Safety

Platinum metals dispersed on a porous carrier e.g. -Al2O3 are used as catalysts for removal of small amounts of hydrogen from the air where the excess of oxygen is significant.<br/>The recombination reaction of H2 and O2 on smooth platinum proceeds at a high rate only in gas mixes with an excess of hydrogen. When the concentration of oxygen exceeds that of hydrogen in terms of stoichiometric ratio the process slows down sharply and eventually stops completely. In research undertaken at the Karpov Institute of Physical Chemistry (Moscow) forty years ago the electrochemical mechanism of red-ox reactions was proposed as an explanation for this inhibition by excess oxygen. The results of ellipsometric analysis pointed to the formation of a protective monolayer of PtO molecules on the Pt surface in an oxygen-rich atmosphere. It was observed that the recombination reaction proceeds at a high rate with the use of a porous catalyst at any concentrations of reactant gases. The reason for that lies in the mechanism of the catalysis: the reaction proceeds at a certain depth in the porous body of the catalyst. Hydrogen which has higher mobility penetrates in larger quantity than oxygen thus creating there the stoichiometric excess. To test the proposed mechanism of recombination the catalytic reaction was studied ) with porous carriers of various thicknesses and b) with metal grids of various porosities covering the catalyst. The data obtained have confirmed unequivocally the earlier hypothesis of hydrogenation of a porous catalyst.<br/>Such insight has allowed the authors to develop more effective prototypes of catalyst for removal of hydrogen. In particular by using a porous grid cover to remove excess heat in the reaction zone of the catalyst plate we achieved a considerable expansion of the region of hydrogen concentrations where the catalyst is both effective and reliable.

The hydrogen detection system is a key component of the hydrogen safety systems (HSS). Any HSS forms a second layer of protection for the assets under accidental conditions when a first layer of protection - passive protection systems (separation at “safe” distance natural ventilation) are inoperable or failed. In this report a performance-based risk-informed methodology for establishing of the explicit quantitative requirements for hydrogen detectors allocation and actuation is proposed. The main steps of the proposed methodology are described. It is suggested (as a first approximation) to use in a process of quantification of a hydrogen detection system performance (from safety viewpoint) a five-tiered hierarchy namely 1) safety goals 2) risk-informed safety objectives 3) performance goal and metrics 4) rational safety criteria 5) safety factors. Unresolved issues of the proposed methodology of Safety Performance Analysis for development of the risk-informed and performance based standards on the hydrogen detection systems are synopsized.<br/><br/>

Research was conducted on hydrogen diffusion behaviour to construct a simulation method for hydrogen leaks into complexly shaped spaces such as around the hydrogen tank of a fuel cell electric vehicle (FCEV). To accurately calculate the hydrogen concentration distribution in the vehicle underfloor space it is necessary to take into account the effects of hydrogen mixing and diffusion due to turbulence. The turbulence phenomena that occur in the event that hydrogen leaks into the vehicle underfloor space were classified into the three elements of jet flow wake flow and wall turbulence. Experiments were conducted for each turbulence element to visualize the flows and the hydrogen concentration distributions were measured. These experimental values were then compared with calculated values to determine the calculation method for each turbulence phenomenon. Accurate calculations could be performed by using the k-ω Shear Stress Transport (SST) model for the turbulence model in the jet flow calculations and the Reynolds Stress Model (RSM) in the wall turbulence calculations. In addition it was found that the large fluctuations produced by wake flow can be expressed by unsteady state calculations with the steady state calculation solutions as the initial values. Based on the above information simulations of hydrogen spouting were conducted for the space around the hydrogen tank of an FCEV. The hydrogen concentration calculation results matched closely with the experimental values which verified that accurate calculations can be performed even for the complex shapes of an FCEV.

Sandia National Laboratories has worked with stakeholders and original equipment manufacturers (OEMs) to develop scientific data that can be used to create risk-informed hydrogen codes and standards for the safe operation of indoor hydrogen fuel-cell forklifts. An important issue is the possibility of an accident inside a warehouse or other enclosed space where a release of hydrogen from the high-pressure gaseous storage tank could occur. For such scenarios computational fluid dynamics (CFD) simulations have been used to model the release and dispersion of gaseous hydrogen from the vehicle and to study the behavior of the ignitable hydrogen cloud inside the warehouse or enclosure. The overpressure arising as a result of ignition and subsequent deflagration of the hydrogen cloud within the warehouse has been studied for different ignition delay times and ignition locations. Both ventilated and unventilated warehouses have been considered in the analysis. Experiments have been performed in a scaled warehouse test facility and compared with simulations to validate the results of the computational analysis.

The project “Towards a Hydrogen Refuelling Infrastructure for Vehicles” (THRIVE) aimed at the determination of conditions to stimulate the building of a sustainable infrastructure for hydrogen as a car fuel in The Netherlands. Economic scenarios were constructed for the development of such an infrastructure for the next one to four decades. The eventual horizon will require the erection of a few hundred to more than a thousand hydrogen refuelling stations (HRS) in The Netherlands. The risk acceptability policy in The Netherlands implemented in the External Safety Establishments decree requires the assessment and management of safety risks imposed on the public by car fuelling stations. In the past a risk-informed policy has been developed for the large scale introduction of liquefied petroleum gas (LPG) as a car fuel and a similar policy will also be required if hydrogen is introduced in the public domain. A risk assessment methodology dedicated to cope with accident scenarios relevant for hydrogen applications is to be developed. Within the THRIVE project a demo risk assessment was conducted for the possible implementation of an HRS within an existing station for conventional fuels. The studied station is located in an urban area occupied with housing and commercial activities. The HRS is based on delivery and on-site storage of liquid hydrogen and dispensing of high pressure gaseous hydrogen into vehicles. The main challenges in the risk assessment were in the modelling of release and dispersion of liquid hydrogen. Definition of initial conditions for computational fluid dynamics (CFD) modelling to evaluate dispersion of a cold hydrogen air mixture appears rather complex and is not always fully understood. The modelling assumptions in the initial conditions determine to a large extent the likelihood and severity of potential explosion effects. The paper shows the results of the investigation and the sensitivity to the basic assumptions in the model input.

In the prospect of a safe use of hydrogen in our society one important task is to evaluate under which conditions the storage of hydrogen systems can reach a sufficient level of safety. One of the most important issues is the use of such system in closed area for example a private garage or an industrial facility. In the scope of this paper we are mainly interested in the following scenario: a relatively slow release of hydrogen (around 5Nl/min) in a closed and almost cubic box representing either a fuel cell at normal scale or a private garage at a smaller scale. For practical reasons helium was used instead of hydrogen in the experiments on which are based our comparisons. This kind of situation leads to the fundamental problem of the dispersion of hydrogen due to a simple vertical source in an enclosure. Many numerical and experimental studies have already been conducted on this problem showing the formation of either a stably stratified distribution of concentration or the formation of a homogeneous layer due to high enough convective flows at the top of the enclosure. Nevertheless most of them consider the cases of accidental situation in which the flow rate is relatively important (higher than 10Nl/min). Numerical simulations carried out with the CEA code Cast3M and a LES turbulence model confirm the differences of results already observed in experimental helium concentration measurements for a same injection flow rate and two different injection nozzle diameters contradicting simple physical models used in safety calculations.

Due to rapid growth in the use of hydrogen powered fuel cell forklifts within warehouse enclosures Sandia National Laboratories has worked to develop scientific methods that support the creation of new hydrogen safety codes and standards for indoor refuelling operations. Based on industry stakeholder input conducted experiments were devised to assess the utility of modelling approaches used to analyze potential consequences from ignited hydrogen leaks in facilities certified according to existing code language. Release dispersion and combustion characteristics were measured within a scaled test facility located at SRI International's Corral Hollow Test Site. Moreover the impact of mitigation measures such as active/passive ventilation and pressure relief panels was investigated. Since it is impractical to experimentally evaluate all possible facility configurations and accident scenarios careful characterization of the experimental boundary conditions has been performed so that collected datasets can be used to validate computational modelling approaches.

In order to gain a better understanding of hazards linked with Hydrogen/Natural gas mixtures transport by pipeline the National Institute of Industrial Environment and Risks (INERIS) alongside with the Atomic Energy Commission (CEA) the industrial companies Air Liquide and GDF SUEZ and the French Research Institutes ICARE and PPRIME (CNRS) have been involved in a project called HYDROMEL. This project was partially funded by the French National Research Agency (ANR) in the framework of its PAN-H program aimed at promoting the R&D activities related to the hydrogen deployment. Firstly the project partners investigated how a NG/H2 mixture may influence the modelling of a hazard scenario i.e. how the addition of a quantity of hydrogen in natural gas can increase the potential of danger. Therefore it was necessary to build an experimental database of physics properties for mixtures. Secondly effect distances in accidental scenarios that could happen on pipelines have been calculated with existing models adapted to the mixtures. This part was preceded by a benchmark exercise between all partners models and experimental results found in the literature. Finally the consortium wrote a good practice guideline for modelling the effects related to the release of natural gas /hydrogen mixture?. The selected models and their comparison with data collected in the literature as well as the experimental results of this project and the main conclusions of the guidelines are presented in this paper.

Compressed natural gas (CNG) is being increasingly used as a clean transportation fuel. However for further reduction in emissions particularly NOx H-CNG mixture with ~ 20 % hydrogen is recommended. Presently most of the H-CNG mixture is produced by blending hydrogen with CNG. For hydrogen production Steam Methane Reforming (SMR) is a major process accounting for more than 90% of hydrogen production by various industries. In this process natural gas is first reformed to syn gas under severe operating conditions (Pressure 20-30 bar temperature 850-950 deg C) followed by conversion of CO to hydrogen in the shift reactor. Other method of hydrogen production such as electrolysis of water is more expensive. Further there are issues of safety with handling of hydrogen its storage and transportation for blending. In order to overcome these problems a single step compact process for the production of H-CNG gaseous mixture through low severity steam methane reforming of natural gas has been developed. It employs a catalyst containing nickel nickel oxide magnesium oxide and silica and has the capability of producing H-CNG mixture in the desired proportion containing 15-20 vol % hydrogen with nil CO production. The process is flexible and rugged allowing H-CNG production as per the demand. The gaseous H-CNG product mixture can directly be used as automobile fuel after compression. The process can help as important step in safe transition towards hydrogen economy. A demonstration unit is being set up at IOC R&D Centre.

An experimental apparatus which was based on the ¼-scale garage previously used for studying helium release and dispersion in our laboratory was used to obtain effective diffusion coefficients of helium and hydrogen (released as forming gas for safety reasons) through gypsum panel. Two types of gypsum panel were used in the experiments. Helium or forming gas was released into the enclosure from a Fischer burner1 located near the enclosure floor for a fixed duration and then terminated. Eight thermal-conductivity sensors mounted at different vertical locations above the enclosure floor were used to monitor the temporal and spatial gas concentrations. An electric fan was used inside the enclosure to mix the released gas to ensure a spatially uniform gas concentration to minimize stratification. The temporal variations of the pressure difference between the enclosure interior and the ambience were also measured. An analytical model was developed to extract the effective diffusion coefficients from the experimental data.

We’ve studied the conditions enabling a detonation to be quenched when interacting with an obstruction and the propensity for establishing subsequent fast-flame. Oxy-hydrogen detonations were found quench more easily than oxy-methane detonations when comparing the ratio of gap size and the detonation cell size. High-speed turbulent deflagrations that re-accelerate back to a detonation were only observed in methane-oxygen mixtures. Separate hot-spot ignition calculations revealed that the higher detonability of methane correlates with its stronger propensity to develop localized hot-spots. The results suggest that fast-flames are more difficult to form in hydrogen than in methane mixtures.

Two vehicle fire tests were conducted to investigate the spread of fire to adjacent vehicles from a hydrogen fuel cell vehicle (HFCV) equipped with a thermal pressure relief device (TPRD) : – 1) an HFCV fire test involving an adjacent gasoline vehicle 2) a fire test involving three adjoining HFCV assuming their transportation in a carrier ship. The test results indicated that the adjacent vehicles were ignited by flames from the interior and exterior materials of the fire origin HFCV but not by the hydrogen flames generated through the activation of TPRD.

The work was done with respect to hydrogen safety of ITER vacuum vessel in cases of loss of cooling and loss of vacuum accidents. Experiments were conducted at sub-atmospheric pressures from 1 bar to 200 mbar and elevated temperatures up to 300 oC. Hydrogen concentration was changed from lower to upper flammability limits in all the range of pressures and temperatures. The experiments were performed in a spherical explosion bomb equipped with two quartz windows. The flame propagation velocity was measured using pressure method and high speed shadow cinematography. The theoretical flame velocities were calculated by Cantera code using Lutz and Mueller mechanisms. The influence of the initial temperature and pressure conditions on the laminar flame speed SL overall reaction order n and Markstein length LM are presented in this work and compared with the results of a theoretical model.

In 2003 the US Department of Energy (DOE) initiated a project to coordinate the development of a national template of hydrogen codes and standards for both vehicular and stationary applications. The process consisted of an initial evaluation to determine where there were gaps in the existing hydrogen codes and standards and the codes and standards required to fill these gaps. These codes and standards were to be developed by several Standards Development Organizations (SDOs). This effort to develop codes and standards has progressed from a position in 2003 when there were relatively few codes and standards that directly addressed hydrogen technology applications to the position at the end of 2008 where requirements to permit hydrogen technologies have been implemented in primary adopted codes- building and fire codes in hydrogen specific codes such as National Fire Protection Association (NFPA) 52 NFPA 55 and NFPA 853 and in many of the hydrogen specific component standards that are referenced primarily in the NFPA codes and standards. This paper describes the three levels of codes and standards that address hydrogen technologies for the built environment:<br/>Level 1. Primary adopted building and fire codes<br/>Level 2. Hydrogen specific codes and standards references in primary adopted code<br/>Level 3. Hydrogen specific component standards referenced in hydrogen specific codes<br/>This paper also describes the progress to date in populating these three levels with the required hydrogen codes and standards. The first two levels are essentially complete and are undergoing refinement and routine revision. Level 3 the hydrogen specific component standards is the furthest from having first edition documents that address requirements for a hydrogen system component.<br/>The DOE is focusing much of their codes and standards development efforts on these hydrogen specific component standards with the expectation that a first edition of most of these standards will be issued by 2010.

An underground mining ventilation testing facility (VTF) was designed and constructed at the HySA facility at the North-West University South Africa. The purpose was to evaluate risks associated with different hydrogen storage technologies in a confined environment. The work included initial calculations of hydrogen movement in specific spaces and the development of simulation tools to compare these modelled results with experimental work. For this purpose hydrogen sensors that could accurately measure hydrogen concentrations during a controlled hydrogen leak at the VTF were required. Hazardous hydrogen sensors capable of measuring >4% hydrogen are not readily available commercially. Typically hydrogen sensors rated for hazardous environments are designed for safety actions (e.g. activating emergency measures when hydrogen is detected) at concentrations of 8%. (Measuring concentrations higher than this is not required for commercial use hence there is no market for such sensors.) At the VTF it is necessary to be able to measure hydrogen concentrations >4% in order to obtain information on the flammable hydrogen concentrations at specified distances and orientations around a controlled hydrogen leak. Initial experimental work was conducted at low pressures resulting in very low hydrogen concentrations. Commercial available original equipment manufacturer (OEM) hydrogen sensors were capable of measuring 0.2% hydrogen which for the low pressures and gas flows here proved sufficient to enable us to make sensible conclusions. However higher pressures and gas flows are essential in practical use hence higher concentrations of hydrogen need to be measured. A custom sensor was developed by HySA while commercial sensors (OEM) were investigated. This work reports on the testing and evaluation of several hydrogen sensors. Results of initial ventilation tests are presented.

The paper will present results of hydrogen/oxygen mixtures ignited by using electric sparks electrostatic discharges a heating element and a flame. Measurements of the lower flammability limit (LFL) was done for each ignition method. The hydrogen mixtures of different concentrations were ignited at the bottom of a combustion chamber leading to an upward propagation of the resulting flame. At some level of concentration the combustion was partial due to the limited upward propagation. The complete combustion of the whole mixture was observed at concentration limits higher than the known LFL of 4% vol. for hydrogen in air. The paper will describe the test facilities and the resulting ignition probabilities for different ignition methods.

The Brazilian Fuel Cell Bus Project is being developed by a consortium comprising 14 national and international partners. The project was initially supported by the GEF/UNDP and MME/FINEP Brazil. The national coordination is under responsibility of MME and EMTU/SP the São Paulo Metropolitan Urban Transport Company that also controls the bus operation and bus routes. This work reports the efforts done in order to obtain the necessary licenses to operate the first fuel cell buses for regular service in Brazil as well as the first commercial hydrogen fueling station to attend the vehicles.

The paper presents results of experimental investigations of different phlegmatizator substances and its binary compounds used for full hydrogen combustion suppression. The work was performed in experimental facilities of three different scales (small medium and large) at normal initial pressure and temperature range 20 ⎯ 120 °С. Ten individual substances and six binary compounds were tested in a small scale experiments. Three individual halogen containing substances capable of full suppression of hydrogen combustion were found in a series of small scale experiments (tube length – 1 m ID – 66 mm). The minimum concentration of the most effective substance was 11% at 20°С and 14% at 120°С in a small scale experiments. Medium scale confined and large scale unconfined experiments confirmed the possibility of full combustion suppression. The minimum concentration of the most effective binary mixture was found to be 12 % at 20°С in a large scale experiments.

The integration of a hydrogen gas storage arrangement in vehicles has not been without its challenges. Gaseous state of hydrogen at ambient temperature combined with the fact that hydrogen is highly flammable results in the requirement of more robust high pressure storage systems that can meet modern safety standards. To develop these new safety standards and to properly predict the phenomena of hydrogen dispersion a better understanding of the resulting flow structures and flammable region from controlled and uncontrolled releases of hydrogen gas must be achieved. With the upper and lower explosive limits of hydrogen known the flammable envelope surrounding the site of a uncontrolled hydrogen release can be found from the concentration field. In this study the subsonic release of hydrogen was emulated using helium as a substitute working fluid. A sharp orifice round turbulent jet is used to emulate releases in which leak geometry is circular. Effects of buoyancy and crossflow were studied over a wide range of Froude numbers. The velocity fields of turbulent jets were characterized using particle image velocimetry (PIV). The mean and fluctuation velocity components were well quantified to show the effect of buoyancy due to the density difference between helium and the surrounding air. In the range of Froude numbers investigated (Fr = 1000 750 500 250 and 50) the increasing effects of buoyancy were seen to be proportional to the reduction of the Fr number. While buoyancy is experienced to have a negligible effect on centerline velocity fluctuations acceleration due to buoyancy in the other hand resulted in a slower decay of time-averaged axial velocity component along the centerline. The obtained results will serve as control reference values for further concentration measurement study and for computational fluid dynamics (CFD) validation.

Spontaneous ignition processes due to high pressure hydrogen releases into air are known phenomena. The sudden expansion of pressurized hydrogen into a pipe filled with ambient air can lead to a spontaneous ignition with a jet fire. This paper presents results of an experimental investigation of the visible flame propagation and pressure measurements in 4 mm extension tubes of up to 1 m length attached to a bulk vessel by a rupture disc. Transparent glass tubes for visual observation and shock wave pressure sensors are used in this study. The effect of the extension tube length on the development of a stable jet fire after a spontaneous ignition is discussed.

Computational Fluid Dynamics solvers are developed for explosion modelling and hazards analysis in Hydrogen air mixtures. The work is presented in two parts. These include firstly a numerical approach to simulate flame acceleration and deflagration to detonation transition (DDT) in hydrogen–air mixture and the second part presents comparisons between two approaches to detonation modelling. The detonation models are coded and the predictions in identical scenarios are compared. The DDT model which is presented here solves fully compressible multidimensional transient reactive Navier–Stokes equations with a chemical reaction mechanism for different stages of flame propagation and acceleration from a laminar flame to a highly turbulent flame and subsequent transition from deflagration to detonation. The model has been used to simulate flame acceleration (FA) and DDT in a 2-D symmetric rectangular channel with 0.04 m height and 1 m length which is filled with obstacles. Comparison has been made between the predictions using a 21-step detailed chemistry as well as a single step reaction mechanism. The effect of initial temperature on the run-up distances to DDT has also been investigated. Comparative study has also been carried out for two detonation solvers. one detonation solver is developed based on the solution of the reactive Euler equations while the other solver has a simpler approach based on Chapman–Jouguet model and the programmed CJ burn method. Comparison has shown that the relatively simple CJ burn approach is unable to capture some very important features of detonation when there are obstacles present in the cloud.

In order to improve risk analyses and influence the design of the future H2 systems an experimental study on “real” leaks qualification and quantification was performed. In H2 energy applications fittings appeared as a significant leakage potential and subsequently explosion and flame hazards. Thus as a part of the “Horizon Hydrogène Energie” French program four kinds of commercial fittings usually employed on H2 systems were tested thanks to a new high pressure test bench – designed setup and operated by INERIS – allowing experiments to be led for H2 pressures until 700 bar. The fittings underwent defined stresses representative of H2 systems lifetime and beyond. The associated leaks – when existing – are characterized in terms of flow rate.

The development of a set of safety codes and standards for hydrogen facilities is necessary to ensure they are designed and operated safely. To help ensure that a hydrogen facility meets an acceptable level of risk code and standard development organizations (SDOs) are utilizing risk-informed concepts in developing hydrogen codes and standards. Two SDOs the National Fire Protection Association (NFPA) and the International Organization for Standardization (ISO) through its Technical Committee (TC) 197 on hydrogen technologies have been developing standards for gaseous hydrogen facilities that specify the facilities have certain safety features use equipment made of material suitable for a hydrogen environment and have specified separation distances. Under Department of Energy funding Sandia National Laboratories (SNL) has been supporting efforts by both of these SDOs to develop the separation distances included in their respective standards. Important goals in these efforts are to use a defensible science-based approach to establish these requirements and to the extent possible harmonize the requirements. International harmonization of regulations codes and standards is critical for enabling global market penetration of hydrogen and fuel cell technologies.

One of the focus areas in the heavy-duty transport industry globally is de-carbonization of trucks dozers shovels semi-trucks buses etc. Hydrogen fuel cells (FCs) technology is one considered solution for the industry due to its zero-emissions its MW scalability and capacity to store large amounts of energy for long duration continuous power operation. Underground deep mines is another option for deployment and operation of hydrogen FCs. Benefits include lower emissions improved health comfort and safety as well as reduced operating costs. Underground mining trucks loaders and other machines have power ratings up to 750 kW which proves difficult for battery and tethered electric energy. Hydrogen FCs have the ability to overcome these power and energy storage limitations. The risks and technologies associated with delivering storing and using hydrogen underground first need to be investigated and proven safe. This work presents the design construction and operation of a mining ventilation test facility (VTF) at the North-West University in South Africa that aims to quantify the risk of hydrogen in confined ventilated environments. Initial work has been conducted on measuring concentrations of hydrogen released in the temporary ventilation site and is discussed.

The design of ventilation system has implications for the safety of life and property and the development of regulations and standards in the space with the hydrogen storage equipment. The impact of both the position and the area of a single vent on the dispersion of hydrogen in a cuboid space (with dimensions L x W x H ¼ 2.90 0.74 1.22 m) is investigated with Computational Fluid Dynamics (CFD) in this study. Nine positions of the vent were compared for the leakage taking place at the floor to understand the gas dispersion. It was shown a cloud of 1% mole fraction has been formed near the ceiling of the space in less than 40 s for different positions of the vent which can activate hydrogen sensors. The models show that the hydrogen is removed more effectively when the vent is closer to the leakage position in the horizontal direction. The study demonstrates that the vent height of 1.00 m is safer for the particular scenario considered. The area of the vent has little effect on the hydrogen concentration for all vent positions when the area of the vent is less than 0.045 m2 and the height of the vent is less than 0.61 m.

During the World Expo Shanghai there were one hundred fuel-cell sight-seeing cars in operation at the Expo Site. The sight-seeing cars were not allowed to drive out of the Expo Site and the stationary hydrogen refuelling station was not permitted to build at the Expo Site for the sake of safety. A flexible solution to refuel the cars was the application of mobile hydrogen refuelling stations. To better understand the hazards and risks associated with the mobile hydrogen refueling stations a risk analysis was preformed to improve the safety of the operations. The risks to the station personnel and to the public were discussed separately. Results show that the stationary risks of the mobile stations to the personnel and refueling customers are lower than the risk acceptance criteria over an order of magnitude so occupational risks and risks to customers are completely acceptable. The third party risks can be acceptable as long as the appropriate mitigation measures are implemented especially well designed parking area and operation time. Leak from boosters is the main risk contributor to the stationary risks because of its highest failure rates according to the generic data and its worst harm effects based on the consequence evaluations. As for the road risks of the mobile stations they can be acceptable as long as the appropriate mitigation measures are implemented especially well-designed moving path and transportation time.

To facilitate the transition to the hydrogen economy the EU project NATURALHY is studying the potential for the existing natural gas pipeline networks to transport hydrogen together with natural gas to end-users. Hydrogen may then be extracted for hydrogen fuel-cell applications or the mixture used directly by consumers in existing gas-fired equipment with the benefit of lower carbon emissions. The existing gas pipeline networks are designed constructed and operated to safely transport natural gas mostly methane. However hydrogen has significantly different properties that may adversely affect both the integrity of the network and thereby increase the likelihood of an accidental leak and the consequences if the leak finds a source of ignition. Consequently a major part of the NATURALHY project is focused on assessing how much hydrogen could be introduced into the network without adversely impacting on the safety of the network and the risk to the public. Hydrogen is more reactive than natural gas so the severity of an explosion following an accidental leak may be increased. This paper describes field-scale experiments conducted to measure the overpressures generated by ignition of methane/hydrogen/air mixtures in a congested but unconfined region. Such regions may be found in the gas handling and metering stations of the pipeline networks. The 3 m x 3 m x 2 m high congested region studied contained layers of pipes. The composition of the methane/hydrogen mixture used was varied from 0% hydrogen to 100% hydrogen. On the basis of the experiments performed the maximum overpressures generated by methane/hydrogen mixtures with 25% (by volume) or less hydrogen content are not likely to be much more than those generated by methane alone. Greater percentages of hydrogen did significantly increase the explosion overpressure.

The production of hydrogen from renewable sources is essential to develop the future hydrogen economy. Biomass is an abundant clean and renewable energy source and it can be important in the production of hydrogen. The Valencian Community due to its great agricultural and forestry activities generates an important quantity of biomass residues that can be used for energy generation approximately 778 kt of wet biomass residues per year. This great quantity of biomass can be transformed into a hydrogen-rich gas by different thermochemical conversion processes. In this article the potential of production of hydrogen-rich gas is analyzed considering several factors affecting the conversion yield of these processes. As a result of this analysis it could be possible to produce 1271 MNm3 of H₂ per year considering the total biomass residues of the community and selecting the gasification processes.

The aim of the present work is to investigate the interaction between a water spray and a laminar hydrogen-air flame in the case of steam inerted mixture. A first work is devoted to study the thermodynamics involved in the phenomena via a lumped parameter code. The flow is two- phase and reactive the gas is multi-component the water spray is polydisperse and the droplet size has certainly an influence on the flame propagation. The energy released by the reaction between hydrogen and oxygen vaporizes suspended droplets. The next step of this study will be to consider a drift-flux model for the droplets and air under hypotheses that the velocity and thermal disequilibria are weak. The multi-component feature of the gas will be further taken into account by studying a gas mixture containing hydrogen air and water vapor. A second study concerns an experimental investigation of the effect of droplets on the flame propagation using a spherical vessel. A Schlieren system is coupled to the spherical vessel in order to record the flame propagation on a digital high speed camera. Both studies will help improve our knowledge of safety relevant phenomena.

Extensive infrastructure exists for the transport of natural gas and it is an obvious step to assess its use for the movement of hydrogen. The Naturalhy project’s objective is to prepare the European natural gas industry for the introduction of hydrogen by assessing the capability of the natural gas infrastructure to accept mixtures of hydrogen and natural gas. This paper presents the ongoing work within both Durability and Integrity Work Packages of the Naturalhy project. This work covers a gap in knowledge on risk assessment required for delivering H2+natural gas blends by means of the existing natural gas grids in safe operation.<br/>Experiments involving several parts of the existing infrastructure will be described that are being carried out to re-examine the major risks previously studied for natural gas including: effect of H2 on failure behaviour and corrosion of transmission pipes and their burst resistance (link to the Work Package Safety) on permeability and ageing of distribution pipes on reliability and ageing of domestic gas meters tightness to H2 of domestic appliances and their connexions. The information will be integrated into existing Durability assessment methodologies originally developed for natural gas.<br/>An Integrity Management Tool will be developed taking account of the effect of hydrogen on the materials properties. The tool should enable a cost effective selection of appropriate measures to control the structural integrity and maintaining equipment. The main measures considered are monitoring non destructive examination (pigging and non pigging) and repair strategies. The tool will cover a number of parameters e.g.: percentage of hydrogen in the gas mixture material of construction operating conditions and condition of cathodic protection. Thus the Integrity Management Tool will yield an inspection and maintenance plan based on the specific circumstances.

The statement of the problem and algorithm of computational modelling of the processes of formation of the hydrogen-air mixture in the atmosphere its explosion (taking into account chemical interaction) and dispersion of the combustion materials in the open space with complex relief are presented. The finite-difference scheme was developed for the case of the three-dimensional system of gas dynamics equations complemented by the mass conservation laws of the gas admixture and combustion materials. The algorithm of the computation of thermal and physical parameters of the gas mixture appearing as a result of the instantaneous explosion taking into account chemical interaction was developed. The algorithm of computational solution of the difference scheme obtained on the basis of Godunov method was considered. The verification of the mathematical model showed its acceptable accuracy in comparison with known experimental data. It allows using the developed model for the modelling of pressure and thermal consequences of possible failures at the industrial enterprises which store and use hydrogen. The computational modelling of an explosion of the gas hydrogen cloud appearing as a result of instantaneous destruction of high pressure containers at the fuelling station was carried out. The analysis of different ways of protection of the surrounding buildings from destructive effects of the shock wave was conducted. The recommendations considering the choice of dimensions of the protection area around the fuelling station were worked out.

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.

Next generation of hydrogen energy based vehicles is expected to come into widespread use in the near future. Various topics related to hydrogen including production storage and application of hydrogen as an energy carrier have become subjects of discussion in the framework of various European and International projects. Safety information is vital to support the successful introduction into mainstream and public acceptance of hydrogen as an energy carrier. One of such issues which is seeking major attention is related to hydrogen powered vehicles parked inside a confined area (such as in a private garage). It is of utmost importance to predict if uncontrolled release of hydrogen from a vehicle parked inside a confined area can create an explosive atmosphere. Subsequently how the preventive measures can be implied to control these explosive atmospheres if present inside a confined area? There is a little guidance currently developed for confined areas accommodating hydrogen fuelled vehicles. It is essential that mitigation measures for such conditions become established.<br/>Characterization of different scenarios those may arise in a real situation from hydrogen fuelled vehicle parked inside a garage and furthermore the investigation of an optimal ventilation rate for hydrogen risk mitigation are some of the main objectives described in the framework of the present study. This work is an effort to provide detail experimental information’s in view of establishing guidelines for hydrogen powered vehicles parked inside a private garage. The present work is developed in the framework of a European Network of Excellence HySafe and French project DRIVE. Present paper describes a purpose built realistic Garage test facility at CEA to study the dispersion of hydrogen leakage. The studied test cases evaluate the influence of injected volumes of hydrogen and the initial conditions at the leakage source on the dispersion and mixing characteristics inside the free volume of the unventilated garage. The mixing process and build-up of hydrogen concentration is measured for the duration of 24 hours. Due to safety reasons helium gas is used to simulate the hydrogen dispersion characteristics.

If the hydrogen economy is to progress more hydrogen refuelling stations are required. In the short term in the absence of a hydrogen distribution network the most likely means of supplying the refuelling stations will be by liquid hydrogen road tanker. This development will clearly increase the number of tanker offloading operations significantly and these may need to be performed in more challenging environments with close proximity to the general public. The work described in this paper was commissioned in order to determine the hazards associated with liquid hydrogen spills onto the ground at rates typical for a tanker hose failure during offloading.

Experiments have been performed to investigate spills of liquid hydrogen at a rate of 60 litres per minute. Measurements were made on both unignited and ignited releases.

These include:

• Concentration of hydrogen in air thermal gradient in the concrete substrate liquid pool formation and temperatures within the pool
• Flame velocity within the cloud thermal radiation IR and visible spectrum video records.
• Sound pressure measurements
• An estimation of the extent of the flammable cloud was made from visual observation video IR camera footage and use of a variable position ignition source.

The BMW Hydrogen 7 is the world’s first premium sedan with a bi-fuelled internal combustion engine concept that has undergone the series development process. This car also displays the BMW typical driving pleasure. During development the features of the hydrogen energy source were emphasized. Engine tank system and vehicle electronics were especially developed as integral parts of the vehicle for use with hydrogen. The safety-oriented development process established additional strict hydrogen-specific standards for the Hydrogen 7. The fulfilment of these standards were demonstrated in a comprehensive experimentation and testing program which included all required tests and a large number of additional hydrogen-specific crash tests such as side impacts to the tank coupling system or rear impacts. Furthermore the behaviour of the hydrogen tank was tested under extreme conditions for instance in flames and after strong degradation of the insulation. Testing included over 1.7 million km of driving; and all tests were passed successfully proving the intrinsic safety of the vehicle and also confirming the success of the safety-oriented development process which is to be continued during future vehicle development. A safety concept for future hydrogen vehicles poses new challenges for vehicles and infrastructure. One goal is to develop a car fuelled by hydrogen only while simultaneously optimizing the safety concept. Another important goal is removal of (self-imposed) restrictions for parking in enclosed spaces such as garages. We present a vision of safety standards requirements and a program for fulfilling them.

INERIS has set up large-scale fully instrumented experiments to study the formation of flammable clouds resulting from a finite duration spillage of hydrogen in a quiescent room (80 m3 chamber). Concentration temperature and mass flow measurements were monitored during the release period and several hours after. Experiments were carried out for mass flow rates ranging from 02 g/s to 1 g/s. The instrumentation allowed the observation and quantification of rich hydrogen layers stratification effects. This paper presents both the experimental facility and the test results. These experimental results can be used to assess and benchmark CFD tools capabilities.

In this paper a case of hydrogen release in a typical research laboratory for the characterisation of hydrogen solid-state storage materials has been considered. The laboratory is equipped with various testing equipments for the assessment of hydrogen capacity in materials typically in the 1 to 200 bar pressure range and temperatures up to 500°C. Hydrogen is delivered at 200 bar by a 50 l gas bottle and a compressor located outside the laboratory. The safety measures directly related to hydrogen hazard consist in a distributed ventilation of the laboratory and air extraction fume hoods located on top of each instrument. Goal of this work is the modelling of hydrogen accidental release in a real laboratory case in order to provide a more fundamental basis for the laboratory safety design and assist the decision on the number and position of the safety sensors. The computational fluid dynamics code (CFD) ANSYS-CFX has been selected in order to perform the numerical investigations. Two basic accidental release scenarios have been assumed both at 200 bar:  a major leak corresponding to a guillotine breaking of the hydrogen distribution line and a smaller leak typical for a not properly tight junction.

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.

Solid state materials such as metal and chemical hydrides have been proposed and developed for high energy density automotive hydrogen storage applications. As these materials are implemented into hydrogen storage systems developers must understand their behavior during accident scenarios or contaminated refueling events. An ability to predict thermal and chemical processes during contamination allows for the design of safe and effective hydrogen storage systems along with the development of appropriate codes and standards. A model for the transport of gases within an arbitrary-geometry reactive metal hydride bed (alane -AlH3) is presented in this paper. We have coupled appropriate Knudsen-regime permeability models for flow through packed beds with the fundamental heat transfer and chemical kinetic processes occurring at the particle level. Using experimental measurement to determine and validate model parameters we have developed a robust numerical model that can be utilized to predict processes in arbitrary scaled-up geometries during scenarios such as breach-in-tank or contaminated refueling. Results are presented that indicate the progression of a reaction front through a compacted alane bed as a result of a leaky fitting. The rate of this progression can be limited by; 1) restricting the flow of reactants into the bed through densification and 2) maximizing the rate of heat removal from the bed.

This paper is concerned with predicting the impact on the probability of failure of adding hydrogen to the natural gas distribution network. Hydrogen has been demonstrated to change the behaviour of crack like defects which may affect the safety of pipeline or make it more expensive to operate. A tool has been developed based on a stochastic approach to assess the failure probability of the gas pipeline due to the existence of crack-lie defects including the operational aspects of the pipeline such as inspection and repair procedures. With various parameters such as crack sizes material properties internal pressure modelled as uncertainties a reliability analysis based on failure assessment diagram is performed through direct Monte Carlo simulation. Inspection and repair procedures are included in the simulation to enable realistic pipeline maintenance scenarios to be simulated. In the data preparation process the accuracy of the probabilistic definition of the uncertainties is crucial as the results are very sensitive to certain variables such as the crack depth length and crack growth rate. The failure probabilities of each defect and the whole pipeline system can be obtained during simulation. Different inspection and repair criteria are available in the Monte Carlo simulation whereby an optimal maintenance strategy can be obtained by comparing different combinations of inspection and repair procedures. The simulation provides not only data on the probability of failure but also the predicted number of repairs required over the pipeline life thus providing data suitable for economic models of the pipeline management. This tool can be also used to satisfy certain target reliability requirement. An example is presented comparing a natural gas pipeline with a pipeline containing hydrogen.

Hydrogen is currently gaining much attention as a possible future substitute for oil in the transport sector. Hydrogen is not a primary energy source but can be produced from other sources of energy. A future hydrogen economy will need the establishment of new infrastructures for producing storing distributing dispensing and using hydrogen. Hydrogen can be produced in large-scale centralized facilities or in smaller scale on-site systems. Large-scale production requires distribution in pipelines or trucks. A major challenge is to plan the new infrastructures to approach an even safer society regarding safe use of hydrogen. The paper will on the basis of some scenarios for hydrogen deployment highlight and evaluate safety aspects related to future hydrogen economy infrastructures.

This paper presents a study on the Standard Operating Procedures (P.O.S.s) for the operation of the Fire Corps squads in the event of accidents with a hydrogen release fire or explosion. This study has been carried out by the Italian Working Group on the fire prevention safety issues as one of its main objectives. The Standard Operating Procedures proved to be a basic tool in order to improve the effectiveness of the Fire Corps rescue activity. The unique physical and chemical properties of the hydrogen its use without odorization and its almost invisible flame require a review of the already codified approaches to the rescue operations where conventional gases are involved. However this is only the first step; a Standard Operating Procedure puts together both the theoretical and practical experience achieved on the management of the rescue operations; therefore its arrangement is a cyclic process by nature always under continuous revision updating and improvement.

It is well known in socio-economics that the success of an innovation process depends to a great extent on public acceptance. The German HyTrust project analyzes the current state of public acceptance in hydrogen technology in the mobility sector. This paper focuses on cutting-edge results of interviews focus groups and a representative survey. Based on these results almost 80% of the Germans are in favor of introducing hydrogen vehicles. But from the perspective of the general public it is important that hydrogen is produced in an environmentally friendly way. HyTrust is the socio-scientific research project that accompanies the German Federal Government's National Innovation Programme.

The UK has committed to significantly reduce greenhouse gas emissions by 2050 to help address climate change. Decarbonising heating is a key part of this and using hydrogen (H2) as a replacement to natural gas (NG) can help in achieving this. The objective of current research including HyDeploy is to demonstrate that NG containing levels of H2 beyond those currently allowed of 0.1 vol% (1000 ppm) [1] can be distributed and utilised safely and efficiently. Initial projects such as HyDeploy are studying the effects of introducing up to 20 vol% H2 in NG but later projects are considering using up to 100 vol% H2.

A key element in the safe operation of a modern gas distribution system is gas detection. However the addition of hydrogen to NG will alter the characteristics of the gas and the impact on gas detection must be considered. It is important that sensors remain sufficiently sensitive to the presence of hydrogen natural gas carbon monoxide (CO) and oxygen (O2) deficiency and that they don’t lead to false positive or false negative readings. The aim of this document is to provide a summary of the requirements for gas detection of hydrogen enriched natural gas for the gas distribution industry and other potentially interested parties. As such it is based on gas detectors presently used by the industry with the only major differences being the effects of hydrogen on the sensitivity of flammable gas sensors and the cross sensitivity of carbon monoxide gas sensors to hydrogen.

There is further information of gas detector concepts and technologies in the appendices.

This report and any attachment is freely available on the ENA Smarter Networks Portal here. IGEM Members can download the report and any attachment directly by clicking on the pdf icon above.

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.

We have modelled sudden hydrogen expansion from a cryogenic pressure vessel. This model considers real gas equations of state single and two-phase flow and the specific “vessel within vessel” geometry of cryogenic vessels. The model can solve sudden hydrogen expansion for initial pressures up to 1210 bar and for initial temperatures ranging from 27 to 400 K. For practical reasons our study focuses on hydrogen release from 345 bar with temperatures between 62 K and 300 K. The pressure vessel internal volume is 151 L. The results indicate that cryogenic pressure vessels may offer a safety advantage with respect to compressed hydrogen vessels because i) the vacuum jacket protects the pressure vessel from environmental damage ii) hydrogen when released discharges first into an intermediate chamber before reaching the outside environment and iii) working temperature is typically much lower and thus the hydrogen has less energy. Results indicate that key expansion parameters such as pressure rate of energy release and thrust are all considerably lower for a cryogenic vessel within vessel geometry as compared to ambient temperature compressed gas vessels. Future work will focus on taking advantage of these favourable conditions to attempt fail-safe cryogenic vessel designs that do not harm people or property even after catastrophic failure of the inner pressure vessel.

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.

The formation of a flammable hydrogen-air mixture is a major safety concern especially for closed space. This hazardous situation can arise when considering permeation from a car equipped with a composite compressed hydrogen tank with a non-metallic liner in a closed garage. In the following paper a scenario is developed and analysed with a simplified approach and a numerical simulation in order to estimate the evolution of hydrogen concentration. The system is composed of typical size garage and hydrogen car’s tank. Some parameters increasing permeation rate (i.e. tank’s material thickness and pressure) have been chosen to have a conservative approach. A close look on the top of tank surface showed that the concentration grows as square root of time and does not exceed 8.2×10-3 % by volume. Also a simplified comparative analysis estimated that the buoyancy of hydrogen-air mixture prevails on the diffusion 35 seconds after permeation starts in good agreement with simulation where time is at about 80 seconds. Finally the numerical simulations demonstrated that across the garage height the hydrogen is nearly distributed linearly and the difference in hydrogen concentration at the ceiling and floor is negligible (i.e. 3×10-3 %).

An accidental hydrogen release in equipment enclosures may result in the presence of a detonable mixture in a confined environment. Numerical simulation is potentially a useful tool for damage assessment in these situations. To assess the value of CFD techniques numerical simulation of detonation was performed for two realistic scenarios. The first scenario starts with a pipe failure in an electrolyzer resulting in a leak of 42 g of hydrogen. The second scenario deals with a failure in a reformer where 84 g of hydrogen is released. In both cases dispersion patterns were first obtained from separate numerical simulation and were then used as initial condition in a detonation simulation based upon the reactive Euler's equations. Energy was artificially added in a narrow region to simulate detonative ignition. In the electrolyzer ignition was assumed to occur 500 ms after beginning of the release. Results show a detonation failing on the top and bottom side but propagating left and right before eventually failing also. Average impulse was 500 Ns/m². For the reformer three cases were simulated with ignition 1.0 1.4 and 2.0 seconds after the beginning of the release. In two cases the detonation wave failed everywhere except in the direction of the release in which it continued propagating until reaching the side wall. In the third the detonation failed everywhere at first but later a deflagration to detonation transition occurred resulting in a strong wave that propagated rapidly toward the side wall. In all three cases the consequences are more serious than in the electrolyzer.

The paper presents an overview of the main results of the EC NOE HySafe activity to estimate an allowable hydrogen permeation rate for automotive legal requirements and standards. The work was undertaken as part of the HySafe internal project InsHyde.<br/>A slow long term hydrogen release such as that due to permeation from a vehicle into an inadequately ventilated enclosed structure is a potential risk associated with the use of hydrogen in automotive applications. Due to its small molecular size hydrogen permeates through the containment materials found in compressed gaseous hydrogen storage systems and is an issue that requires consideration for containers with non-metallic (polymer) liners. Permeation from compressed gaseous hydrogen storage systems is a current hydrogen safety topic relevant to regulatory and standardisation activities at both global and regional levels.<br/>Various rates have been proposed in different draft legal requirements and standards based on different scenarios and the assumption that hydrogen dispenses homogeneously. This paper focuses on the development of a methodology by HySafe Partners (CEA NCSRD. University of Ulster and Volvo Technology) to estimate an allowable upper limit for hydrogen permeation in automotive applications by investigating the behaviour of hydrogen when released at small rates with a focus on European scenario. The background to the activity is explained. reasonable scenarios are identified a methodology proposed and a maximum hydrogen permeation rate from road vehicles into enclosed structures is estimated The work is based on conclusions from the experimental and numerical investigations described by CEA NCSRD and the University of Ulster in related papers.