Safety

Hydrogen-air mixtures are flammable in a wide range of compositions and have a low ignition energy compared to gaseous hydrocarbons. Due to its low density high buoyancy and diffusivity the mixing is strongly enhanced which supports distribution into large volumes if accidentally released. Economically valuable discontinuous transportation over large distances is only expected using liquid hydrogen (LH2). Releases of LH2 at its low temperature (20.3 K at 0.1 MPa) have additional hazards besides the combustible character of gaseous hydrogen (GH2). Hazard assessment requires simulation tools capable of calculating the pool spreading as well as the gas distribution for safety assessments of existing the future liquid hydrogen facilities. Evaluating possible risks the following process steps are useful:

• Possible accident release scenarios need to be identified for a given plant layout.
• Environmental boundary conditions such as wind conditions and humidity need to be identified and worst case scenarios have to be identified.
• A model approach based on this information which is capable of simulating LH2 releases vaporization rates and atmospheric dispersion of the gaseous hydrogen.
• Evaluate and verify safety distances identify new risks and/or extract certain design rules.

The process steps have been performed using the new validated 3D transient multiphase - multicomponent CFD model approach developed at Forschungszentrum Julich. A demonstration plant layout obtained from the IDEALHY project (Berstad et al.[1]) and two HAZID assessments (Hankinson et al.[2]) have been used for identifying a plant and a possible accident scenario. A general weather analysis at a possible location has been performed to identify weather conditions. Finally a full transient parameter calculation has been set up varying the LH2 release rate and the wind speed. The results have been analyzed and general conclusions have been derived.

Laminar burning velocities (SL) of hydrogen/ammonia mixtures in air at atmospheric pressure were studied experimentally and numerically. The blending of hydrogen with ammonia two fuels that have been proposed as promising carriers for renewable energy causes the laminar flame speed of the mixture SL to decrease significantly. However details of this have not previously available. Systematic measurements were therefore performed for a series of hydrogen/ammonia mixtures with wide ranges of mole fractions of blended ammonia (XNH3) and equivalence ratio using a heat flux method based on heat flux of a flat flame transferred to the burner surface. It was found that the mixture of XNH3 = 40% has a value of SL close to that of methane which is the dominant component of natural gas. Using three chemical kinetic mechanisms available in the literature i.e. the well-known GRI-Mech 3.0 mechanism and two mechanisms recently released SL were also modelled for the cases studied. However the discrepancies between the experimental and numerical results can exceed 50% with the GRI-Mech 3.0 mechanism. Discrepancies were also found between the numerical results obtained with different mechanisms. These results can contribute to an increase in both the safety and efficiency of the coutilization of these two types of emerging renewable fuel and to guiding the development of better kinetic models.

Power to gas could get an important issue in future permitting the valorisation of green electric excess energy by producing hydrogen mixing it with natural gas (NG) and use the NG grid as temporary storage. NG grid stakeholders expect that blends up to 20% seem to be a realistic scenario. The knowledge of the explosion group for these hydrogen/NG (H2NG) mixtures is a necessary information for the choice of equipment and protective systems intended for the use in potentially explosive atmospheres of these mixtures. Therefore we determined experimentally the minimum ignition current (MIC) the MIC ratios referenced on MIC of pure methane corresponding to IEC 60079-20-1 standard. The results are compared to those obtained by maximum experimental safe gap (MESG) the second standardized method. The tested gas mixtures started from 2 vol.% volume admixture in methane rising in 2% steps up to 20 vol.% of hydrogen. The interpretation of these results could conduct to consider methane/hydrogen mixtures containing more than 14 vol.% of hydrogen as Group IIB gases.

As the energy crisis and environment pollution growing severely the hydrogen fuel motor vehicle has got more and more attention many automobile companies and research institutions invest significant R&D resources to research and develop the hydrogen fuel vehicles. With the development of the hydrogen fuel cell vehicles and hydrogen fuel motor vehicles the hydrogen had more to more extensive application. According to the categories of the hydrogen fuel vehicles the characteristics of hydrogen fuel vehicle fire risk and accidents are analyzed in this paper. As for hydrogen fuel cell vehicles the function of its key components such as the fuel cell the high-pressure storage tank is presented firstly. Then based on the low density fast diffusion and flammable of hydrogen the probable scenarios of accident such as fuel leak jet flame are analyzed and the fire risk of the key components and the whole vehicle is evaluated. Finally the development trend of the emergency warning system of hydrogen fuel cell vehicles is analyzed and some recommendations are proposed referring to the detection pre-warning and control technologies used in the industrial sites. Aiming at the hydrogen car structure characteristics and the fire accident modes and accidents evolution rules the emergency disposal technology system for hydrogen fuel motor vehicles is put forward.

The paper presents the outcomes of the HyResponse project i.e. the European Hydrogen Safety Training Programme for first responders. The threefold training is described: the content of the educational training is presented the operational training platform and its mock-up real scale transport and hydrogen stationary installations are detailed and the innovative virtual tools and training exercises are highlighted. The paper underlines the outcomes the three pilot sessions as well as the Emergency Response Guide available on the HyResponse’s public website. The next steps for widespread dissemination into the community are discussed.

We have analyzed vacuum insulation failure in an automotive cryogenic pressure vessel (also known as cryo-compressed vessel) storing hydrogen (H2). Vacuum insulation failure increases heat transfer into cryogenic vessels by about a factor of 100 potentially leading to rapid pressurization and venting to avoid exceeding maximum allowable working pressure (MAWP). H2 release to the environment may be dangerous if the vehicle is located in a closed space (e.g. a garage or tunnel) at the moment of insulation failure. We therefore consider utilization of the hydrogen in the vehicle fuel cell and electricity dissipation through operation of vehicle accessories or battery charging as an alternative to releasing hydrogen to the environment. We consider two strategies: initiating hydrogen extraction immediately after vacuum insulation failure or waiting until MAWP is reached before extraction. The results indicate that cryogenic pressure vessels have thermodynamic advantages that enable slowing down hydrogen release to moderate levels that can be consumed in the fuel cell and dissipated onboard the vehicle even in the worst case when the vacuum fails with a vessel storing hydrogen at maximum refuel density (70 g/L at 300 bar). The two proposed strategies are therefore feasible and the best alternative can be chosen based on economic and/or implementation constraints.

A hydrogen leak from a facility which uses highly compressed hydrogen gas (714 bar 800 K) during operation was studied. The investigated scenario involves supersonic hydrogen release from a 10 cm2 leak of the pressurized reservoir turbulent hydrogen dispersion in the facility room followed by an accidental ignition and burn-out of the resulting H2-air cloud. The objective is to investigate the maximum possible flame velocity and overpressure in the facility room in case of a worst-case ignition. The pressure loads are needed for the structural analysis of the building wall response. The first two phases namely unsteady supersonic release and subsequent turbulent hydrogen dispersion are simulated with GASFLOW-MPI. This is a well validated parallel all-speed CFD code which solves the compressible Navier-Stokes equations and can model a broad range of flow Mach numbers. Details of the shock structures are resolved for the under-expanded supersonic jet and the sonic-subsonic transition in the release. The turbulent dispersion phase is simulated by LES. The evolution of the highly transient burnable H2-air mixture in the room in terms of burnable mass volume and average H2-concentration is evaluated with special sub-routines. For five different points in time the maximum turbulent flame speed and resulting overpressures are computed using four published turbulent burning velocity correlations. The largest turbulent flame speed and overpressure is predicted for an early ignition event resulting in 35–71 m/s and 0.13–0.27 bar respectively.

A series of experiments in a thin layer geometry performed at the HYKA test site of the KIT. The experiments on different combustion regimes for lean and stoichiometric H2/air mixtures were performed in a rectangular chamber with dimensions of 20 x 90 x h cm3 where h is the thickness of the layer (h = 1 2 4 6 8 10 mm). Three different layer geometries:

• a smooth channel without obstructions;
• the channel with a metal grid filled 25% of length and
• a metal grid filled 100% of length. 

Detail measurement of H2/air combustion behaviour including flame acceleration (FA) and DDT in closed rectangular channel have been done. Five categories of flame propagation regimes were classified. Special attention was paid to the analysis of critical condition for different regimes of flame propagation as function of the layer thickness and roughness of the channel. It was found that thinner layer suppresses the detonation onset and even with a roughness the flame is available to accelerate to speed of sound. The detonation may occur only in a channel thicker than 6 mm.

Consequence modelling of high potential risks of usage and transportation of cryogenic liquids yet requires substantial improvements. Among the cryogenics liquid hydrogen (LH2) needs especial treatments and a comprehensive understanding of spill and spread of liquid and dispersion of vapor. Even though many of recent works have shed lights on various incidents such as spread dispersion and explosion of the liquid over land less focus was given on spill and spread of LH2 onto water. The growing trend in ship transportation has enhanced risks such as ships’ accidental releases and terrorist attacks which may ultimately lead to the release of the cryogenic liquid onto water. The main goal of the current study is to present a computational fluid dynamic (CFD) approach using OpenFOAM to model release and spread of LH2 over water substrate and discuss previous approaches. It also includes empirical heat transfer equations due to boiling and computation of evaporation rate through an energy balance. The results of the proposed model will be potentially used within another coupled model that predicts gas dispersion]. This work presents a good practice approach to treat pool dynamics and appropriate correlations to identify heat flux from different sources. Furthermore some of the previous numerical approaches to redistribute or in some extend manipulate the LH2 pool dynamic are brought up for discussion and their pros and cons are explained. In the end the proposed model is validated by modelling LH2 spill experiment carried out in 1994 at the Research Centre Juelich in Germany.

Catastrophic rupture of onboard hydrogen storage in a fire is a safety concern. Different passive e.g. fireproofing materials the thermally activated pressure relief device (TPRD) and active e.g. initiation of TPRD by fire sensors safety systems are being developed to reduce hazards from and associated risks of high-pressure hydrogen storage tank rupture in a fire. The probability of such low-frequency highconsequences event is a function of fire resistance rating (FRR) i.e. the time before tank without TPRD ruptures in a fire the probability of TPRD failure etc. This safety issue is “confirmed” by observed recently cases of CNG tanks rupture due to blocked or failed to operate TPRD etc. The increase of FRR by any means decreases the probability of tank rupture in a fire particularly because of fire extinction by first responders on arrival at an accident scene.<br/>This study of socio-economic effects of safety applies a quantitative risk assessment (QRA) methodology to an example of hydrogen vehicles with passive tank protection system on roads in London.<br/>The risk is defined here through the cost of human loss per fuel cell hydrogen vehicle (FCHV) fire accident and fatality rate per FCHV per year. The first step in the methodology is the consequence analysis based on validated deterministic engineering tools to estimate the main identified hazards: overpressure in the blast wave at different distances and the thermal hazards from a fireball in the case of catastrophic tank rupture in a fire. The population can be exposed to slight injury serious injury and fatality after an accident. These effects are determined based on criteria by Health and Safety Executive (UK) and a cost metrics is applied to the number of exposed people in these three harm categories to estimate the cost per an accident. The second step in the methodology is either the frequency or the probability analysis. Probabilities of a vehicle fire and failure of the thermally activated pressure relief device are taken from published sources. A vulnerability probit function is employed to calculate the probability of emergency operations’ failure to prevent tank rupture as a function of a storage tank FRR and time of fire brigade arrival. These later results are integrated to estimate the tank rupture frequency and fatality rate. The risk is presented as a function of fire resistance rating.<br/>The QRA methodology allows to calculate the cost of human loss associated with an FCHV fire accident and demonstrates how the increase of FRR of onboard storage as a safety engineering measure would improve socio-economics of FCHV deployment and public acceptance of the technology.

Stationary pressure vessels for the storage of large volumes of gaseous hydrogen at high pressure (>70 MPa) are typically manufactured from Cr-Mo steels. These steels display hydrogen-enhanced fatigue crack growth but pressure vessels can be manufactured using defect-tolerant design methodologies. However storage volumes are limited by the wall thickness that can be reliably manufactured for quench and tempered Cr-Mo steels typically not more than 25-35 mm. High-hardenability steels can be manufactured with thicker walls which enables larger diameter pressure vessels and larger storage volumes. The goal of this study is to assess the fracture and fatigue response of high hardenability Ni-Cr-Mo pressure vessel steels for use in high-pressure hydrogen service at pressure in excess of 1000 bar. Standardized fatigue crack growth tests were performed in gaseous hydrogen at frequency of 1Hz and for R-ratios in the range of 0.1 to 0.7. Elastic-plastic fracture toughness measurements were also performed. The measured fatigue and fracture behavior is placed into the context of previous studies on fatigue and fracture of Cr-Mo steels for gaseous hydrogen.

Sustainable electricity generation is gaining importance across the globe against the backdrop of ever- diminishing resources and to achieve significant reductions in CO2 emissions. One of the challenges is storing excess energy generated from wind and solar power. Siemens developed an electrolysis system based on proton exchange membrane (PEM) technology enabling large volumes of energy to be stored through the conversion of electrical energy into hydrogen. In developing this new product range Siemens worked intensively on safe operation with a special focus on safety measures (primary secondary and tertiary). Indeed hydrogen is not only a rapidly diffusing gas with a wide range of flammability but frequent lack of information leads to insecurity among the public. Siemens PEM water electrolyzer operates at a working pressure of 50 bar / 5 MPa. The current product generation is being used for demonstration purposes and fits into a 30 ft. / 9.14 m container. Further industrialized product lines up to double-digit medium voltage ranges will be available on the market short- and mid-term. The system is designed to operate self-sustaining. Therefore special features such as back-up and fail-safe mode supported by remote monitoring and access have been implemented. This paper includes Siemens' approach to develop and implement a safety concept for the PEM water electrolyzer leading into the approval and certification by a Notified Body as well as the lessons learnt from test stand and field experience in this new application field

Just in line with any emerging alternative transportation fuel incidents involving hydrogen used as transportation fuel are learning opportunities for this new and growing industry. This paper includes discussion of many topics in hydrogen safety surrounding the installation operation and maintenance of commercial hydrogen stations or compression storage and dispensing systems.

Most studies on blast waves generated by gas explosions have focused on gas explosions occurring in open spaces. However accidental gas explosions often occur in confined spaces and the blast wave generates from a bursting vessel as a result of an increase in pressure caused by the gas explosion. In this study blast waves from bursting plastic vessels in which gas explosions occurred are investigated. The flammable mixtures used in the experiments were hydrogen-air mixtures at several equivalence ratios and a stoichiometric methane-air mixture. The overpressures of the blast waves were generated by venting high-pressure gas in the enclosure and volumetric expansion with a combustion reaction. The measured intensities of the blast waves were greater than the calculated values resulting from high-pressure bursting without a combustion reaction. The intensities of the blast waves resulting from the explosions of hydrogen-air mixtures were much greater than those of the methane-air mixture.

This paper demonstrates experimental and numerical study on spontaneous ignition of H2–N2 mixtures during high-pressure release into air through the tubes of various diameters and lengths. The mixtures included 5% and 10% (vol.) N2 addition to hydrogen being at initial pressure in range of 4.3–15.9 MPa. As a point of reference pure hydrogen release experiments were performed with use of the same experimental stand experimental procedure and extension tubes. The results showed that N2 addition may increase the initial pressure necessary to self-ignite the mixture as much as 2.12 or 2.85 – times for 5% and 10% N2 addition respectively. Additionally simulations were performed with use of Cantera code (0-D) based on the ideal shock tube assumption and with the modified KIVA3V code (2-D) to establish the main factors responsible for ignition and sustained combustion during the release.

Hot surface ignition is relevant in the context of industrial safety. In the present work two-dimensional simulations with detailed chemistry and study of the reaction pathways of the buoyancy-driven flow and ignition of a stoichiometric hydrogen-air mixture by a rapidly heated surface (glowplug) are reported. Experimentally ignition is observed to occur regularly at the top of the glowplug; numerical results for hydrogen-air reproduce this trend and shed light on this behaviour. The simulations show the importance of flow separation in creating zones where convective losses are minimized and heat diffusion is maximized resulting in the critical conditions for ignition to take place.

We present an experimental investigation of the different concentration build-up regimes encountered during a release of helium/air mixture in an empty enclosure without ventilation. The release is a vertical jet issuing from a nozzle located near the floor. The nozzle diameter the flow rate and the composition of the injected mixture have been varied such that the injection Richardson number ranges from 6 × 10−6 to 190. The volume Richardson number which gives the ability of the release to mix the enclosure content ranges from 2 × 10−3 to 2 × 104. This wide range allowed reaching three distinct regimes: stratified stratified with a homogeneous upper layer and homogenous.

The accidents that hydrogen ignites without ignition source are reported in several cases which phenomenon is called “auto-ignition.” Since the use of high pressure hydrogen will be increased for the hydrogen society it must be necessary to understand auto-ignition mechanism in detail to prevent such accidents. In this study we performed three-dimensional numerical simulations to clarify the autoignition mechanism using the three-dimensional compressive Navier-Stokes equations and a hydrogen chemical reaction model including nine species and twenty elementary reactions. We focus on the effects of the shape of the cross-section on the hydrogen auto-ignition mechanism applying for a rectangular and cylindrical tube. The results obtained indicate that the Richtmyer-Meshukov instability involves these auto-ignition.

Polymer electrolyte membrane (PEM) water electrolysis is an efficient and environmental friendly method that can be used for the production of molecular hydrogen of electrolytic grade using zero-carbon power sources such as renewable and nuclear. However market applications are asking for cost reduction and performances improvement. This can be achieved by increasing operating current density and lifetime of operation. Concerning performance safety reliability and durability issues the membrane-electrode assembly (MEA) is the weakest cell component. Most performance losses and most accidents occurring during PEM water electrolysis are usually due to the MEA. The purpose of this communication is to report on some specific degradation mechanisms that have been identified as a potential source of performance loss and membrane failure. An accelerated degradation test has been performed on a MEA by applying galvanostatic pulses. Platinum has been used as electrocatalyst at both anode and cathode in order to accelerate degradation rate by maintaining higher cell voltage and higher anodic potential that otherwise would have occurred if conventional Ir/IrOx catalysts had been used. Experimental evidence of degradation mechanisms have been obtained by post-mortem analysis of the MEA using microscopy and chemical analysis. Details of these degradation processes are presented and discussed.

Hydrogen impinging jets can be formed in the case of an accidental release indoors or outdoors. The CFD simulation of hydrogen impinging jets suffers from numerical errors resulting in a non-physical velocity and hydrogen concentration field with a butterfly like structure. In order to minimize the numerical errors and to avoid the butterfly effect high order schemes need to be used. The aim of this work is to give best practices guidelines for hydrogen impinging jet simulations. A number of different numerical schemes is evaluated. The number of cells which discretize the source is also examined.

Within the scope of the HyResponse project the development of a specialised training programme is currently underway. Utilizing an andragogy approach to teaching distance learning is mixed with classroom instructors-led activities while hands-on training on a full-scale simulator is coupled with an innovative virtual reality based experience. Although the course is dedicated mainly to first responders provision has been made to incorporate not only simple table-top and drill exercises but also full-scale training involving all functional emergency response organisations at multi-agency cooperation level. The developed curriculum includes basics of hydrogen safety first responders' procedures and incident management expectations

This paper describes work performed by a consortium led by the UK Health and Safety Laboratory(HSL)to identify the safe operating conditions for combined cycle power generating systems running on high hydrogen fuels. The work focuses on hydrogen and high hydrogen syngas and biogas waste-stream fuel mixtures which may prove hazardous in the event of a turbine or engine flame out resulting in a flammable fuel mixture entering the hot exhaust system and igniting. The paper describes the project presenting some initial results from this work including the development of large scale experimental facilities on the550 acre HSL site near Buxton Derbyshire UK. It describes the large scale experimental facility which utilises the exhaust gas from a Rolls-Royce Viper jet-engine (converted to run on butane) feeding into a 12 m long 0.60 m diameter instrumented tube at a pre-combustion velocity of 22 m/s. A variable geometry simulated heat exchanger with a 40 %2blockage ratio is present in the tube. Flammable mixtures injected into the tube close to the Viper outlet together with make-up oxygen are then ignited. Extensive optical ionisation temperature and pressure sensors are employed along the length of the tube to measure the pressures and flame speeds resulting from the combustion event. Some preliminary results from the test programme are discussed including deflagration to detonation transitions at high equivalence ratios.

NFPA 2 Hydrogen Technologies Code allows the use of risk-informed approaches to permitting hydrogen fuelling installations through the use of performance-based evaluations of specific hydrogen hazards. However the hydrogen fuelling industry in the United States has been reluctant to implement the performance-based option because the perception is that the required effort is cost prohibitive and there is no guarantee that the Authority Having Jurisdiction (AHJ) would accept the results. This report provides a methodology for implementing a performance-based design of an outdoor hydrogen refuelling station that does not comply with specific prescriptive separation distances. Performance-based designs are a code-compliant alternative to meeting prescriptive requirements. Compliance is demonstrated by evaluating a compliant prescriptive-based refuelling station design with a performance-based design approach using Quantitative Risk Assessment (QRA) methods and hydrogen risk tools. This template utilizes the Sandia-developed QRA tool Hydrogen Risk Analysis Model (HyRAM) to calculate risk values when developing risk-equivalent designs. HyRAM combines reduced-order deterministic models that characterize hydrogen release and flame behaviour with probabilistic risk models to quantify risk values. Each project is unique and this template is not intended to cover unique site-specific characteristics. Instead example content and a methodology are provided for a representative hydrogen refuelling site which can be built upon for new hydrogen applications.

In this study the spread of cryogenic liquid due to a limited period of release is investigated for the first time to clarify the unclear conventional concept regarding two release types continuous and instantaneous release. In describing instantaneous release a discharge time has been assumed to be infinitesimally small; however such an assumption is unreal because there exists a finite period of release no matter how rapid it is. If the discharge time is less than the entire time domain the instantaneous release model should be added to the continuous model from the end of the time. This combined release that consists of the initial continuous model and subsequent instantaneous model is more realistic than the instantaneous release. The physical phenomenon is governed by three parameters: the evaporation rate per unit area release time and spill quantity. Third-order perturbation solutions are obtained and compared with a numerical solution to verify the perturbation solution. For the same spill quantity the combined model that consists of continuous and subsequent instantaneous model is necessary for small release times whereas the continuous model is only required for large release times. Additionally the combined release model is necessary for a small spill quantity at a fixed release time. These two release models are clearly distinguished using the perturbation solution.

This study addresses one of knowledge gaps in hydrogen safety science and engineering i.e. a predictive model for calculation of deterministic separation distances defined by the parameters of a blast wave generated by a high-pressure gas storage tank rupture in a fire. An overview of existing methods to calculate stored in a tank internal (mechanical) energy and a blast wave decay is presented. Predictions by the existing technique and an original model developed in this study which accounts for the real gas effects and combustion of the flammable gas released into the air (chemical energy) are compared against experimental data on high-pressure hydrogen tank rupture in the bonfire test. The main reason for a poor predictive capability of the existing models is the absence of combustion contribution to the blast wave strength. The developed methodology is able to reproduce experimental data on a blast wave decay after rupture of a stand-alone hydrogen tank and a tank under a vehicle. In this study the chemical energy is dynamically added to the mechanical energy and is accounted for in the energy-scaled non-dimensional distance. The fraction of the total chemical energy of combustion released to feed the blast wave is 5% and 9% however it is 1.4 and 30 times larger than the mechanical energy in the stand-alone tank test and the under-vehicle tank test respectively. The model is applied as a safety engineering tool to four typical hydrogen storage applications including onboard vehicle storage tanks and a stand-alone refuelling station storage tank. Harm criteria to people and damage criteria for buildings from a blast wave are selected by the authors from literature to demonstrate the calculation of deterministic separation distances. Safety strategies should exclude effects of fire on stationary storage vessels and require thermal protection of on-board storage to prevent dangerous consequences of high-pressure tank rupture in a fire.