Safety
Effect of Deformation Microstructures on Hydrogen Embrittlement Sensitivity and Failure Mechanism of 304 Austenitic Stainless Steel: The Significant Role of Rolling Temperature
Feb 2022
Publication
Metastable austenitic stainless steels (ASSs) have excellent ductility but low strength so that their usage as load-bearing components is significantly limited. Rolling is an effective method of increasing strength whereas the effect of rolling temperature on microstructural evolution the hydrogen embrittlement (HE) sensitivity and fracture mechanisms is still unclear. In present study the effect of cold/warm rolling on detailed microstructural characteristics of 304 ASS was quantitatively investigated and the corresponding HE sensitivity was evaluated via slow strain rate test. The results suggest that cold-rolling led to high strength but poor plasticity and deteriorated HE sensitivity while warm-rolled samples provided combination of high strength and ductility and also superior HE resistance. Compared with 18% α′-martensite in cold -rolled steel warm-rolled specimens consisted of complete austenite less twins and lower dislocation density,moreover the favorable {112} ND and {110} ND textures replaced the harmful {001} ND texture. Based on in-situ EBSD observation during SSRT the HE sensitivity was governed by the combined effect of pre-deformation microstructures and the dynamic microstructural evolution. Advanced method of time-of-flight secondary ion mass spectrometry was used to observe the distribution of hydrogen and the hydrogen content of specimens was determined by the gas chromatograph thermal desorption analysis method. An exceedingly small amount of hydrogen entered the warm-rolled samples while a large amount of hydrogen was trapped at grain boundaries of cold-rolled sample leading to complete intergranular fracture. Therefore warm rolling is an effective pathway for obtaining high combination of strength and ductility together with excellent HE sensitivity.
Development of a Tangential Neutron Radiography System for Monitoring the Fatigue Cracks in Hydrogen Fuel Tanks
Jun 2016
Publication
Purpose- To present an overview of the research and development carried out in a European funded framework 7 (FP7) project called SafeHPower for the implementation of neutron radiography to inspect fatigue cracks in vehicle and storage hydrogen fuel tanks. Project background– Hydrogen (H2) is the most promising replacement fuel for road transport due to its abundance efficiency low carbon footprint and the absence of harmful emissions. For the mass market of hydrogen to take off the safety issue surrounding the vehicle and storage hydrogen tanks needs to be addressed. The problem is the residual and additional stresses experienced by the tanks during the continuous cyclic loading between ambient and storage pressure which can result in the development of fatigue cracks. Steel tanks used as storage containers at service stations and depots and/or the composite tanks lined with steel are known to suffer from hydrogen embrittlement (HE). Another issue is the explosive nature of hydrogen (when it is present in the 18-59% range) where it is mixed with oxygen which can lead to catastrophic consequences including loss of life. Monitoring systems that currently exist in the market impose visual examination tests pressure tests and hydrostatic tests after the tank installation [1] [2]. Three inspection systems have been developed under this project to provide continuous monitoring solutions. Approach and scope- One of the inspection systems based on the neutron radiography (NR) technology that was developed in different phases with the application of varied strategies has been presented here. Monte Carlo (MCNP) simulation results to design and develop a bespoke collimator have been presented. A limitation of using an inertial electrostatic Deuterium-Tritium (D-T) pulsed neutron generator for fast neutron radiography has been discussed. Radiographs from the hydrogen tank samples obtained using thermal neutrons from a spallation neutron source at ISIS Rutherford laboratory UK have been presented. Furthermore radiograph obtained using thermal neutrons from a portable D-T neutron generator has been presented. In conclusion a proof in principle has been made to show that the defects in the hydrogen fuel tank can be detected using thermal neutron radiography.
Deflagration Safety Study of Mixtures of Hydrogen and Natural Gas in a Semi-open Space
Sep 2007
Publication
In the transition to a hydrogen economy it is likely that hydrogen will be used or stored in close proximity to other flammable fuels and gases. Accidents can occur that result in the release of two or more fuels such as hydrogen and natural gas that can mix and form a hazard. A series of five medium-scale semi-open-space deflagration experiments have been conducted with hydrogen natural gas and air mixtures. The natural gas consisted of 90% methane 6% ethane 3% propane and 1% butane by volume. Mixtures of hydrogen and natural gas were created with the hydrogen mole fraction in the fuel varying from 1.000 to 0.897 and the natural gas mole fraction varying from 0.000 to 0.103. The hydrogen and natural gas mixture was then released inside a 5.27-m³ thin plastic tent. The stoichiometric fuel-air mixtures were ignited with a 40-J spark located at the bottom center of the tent. Overpressure and impulse data were collected using pressure transducers located within the mixture volume and in the free field. Flame front time-of-arrival was measured using fast response thermocouples and infrared video. Flame speeds relative to a fixed observer were measured between 36.2 m/s and 19.7 m/s. Average peak overpressures were measured between 2.0 kPa and 0.3 kPa. The addition of natural gas inhibited the combustion when the hydrogen mole fraction was less than or equal to 0.949. For these mixtures there was a significant decrease in overpressures. When the hydrogen mole fraction in the fuel was between 0.999 and 0.990 the overpressures were slightly higher than for the case of hydrogen alone. This could be due to experimental scatter or there may be a slight enhancement of the combustion when a very small amount of natural gas was present. From a safety standpoint variation in overpressure was small and should have little effect on safety considerations.
A Homogeneous Non-equilibrium Two-phase Critical Flow Model
Sep 2011
Publication
A non-equilibrium two-phase single-component critical (choked) flow model for cryogenic fluids is developed from first principle thermodynamics. Modern equations-of-state (EOS) based upon the Helmholtz free energy concepts are incorporated into the methodology. Extensive validation of the model is provided with the NASA cryogenic data tabulated for hydrogen methane nitrogen and oxygen critical flow experiments performed with four different nozzles. The model is used to develop a hydrogen critical flow map for stagnation states in the liquid and supercritical regions.
PRD Hydrogen Release and Dispersion, a Comparison of CFD Results Obtained from Using Ideal and Real Gas Law Properties.
Sep 2005
Publication
In this paper CFD techniques were applied to the simulations of hydrogen release from a 400-bar tank to ambient through a Pressure Relieve Device (PRD) 6 mm (¼”) opening. The numerical simulations using the TOPAZ software developed by Sandia National Laboratory addressed the changes of pressure density and flow rate variations at the leak orifice during release while the PHOENICS software package predicted extents of various hydrogen concentration envelopes as well as the velocities of gas mixture for the dispersion in the domain. The Abel-Noble equation of state (AN-EOS) was incorporated into the CFD model implemented through the TOPAZ and PHOENICS software to accurately predict the real gas properties for hydrogen release and dispersion under high pressures. The numerical results were compared with those obtained from using the ideal gas law and it was found that the ideal gas law overestimates the hydrogen mass release rates by up to 35% during the first 25 seconds of release. Based on the findings the authors recommend that a real gas equation of state be used for CFD predictions of high-pressure PRD releases.
Hydrogen Fuelling Station, CEP-Berlin – Safety Risk Assessment and Authority Approval Experience and Lessons Learned
Sep 2005
Publication
The CEP (Clean Energy Partnership) – Berlin is one of the most diversified hydrogen demonstration projects at present. The first hydrogen fuelling station serving 16 cars is fully integrated in an ordinary highly frequented Aral service station centrally located at Messedamm in Berlin. Hydro has supplied and is the owner of the electrolyser with ancillary systems. This unit produces gaseous hydrogen at 12 bar with use of renewable energy presently serving 13 of the cars involved. The CEP project is planned to run for a period of five years and is supported by the German Federal Government and is part of the German sustainability strategy. During the planning and design phase there have been done several safety related assessments and analyses:
- Hydro has carried out a HAZOP (HAZard and OPerability) analysis of the electrolyser and ancillary systems delivered by Hydro Electrolysers.
- Hydro arranged with support from the partners a HAZOP analysis of the interface between the electrolyser and the compressor an interface with two different suppliers on each side.
- A QRA (Quantitative Risk Assessment) of the entire fuelling station has been carried out.
- Hydro has carried out a quantitative explosion risk analysis of the electrolyser container supplied by Hydro Electrolysers.
Explosion Characteristics of Hydrogen Gas in Varying Ship Ventilation Tunnel Geometries: An Experimental Study
Apr 2022
Publication
Hydrogen is widely regarded as a key element of prospective energy solutions for alleviating environmental emission problems. However hydrogen is classified as a high-risk gas because of its wide explosive range high overpressure low ignition energy and fast flame propagation speed compared with those of hydrocarbon-based gases. In addition deflagration can develop into detonation in ventilation or explosion guide tunnels if explosion overpressure occurs leading to the explosion of all combustible gases. However quantitative evidence of an increase in the explosion overpressure of ventilation tunnels is unavailable because the explosive characteristics of hydrogen gas are insufficiently understood. Therefore this study investigated an explosion chamber with the shape of a ventilation pipe in a ship compartment. The effect of tunnel length on explosion overpressure was examined experimentally. For quantitative verification the size of the hydrogen gas explosion overpressure was analyzed and compared with experimental values of hydrocarbon-based combustible gases (butane and LPG (propane 98%)). The experimental database can be used for explosion risk analyses of ships when designing ventilation holes and piping systems and developing new safety guidelines for hydrogen carriers and hydrogen-fueled ships.
Simulations of Hydrogen Releases from a Storage Tanks- Dispersion and Consequences of Ignition
Sep 2005
Publication
We present results from hydrogen dispersion simulations from a pressurized reservoir at constant flow rate in the presence and absence of a wall. The dispersion simulations are performed using a commercial finite volume solver. Validation of the approach is discussed. Constant concentration envelopes corresponding to the 2% 4% and 15% hydrogen concentration in air are calculated for a subcritical vertical jet and for an equivalent subcritical horizontal jet from a high pressure reservoir. The consequences of ignition and the resulting overpressure are calculated for subcritical horizontal and vertical hydrogen jets and in the latter case compared to available experimental data.
Vertical Turbulent Buoyant Helium Jet - CFD Modelling and Validation
Sep 2005
Publication
In this paper a vertical turbulent round jet of helium was studied numerically using the PHOENICS software package. The flow was assumed to be steady incompressible and turbulent. The jet discharge Froude number was 14000 and the turbulent Schmidt number was 0.7. The incompressible Reynolds average Navier-Stokes equations and helium transport equation expressed in 2-D axisymmetric domain were applied to model the underlying helium release. The k-e RNG turbulence model was used for the calculations of the corresponding turbulent viscosity diffusivity velocity and concentration fields in the domain. The simulation results are compared with the experimental measurements from the earlier published studies on helium jets in non-buoyant jet region (NBJ) intermediate region (I) and buoyant plume region (BP). The numerical results show that the radial profiles of mean velocity and mean concentration are consistent with the empirical data scaled by the effective diameter and density-ratio dependence. The mean velocity and concentration fields along the axis of the jet agree with the decay laws correlated from the previous experiments. The discrepancy between the numerical and experimental data is within 10% proving that the current CFD model for gas release and dispersion is robust accurate and reliable and that the CFD technique can be used as an alternative to the experiments with similar helium jets. The authors believe that the current CFD model is well validated through this study and can be further extended to predict similar hydrogen releases and dispersion if the model is properly applied with hydrogen properties.
Statistics, Lessons Learned and Recommendations from Analysis of HIAD 2.0 Database
Mar 2022
Publication
The manuscript firstly describes the data collection and validation process for the European Hydrogen Incidents and Accidents Database (HIAD 2.0) a public repository tool collecting systematic data on hydrogen-related incidents and near-misses. This is followed by an overview of HIAD 2.0 which currently contains 706 events. Subsequently the approaches and procedures followed by the authors to derive lessons learned and formulate recommendations from the events are described. The lessons learned have been divided into four categories including system design; system manufacturing installation and modification; human factors and emergency response. An overarching lesson learned is that minor events which occurred simultaneously could still result in serious consequences echoing James Reason's Swiss Cheese theory. Recommendations were formulated in relation to the established safety principles adapted for hydrogen by the European Hydrogen Safety Panel considering operational modes industrial sectors and human factors. This work provide an important contribution to the safety of systems involving hydrogen benefitting technical safety engineers emergency responders and emergency services. The lesson learned and the discussion derived from the statistics can also be used in training and risk assessment studies being of equal importance to promote and assist the development of sound safety culture in organisations.
Safe Storage of Compressed Hydrogen at Ambient and Cryogenic Temperatures in Flexible Glass Capillaries
Sep 2013
Publication
We have demonstrated that the strength of produced flexible quartz capillaries can be high enough to withstand the internal hydrogen pressure up to 233 MPa at normal and cryogenic temperature. According to the experimental results the cryo-compressed storage of hydrogen in the capillaries at moderate pressure can enable one to reach DOE 2015 aims for the gravimetric and volumetric capacities of vessels for the safe mobile hydrogen storage. Furthermore flexible capillaries in a bundle can probably serve as a high-pressure pipes for the transportation of gases over long distances. The developed technology of hydrogen storage can be applied to methane and hythane (H₂ - CH₄ mixture) which bridge the gap between conventional fossil fuels and the clean future of a hydrogen economy. It can be also applied to other gases i.e. air oxygen and helium-oxygen mixtures widely used in autonomic breathing devices.
Influence of Doping Element in Distributed Hydrogen Optical Fiber Densors with Brillouin Scattering
Sep 2013
Publication
Distributed hydrogen optical fiber sensor with Brillouin scattering is an innovative solution to measure hydrogen in harsh environment as nuclear industry. Glass composition is the key point to enhance the sensing parameter of the fiber in the target application. Several optical fiber with different doping element were used for measuring hydrogen saturation. Permeability of optical plays a major role to the kinetic of hydrogen diffusion. Fluorine doped fiber increase the sorption and the desorption of hydrogen.
Experimental Determination of Minimum Ignition Current (MIC) for Hydrogen & Methane Mixtures for the Determination of the Explosion Group Corresponding to IEC 60079-20-1
Sep 2017
Publication
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.
Security Risk Analysis of a Hydrogen Fueling Station with an On-site Hydrogen Production System Involving Methylcyclohexane
Sep 2017
Publication
Although many studies have looked at safety issues relating to hydrogen fuelling stations few studies have analyzed the security risks such as deliberate attack of the station by threats such as terrorists and disgruntled employees. The purpose of this study is to analyze security risks for a hydrogen fuelling station with an on-site production of hydrogen from methylcyclohexane. We qualitatively conducted a security risk analysis using American Petroleum Institute Standard 780 as a reference for the analysis. The analysis identified 93 scenarios including pool fires. We quantitatively simulated a pool fire scenario unique to the station to analyze attack consequences. Based on the analysis and the simulation we recommend countermeasures to prevent and mitigate deliberate attacks.
Comparison of Two-layer Model for High Pressure Hydrogen Jets with Notional Nozzle Model Predictions and Experimental Data
Oct 2015
Publication
A two-layer reduced order model of high pressure hydrogen jets was developed which includes partitioning of the flow between the central core jet region leading to the Mach disk and the supersonic slip region around the core. The flow after the Mach disk is subsonic while the flow around the Mach disk is supersonic with a significant amount of entrained air. This flow structure significantly affects the hydrogen concentration profiles downstream. The predictions of this model are compared to previous experimental data for high pressure hydrogen jets up to 20 MPa and to notional nozzle models and CFD models for pressures up to 35 MPa using ideal gas properties. The results show that this reduced order model gives better predictions of the mole fraction distributions than previous models for highly underexpanded jets. The predicted locations of the 4% lower flammability limit also show that the two-layer model much more accurately predicts the measured locations than the notional nozzle models. The comparisons also show that the CFD model always underpredicts the measured mole fraction concentrations.
Regulations, Codes, and Standards (RCS) For Large Scale Hydrogen Systems
Sep 2017
Publication
Hydrogen has potential applications that require larger-scale storage use and handling systems than currently are employed in emerging-market fuel cell applications. These potential applications include hydrogen generation and storage systems that would support electrical grid systems. There has been extensive work evaluating regulations codes and standards (RCS) for the emerging fuel cell market such as the infrastructure required to support fuel cell electric vehicles. However there has not been a similar RCS evaluation and development process for these larger systems. This paper presents an evaluation of the existing RCS in the United States for large-scale systems and identifies potential RCS gaps. This analysis considers large-scale hydrogen technologies that are currently being employed in limited use but may be more widely used as large-scale applications expand. The paper also identifies areas of potential safety research that would need to be conducted to fill the RCS gaps. U.S. codes define bulk hydrogen storage systems but do not define large-scale systems. This paper evaluates potential applications to define a large-scale hydrogen system relative to the systems employed in emerging technologies such as hydrogen fuelling stations. These large-scale systems would likely be of similar size to or larger than industrial hydrogen systems.
An Analysis of the Experiments Carried Out by HSL in the HyIndoor European Project Studying Accumulation of Hydrogen Released into a Semi-confined Enclosure
Oct 2015
Publication
Experimental work on hydrogen releases consequences in a 31-m3 semi-confined enclosure was performed in the framework of the collaborative European Hyindoor project. Natural ventilation effectiveness on hydrogen build-up limitation in a confined area was studied for several configurations of ventilation openings and of release conditions in real environmental conditions [1]; influence of wind on gas build-up was observed as well. This paper proposes a critical analysis of these experiments carried out by HSL and compares results with analytical approaches available in open scientific literature. The validity of these models in presence of wind was broached.
An Inter-comparison Exercise on Engineering Models Capabilities to Simulate Hydrogen Vented Explosions
Sep 2013
Publication
A benchmark exercise on vented explosion engineering model was carried out against the maximum overpressures (one or two peaks) of published experiments. The models evaluated are Bauwens et al. (2012-1 and 2012-2) [4 7] models Molkov Vent Sizing Technology 1999 2001 and 2008 models [12 13 6]. The experiments in consideration are Pasman et al. experiments (1974) (30% H2 - 1m3) [1] Bauwens et al. (2012) experiments (64m3) [4] Daubech et al. (2011) experiments (10 to 30% H2 - 1 and 10 m3) [2] and Daubech et al. (2013) [5] experiments (4 m3 – H2 10 to 30%). On this basis recommendations and limits of use of these models are proposed.
Vented Hydrogen-air Deflagrations in Low Strength Equipment and Buildings
Sep 2013
Publication
This paper aims to improve prediction capability of the vent sizing correlation presented in the form of functional dependence of the dimensionless deflagration overpressure on the turbulent Bradley number similar to our previous studies. The correlation is essentially upgraded based on recent advancements in understanding and modelling of combustion phenomena relevant to hydrogen-air vented deflagrations and unique large-scale tests carried out by different research groups. The focus is on hydrogen-air deflagrations in low-strength equipment and buildings when the reduced pressure is accepted to be below 0.1 MPa. The combustion phenomena accounted for by the correlation include: turbulence generated by the flame front itself; leading point mechanism stemming from the preferential diffusion of hydrogen in air in stretched flames; growth of the fractal area of the turbulent flame surface; initial turbulence in the flammable mixture; as well as effects of enclosure aspect ratio and presence of obstacles. The correlation is validated against the widest range of experimental conditions available to date (76 experimental points). The validation covers a wide range of test conditions: different shape enclosures of volume up to 120 m3; initially quiescent and turbulent hydrogen-air mixtures; hydrogen concentration in air from 6% to 30% by volume; ignition source location at enclosure centre near and far from a vent; empty enclosures and enclosures with obstacles.
Hydrogen Combustion Experiments in a Vertical Semi-confined Channel
Sep 2017
Publication
Experiments in an obstructed semi-confined vertical combustion channel with a height of 6 m (cross-section 0.4 × 0.4 m) inside a safety vessel of the hydrogen test center HYKA at the Karlsruhe Institute of Technology (KIT) are reported. In the work homogeneous hydrogen-air-mixtures as well as mixtures with different well-defined H2-concentration gradients were ignited either at the top or at the bottom end of the channel. The combustion characteristics were recorded using pressure sensors and sensors for the detection of the flame front that were distributed along the complete channel length. In the tests slow subsonic and fast sonic deflagrations as well as detonations were observed and the conditions for the flame acceleration (FA) to speed of sound and deflagration-to-detonation transition (DDT) are compared with the results of similar experiments performed earlier in a larger semi-confined horizontal channel.
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