Safety
Nanotechnology Enabled Hydrogen Gas Sensing
Sep 2019
Publication
An important contribution to industry standards and to effective installation of hybrid renewable energy systems is evaluation of hydrogen (H2) monitoring techniques under pilot-scale and/or real-world conditions. We have designed a hybrid system to integrate solar power electrolysis and hydrogen fuel cell components in a DC micro-grid with capacity to evaluate novel nanomaterials for enhanced H2 gas sensing performance. In general enhanced hydrogen sensing performance is evaluated by high sensitivity selectivity and stability as well as low power consumption. Unique properties such as high surface area to volume ratio a large number of surface active sites high specific surface area and reactivity are key attributes of nanomaterials used for gas sensing. These attributes enable sensors to be embedded in Internet-of-Things applications or in mobile systems. With rapid development of hydrogen-based technologies for clean energy applications there remains a requirement for faster accurate and selective H2 sensors with low cost and low power consumption. Operating principles for these sensors include catalytic thermal conductivity electrochemical resistance based optical and acoustic methods. In this paper we review performance of H2 gas sensors based on conductometric devices operating at room temperature up to 200 °C. The focus of this work includes nanostructured metal oxides graphene materials and transition metal dichalcogenides employed as sensing materials.
Preliminary Risk Assessment (PRA) for Tests Planned in a Pilot Salt Cavern Hydrogen Storage in the Frame of the French Project STOPIL-H2
Sep 2021
Publication
The STOPIL-H2 project supported by the French Geodenergies research consortium aims to design a demonstrator for underground hydrogen storage in cavern EZ53 of the Etrez gas storage (France) operated by Storengy. Two types of tests are planned in this cavern: a tightness test with nitrogen and hydrogen then a cycling test during which the upper part of the cavern (approximately 200 m3) will be filled with hydrogen during 6 to 9 months. In this paper the PRA for the cycling test is presented comprising the identification of the major hazards and the proposed prevention and protection measures. The implemented methodology involves the following steps: data mining from the description of the project; analysis of lessons learned from accidents that occurred in underground gas storage and subface facilities; identification of the potential hazards pertaining to the storage process; analysis of external potential aggressors. Resulting as one of the outcomes of the PRA major accidental scenarios are presented and classified according to concerned storage operation phases as well as determined preventive or protective barriers able to prevent their occurrence of mitigate their consequences.
A Chicken and Egg Situation: Enhancing Emergency Service Workers' Knowledge of Hydrogen
Sep 2021
Publication
This paper reports on the results of interviews conducted with 21 representatives from emergency services organisations within Australia and New Zealand. With a relative emergent industry such as future fuels a chicken and egg situation does emerge with regards to how much training needs to be in place in advance of large-scale industry development or not. These respondents were employed in a variety of roles being directly involved in research and training of emerging technologies frontline operational managers and other senior roles across the emergency services sector. Participants' responses to a series of questions were able to provide insights into the state of knowledge and training requirements within their organisations in relation to hydrogen and other future fuels. The findings suggest that formal and informal processes currently exist to support the knowledge development and transferal around the adoption of hydrogen and other future fuels. From the interviews it became clear that there are a number of processes that have emerged from the experiences gained through the implementation of rooftop solar PV and battery storage that provide some background context for advancing future fuels information across the sector. Because safety is a critical component for securing a social licence to operate engagement and knowledge sharing with any representatives from across this sector will only help to build confidence in the industry. Similarly because interviewees were very keen to access information they expressed a clear willingness to learn more through more formalised relationships rather than an ad hoc information seeking that has been employed to date. The presentation will identify key recommendations and also highlight the importance of QR Codes in the emergency responder landscape. Implications for industry and policy makers are discussed.
Rethinking "BELVE Explosion" After Liquid Hydrogen Storage Tank Rupture in a Fire
Sep 2022
Publication
The underlying physical mechanisms leading to the generation of blast waves after liquid hydrogen (LH2) storage tank rupture in a fire are not yet fully understood. This makes it difficult to develop predictive models and validate them against a very limited number of experiments. This study aims at the development of a CFD model able to predict maximum pressure in the blast wave after the LH2 storage tank rupture in a fire. The performed critical review of previous works and the thorough numerical analysis of BMW experiments (LH2 storage pressure in the range 2.0e11.3 bar abs) allowed us to conclude that the maximum pressure in the blast wave is generated by gaseous phase starting shock enhanced by combustion reaction of hydrogen at the contact surface with heated by the shock air. The boiling liquid expanding vapour explosion (BLEVE) pressure peak follows the gaseous phase blast and is smaller in amplitude. The CFD model validated recently against high-pressure hydrogen storage tank rupture in fire experiments is essentially updated in this study to account for cryogenic conditions of LH2 storage. The simulation results provided insight into the blast wave and combustion dynamics demonstrating that combustion at the contact surface contributes significantly to the generated blast wave increasing the overpressure at 3 m from the tank up to 5 times. The developed CFD model can be used as a contemporary tool for hydrogen safety engineering e.g. for assessment of hazard distances from LH2 storage.
Blast Wave Generated by Delayed Ignition of Under-Expanded Hydrogen Free Jet at Ambient and Cryogenic Temperatures
Nov 2022
Publication
An under-expanded hydrogen jet from high-pressure equipment or storage tank is a potential incident scenario. Experiments demonstrated that the delayed ignition of a highly turbulent under-expanded hydrogen jet generates a blast wave able to harm people and damage property. There is a need for engineering tools to predict the pressure effects during such incidents to define hazard distances. The similitude analysis is applied to build a correlation using available experimental data. The dimensionless blast wave overpressure generated by delayed ignition and the follow-up deflagration or detonation of hydrogen jets at an any location from the jet ∆Pexp/P0 is correlated to the original dimensionless parameter composed of the product of the dimensionless ratio of storage pressure to atmospheric pressure Ps/P0 and the ratio of the jet release nozzle diameter to the distance from the centre of location of the fast-burning near-stoichiometric mixture on the jet axis (30% of hydrogen in the air by volume) to the location of a target (personnel or property) d/Rw. The correlation is built using the analysis of 78 experiments regarding this phenomenon in the wide range of hydrogen storage pressure of 0.5–65.0 MPa and release diameter of 0.5–52.5 mm. The correlation is applicable to hydrogen free jets at ambient and cryogenic temperatures. It is found that the generated blast wave decays inversely proportional to the square of the distance from the fast-burning portion of the jet. The correlation is used to calculate the hazard distances by harm thresholds for five typical hydrogen applications. It is observed that in the case of a vehicle with onboard storage tank at pressure 70 MPa the “no-harm” distance for humans reduces from 10.5 m to 2.6 m when a thermally activated pressure relief device (TPRD) diameter decreases from 2 mm to a diameter of 0.5 mm.
Comparative Risk Assessment of a Hydrogen Refueling Station Using Gaseous Hydrogen and Formic Acid as the Hydrogen Carrier
Mar 2023
Publication
To realize a hydrogen economy many studies are being conducted regarding the development and analysis of hydrogen carriers. Recently formic acid has been receiving attention as a potential hydrogen carrier due to its high volumetric energy density and relatively safe characteristics. However hydrogen refueling systems using formic acid are very different from conventional hydrogen refueling stations and quantitative risks assessments need to be conducted to verify their safe usage. In this study a comparative safety analysis of a formic acid hydrogen refueling station (FAHRS) and a gaseous hydrogen refueling station (GHRS) was conducted. Since there is no FAHRS under operation a process simulation model was developed and integrated with quantitative risk assessment techniques to perform safety analysis. Results of the analysis show that the FAHRS poses less risk than the GHRS where the vapor cloud explosion occurring in the buffer tank is of greatest consequence. A GHRS poses a greater risk than an FAHRS due to the high pressure required to store hydrogen in the tube trailer. The mild operating conditions required for storage and dehydrogenation of formic acid contribute to the low risk values of an FAHRS. For risk scenarios exceeding the risk limit risk mitigation measures were applied to design a safe process for GHRS. The results show that the installation of active safety systems for the GHRS allow the system to operate within acceptable safety regions.
Safety Issues of a Hydrogen Refueling Station and a Prediction for an Overpressure Reduction by a Barrier Using OpenFOAM Software for an SRI Explosion Test in an Open Space
Oct 2022
Publication
Safety issues arising from a hydrogen explosion accident in Korea are discussed herein. In order to increase the safety of hydrogen refueling stations (HRSs) the Korea Gas Safety Corporation (KGS) decided to install a damage-mitigation wall also referred to as a barrier around the storage tanks at the HRSs after evaluating the consequences of hypothetical hydrogen explosion accidents based on the characteristics of each HRS. To propose a new regulation related to the barrier installation at the HRSs which can ensure a proper separation distance between the HRS and its surrounding protected facilities in a complex city KGS planned to test various barrier models under hypothetical hydrogen explosion accidents to develop a standard model of the barrier. A numerical simulation to investigate the effect of the recommended barrier during hypothetical hydrogen explosion accidents in the HRS will be performed before installing the barrier at the HRSs. A computational fluid dynamic (CFD) code based on the open-source software OpenFOAM will be developed for the numerical simulation of various accident scenarios. As the first step in the development of the CFD code we conducted a hydrogen vapor cloud explosion test with a barrier in an open space which was conducted by the Stanford Research Institute (SRI) using the modified XiFoam solver in OpenFOAMv1912. A vapor cloud explosion (VCE) accident may occur due to the leakage of gaseous hydrogen or liquefied hydrogen owing to a failure of piping connected to the storage tank in an HRS. The analysis results using the modified XiFoam predicted the peak overpressure variation from the near field to the far field of the explosion site through the barrier with an error range of approximately ±30% if a proper analysis methodology including the proper mesh distribution in the grid model is chosen. In addition we applied the proposed analysis methodology using the modified XiFoam to barrier shapes that varied from that used in the test to investigate its applicability to predict peak overpressure variations with various barrier shapes. Through the application analysis we concluded that the proposed analysis methodology is sufficient for evaluating the safety effect of the barrier which will be recommended through experimental research during VCE accidents at the HRSs.
Towards Accident Prevention on Liquid Hydrogen: A Data-driven Approach for Releases Prediction
Mar 2023
Publication
Hydrogen is a clean substitute for hydrocarbon fuels in the marine sector. Liquid hydrogen (2 ) can be used to move and store large amounts of hydrogen. This novel application needs further study to assess the potential risk and safety operation. A recent study of 2 large-scale release tests was conducted to replicate spills of 2 inside the ship’s tank connection space and during bunkering operations. The tests were performed in a closed and outdoor facility. The 2 spills can lead to detonation representing a safety concern. This study analyzed the aforementioned 2 experiments and proposed a novel application of the random forests algorithm to predict the oxygen phase change and to estimate whether the hydrogen concentration is above the lower flammability limit (LFL). The models show accurate predictions in different experimental conditions. The findings can be used to select reliable safety barriers and effective risk reduction measures in 2 spills.
Numerical Study of the Action of Convection on the Volume and Length of the Flammable Zone Formed by Hydrogen Emissions from the Vent Masts Installed on an International Ship
Nov 2021
Publication
International ships carrying liquefied fuel are strongly recommended to install vent masts to control the pressure of cargo tanks in the event of an emergency. However the gas emitted from a vent mast may be hazardous for the crew of the ship. In the present study the volume and length of the flammable zone (FZ) created by the emitted gas above the ship was examined. Various scenarios comprising four parameters namely relative wind speed arrangement of vent masts combination of emissions among four vent masts and direction of emission from the vent-mast outlet were considered. The results showed that the convection acts on the volume and length of an FZ. The volume of an FZ increases when there is a reduction in convection reaching the FZ and when strong convection brings hydrogen from a nearby FZ. The length of the FZ is also related to convection. An FZ is elongated if the center of a vortex is located inside the FZ because this vortex traps hydrogen inside the FZ. The length of an FZ decreases if the center of the vortex is located outside the FZ as such a vortex brings more fresh air into the FZ.
Discharge Modeling of Large Scale LH2 Experiments with an Engineering Tool
Sep 2021
Publication
Accurate estimation of mass flow rate and release conditions is important for the design of dispersion and combustion experiments for the subsequent validation of CFD codes/models for consequence assessment analysis within related risk assessment studies and for associated Regulation Codes and Standards development. This work focuses on the modelling of the discharge phase of the recent large scale LH2 release and dispersion experiments performed by HSE within the framework of PRESLHY project. The experimental conditions covered sub-cooled liquid stagnation conditions at two pressures (2 and 6 bara) and 3 release nozzle diameters (1 ½ and ¼ inches). The simulations were performed using a 1d engineering tool which accounts for discharge line effects due to friction extra resistance due to fittings and area change. The engineering tool uses the Possible Impossible Flow (PIF) algorithm for choked flow calculations and the Helmholtz Free Energy (HFE) EoS formulation. Three different phase distribution models were applied. The predictions are compared against measured and derived data from the experiments and recommendations are given both regarding engineering tool applicability and future experimental design.
Crack Management of Hydrogen Pipelines
Sep 2021
Publication
The climate emergency is one of the biggest challenges humanity must face in the 21st century. The global energy transition faces many challenges when it comes to ensuring a sustainable reliable and affordable energy supply. A likely outcome is decarbonizing the existing gas infrastructure. This will inevitably lead to greater penetration of hydrogen. While the introduction of hydrogen into natural gas transmission and distribution networks creates challenges there is nothing new or inherently impossible about the concept. Indeed more than 4000 kilometers of hydrogen pipelines are currently in operation. These pipelines however were (almost) all built and operated exclusively in accordance with specific hydrogen codes which tend to be much more restrictive than their natural gas equivalents. This means that the conversion of natural gas pipelines which have often been in service for decades and have accumulated damage and been subject to cracking threats (e.g. fatigue or stress corrosion cracking (SCC)) throughout their lifetime can be challenging. This paper will investigate the impact of transporting hydrogen on the crack management of existing natural gas pipelines from an overall integrity perspective. Different cracking threats will be described including recent industry experience of those which are generic to all steel pipelines but exacerbated by hydrogen and those which are hydrogen specific. The application of a Hydrogen Framework to identify characterise and manage credible cracking threats to pipelines in order to help enable the safe economic and successful introduction of hydrogen into the natural gas network will be discussed.
Towards the Efficient and Time-accurate Simulations of Early Stages of Industrial Explosions
Sep 2021
Publication
Combustion during a nuclear reactor accident can result in pressure loads that are potentially fatal for the structural integrity of the reactor containment or its safety equipment. Enabling efficient modelling of such safety-critical scenarios is the goal of ongoing work. In this paper attention is given to capturing early phases of flame propagation. Transient simulations that are not prohibitively expensive for use at industrial scale are required given that a typical flame propagation study takes a large number of simulation time steps to complete. An improved numerical method used in this work is based on explicit time integration by means of Strong Stability Preserving (SSP) Runge-Kutta schemes. These allow an increased time step size for a given level of accuracy—reducing the overall computational effort. Furthermore a wide range of flow conditions is encountered in analysis of accelerating flames: from incompressible to potentially supersonic. In contrast numerical schemes for spatial discretization would often prove lacking in either stability or accuracy outside the intended flow regime—with density-based schemes being traditionally designed and applied to compressible (Ma>0.3) flows. In the present work a formulation of an all-speed density-based numerical flux scheme is used for simulation of slow flames starting from ignition. Validation was carried out using experiments with spherical lean hydrogen flames at laboratory scale. Turbulence conditions in the experiments correspond to those that can arise in a nuclear reactor containment during an accident. Results show that the new numerical method has the potential to predict flame speed and pressure rise at a reduced computational effort.
Analysis of Hydrogen-Induced Changes in the Cyclic Deformation Behaviour of AISI 300–Series Austenitic Stainless Steels Using Cyclic Indentation Testing
Jun 2021
Publication
The locally occurring mechanisms of hydrogen embrittlement significantly influence the fatigue behaviour of a material which was shown in previous research on two different AISI 300-series austenitic stainless steels with different austenite stabilities. In this preliminary work an enhanced fatigue crack growth as well as changes in crack initiation sites and morphology caused by hydrogen were observed. To further analyze the results obtained in this previous research in the present work the local cyclic deformation behaviour of the material volume was analyzed by using cyclic indentation testing. Moreover these results were correlated to the local dislocation structures obtained with transmission electron microscopy (TEM) in the vicinity of fatigue cracks. The cyclic indentation tests show a decreased cyclic hardening potential as well as an increased dislocation mobility for the conditions precharged with hydrogen which correlates to the TEM analysis revealing courser dislocation cells in the vicinity of the fatigue crack tip. Consequently the presented results indicate that the hydrogen enhanced localized plasticity (HELP) mechanism leads to accelerated crack growth and change in crack morphology for the materials investigated. In summary the cyclic indentation tests show a high potential for an analysis of the effects of hydrogen on the local cyclic deformation behaviour.
Three-dimensional Structures of N2-Diluted Stoichiometric H2-O2 Flames in Narrow Channels
Sep 2021
Publication
Flame propagation and acceleration in unobstructed channels/tubes is usually assumed as symmetric. A fully optically accessible narrow channel that allows to perform simultaneous high-speed schlieren visualization from two mutually perpendicular directions was built to asses the validity of the aforementioned assumption. Here we provide experimental evidence of the interesting three-dimensional structures and asymmetries that develop during the acceleration phase and show how these may control detonation onset in N2-diluted stoichiometric H2-O2 mixtures.
Studies on the Impact of Hydrogen on the Results of THT Measurement Devices
Dec 2021
Publication
An essential prerequisite for safe transport and use of natural gas is their appropriate odorization. This enables the detection of uncontrolled gas leaks. Proper and systematic odorization inspection ensures both safe use of gas and continuity of the process itself. In practice it is conducted through among others measuring odorant concentrations in gas. Control devices for rapid gas odorization measurements that are currently used on a large scale in the gas industry are equipped with electrochemical detectors selective for sulfur compounds like tetrahydrothiophene (THT). Because the selectivity of electrochemical detector response to one compound (e.g. THT) the available declarations of manufacturers show that detector sensitivity (indirectly also the quality of the measurement result) is influenced by the presence of increased e.g. sulfur or hydrogen compound content in the gas. Because of the lack of sufficient source literature data in this field it was necessary to experimentally verify this impact. The results of studies on experimental verification of suspected influence of increased amounts of hydrogen in gas on the response of electrochemical detector was carried out at the Oil and Gas Institute—National Research Institute (INiG—PIB). They are presented in this article. The data gathered in the course of researching the dependence between THT concentration measurement result quality and hydrogen content in gas composition enabled a preliminary assessment of the threat to the safety of end users of gaseous fuels caused by the introduction of this gas into the distribution network. Noticing the scope of necessary changes in the area of odorization is necessary to guarantee this safety.
Development of Liquid Hydrogen Leak Frequencies Using a Bayesian Update Process
Sep 2021
Publication
To quantify the risk of an accident in a liquid hydrogen system it is necessary to determine how often a leak may occur. To do this representative component leakage frequencies specific to liquid hydrogen can be determined as a function of the normalized leak size. Subsequently the system characteristics (e.g. system pressure) can be used to calculate accident consequences. Operating data (such as leak frequencies) for liquid hydrogen systems are very limited; rather than selecting a single leak frequency value from a literature source data from different sources can be combined using a Bayesian model. This approach provides leakage rates for different amounts of leakage distributions for leakage rates to propagate through risk assessment models to establish risk result uncertainty and a means for incorporating liquid hydrogen-specific leakage data with leakage frequencies from other fuels. Specifically other cryogenic fluids like liquefied natural gas are used as a baseline for the Bayesian analysis. This Bayesian update process is used to develop leak frequency distributions for different system component types and leak sizes. These leak frequencies can be refined as liquid hydrogen data becomes available and may then inform safety code requirements based on the likelihood of liquid hydrogen release for different systems.
RANS Simulation of Hydrogen Flame Propagation in an Acceleration Tube: Examination of k-ω SST Model Parameters
Sep 2021
Publication
Due to practical computational resource limits current simulations of premixed turbulent combustion experiments are often performed using simplified turbulence treatment. From all available RANS models k-ε and k-ω SST are the most widely used. k-ω SST model is generally expected to be more accurate in bounded geometries since it corresponds to k-ε model further from the walls but switches to more appropriate k-ω model near the walls. However k-ε is still widely used and in some instances is shown to provide better results. In this paper we perform RANS simulations of premixed hydrogen flame propagation in an acceleration tube using k-ε and k-ω SST models. Accuracy of the models is assessed by comparing obtained results with the experiment. In order to better understand differences between k-ε and k-ω-SST results parameters of main k-ω-SST model features are examined. The distribution of the blending functions values and corresponding zones of are analysed in relation to flame position and resulting observed propagation velocity. We show that in the simulated case biggest difference between k-ω-SST and k-ε model results can be attributed to turbulent eddy viscosity limiting by shear strain rate in the k-ω-SST model.
Hydrogen Compatability of Structural Materials in Natural Gas Networks
Sep 2021
Publication
There is growing interest in utilizing existing infrastructure for storage and distribution of hydrogen. Gaseous hydrogen for example could be added to natural gas in the short-term whereas entire systems can be converted to transmission and distribution networks for hydrogen. Many active programs around the world are exploring the safety and feasibility of adding hydrogen to these networks. Concerns have been raised about the structural integrity of materials in these systems when exposed to hydrogen. In general the effects of hydrogen on these materials are grossly misunderstood. Hydrogen unequivocally degrades fatigue and fracture resistance of structural steels in these systems even for low hydrogen partial pressure (-l bar). In most systems however hydrogen effects will not be apparent because the stresses in these systems remain very low. Another misunderstanding results from the kinetics of the hydrogen effects: hydrogen degrades fatigue and fracture properties immediately upon exposure to gaseous hydrogen and those effects disappear when the hydrogen environment is removed even after prolonged exposure. There is also a misperception that materials selection can mitigate hydrogen effects. While some classes of materials perform better in hydrogen environments than other classes for most practical circumstances the range of response for a given class of material in gaseous hydrogen environments is rather narrow. These observations can be systematically characterized by considering the intersection of materials environmental and mechanical variables associated with the service application. Indeed any safety assessment of a hydrogen pressure system must quantitatively consider these aspects. In this report we quantitatively evaluate the importance of the materials environmental and mechanical variables in the context of hydrogen additions to natural gas piping and pipeline systems with the aim of providing an informed perspective on parameters relevant for assessing structural integrity of natural gas systems in the presence of gaseous hydrogen.
Study of Attenuation Effect of Water Droplets on Shockwaves from Hydrogen Explosion
Sep 2021
Publication
The increasing demand for renewable energy storage may position hydrogen as one of the major players in the future energy system. However to introduce such technology high level of safety must be offered. In particular for the accident scenarios with combustion or explosion of the unintendedly released hydrogen in partially or fully confined volumes such as e.g. road tunnel the effective countermeasures preventing or reducing the risk of equipment damages and person injuries should be established. A mitigation strategy could be the use of existing fire suppression system which can inject water as a spray. The shock waves resulted from hydrogen explosion could be weakened by the water droplets met on the shock path. In the presented work an attenuation effect of water droplets presence on the strength of the passing shock was studied. The analysis of the different attenuation mechanisms was performed and estimation of the effect of spray parameters such as droplet size and spray density on the shock wave was carried out. For the quantitative evaluation of the attenuation potential a numerical model for the COM3D combustion code was developed. The novel model for the droplet behavior accounting for the realistic correlations for the fluid (water) particle drag force linked with the corresponding droplet breakup model describing droplet atomization is presented. The model was validated against literature experimental data and was used for the blind simulations of the hydrogen test facility in KIT.
CFD Modeling on Natural and Forced Ventilation During Hydrogen Leaks in a Pressure Regulator Process of a Residential Area
Mar 2022
Publication
Hydrogen fuel cells have been installed in more than 100 facilities and numerous homes in Ulsan hydrogen town in the Republic of Korea. Despite the advantages of hydrogen accidents can still occur near residential areas. Thus appropriate risk mitigation plans should be established. In this study a computational fluid dynamics (CFD) model of natural and forced ventilation is presented as an emergency response to hydrogen leakages in pressure regulator equipment housing. The CFD model is developed and investigated using three vent configurations: UP CROSS and UP-DOWN. The simulation results indicate that the UPDOWN configuration achieves the lowest internal hydrogen concentration out of the three. In addition the relationship between the total vent size and internal hydrogen concentration is determined. A vent size of 12% of the floor area has the lowest hydrogen concentration. The use of nitrogen for forced ventilation during emergencies is proposed to ensure that the hydrogen concentration of the released gas is less than one-fourth of the lower flammability 2 / 25 limit of hydrogen. Compared to natural ventilation the time required to reach safe conditions is decreased when nitrogen forced ventilation is used.
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