Safety

Hydrogen is a key parameter to monitor radioactive disposal facility such as the envisioned French geological repository for nuclear wastes. The use of microcantilevers as chemical sensors usually involves a sensitive layer whose purpose is to selectively sorb the analyte of interest. The sorbed substance can then be detected by monitoring either the resonant frequency shift (dynamic mode) or the quasi-static deflection (static mode). The objective of this paper is to demonstrate the feasibility of eliminating the need for the sensitive layer in the dynamic mode thereby increasing the long-term reliability. The microcantilever resonant frequency allows probing the mechanical properties (mass density and viscosity) of the surrounding fluid and thus to determine the concentration of a species in a binary gaseous. Promising preliminary work has allowed detecting concentration of 200 ppm of hydrogen in air with non-optimized geometry of silicon microcantilever with integrated actuation and read-out.

Polymers for O-rings valve seats gaskets and other sealing applications in the hydrogen infrastructure face extreme conditions of high-pressure H2 (0.1 to 100 MPa) during normal operation. To fill current knowledge gaps and to establish standard test methods for polymers in H2 environments these materials can be tested in laboratory scale H2 manifolds mimicking end use pressure and temperature conditions. Beyond the influence of high pressure H2 the selection of gases used for leak detection in the H2 test manifold their pressures and times of exposure gas types relative diffusion and permeation rates are all important influences on the polymers being tested. These effects can be studied ex-situ with post-exposure characterization. In a previous study four polymers (Viton A Buna N High Density Polyethylene (HDPE) and Polytetrafluoroethylene (PTFE)) commonly used in the H2 infrastructure were exposed to high-pressure H2 (100 MPa). The observed effects of H2 were consistent with typical polymer property-structure relationships; in particular H2 affected elastomers more than thermoplastics. However since high pressure He was used for purging and leak detection prior to filling with H2 a study of the influence of the purge gas on these polymers was considered necessary to isolate the effects of H2 from those of the purge gas. Therefore in this study Viton A Buna N and PTFE were exposed to the He purge procedure without the subsequent H2 exposure. Additionally six polymers Viton A Buna N PTFE Polyoxymethylene (POM) Polyamide 11 (Nylon) and Ethylenepropylenediene monomer rubber (EPDM) were subjected to high pressure Ar (100 MPa) followed by high pressure H2 (100 MPa) under the same static isothermal conditions to identify the effect of a purge gas with a significantly larger molecular size than He. Viton A and Buna N elastomers are more prone to irreversible changes as a result of H2 exposure from both Ar and He leak tests as indicated by influences on storage modulus extent of swelling and increased compression set. EPDM even though it is an elastomer is not as prone to high-pressure gas influences. The thermoplastics are generally less influenced by high pressure regardless of the gas type. Conclusions from these experiments will provide insight into the influence of purging processes and purge gases on the subsequent testing in high pressure gaseous H2. Control for the influence of purging on testing results is essential for the development of robust test methods for evaluating the effects of H2 and other high-pressure gases on the properties of polymers.

An accident modelling approach is used to assess the safety of a hydrogen station as part of a ground transportation network. The method incorporates prevention barriers associated to human factors management and organizational failures in a risk assessment framework. Failure probabilities of these barriers and end-states events are predicted using Fault Tree Analysis and Event Tree Analysis respectively. Results from the case study considered revealed the capability of the proposed method in estimating the likelihood of various outcomes as well as predicting the future probability. In addition the scheme offers opportunity to provide dynamic adjustment by updating the failure probability with actual plant data. Results from the analysis can be used to plan maintenance and management of change as required by the plant condition.

We at Kawasaki Heavy Industries have proposed a "CO2-Free H2 supply chain" using abundant brown coal of Australian origin as the energy source. This chain will store CO2 generated during the process for producing hydrogen from brown coal in a project (Carbon Net) that the Australia Government is promoting. Thus Japan can import CO2-free hydrogen. The supply chain consists of the hydrogen production system the hydrogen transport/storage system and the hydrogen use system. Related to their designs we have to consider their hazards polluted scenarios and safety measures via a safety assessment process that is compliant with international risk assessment standards. To verify safety designs related experiments and analyses will be conducted. This paper describes the approach to safety design for especially the related liquid hydrogen facilities.

In the present study the phenomena of blast wave and fireball generated by high pressure (35 MPa) hydrogen tank (72 l) rupture have been investigated numerically. The realizable k-ε turbulence model was applied. The simulation of the combustion process is based on the eddy dissipation model coupled with the one step chemical reaction mechanism. Simulation results are compared with experimental data from a stand-alone hydrogen fuel tank rapture following a bonfire test. The model allows the study of the interaction between combustion process and blast wave propagation. Simulation results (blast wave overpressure fireball shape and size) follow the trends observed in the experiment.

This study deals with the TNO Multi-Energy and Baker-Strehlow-Tang (BST) methods for estimating the positive overpressures and positive impulses resulting from hydrogen-air explosions. With these two methods positive overpressure and positive impulse results depend greatly on the choice of the class number for the TNO Multi-Energy method or the Mach number for the BST methods. These two factors permit the user to read the reduced parameters of the blast wave from the appropriate monographs for each of these methods i.e. positive overpressure and positive duration phase for the TNO Multi-Energy method and positive overpressure and positive impulse for the BST methods. However for the TNO Multi-Energy method the determination of the class number is not objective because it is the user who makes the final decision in choosing the class number whereas with the BST methods the user is strongly guided in their choice of an appropriate Mach number. These differences in the choice of these factors can lead to very different results in terms of positive overpressure and positive impulse. Therefore the objective of this work was to compare the positive overpressures and positive impulses predicted with the TNO Multi-Energy and BST methods with data available from large-scale experiments.

This work presents a parametric study on the similitude between hydrogen and helium distribution when released in the air by a source located inside of a naturally ventilated enclosure with two vents. Several configurations were experimentally addressed in order to improve knowledge on dispersion. Parameters were chosen to mimic operating conditions of hydrogen energy systems. Thus the varying parameters of the study were mainly the source diameter the releasing flow rate the volume and the geometry of the enclosure. Two different experimental set-ups were used in order to vary the enclosure's height between 1 and 2 m. Experimental results obtained with helium and hydrogen were compared at equivalent flow rates determined with existing similitude laws. It appears for the plume release case that helium can suitably be used for predicting hydrogen dispersion in these operating designs. On the other hand – when the flow turns into a jet – non negligible differences between hydrogen and helium dispersion appear. In this case helium – used as a direct substitute to hydrogen – will over predict concentrations we would get with hydrogen. Therefore helium concentration read-outs should be converted to obtain correct predictions for hydrogen. However such a converting law is not available yet.

Hydrogen is being considered as a pathway to decarbonize large energy systems and for utility-scale energy storage. As these applications grow transportation infrastructure that can accommodate large quantities of hydrogen will be needed. Many millions of tons of hydrogen are already consumed annually some of which is transported in dedicated hydrogen pipelines. The materials and operation of these hydrogen pipeline systems however are managed with more constraints than a conventional natural gas pipeline. Transitional strategies for deep decarbonization of energy systems include blending hydrogen into existing natural gas systems where the materials and operations may not have the same controls. This study explores the hydrogen compatibility of existing pipeline steels and the suitability of these steels in hydrogen pipeline systems. Representative fracture and fatigue properties of pipeline grade steels in gaseous hydrogen are summarized from the literature. These properties are then considered in idealized design life calculations to inform materials performance for a typical gas pipeline.

The addition of hydrogen to natural gas for heating and cooking is being considered as a route to reducing carbon emissions in the United Kingdom (UK). The HyDeploy programme (hereafter referred to as HyDeploy) aims to demonstrate that hydrogen can be added to the natural gas supply without compromising public safety or appliance performance. This paper relates to the preparatory work for hydrogen injection on a live site at Keele University closed network comprising domestic premises multi-occupancy buildings and light commercial premises. The project is based around the injection of up to 20 %mol/mol hydrogen into mains natural gas at pressures below 2 barg. Work streams addressed during the pre-trial preparation included; assessment of material interaction with hydrogen blends for all distribution system components and appliances; understanding of gas appliance behaviour; review of: gas detection systems fire and explosion considerations routine and emergency procedural considerations; and the design of a new hydrogen injection grid entry unit. This paper describes the safety and regulatory challenges that were encountered during preparation of the project including obtaining the necessary regulatory permissions to blend hydrogen gas.

Experimental data from vented explosion tests using lean hydrogen–air mixtures with concentrations from 12 to 19% vol. are presented. A 63.7-m3 chamber was used for the tests with a vent size of either 2.7 or 5.4 m2. The tests were focused on the effect of hydrogen concentration ignition location vent size and obstacles on the pressure development of a propagating flame in a vented enclosure. The dependence of the maximum pressure generated on the experimental parameters was analyzed. It was confirmed that the pressure maxima are caused by pressure transients controlled by the interplay of the maximum flame area the burning velocity and the overpressure generated outside of the chamber by an external explosion. A model proposed earlier to estimate the maximum pressure for each of the main pressure transients was evaluated for the various hydrogen concentrations. The effect of the Lewis number on the vented explosion overpressure is discussed.

A key element in the safe operation of a modern gas distribution system is gas detection. The addition of hydrogen to natural gas will alter the characteristics of the fuel and therefore its impact on gas detection must be considered. It is important that gas detectors remain sufficiently sensitive to the presence of hydrogen and natural gas mixtures and that they do not lead to false readings. This paper presents analyses of work performed as part of the Office for Gas and Energy Markets (OFGEM) funded HyDeploy project on the response of various natural gas industry detectors to blended mixtures up to 20 volume percent (vol%) of hydrogen in natural gas. The scope of the detectors under test included survey instruments and personal monitors that are used in the gas industry. Four blend ratios were analysed (0 10 15 and 20 vol% hydrogen in natural gas). The laboratory testing undertaken investigated the following:

• Flammable response to blends in the ppm range (0-0.2 vol%);
• Flammable response to blends in the lower explosion limit range (0.2-5 vol%);
• Flammable response to blends in the volume percent range (5-100 vol%);
• Oxygen response to blends in the volume percent range (0-25 vol%); and
• Carbon monoxide response to blends in the ppm range (0-1000 ppm).

Catalytic and thermal conductivity based flammable detectors in the volume percent range are as expected affected in the form of a relative increase in output. All of the carbon monoxide detectors tested were found to be cross-sensitive to hydrogen in the blended mixtures tested at levels which have the potential to cause false alarms at current permissible leakage rates. In summary a number of measurement ranges across multiple detectors commonly used in the gas industry have been found to be cross-sensitive to hydrogen in natural gas blends to differing degrees. This required the HyDeploy project to select alternative instruments for the purpose of gas detection as part of the trial. This paper relates to the preparatory work to introduce hydrogen into the Keele closed network.

For safety issues related to the storage of hydrogen under high pressure it is necessary to determine how the gas is released in the case of failure. In particular there exist limited quantitative information on the near-field properties of the gas jets which are important for establishing proper decay laws in the far-field. This paper reports recent CFD results for air and helium obtained in the near-field of the highly under-expanded jets. The gas jets are released from a 30-bar tank with the same opening (orifice). The Reynolds number based on the diameter of the orifice and corresponding gas conditions at the exit was well beyond 106 . The 3D Compressible Multi-Component Navier-Stokes equations were solved directly without relying on the compressibility-corrected turbulence models. The numerical model was initially tested on a one-component (air-air) case where a few aerospace-driven data sets are available for validation. The shock geometry is characterized through the Mach disk position and diameter. These are compared to the results known from the literature and to the scaling laws developed based on the dimensional analysis. In the second two-component (helium-air) jet scenario the density field was validated and examined together with other fields in the attempt to suggest potential initial conditions for the forthcoming far-field simulations.

To advance hydrogen into the energy market it is necessary to consider risk assessment for scenarios that are complicated by accidental hydrogen release mixing with other combustible hydrocarbon fuels. The paper is aimed at examining the effect of mixing the hydrocarbon and inert gas into the hydrogen flame on the kinetic mechanisms the laminar burning velocity and the flame stability. The influences of hydrogen concentration on the flame burning velocity were determined for the hydrogen/propane (H2-C3H8) hydrogen/ethane (H2-C2H6) hydrogen/methane (H2-CH4) and hydrogen/carbon dioxide (H2-CO2) mixtures. Experimental tests were carried out to determine the lift-off blow-out and blowoff stability limits of H2 H2-C3H8 H2-C2H6 H2-CH4 and H2-CO2 jet flames in a 2 mm diameter burner. The kinetic mechanisms of hydrogen interacting with C3 C2 and C1 fuels is analysed using the kinetic mechanisms for hydrocarbon combustion.

Previous experiments demonstrated that the accidental release of high pressure hydrogen into air can lead to the possibility of spontaneous ignition. It is believed that this ignition is due to the heating of the mixing layer between hydrogen and air that is caused by the shock wave driven by the pressurized hydrogen during the release. Currently this problem is poorly understood and not amenable to direct numerical simulation. This is due to the presence of a wide range of scales between the sizes of the blast wave driven and the very thin mixing layer. The present study addresses this fundamental ignition problem and develops a solution framework in order to predict the ignition event for given hydrogen storage pressures and dimension of the release hole. In this problem only the mixing layer between the hydrogen and air is considered. This permits us to use much higher resolution than previous studies. This mixing layer at the jet head is advected as a Lagrangian fluid particle. The key physical processes in the problem are identified to be the mixing of the two gases at the mixing layer the initial heating by the shock wave and a cooling effect due to the expansion of the mixing layer. The results of the simulations indicate that for every storage pressure there exists a critical hole size below which ignition is prevented during the release process. Close inspection of the results indicate that this limit is due to the competition between the heating provided by the shock wave and the cooling due to expansion. Furthermore the results also indicate that the details of the mixing process do not play a significant role to leading order. The limiting ignition criteria were found to be well approximated by the Homogeneous Ignition Model of Cuenot and Poinsot supplemented by a heat loss term due to expansion. Therefore turbulent mixing occurring in reality is not likely to affect the ignition limits derived in the present study. Comparison with existing experiments showed very good agreement.

The aim of the study is to identify and quantify the additional risks related to hydrogen explosions during the operation of a hydrogen-driven car. In a first attempt the accidents or failures of a simple one-tank hydrogen storage system have been studied as a main source of risk. Three types of initiators are taken into account: crash accidents fire accidents without crash (no other cars are involved) and hydrogen leakages in normal situation with following ignition. The consequences of hydrogen ignition and/or explosion depend strongly on environmental conditions (geometry wind etc.) therefore the different configurations of operational and environmental conditions are specified.<br/>Then Event Tree/Fault Tree methods are applied for the risk assessment.<br/>The results of quantification permit to draw conclusions about the overall added risk of hydrogen technology as well as about the main contributors to the risk. Results of this work will eventually contribute to the on-going pre-normative research in the field of hydrogen safety.

Spontaneous ignition of compressed hydrogen release through a length of tube with different internal geometries is numerically investigated using our previously developed model. Four types of internal geometries are considered: local contraction local enlargement abrupt contraction and abrupt enlargement. The presence of internal geometries was found to significantly increase the propensity to spontaneous ignition. Shock reflections from the surfaces of the internal geometries and the subsequent shock interactions further increase the temperature of the combustible mixture at the contact region. The presence of the internal geometry stimulates turbulence enhanced mixing between the shock-heated air and the escaping hydrogen resulting in the formation of more flammable mixture. It was also found that forward-facing vertical planes are more likely to cause spontaneous ignition by producing the highest heating to the flammable mixture than backward-facing vertical planes.

There are currently projects and demonstration programs aiming at introducing Hydrogen powered Fuel Cell (HFC) vehicles into the market. Regione Toscana has been cofounder of the project “H2 Filiera Idrogeno” whose goal is to achieve a clean and sustainable mobility through HFC vehicle studies covering their production storage and use. Among the goals of the project was the substitution of the electric propulsion system with a hydrogen fuel cells propulsion system. This work presents a brief overview of the necessary modifications of the electric propulsion version of a Piaggio Porter to host a H2 fuel cell and experimental studies of realistic H2 releases from the vehicle. The scenarios covered H2 unintended releases underneath the vehicle when at rest and focused on three types of releases diffusive major and minor that might reach the interior of the vehicle and potentially pose a direct risk to the passengers.

HELION a subsidiary of AREVA in charge of the business unit Hydrogen and energy storage is deploying for the first time in a French public building a hydrogen-based energy storage system the Greenergy Box™. The 50 kWe system is coupled with a photovoltaic farm to ensure up to 45% electrical autonomy and power backup to the building. The safety system and siting measures of the complete hydrogen chain are described. The paper also highlights the work accomplished with Fire Authorities and Public to gain the acceptance of the project and allow the deployment of four other hydrogen-based green buildings.

An increase in the number of hydrogen-fuelled applications in the marketplace will require a better understanding of the potential for fires and explosion associated with the unintended release of hydrogen within a structure. Predicting the temporally evolving hydrogen concentration in a structure with unknown release rates leak sizes and leak locations is a challenging task. A simple analytical model was developed to predict the natural and forced mixing and dispersion of a buoyant gas released in a partially enclosed compartment with vents at multiple levels. The model is based on determining the instantaneous compartment over-pressure that drives the flow through the vents and assumes that the helium released under the automobile mixes fully with the surrounding air. Model predictions were compared with data from a series of experiments conducted to measure the volume fraction of a buoyant gas (at 8 different locations) released under an automobile placed in the center of a full-scale garage (6.8 m × 5.4 m × 2.4 m). Helium was used as a surrogate gas for safety concerns. The rate of helium released under an automobile was scaled to represent 5 kg of hydrogen released over 4 h. CFD simulations were also performed to confirm the observed physical phenomena. Analytical model predictions for helium volume fraction compared favourably with measured experimental data for natural and forced ventilation. Parametric studies are presented to understand the effect of release rates vent size and location on the predicted volume fraction in the garage. Results demonstrate the applicability of the model to effectively and rapidly reduce the flammable concentration of hydrogen in a compartment through forced ventilation.

Hydrogen transportation systems require very high pressure hydrogen storage containers to enable sufficient vehicle range for practical use. Current proposed designs have pressures up to 70 MPa with leakage due to damage or deterioration at such high pressures a great safety concern. Accurate models are needed to predict the flammability envelopes around such leaks which rapidly vary with time. This paper compares CFD predictions of jet flows for low pressure jets with predictions using the integral turbulent buoyant jet model. The results show that the CFD model predicts less entrainment and that the turbulent Schmidt number should be smaller with 0.55 giving better results. Then CFD predictions for very high pressure flows are compared with analytical models for choked flows that generate underexpanded jets into the ambient to evaluate the effects of the model assumptions and the effects of real exit geometries. Real gas effects are shown to accelerate the blowdown process and that real flow effects in the CFD model slow the flow rate and increase the exit temperature.

The paper describes CFD modelling of lean hydrogen mixture deflagrations. Large eddy simulation (LES) premixed combustion model developed at the University of Ulster to account phenomena related to large-scale deflagrations was adjusted specifically for lean hydrogen-air flames. Experiments by Kumar (2006) on lean hydrogen-air mixture deflagrations in a 120 m3  vessel at initially quiescent conditions were simulated. 10% by volume hydrogen-air mixture was chosen for simulation to provide stable downward flame propagation; experiments with the smallest vent area 0.55 m2  were used as having the least apparent flame instabilities affecting the pressure dynamics. Deflagrations with igniter located centrally near vent and at far from the vent wall were simulated. Analysis of simulation results and experimental pressure dynamics demonstrated that flame instabilities developing after vent opening made the significant contribution to maximum overpressure in the considered experiments. Potential causes of flame instabilities are discussed and their comparative role for different igniter locations is demonstrated.

During the synthesis of hydrogen by methane steam reforming mixtures composed of H2 CH4 CO and CO2 are produced in the process. In this work the explosion reactivity of these mixtures on the basis of detonation cell size and laminar flame speed is calculated using a reactant assimilation simplification and a kinetic approach. The detonation cells width are calculated using the Cell_CH Kurchatov institute method and the laminar flame velocities are calculated with Chemkin Premix using different detailed chemical kinetic mechanisms. These calculations are used to define if these mixtures could be considered having a medium or a high reactivity for risk assessment in case of leak in the hydrogen plants.

A numerical approach is developed to simulate detonation propagation attenuation failure and re-initiation in hydrogen–air mixture. The aim is to study the condition under which detonations may fail or re-initiate in bifurcated tubes which is important for risk assessment in industrial accidents. A code is developed to solve compressible multidimensional transient reactive Navier–Stokes equations. An Implicit Large Eddy Simulation approach is used to model the turbulence. The code is developed and tested to ensure both deflagrations (when detonation fails) and detonations are simulated correctly. The code can correctly predict the flame properties as well as detonation dynamic parameters. The detonation propagation predictions in bifurcated tubes are validated against the experimental work of Wang et al. [12] and found to be in good agreement with experimental observations.

The detonation propensity of hydrogen-air mixtures with addition of methane ethane or propane in wide range of compositions is analyzed. The analysis concerned the detonation cell width ignition delay time RSB and parameters. Results are presented as a function of hydrogen molar fraction. Computations were performed with the use of three Cantera 2.1.1. scripts in the Matlab R2010b environment. The validated mechanisms of chemical reactions based on data available in the literature were used. Six mechanisms were assessed: GRI-Mech 3.0 LLNL SanDiego Wang POLIMI and AramcoMech. In conclusion the relation between detonation propensity parameters is discussed.

Any technical installation need appropriate safety barriers installed to prevent or mitigate any adverse effects concerning people property and environment. In this context a safety barrier is a series of elements each consisting of a technical system or human action that implement a planned barrier function to prevent control or mitigate the propagation of a condition or event into an undesired condition or event. This is also important for new technologies as hydrogen refuelling stations being operated at very high pressures up to 900bar. In order to establish the needed barriers a hazard identification of the installation has to be carried out to identify the possible hazardous events. In this study this identification was done using the generic layout of a future large hydrogen refuelling station that has been developed by the EU NoE HySafe. This was based on experiences with smaller scale refuelling stations that has been in operation for several years e.g. being used in the former CUTE and ECTOS projects. Using this approach the object of the study is to support activities to further improve the safety performance of future larger refuelling stations. This will again help to inform the authorities and the public to achieve a proper public awareness and to support building up a realistic risk and safety perception of the safety on such future refuelling stations. In the second step the hazardous events that may take place and the barriers installed to stop hazards and their escalation are analysed also using in-house developed software to model the barriers and to quantify their performance. The paper will present an overview and discuss the state-of-the-art of the barriers established in the generic refuelling station.