Safety

As hydrogen-air mixtures are flammable in a wide range of concentrations and the minimum ignition energy is low compared to hydrocarbon fuels the safe handling of hydrogen is of utmost importance. Additional hazards may arise with the accidental spill of liquid hydrogen. Such a release of LH2 leads to a formation of a cryogenic pool a dynamic vaporization process and consequently a dispersion of gaseous hydrogen into the environment. Several LH2 release experiments as well as modelling approaches address this phenomenology. In contrast to existing approaches a new CFD model capable of simulating liquid and gaseous distribution was developed at Forschungszentrum Jülich. It is validated against existing experiments and yields no substantial lacks in the physical model and reveals a qualitatively consistent prediction. Nevertheless the deviation between experiment and simulation raises questions on the completeness of the database in particular with regard to the boundary conditions and available measurements.

The study of hydrogen as an alternative fuel clean and “environment friendly” has been in the last years and continues to be object of many studies international projects and standard development. Hydrogen is a fundamental energy carrier to be developed together with other renewable resources for the transition to a sustainable energy system.<br/>But experience has shown how often the introduction and establishment of a new technology does not necessarily pass through radical changes but can be stimulated by slight modifications to the “present situation”.<br/>So the worldwide experience with natural gas as industrial automotive and domestic fuel has been the incentive to the present interest towards hydrogen–methane mixtures. The possible use of existing pipeline networks for mixtures of natural gas and hydrogen offers a unique and cost-effective opportunity to initiate the progressive introduction of hydrogen as part of the development of a full hydrogen system.<br/>The aim of the work presented in this paper is the investigation of the dispersion and stratification properties of hydrogen and methane mixtures. Experimental activities have been carried out in a large scale closed apparatus characterized by a volume of about 25 m3 both with and without natural ventilation. Mixtures of 10%vol. hydrogen – 90%vol. methane and 30%vol. hydrogen – 70%vol. methane have been studied with the help of oxygen sensors and gas chromatography.

The response of a typical steel-lined reinforced concrete nuclear reactor containment to postulated internal hydrogen detonations is investigated by detailed axisymetric non-linear dynamic finite element analysis. The wall pressure histories are calculated for hydrogen detonations using a technique that reproduces the sharp discontinuity at the shock front. The pressure results can be applied to geometrically similar vessels. The analysis indicates that the response is more sensitive to the point of initiation than to the strength of the detonation. Approximate solutions based on a pure impulse assumption where the containment is modelled as a single-degree-of freedom (SDOF) system may be seriously unconservative. This work becomes relevant because new nuclear reactors are foreseen as a primary of source of hydrogen supply.<br/><br/>

Hydrogen jet flames resulting from ignition of unintended releases can be extensive in length and pose significant radiation and impingement hazards. Depending on the leak diameter and source pressure the resulting consequence distances can be unacceptably large. One possible mitigation strategy to reduce exposure to jet flames is to incorporate barriers around hydrogen storage and delivery equipment. An experimental and modeling program has been performed at Sandia National Laboratories to better characterize the effectiveness of barrier walls to reduce hazards. This paper describes the experimental and modeling program and presents results obtained for various barrier configurations. The experimental measurements include flame deflection using standard and infrared video and high-speed movies (500 fps) to study initial flame propagation from the ignition source. Measurements of the ignition overpressure wall deflection radiative heat flux and wall and gas temperature were also made at strategic locations. The modeling effort includes three-dimensional calculations of jet flame deflection by the barriers computations of the thermal radiation field around barriers predicted overpressure from ignition and the computation of the concentration field from deflected unignited hydrogen releases. The various barrier designs are evaluated in terms of their mitigation effectiveness for the associated hazards present. The results show that barrier walls are effective at deflecting jet flames in a desired direction and can help attenuate the effects of ignition overpressure and flame radiative heat flux.

There exists an international commitment to increase the utilization of hydrogen as a clean and renewable alternative to carbon-based fuels. The availability of hydrogen safety sensors is critical to assure the safe deployment of hydrogen systems. Already the use of hydrogen safety sensors is required for the indoor fueling of fuel cell powered forklifts (e.g. NFPA 52 Vehicular Fuel Systems Code [1]). Additional Codes and Standards specific to hydrogen detectors are being developed [2 3] which when adopted will impose mandatory analytical performance metrics. There are a large number of commercially available hydrogen safety sensors. Because end-users have a broad range of sensor options for their specific applications the final selection of an appropriate sensor technology can be complicated. Facility engineers and other end-users are expected to select the optimal sensor technology choice. However some sensor technologies may not be a good fit for a given application. Informed decisions require an understanding of the general analytical performance specifications that can be expected by a given sensor technology. Although there are a large number of commercial sensors most can be classified into relatively few specific sensor types (e.g. electrochemical metal oxide catalytic bead and others). Performance metrics of commercial sensors produced on a specific platform may vary between manufacturers but to a significant degree a specific platform has characteristic analytical trends advantages and limitations. Knowledge of these trends facilitates the selection of the optimal technology for a specific application (i.e. indoor vs. outdoor environments). An understanding of the various sensor options and their general analytical performance specifications would be invaluable in guiding the selection of the most appropriate technology for the designated application.

Element One Inc. is developing novel indicators for hydrogen gas for applications as a complement to conventional electronic hydrogen sensors or as a low-cost alternative in situations where an electronic signal is not needed. The indicator consists of a thin film coating or a pigment of a transition metal oxide such as tungsten oxide or molybdenum oxide with a catalyst such as platinum or palladium. The oxide is partially reduced in the presence of hydrogen in concentrations as low as 300 parts per million and changes from transparent to a dark colour. The colour change is fast and easily seen from a distance. In air the colour change reverses quickly when the source of hydrogen gas is removed in the case of tungsten oxide or is nearly irreversible in the case of molybdenum oxide. A number of possible implementations have been successfully demonstrated in the laboratory including hydrogen indicating paints tape cautionary decals and coatings for hydrogen storage tanks. These and other implementations may find use in vehicles stationary appliances piping refuelling stations and in closed spaces such as maintenance and residential garages for hydrogen-fuelled vehicles. The partially reduced transition metal oxide becomes semi conductive and increases its electrical conductivity by several orders of magnitude when exposed to hydrogen. The integration of this electrical resistance sensor with an RFID tag may extend the ability of these sensors to record and transmit a history of the presence or absence of leaked hydrogen over long distances. Over long periods of exposure to the atmosphere the indicator’s response may slow due to catalyst degradation. Our current emphasis is on controlling this degradation. The kinetics of the visual indicators is being investigated along with their durability in collaboration with the NASA Kennedy Space Center.

High pressure storage of hydrogen in tanks is a promising option to provide the necessary fuel for transportation purposes. The fill process of a high-pressure tank should be reasonably short but must be designed to avoid too high temperatures in the tank. The shorter the fill should be the higher the maximum temperature in the tank climbs. For safety reasons an upper temperature limit is included in the requirements for refillable hydrogen tanks (ISO 15869) which sets the limit for any fill optimization. It is crucial to understand the phenomena during a tank fill to stay within the safety margins.<br/>The paper describes the fast filling process of hydrogen tanks by simulations based on the Computational Fluid Dynamics (CFD) code CFX. The major result of the simulations is the local temperature distribution in the tank depending on the materials of liner and outer thermal insulation. Different material combinations (type III and IV) are investigated.<br/>Some measurements from literature are available and are used to validate the approach followed in CFX to simulate the fast filling of tanks. Validation has to be continued in future to further improve the predictability of the calculations for arbitrary geometries and material combinations.

Correct selection and application of materials is essential to ensure safety and economy in production transportation and storage of hydrogen. There are several sources of materials challenges related to hydrogen. Established component producers may have limited experience in this specific field. Process developments may involve new process conditions with new demands on the materials. Further new materials will be added to the engineering toolbox to be used. The behaviour of these materials for hydrogen service may need additional documentation. Finally focus on hydrogen susceptibility and hydrogen damages alone may take away awareness of other subjects as trace elements by-products and change in raw materials which may be of as high importance for safety and quality. This overview of challenges and recommendations is made with emphasis on water electrolysis.

Underground or partial underground tunnels form a very important part of modern road transportation systems. As the development of hydrogen cars advancing into the markets it is unavoidable in the near future that hydrogen cars would become the users of ordinary road tunnels. This paper discusses potential fire scenarios and fire hazards of hydrogen cars in road tunnels and implications on the fire safety measures and ventilation systems in existing tunnels. The information needed for carry out risk assessment of hydrogen cars in road tunnels are discussed. hydrogen has a low ignition energy and wide flammable range suggesting that leaks have a high probability of ignition and result hydrogen flame. CFD simulations of hydrogen fires in a full scale 5m by 5m square cross-section tunnel were carried out. The effect of the ventilation on controlling the back-layering and the downstream flame are discussed.

We analytically investigated the influence of light hydrocarbons on turbulent premixed H2/air atmospheric flames under lean conditions in view of safe handling of H2 systems applications in H2 powered IC engines and gas turbines and also with an orientation towards modelling of H2 combustion. For this purpose an algebraic flame surface wrinkling model included with pressure and fuel type effects is used. The model predictions of turbulent premixed flames are compared with the set of corresponding experimental data of Kido et al. (Kido Nakahara et al. 2002). These expanding spherical flame data include H2–air mixtures doped with CH4 and C3H8 while the overall equivalence ratio of all the fuel/air mixtures is fixed at 0.8 for constant unstretched laminar flame speed of 25 cm/s by varying N2 composition. The model predictions show that there is little variation in turbulent flame speed ST for C3H8 additions up to 20-vol%. However for 50 vol% doping flame speed decreases by as much as 30 % from 250 cm/s that of pure H2–air mixtures for turbulence intensity of 200 cm/s. With respect to CH4 for 50 vol% doping ST reduces by only 6 % cf. pure H2/air mixture. In the first instance the substantial decrease of ST with C3H8 addition may be attributed to the increase in the Lewis number of the dual-fuel mixture and proportional restriction of molecular mobility of H2. That is this decrease in flame speed can be explained using the concept of leading edges of the turbulent flame brush (Lipatnikov and Chomiak 2005). As these leading edges have mostly positive curvature (convex to the unburned side) preferential-diffusive-thermal instabilities cause recognizable impact on flame speed at higher levels of turbulence with the effect being very strong for lean H2 mixtures. The lighter hydrocarbon substitutions tend to suppress the leading flame edges and possibly transition to detonation in confined structures and promote flame front stability of lean turbulent premixed flames. Thus there is a necessity to develop a predictive reaction model to quantitatively show the strong influence of molecular transport coefficients on ST.