Safety

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.

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.

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.

This paper shows the experimental results and findings of field explosion tests conducted to obtain fundamental data concerning the explosion of hydrogen-air mixtures. A tent covered with thin plastic sheets was filled with hydrogen/air mixed gas and subsequently ignited by an electric-spark or explosives to induce deflagration and/or detonation. Several experiments with different concentrations and/or volumes of mixture were carried out. The static overpressure of blast waves was measured using piezoelectric pressure sensors. The recorded data show that the shape of the pressure-time histories of the resulting blast waves depends on the difference in the ignition method used. The pictures of the explosion phenomenon (deflagration and/or detonation) were taken by high-speed cameras.

A phenomenological approach is developed to calculate the velocity of flame propagation and to estimate the value of pressure peak when igniting gaseous combustible mixtures in a congested space. The basic idea of this model is afterburning of the remanent fuel in pockets of congested space behind the flame front. The estimation of probable overpressure peak is based on solution of one-dimensional problem of the piston (having corresponding symmetry) moving with given velocity in polytropic gas. Submitted work is the first representation of such phenomenological approach and is realized for the simplest situation close to one-dimensional.

Over the last century there have been reports of high pressure hydrogen leaks igniting for no apparent reason and several ignition mechanisms have been proposed. Although many leaks have ignited there are also reported leaks where no ignition has occurred. Investigations of ignitions where no apparent ignition source was present have often been superficial with a mechanism postulated which whilst appearing to satisfy the conditions prevailing at the time of the release simply does not stand up to rigorous scientific analysis. Some of these proposed mechanisms have been simulated in a laboratory under superficially identical conditions and appear to be rigorous and scientific but the simulated conditions often do not have the same large release rates or quantities mainly because of physical constraints of a laboratory. Also some of the release scenarios carried out or simulated in laboratories are totally divorced from the realistic situation of most actual leaks. Clearly there are gaps in the knowledge of the exact ignition mechanism for releases of hydrogen particularly at the high pressures likely to be involved in future storage and use. Mechanisms which have been proposed in the past are the reverse Joule-Thomson effect; electrostatic charge generation; diffusion ignition; sudden adiabatic compression; and hot surface ignition. Of these some have been characterized by means of computer simulation rather than by actual experiment and hence are not validated. Consequently there are discrepancies between the theories releases known to have ignited and releases which are known to have not ignited. From this postulated ignition mechanisms which are worthy of further study have been identified and the gaps in information have been highlighted. As a result the direction for future research into the potential for ignition of hydrogen escapes has been identified.

It is necessary to investigate cylinder crush behavior for improvement of fuel cell vehicle crash safety. However there have been few crushing behaviour investigations of high pressurized cylinders subjected to external force. We conducted a compression test of pressurized cylinders impacted by external force. We also investigated the cylinder strength and crushing behaviour of the cylinder. The following results were obtained.

• The crush force of high pressurized cylinders is different from the direction of external force. The lateral crush force of high pressurized cylinders is larger than the external axial crush force.
• Tensile stress occurs in the boundary area between the cylinder dome and central portion when the pressurized cylinder is subjected to axial compression force and the cylinder is destroyed.
• However the high pressurized cylinders tested had a high crush force which exceeded the assumed range of vehicle crash test procedures

We prepared several gas barrier resins based on amorphous PVA derivative that has the T1C (13C spin-lattice relaxation time) of a long time component in amorphous phase. We confirmed it was important to control state in amorphous phase of gas barrier resin in order to achieve both moldability and good gas barrier property. Polymer alloy was designed to improve flexibility. Polymer alloy made of amorphous PVA and elastomer resin showed good hydrogen resistance. Even after its polymer alloy were repeatedly exposed to 70MPa hydrogen gas the influence on higher-order structure in amorphous phase was in negligible level.

The present paper reviews the state-of-the-art of integrated structural integrity monitoring systems applicable to hydrogen on-board applications. Storage safety and costs are key issues for the success of the hydrogen technology considered for replacing the conventional fuel systems in transport applications. An in-service health monitoring procedure for high pressure vessels would contribute to minimize the risks associated to high pressure hydrogen storage and to improve the public acceptance. Such monitoring system would also enable a reduction on design burst criteria enabling savings in material costs and weight. This paper reviews safety and maintenance requirements based on present standards for high pressure vessels. A state-of-the-art of storage media and materials for onboard storage tank is presented as well as of current European programmes on hydrogen storage technologies for transport applications including design safety and system reliability. A technological road map is proposed for the development and validation of a prototype within the framework of the Portuguese EDEN project. To ensure safety an exhaustive test procedure is proposed. Furthermore requirements of a safety on-board monitoring system is defined for filament wound hydrogen tanks.

The hazard associated with flame acceleration to supersonic speeds in hydrogen mixtures is discussed. A set of approximate models for evaluation of the run-up distances to supersonic flames in relatively smooth tubes and tubes with obstacles is presented. The model for smooth tubes is based on general relationships between the flame area turbulent burning velocity and the flame speed combined with an approximate description for the boundary layer thickness ahead of an accelerated flame. The unknown constants of the model are evaluated using experimental data. This model is then supplemented with the model for the minimum run-up distance for FA in tubes with obstacles developed earlier. On the basis of these two models solutions for the determination of the critical runup distances for FA and deflagration to detonation transition in tubes and channels for various hydrogen mixtures initial temperature and pressure tube size and tube roughness are presented.