Safety

Hydrogen is widely recognized as an attractive energy carrier due to its low-level air pollution and its high mass-related energy density. However its wide flammability range and high burning velocity present a potentially significant hazard. A significant fraction of hydrogen is stored and transported as a cryogenic liquid (liquid hydrogen or LH2) as it requires much less volume compared to gaseous hydrogen. In order to exist as a liquid H2 must be cooled to a very low temperature 20.28 K. LH2 is a common liquid fuel for rocket applications. It can also be used as the fuel storage in an internal combustion engine or fuel cell for transport applications. Models for handling liquid releases both two-phase flashing jets and pool spills have been developed in the CFD-model FLACS. The very low normal boiling point of hydrogen (20 K) leads to particular challenges as this is significantly lower than the boiling points of oxygen (90 K) and nitrogen (77 K). Therefore a release of LH2 in the atmosphere may induce partial condensation or even freezing of the oxygen and nitrogen present in the air. A pool model within the CFD software FLACS is used to compute the spreading and vaporization of the liquid hydrogen depositing on the ground where the partial condensation or freezing of the oxygen and nitrogen is also taken into account. In our computations of two-phase jets the dispersed and continuous phases are assumed to be in thermodynamic and kinematic equilibrium. Simulations with the new models are compared against selected experiments performed at the Health and Safety Laboratory (HSL).

The EC 6th framework research project HyApproval will draft a Handbook which will describe all relevant issues to get approval to construct and operate a Hydrogen Refuelling Station (HRS) for hydrogen vehicles. In WP3 of the HyApproval project it is under investigation which safety information competent authorities require to give a licence to construct an operate an HRS. The paper describes the applied methodology to collect the information from the authorities in 5 EC countries and the USA. The results of the interviews and recommendations for the information to include in the Handbook are presented.

The development of hydrogen as energy carrier is promoted by the increasing in energy demand depletion of fossil resources and the global warming. However this issue relies primarily on the safety aspect which requires the knowledge in the case of gas release of the quantities such as the flammable cloud size release path and the location of the lower flammability limit of the mixture. The integral models for predicting the atmospheric dispersion were extensively used in previous works for low pressure releases such as pollutant and  flammable gas transport. In the present investigation this approach is extended to the high pressure gas releases. The model is developed in the non-Boussinesq approximation and is based on Gaussian profiles for buoyant variable density jet or plume in stratified atmosphere with a crossflow. Validations have been performed on a broad range of hydrogen methane and air dispersion cases including vertical or horizontal jets or plumes into a quiescent atmosphere or with crosswind.

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.

The first part of the present work is to validate a detailed kinetic mechanism for the oxidation of hydrogen – methane – air mixtures in a detonation waves. A series of experiments on auto-ignition delay times have been performed by shock tube technique coupled with emission spectrometry for H2 / CH4 / O2 mixtures highly diluted in argon. The CH4/H2 ratio was varied from 0 to 4 and the equivalence ratio from 0.4 up to 1. The temperature range was from 1250 K to 2000 K and the pressure behind reflected shock waves was between 0.15 and 1.6 MPa. A correlation was proposed between temperature (K) concentration of chemical species (mol m-3) and ignition delay times. The experimental auto-ignition delay times were compared to the modelled ones using four different mechanisms from the literature: GRI [22] Marinov et al. [23] Hughes et al. [24] Konnov [25]. A large discrepancy was generally found between the different models. The Konnov’s model that predicted auto-ignition delay times close to the measured ones has been selected to calculate the ignition delay time in the detonation waves. The second part of the study concerned the experimental determination of the detonation properties namely the detonation velocity and the cell size. The effect of the initial composition hydrogen to methane ratio and the amount of oxygen in the mixture as well as the initial pressure on the detonation velocity and on the cell size were investigated. The ratio of methane / (methane + hydrogen) varied between 0 and 0.6 for 2 different equivalence ratio (0.75 and 1) while the initial pressure was fixed to 10 kPa. A correlation was established between the characteristic cell size and the ignition delay time behind the leading shock of the detonation. It was clearly showed that methane has an important inhibitor effect on the detonation of these combustible mixtures.

Burning hydrogen emits thermal radiation in UV NIR and IR spectral range. Especially in the case of large cloud explosion the risk of heat radiation is commonly underestimated due to the non-visible flame of hydrogen-air combustion. In the case of a real explosion accident organic substances or inert dust might be entrained from outer sources to produce soot or heated solids to substantially increase the heat release by continuum radiation. To investigate the corresponding combustion phenomena different hydrogen-air mixtures were ignited in a closed vessel and the combustion was observed with fast scanning spectrometers using a sampling rate up to 1000 spectra/s. In some experiments to take into account the influence of organic co-combustion a spray of a liquid glycol-ester and milk powder was added to the mixture. The spectra evaluation uses the BAM code of ICT to model bands of reaction products and thus to get the temperatures. The code calculates NIR/IR-spectra (1 - 10 μm) of non-homogenous gas mixtures of H2O CO2 CO NO and HCl taking into consideration also emission of soot particles. It is based on a single line group model and makes also use of tabulated data of H2O and CO2 and a Least Squares Fit of calculated spectra to experimental ones enables the estimation of flame temperatures. During hydrogen combustion OH emits an intense spectrum at 306 nm. This intermediary radical allows monitoring the reaction progress. Intense water band systems between 1.2 and 3 μm emit remarkable amounts of heat radiation according to a measured flame temperature of 2000 K. At this temperature broad optically-thick water bands between 4.5 μm and 10 μm contribute only scarcely to the total heat output. In case of co-combustion of organic materials additional emission bands of CO and CO2 as well as a continuum radiation of soot and other particles occur and particularly increase the total thermal output drastically.

An essential problem for the operation of high pressure water electrolyzers and fuel cells is the permissible contamination of hydrogen and oxygen. This contamination can create malfunction and in the worst case explosions in the apparatus and gas cylinders. In order to avoid dangerous conditions the exact knowledge of the explosion characteristics of hydrogen/air and hydrogen/oxygen mixtures is necessary. The common databases e.g. the CHEMSAFE® database published by DECHEMA BAM and PTB contains even a large number of evaluated safety related properties among other things explosion limits which however are mainly measured according to standard procedures under atmospheric conditions.<br/>Within the framework of the European research project “SAFEKINEX” and other research projects the explosion limits explosion pressures and rates of pressure rise (KG values) of H2/air and H2/O2 mixtures were measured at elevated conditions of initial pressures and temperatures by the Federal Institute of Materials Research and Testing (BAM). Empirical equations of the temperature influence could be deduced from the experimental values. An anomaly was found at the pressure influence on the upper explosion limits of H2/O2 and H2/air mixtures in the range of 20 bars. In addition explosion pressures and also rates of pressure rises have been measured for different hydrogen concentrations inside the explosion range. Such data are important for constructive explosion protection measures. Furthermore the mainly used standards for the determination of explosion limits have been compared. Therefore it was interesting to have a look at the systematic differences between the new EN 1839 tube and bomb method ASTM E 681-01 and German DIN 51649-1.

Hydrogen is not more dangerous than current fossil energy carriers but it behaves differently. Therefore hydrogen specific analyses and countermeasures will be needed to support the development of safe hydrogen technologies. A systematic step-by-step procedure for the mechanistic analysis of hydrogen behaviour and mitigation in accidents is presented. The procedure can be subdivided into four main parts:<br/>1) 3D modelling of the H2-air mixture generation<br/>2) hazard evaluation for this mixture based on specifically developed criteria for flammability flame acceleration and detonation on-set<br/>3) numerical simulation of the appropriate combustion regime using verified 3D-CFD codes and<br/>4) consequence analysis based on the calculated pressure and temperature loads.

This paper presents a compilation of the results supplied by HySafe partners participating in the Standard Benchmark Exercise Problem (SBEP) V2 which is based on an experiment on hydrogen combustion that is first described. A list of the results requested from participants is also included. The main characteristics of the models used for the calculations are compared in a very succinct way by using tables. The comparison between results together with the experimental data when available is made through a series of graphs. The results show quite good agreement with the experimental data. The calculations have demonstrated to be sensitive to computational domain size and far field boundary condition.