number of release cases (scenarios). The partners in the project agreed to assess specific scenarios in order to identify the differences in consequence assessment approaches. The results of this phase provide a better understanding of the influence of modelling assumptions and limitations on the eventual conclusions with regard to risk to on-site people and to the off-site public. This paper presents the results and conclusions of both stages of the exercise.

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.

A 50-litre standard hydrogen gas cylinder was temporarily placed in a laboratory to supply hydrogen gas to a flame ionization detector (FID) for use in gas chromatography (GC). On 20 January 2015 the safety relief valve on the pressure regulator failed and released about 0.34 kg of hydrogen into the laboratory. The gas cloud did not ignite so there was no injury or damage. The results of a full investigation with a complete course of action and reconstruction are presented that verify the cause of the leakage and estimate the gas concentration of the dispersion and gas cloud. A preliminary simulation of the likely explosion is provided. If the gas cloud had ignited the explosion would most likely have caused significant structural damage to doors windows and possibly the walls.

The effect of irregular polygonal grain size and random grain boundary on hydrogen diffusion in polycrystalline nickel is investigated. Hydrogen diffusion behavior in micropolycrystalline nickel is compared with that in nanopolycrystalline nickel through numerical analysis. The two dimensional computational finite element microstructural and nanostructural analyses are based on Fick's law corresponding to heterogeneous polycrystalline model geometry. The heterogeneous polycrystalline model consists of random irregular polygonal grains. These grains are divided into internal grain and grain boundary regions the size of which is determined from the grain size. The computational analysis results show that hydrogen diffusion in nanostructural irregular polycrystalline nickel is higher in magnitude than the microstructural irregular polycrystalline nickel. However models of voids traps and micro and nano clustered grains are yet to be included.

On October 16-17 2012 the International Association for Hydrogen Safety (HySafe) in cooperation with the Institute for Energy and Transport of the Joint Research Centre of the European Commission (JRC IET Petten) held a two-day workshop dedicated to Hydrogen Safety Research Priorities. The workshop was hosted by Federal Institute for Materials Research and Testing (BAM) in Berlin Germany. The main idea of the Workshop was to bring together stakeholders who can address the existing knowledge gaps in the area of the hydrogen safety including identification and prioritization of such gaps from the standpoint of scientific knowledge both experimental and theoretical including numerical. The experience highlighting these gaps which was obtained during both practical applications (industry) and risk assessment should serve as reference point for further analysis. The program included two sections: knowledge gaps as they are addressed by industry and knowledge gaps and state-of-the-art by research. In the current work the main results of the workshop are summarized and analysed.