Safety

Potential risk exposure of 3rd parties i.e. people not involved in the actual operation of a plant is often a critical factor to gain authority approval and public acceptance for a development project. This is also highly relevant for development of demonstration facilities for hydrogen production and refuelling infrastructure. This paper presents and discusses results for risk exposure of 3rd parties based on risk assessment studies performed for the planned Hydrogen Technology Research Centre Hytrec in Trondheim. The methodology applied is outlined. Key assumptions and study uncertainties are identified and how these might affect the results are discussed.<br/>The purpose of Hytrec is to build a centre for research development and demonstration of hydrogen as an energy carrier. Hydrogen will be produced both by reforming of natural gas with CO2 capture and by electrolysis of water. The plant also includes a SOFC that will run on natural gas or hydrogen and produce heat and electricity for the Hytrec visitor centre. Hytrec will be located in a populated area without access control. Most of the units will be located within cabinets and modules.<br/>The authors acknowledge the Hytrec project and the Hytrec project partners Statoil Statkraft and DNV for their support and for allowing utilisation of results from the Hytrec QRA in this paper.

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.

Polymer electrolyte membrane (PEM) water electrolysis has demonstrated its potentialities in terms of cell efficiency (energy consumption ≈ 4.0-4.2 kW/Nm3 H2) and gas purity (> 99.99% H2). Current research activities are aimed at increasing operating pressure up to several hundred bars for direct storage of hydrogen in pressurized vessels. Compared to atmospheric pressure electrolysis high-pressure operation yields additional problems especially with regard to safety considerations. In particular the rate of gases (H2 and O2) cross-permeation across the membrane and their water solubility both increase with pressure. As a result gas purity is affected in both anodic and cathodic circuits and this can lead to the formation of explosive gas mixtures. To prevent such risks two different solutions reported in this communication have been investigated. First the chemical modification of the solid polymer electrolyte in order to reduce cross-permeation phenomena. Second the use of catalytic H2/O2 recombiners to maintain H2 levels in O2 and O2 levels in H2 at values compatible with safety requirements.

Simulation of hydrogen-air mixture explosions in a closed large-scale vessel with uniform and nonuniform mixture compositions was performed by the group of partners within the EC funded project “Hydrogen Safety as an Energy Carrier” (HySafe). Several experiments were conducted previously by Whitehouse et al. in a 10.7 m3 vertically oriented (5.7-m high) cylindrical facility with different hydrogen-air mixture compositions. Two particular experiments were selected for simulation and comparison as a Standard Benchmark Exercise (SBEP) problem: combustion of uniform 12.8% (vol.) hydrogen-air mixture and combustion of non-uniform hydrogen-air mixture with average 12.6% (vol.) hydrogen concentration across the vessel (vertical stratification 27% vol. hydrogen at the top of the vessel 2.5% vol. hydrogen at the bottom of the vessel); both mixtures were ignited at the top of the vessel. The paper presents modelling approaches used by the partners comparison of simulation results against the experiment data and conclusions regarding the non-uniform mixture combustion modelling in real-life applications.

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.

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.

In order to achieve a high level of safety while using hydrogen as a vehicle fuel the possible hazards must be estimated. Especially hydrogen release tests with defined ignition represent a very important way to characterize the basics of hydrogen combustion in a potential accident. So ICT participated on a hydrogen jet release campaign at HSL (Buxton) in 2008 to deploy their measurement techniques and evaluation methods to visualize jets ignition and subsequent flames. The following paper shows the application of high speed cinematography in combination with image processing techniques the Background Oriented Schlieren (BOS) and a difference method to visualize the shape of hydrogen jet. In addition these methods were also used to observe ignition and combustion zone after defined initiation. In addition the combustion zone was recorded by a fast spectral radiometer and a highspeed-IR-camera. The IR-camera was synchronized with a rotating filter wheel to generate four different motion pictures at 100Hz each on a defined spectral range. The results of this preliminary evaluation provide some detailed information that might be used for improving model predictions.

The ignition limits of hydrogen/air mixtures in turbulent jets are necessary to establish safety distances based on ignitable hydrogen location for safety codes and standards development. Studies in turbulent natural gas jets have shown that the mean fuel concentration is insufficient to determine the flammable boundaries of the jet. Instead integration of probability density functions (PDFs) of local fuel concentration within the quiescent flammability limits termed the flammability factor (FF) was shown to provide a better representation of ignition probability (PI). Recent studies in turbulent hydrogen jets showed that the envelope of ignitable gas composition (based on the mean hydrogen concentration) did not correspond to the known flammability limits for quiescent hydrogen/air mixtures. The objective of this investigation is to validate the FF approach to the prediction of ignition in hydrogen leak scenarios. The PI within a turbulent hydrogen jet was determined using a pulsed Nd:YAG laser as the ignition source. Laser Rayleigh scattering was used to characterize the fuel concentration throughout the jet. Measurements in methane and hydrogen jets exhibit similar trends in the ignition contour which broadens radially until an axial location is reached after which the contour moves inward to the centerline. Measurements of the mean and fluctuating hydrogen concentration are used to characterize the local composition statistics conditional on whether the laser spark results in a local ignition event or complete light-up of a stable jet flame. The FF is obtained through direct integration of local PDFs. A model was developed to predict the FF using a presumed PDF with parameters obtained from experimental data and computer simulations. Intermittency effects that are important in the shear layer are incorporated in a composite PDF. By comparing the computed FF with the measured PI we have validated the flammability factor approach for application to ignition of hydrogen jets.

Hydrogen vehicles may emerge as a leading contender to replace today’s internal combustion engine powered vehicles. A Phenomena Identification and Ranking Table exercise conducted as part of the European Network of Excellence on Hydrogen Safety (HySafe) identified the use of hydrogen vehicles in road tunnels as a topic of important concern. An internal project called HyTunnel was duly established within HySafe to review identify and analyse the issues involved and to contribute to the wider activity to establish the true nature of the hazards posed by hydrogen vehicles in the confined space of a tunnel and their relative severity compared to those posed by vehicles powered by conventional fuels including compressed natural gas (CNG). In addition to reviewing current hydrogen vehicle designs tunnel design practice and previous research a programme of experiments and CFD modelling activities was performed for selected scenarios to examine the dispersion and explosion hazards potentially posed by hydrogen vehicles. Releases from compressed gaseous hydrogen (CGH2) and liquid hydrogen (LH2) powered vehicles have been studied under various tunnel geometries and ventilation regimes. The findings drawn from the limited work done so far indicate that under normal circumstances hydrogen powered vehicles do not pose a significantly higher risk than those powered by petrol diesel or CNG but this needs to be confirmed by further research. In particular obstructions at tunnel ceiling level have been identified as a potential hazard in respect to fast deflagration or even detonation in some circumstances which warrants further investigation. The shape of the tunnel tunnel ventilation and vehicle pressure relief device (PRD) operation are potentially important parameters in determining explosion risks and the appropriate mitigation measures.