Safety

During the early phase of the transient process following a hydrogen leak into the atmosphere a contact surface appears separating air heated by the leading shock from hydrogen cooled by expansion. Locally the interface is approximately planar. Diffusion leads to a temperature decrease on the air side and an increase in the hydrogen-filled region and mass diffusion of hydrogen into air and of air into hydrogen potentially resulting in ignition. This process was analyzed by Li ˜nan and Crespo [1] for unity Lewis number and Li ˜nan and Williams [2] for Lewis number less than unity. We included in the analysis the effect of a slow expansion [3 4] leading to a slow drop in temperature which occurs in transient jets. Chemistry being very temperature-sensitive the reaction rate peaks close to the hot side of the interface where only a small fuel concentration present close to the warm air-rich side which depends crucially upon the fuel Lewis number. For Lewis number unity the fuel concentration due to diffusion is comparable to the rate of consumption by chemistry. If the Lewis number is less than unity diffusion brings in more fuel than temperature-controlled chemistry consumes. For a Lewis number greater than unity diffusion is not strong enough to bring in as much fuel as chemistry would burn; combustion is controlled by fuel diffusion. If the temperature drop due to expansion associated with the multidimensional jet does not lower significantly the reaction rate up to that point analysis shows that ignition in the jet takes place. For fuel Lewis number greater than unity chemistry does not lead to a defined explosion so that eventually expansion will affect the process; ignition does not take place [3 4]. In the current paper these results are extended to consider multistep chemical kinetics but for otherwise similar assumptions. High activation energy is no longer applicable. Instead results are obtained in the short time limit still as a perturbation superimposed to the self-similar solution to the chemically frozen diffusion solution. In that approximation the initiation step which consumes fuel and oxidant is taken to be slow compared with steps that consume one of the reactants and an intermediate species. The formulation leads to a two point boundary value problem for set of coupled rate equations plus an energy equation for perturbations. These equations are linear with variable co-effcients. The coupled problem is solved numerically using a split algorithm in which chemical reaction is solved for frozen diffusion while diffusion is solved for frozen chemistry. At each time step the still coupled linear problem is solved exactly by projecting onto the eigenmodes of the stiff matrix so that the solution is unaffected by stiffness. Since in the short time limit temperature is only affected at the perturbation level the matrix depends only on the similarity variable x t but it is otherwise time-independent. As a result determination of the eigenvalues and eigenvectors is only done once (using Maple) for the entire range of discretized values of the similarity variable. The diffusion problem consists of a set of independent equations for each species. Each of these is solved using orthogonal decomposition onto Hermite polynomials for the homogeneous part plus a particular solution proportional to time for the non-homogeneous (source) terms. That approach can be implemented for different kinetic schemes.

The separation storage and recovery of hydrogen are key requirements for the efficient development of advanced hydrogen fuel technologies. The ideal hydrogen separation membrane should have high hydrogen permeability and good mechanical properties at a range of temperatures and pressures. Tantalum is a potential candidate with highest permeability to hydrogen among pure materials for hydrogen separation membrane. Isothermal as well as isobaric PCT equilibrium studies have been done in the temperature range of 673 – 873 K and hydrogen pressure range of 0.60 – 1.20 atmospheres for pure Ta and its solid solution alloys with Fe in different compositions. Results are presented.

Metallic hydrides represent a safe way of storing hydrogen minimising explosion and flammability risks. Nowadays there are several methods for the storage of hydrogen and the more conventional techniques are high-pressure tanks for gaseous hydrogen and cryogenic vessels for liquid hydrogen. However there are two main drawbacks in the storage of gaseous and liquid hydrogen. First as a fuel hydrogen in the gaseous and liquid states is very combustible and the related law imposes strict regulations on its utilization storage and transportation. Secondly even under a high pressure hydrogen gas is not dense enough for compact storage. Moreover the gas storage at high pressure involves significant safety risks. Hydrogen storage in the metal hydrides does not have such deficiencies. Metal hydrides are safe and can be easily store and transported. For that reason it should be stressed that metallic hydrides represent a safe way of storing hydrogen minimising explosion and flammability risks. Among metallic hydrides one of the most promising hydrides in terms of absorbed hydrogen content is Mg2NiH4. However it is difficult to obtain Mg2Ni by the conventional melting method because of the large difference in vapour pressure and melting point between magnesium and nickel. This paper presents an alternative and safe method for obtaining such hydride: HCS (Hydriding Combustion Synthesis). This method presents some interesting advantages over its conventional counterpart: the process is carried out at lower reaction process which means safer process and the alloy stoichiometry is closer to the nominal (Mg2Ni) which allow better hydrogen absorption behaviour. The aim of this work is to investigate the formation mechanism of this compound and to study some parameters of the process.

At the JRC-IET on-board hydrogen tanks have been subjected to filling–emptying cycles to investigate their long-term mechanical and thermal behaviour and their safety performance. The local temperature history inside the tanks has been measured and compared with the temperatures outside and at the tank metallic bosses which is the measurement location identified by some standards. The outcome of these activities is a set of experimental data which will be made publicly available as reference for safety studies and validation of computational fluid dynamics.

Compressed hydrogen is delivered by trailers in steel cylinders at 19.6 MPa in Japan. Kawasaki Heavy Industries Ltd. developed two compressed hydrogen trailers with composite cylinders in collaboration with JX Nippon Oil in a project of the New Energy and Industrial Technology Development Organization (NEDO).<br/>The first trailer which was the first hydrogen trailer with composite cylinder in Japan has 35 MPa cylinders and the second trailer has 45 MPa cylinders. These trailers have been operated transporting hydrogen and feedstock to hydrogen refuelling stations without the accident. This paper describes the safety design including compliance with regulations the influence of vibrations and safety verification in case of a collision.

This work is driven by the need to understand the hazards resulting from the rapid ignited release of hydrogen from onboard storage tanks through a thermally activated pressure relief device (TPRD) inside a garage-like enclosure with low natural ventilation i.e. the consequences of a jet fire which has been immediately ignited. The resultant overpressure is of particular interest. Previous work [1] focused on an unignited release in a garage with minimum ventilation. This initial work demonstrated that high flow rates of unignited hydrogen through a thermally activated pressure relief device (TPRD) in ventilated enclosures with low air change per hour can generate overpressures above the limit of 10- 15 kPa which a typical civil structure like a garage could withstand. This is due to the pressure peaking phenomenon. Both numerical and phenomenological models were developed for an unignited release and this has been recently validated experimentally [2]. However it could be expected that the majority of unexpected releases through a TPRD may be ignited; leading to even greater overpressures and to date whilst there has been some work on fires in enclosures the pressure peaking phenomenon for an ignited release has yet to be studied or compared with that for an equivalent unignited release. A numerical model for ignited releases in enclosures has been developed and computational fluid dynamics has then been used to examine the pressure dynamics of an ignited hydrogen release in a real scale garage. The scenario considered involves a high mass flow rate release from an onboard hydrogen storage tank at 700 bar through a 3.34 mm diameter orifice representing the TPRD in a small garage with a single vent equivalent in area to small window. It is shown that whilst this vent size garage volume and TPRD configuration may be considered “safe” from overpressures in the event of an unignited release the overpressure resulting from an ignited release is two orders of magnitude greater and would destroy the structure. Whilst further investigation is needed the results clearly indicate the presence of a highly dangerous situation which should be accounted for in regulations codes and standards. The hazard relates to the volume of hydrogen released in a given timeframe thus the application of this work extends beyond TPRDs and is relevant where there is a rapid ignited release of hydrogen in an enclosure with limited ventilation.

"The current practise of focusing the periodic retesting of composite cylinders primarily on the hydraulic pressure test has to be evaluated as critical - with regard to the damage of the specimen as well as in terms of their significance. This is justified by micro damages caused to the specimen by the test itself and by a lack of informative values. Thus BAM Federal Institute of Materials Research and Testing (Germany) uses a new approach of validation of composite for the determination of re-test periods. It enables the description of the state of a population of composite cylinders based on destructive tests parallel to operation.<br/>An essential aspect of this approach is the prediction of residual safe service life. In cases where it cannot be estimated by means of hydraulic load cycle tests as a replacement the creep or burst test remains. As a combination of these two test procedures BAM suggests the ""slow burst test SBT"". On this a variety of about 150 burst test results on three design types of cylinders with plastic liners are presented. For this purpose both the parameters of the test protocol as well as the nature and intensity of the pre-damage artificially aged test samples are analysed statistically. This leads first to an evaluation of the different types of artificial ageing but also to the clear recommendation that conventional burst tests be substituted totally if indented for assessment of composite pressure receptacles."

This paper presents results of an experimental investigation on detonation wave propagation in semi-confined geometries. Large scale experiments were performed in layers up to 0.6 m filled with uniform and non-uniform hydrogen–air mixtures in a rectangular channel (width 3 m; length 9 m) which is open from below. A semi confined driver section is used to accelerate hydrogen flames from weak ignition to detonation. The detonation propagation was observed in a 7 m long unobstructed part of the channel. Pressure measurements ionization probes soot-records and high speed imaging were used to observe the detonation propagation. Critical conditions for detonation propagation in different layer thicknesses are presented for uniform H2/air-mixtures as well as experiments with uniform H2/O2 mixtures in a down scaled transparent channel. Finally detail investigations on the detonation wave propagation in H2/air-mixtures with concentration gradients are shown.

Jet fires develop on release of hydrogen from pressurized storage depending on orifice pressures and volumes. Risks arise from flame contact dispersion of hot gases and heat radiation. The latter varies strongly in time at short scales down to milliseconds caused by turbulent air entrainment and fluctuations. These jets emit bands of OH in the UV and water in the NIR and IR spectral range. These spectra enable the temperature measurement and the estimation of the air number of the measuring spot which can be used to estimate the total radiation at least from the bright combustion zones. Compared to video and IR camera frames the radiation enables to estimate species and temperatures distributions and total emissions. Impurities generate continuum radiation and the emission of CO2 in the IR indicates air entrainment which can be compared to CHEMKIN II calculation of the reaction with air.

The number of eco friendly vehicle which is using green energy such as natural gas(NG) and hydrogen(H2) is rapidly increasing in the world. Almost all of the car manufacturers are adopting the pressurizing fuel method to storage gas. The fuel storage system which can pressurize the fuel as high as possible is necessary to maximize the mileage of the vehicle. In Korea the most important issue is that makes sure of safety of the fuel storage system and several tests are performed to verify safety of the composite cylinder especially for Type 3 and Type 4. In this research an empirical study on the internal temperature change of Type 3 and Type 4 composite cylinder during filling is performed by gas cycling test equipment. In order to measure the temperature totally twelve sensors(every four sensors on the top middle and bottom) are installed in each cylinder. As a consequence large amount of compression heat is generated during rapid filling and the result temperature change in Type 4 is greater than Type 3 is confirmed depending on property of the liner material such as thermal conduction and thickness of carbon composite.