Safety
Safety Concept of a self-sustaining PEM Hydrogen Electrolyzer System
Sep 2013
Publication
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
Failure of PEM Water Electrolysis Cells: Case Study Involving Anode Dissolution and Membrane Thinning
Sep 2013
Publication
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.
Safety Assessment of Unignited Hydrogen Discharge from Onboard Storage in Garages with Low Levels of Natural Ventilation
Sep 2011
Publication
This study is driven by the need to understand requirements to safe blow-down of hydrogen onboard storage tanks through a pressure relief device (PRD) inside a garage-like enclosure with low natural ventilation. Current composite tanks for high pressure hydrogen storage have been shown to rupture in 3.5–6.5 min in fire conditions. As a result a large PRD venting area is currently used to release hydrogen from the tank before its catastrophic failure. However even if unignited the release of hydrogen from such PRDs has been shown in our previous studies to result in unacceptable overpressures within the garage capable of causing major damage and possible collapse of the structure. Thus to prevent collapse of the garage in the case of a malfunction of the PRD and an unignited hydrogen release there is a clear need to increase blow-down time by reducing PRD venting area. Calculations of PRD diameter to safely blow-down storage tanks with inventories of 1 5 and 13 kg hydrogen are considered here for a range of garage volumes and natural ventilation expressed in air changes per hour (ACH). The phenomenological model is used to examine the pressure dynamics within a garage with low natural ventilation down to the known minimum of 0.03 ACH. Thus with moderate hydrogen flow rate from the PRD and small vents providing ventilation of the enclosure there will be only outflow from the garage without any air intake from outside. The PRD diameter which ensures that the pressure in the garage does not exceed a value of 20 kPa (accepted in this study as a safe overpressure for civil structures) was calculated for varying garage volumes and natural ventilation (ACH). The results are presented in the form of simple to use engineering nomograms. The conclusion is drawn that PRDs currently available for hydrogen-powered vehicles should be redesigned along with either a change of requirements for the fire resistance rating or innovative design of the onboard storage system as hydrogen-powered vehicles are intended for garage parking. Further research is needed to develop safety strategies and engineering solutions to tackle the problem of fire resistance of onboard storage tanks and requirements to PRD performance. Regulation codes and standards in the field should address this issue.
Hydrogen Venting Under Variable Flow Conditions
Sep 2011
Publication
Safety distances for hydrogen plumes are currently derived using models developed for hydrocarbon releases. It is well known that hydrogen behaves in a significantly different manner to that of hydrocarbons when released to atmosphere. There are two main aspects involved with the development of safety distances for credible hydrogen releases; the intensity of the thermal radiation from such a plume should it be ignited and the distance downwind from the release point to the point where a flammable mixture with air no longer exists. A number of distinct areas of venting behaviour were investigated; Thermal radiation from ignited plumes from vertical open ended vent pipes Far field radiation measurements for direct comparison with models Thermal radiation from ignited plumes from vertical vent pipes terminating in a T-piece Thermal radiation measurements from ignited hydrogen with a 45 vent termination Hydrogen concentration measurements with a T-piece.
Numerical Simulations of Spontaneous Ignition of High-pressure Hydrogen Based on Detailed Chemical Kinetics
Sep 2013
Publication
A two-dimensional (2-D) simulation of spontaneous ignition of high-pressure hydrogen in a length of duct is conducted in order to explore its underlying ignition mechanisms. The present study adopts a 2-D rectangular duct (i.e. not axisymmetric geometry) and focuses on the effects of initial diaphragm shape on the spontaneous ignitions. The Navier-Stokes equations with a detailed chemical kinetics mechanism are solved in a manner of direct numerical simulation. The detailed mechanisms of spontaneous ignition are discussed for each initial diaphragm shape. For a straight diaphragm shape it is found that the ignition occurs only near the wall due to the adiabatic wall condition while the three ignition events: ignitions due to leading shock wave reflection at the wall hydrogen penetration into shock-heated air near the wall and deep penetration of hydrogen into shock-heated air behind the leading shock wave are identified for a largely deformed diaphragm shape.
Ignition of Hydrogen Jet Fires from High Pressure Storage
Sep 2013
Publication
Highly transient jets from hydrogen high pressure tanks were investigated up to 30 MPa. These hydrogen jets might self-initiate when released from small orifices of high pressure storage facilities. The related effects were observed by high speed video technics including time resolved spectroscopy. Ignition flame head jet velocity flame contours pressure wave propagation reacting species and temperatures were evaluated. The evaluation used video cross correlation method BOS brightness subtraction and 1 dimensional image contraction to obtain traces of all movements. On burst of the rupture disc the combustion of the jet starts close to the nozzle on the outer shell of it at the boundary layer to the surrounding air. It propagates with a deceleration approximated by a drag force of constant value which is obtained by analysing the head velocity. The burning at the outer shell develops to an explosion converting a nearly spherical volume at the jet head the movement of the centroid is nearly unchanged and follows the jet front in parallel. The progress of the nearly spherical explosion could be evaluated on an averaged flame ball radius. An apparent flame velocity could be derived to be about 20 m/s. It seems to increase slightly on the pressure in the tank or the related initial jet momentum. Self-initiation is nearly always achieved especially induced the interaction of shock waves and their reflections from the orifice. The results are compared to thermodynamic calculations and radiation measurements. The combustion process is composed of a shell combustion of the jet cone at the bases with a superimposed explosion of the decelerating jet head volume.
CFD and VR for Risk Communication and Safety Training
Sep 2011
Publication
There are new safety challenges with an increased use of hydrogen e.g. that people may not see dangerous jet flames in case of an incident. Compared to conventional fuels hydrogen has very different characteristics and physical properties and is stored at very high pressure or at very low temperatures. Thus the nature of hazard scenarios will be very different. Consequence modelling of ventilation releases explosions and fires can be used to predict and thus understand hazards. In order to describe the detailed development of a hazard scenario and evaluate ways of mitigation 3D Computational Fluid Dynamics (CFD) models will be required. Even with accurate modelling the communication of risk can be challenging. For this visualization in virtual reality (VR) may be of good help in which the CFD model predictions are presented in a realistic 3D environment with the possibility to include sounds like noise from a high pressure release explosion or fire. In cooperation with Statoil Christian Michelsen Research (CMR) and GexCon have developed the VRSafety application. VRSafety can visualize simulation results from FLACS (and another CFD-tool KFX) in an immersive VR-lab or on a PC. VRSafety can further be used to interactively control and start new CFD-simulations during the sessions. The combination of accurate CFD-modelling visualization and interactive use through VRSafety represents a powerful toolbox for safety training and risk communication to first-responders employees media and other stakeholders. It can also be used for lessons learned sessions studying incidents and accidents and to demonstrate what went wrong and how mitigation could have prevented accidents from happening. This paper will describe possibilities with VRSafety and give examples of use.
The Effect of Tube Internal Geometry on the Propensity to Spontaneous Ignition in Pressurized Hydrogen Release
Sep 2013
Publication
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.
Validation of Cryo-Compressed Hydrogen Storage (CCH2) – A Probabilistic Approach
Sep 2011
Publication
Due to its promising potential to overcome the challenge of thermal endurance of liquid hydrogen storage systems cryo-compressed hydrogen storage (CcH2) is regarded as a verypromising physical storage solution in particular for use in larger passenger vehicles with high energy and long range requirements. A probabilistic approach for validation of safe operation of CcH2 storage systems under automotive requirements and experimental results on life-cycle testing is presented. The operational regime of BMW's CcH2 storage covers pressures of up to 35 MPa and temperatures from +65 C down to -240 C applying high loads on composite and metallic materials of the cryogenic pressure vesselcompared to ambient carbon fiber reinforced pressure vessels. Thus the proof of fatigue strength under combined pressure and deep temperature cyclic loads remains a challenging exercise. Furthermore it will be shown that the typical automotive safety and life-cycle requirements can be fulfilled by the CcH2 vehicle storage system and moreover that the CcH2 storage system can even feature safety advantages over a CGH2 storage system mainly due to the advantageous thermodynamic properties of cryogenic hydrogen the lower storage pressure and due to the intrinsic protection against intrusion through the double-shell design.
Quantifying the Hydrogen Embrittlement of Pipeline Steels for Safety Considerations
Sep 2011
Publication
In a near future with an increasing use of hydrogen as an energy vector gaseous hydrogen transport as well as high capacity storage may imply the use of high strength steel pipelines for economical reasons. However such materials are well known to be sensitive to hydrogen embrittlement (HE). For safety reasons it is thus necessary to improve and clarify the means of quantifying embrittlement. The present paper exposes the changes in mechanical properties of a grade API X80 steel through numerous mechanical tests i.e. tensile tests disk pressure test fracture toughness and fatigue crack growth measurements WOL tests performed either in neutral atmosphere or in high-pressure of hydrogen gas. The observed results are then discussed in front of safety considerations for the redaction of standards for the qualification of materials dedicating to hydrogen transport.
Applying Risk Management Strategies Prudently
Sep 2011
Publication
During the current global financial crisis the term “Risk Management” is often heard. Just as the causes for the financial problems are elusive so is a complete definition of what Risk Management means. The answer is highly dependent upon your perceptions of “risk” and your appetite for assuming risks. The proposed paper will explore these issues with some brief case studies as they apply to hydrogen industrial applications hydrogen refuelling stations and fuel cell technologies for distributed generation.
Specifically the paper will identify the various risk exposures from the perspective of the project developers original equipment suppliers end users project funding sources and traditional insurance providers. What makes this evaluation intriguing is that it is a mixed bag of output capacities Combine Heat & Power (CHP) potential and technology maturity. Therefore the application considerations must be part of any overall Risk Management program.
Specifically the paper will identify the various risk exposures from the perspective of the project developers original equipment suppliers end users project funding sources and traditional insurance providers. What makes this evaluation intriguing is that it is a mixed bag of output capacities Combine Heat & Power (CHP) potential and technology maturity. Therefore the application considerations must be part of any overall Risk Management program.
Numerical Study on Detailed Mechanism of H2-Air Flame Jet Ignition
Sep 2013
Publication
Jet ignition was recognized in the 1970s and has since been applied to automobile engines such as the Honda CVCC. In the 1990s jet ignition was observed in explosions and was seen as a problem that may relate to jet ignition. Our group presented jet ignition experimentally and numerically in 1999 and later using LIF measurements with the same experimental vessel as used in 1999. However the detailed mechanism of jet ignition was not clarified at that time. The target of this study is to clarify how jet ignition happens and to understand the detailed mechanism of flame jet ignition.
Development of an Italian Fire Prevention Technical Rule For Hydrogen Pipelines
Sep 2011
Publication
This paper summarizes the current results of the theoretical and experimental activity carried out by the Italian Working Group on the fire prevention safety issues in the field of the hydrogen transport in pipelines. From the theoretical point of view a draft document has been produced beginning from the regulations in force on the natural gas pipelines; these have been reviewed corrected and integrated with the instructions suitable to the use of hydrogen. From the experimental point of view an apparatus has been designed and installed at the University of Pisa; this apparatus has allowed the simulation of hydrogen releases from a pipeline with and without ignition of hydrogen-air mixture. The experimental data have helped the completion of the above-mentioned draft document with the instructions about the safety distances. The document has been improved for example pipelines above ground (not buried) are allowed due to the knowledge acquired by means of the experimental campaign. The safety distances related to this kind of piping has been chosen on the base of risk analysis. The work on the text contents is concluded and the document is currently under discussion with the Italian stakeholders involved in the hydrogen applications.
Risk Reduction Potential of Accident Prevention and Mitigation Features
Sep 2011
Publication
Quantitative Risk Assessment (QRA) can help to establish a set of design and operational requirements in hydrogen codes and standards that will ensure safe operation of hydrogen facilities. By analyzing a complete set of possible accidents in a QRA the risk drivers for these facilities can be identified. Accident prevention and mitigation features can then be analyzed to determine which are the most effective in addressing these risk drivers and thus reduce the risk from possible accidents. Accident prevention features/methods such as proper material selection and preventative maintenance are included in the design and operation of facilities. Accident mitigation features are included to reduce or terminate the potential consequences from unintended releases of hydrogen. Mitigation features can be either passive or active in nature. Passive features do not require any component to function in order to prevent or mitigate a hydrogen release. Examples of passive mitigation features include the use of separation distances barriers and flow limiting orifices. Active mitigation features initiate when specific conditions occur during an accident in order to terminate an accident or reduce its consequences. Examples of active mitigation features include detection and isolation systems fire suppression systems and purging systems. A concept being pursued by the National Fire Protection Association (NFPA) hydrogen standard development is to take credit for prevention and mitigation features as a means to reduce separation distances at hydrogen facilities. By utilizing other mitigation features the risk from accidents can be decreased and risk-informed separation distances can be reduced. This paper presents some preliminary QRA results where the risk reduction potential for several active and passive mitigation features was evaluated. These measures include automatic leak detection and isolation systems the use of flow limiting orifices and the use of barriers. Reducing the number of risk-significant components in a system was also evaluated as an accident prevention method. In addition the potential reduction in separation distances if such measures were incorporated at a facility was also determined.
Threshold Stress Intensity Factor for Hydrogen Assisted Cracking of Cr-Mo Steel Used as Stationary Storage Buffer of a Hydrogen Refueling Station
Oct 2015
Publication
In order to determine appropriate value for threshold stress intensity factor for hydrogen-assisted cracking (KIH) constant-displacement and rising-load tests were conducted in high-pressure hydrogen gas for JIS-SCM435 low alloy steel (Cr-Mo steel) used as stationary storage buffer of a hydrogen refuelling station with 0.2% proof strength and ultimate tensile strength equal to 772 MPa and 948 MPa respectively. Thresholds for crack arrest under constant displacement and for crack initiation under rising load were identified. The crack arrest threshold under constant displacement was 44.3 MPa m1/2 to 44.5 MPa m1/2 when small-scale yielding and plane-strain criteria were satisfied and the crack initiation threshold under rising load was 33.1 MPa m1/2 to 41.1 MPa m1/2 in 115 MPa hydrogen gas. The crack arrest threshold was roughly equivalent to the crack initiation threshold although the crack initiation threshold showed slightly more conservative values. It was considered that both test methods could be suitable to determine appropriate value for KIH for this material.
Hydrogen Safety Training for Laboratory Researchers and Technical Personnel
Sep 2011
Publication
We have developed a web-based hydrogen safety class and are developing a hands-on hydrogen safety class. The 4-h web-based class is directed to laboratory researchers who need basic hydrogen safety information (free online access at http://www.h2labsafety.org/) and it addresses hydrogen fundamentals: properties pressure and cryogenic safety emergency response and codes and standards. Technical operators in charge of building and testing experimental hydrogen equipment will also soon benefit from a more comprehensive 3-day hands-on safety class that will present detailed information for installation testing and operation of hydrogen pressurized systems. The hands-on class includes a full day of classroom instruction followed by two days of laboratory work where students assemble test and operate a pressure system based on a schematic and component description.
Simulation of the Efficiency of Hydrogen Recombiners as Safety Devices
Sep 2011
Publication
Passive auto-catalytic recombiners (PARs) are used as safety devices in the containments of nuclear power plants (NPPs) for the removal of hydrogen that may be generated during specific reactor accident scenarios. In the presented study it was investigated whether a PAR designed for hydrogen removal inside a NPP containment would perform principally inside a typical surrounding of hydrogen or fuel cell applications. For this purpose a hydrogen release scenario inside a garage – based on experiments performed by CEA in the GARAGE facility (France) – has been simulated with and without PAR installation. For modelling the operational behaviour of the PAR the in-house code REKO-DIREKT was implemented in the CFD code ANSYS-CFX. The study was performed in three steps: First a helium release scenario was simulated and validated against experimental data. Second helium was replaced by hydrogen in the simulation. This step served as a reference case for the unmitigated scenario. Finally the numerical garage setup was enhanced with a commercial PAR model. The study shows that the PAR works efficiently by removing hydrogen and promoting mixing inside the garage. The hot exhaust plume promotes the formation of a thermal stratification that pushes the initial hydrogen rich gas downwards and in direction of the PAR inlet. The paper describes the code implementation and simulation results.
Measurements of Effective Diffusion Coefficient of Helium and Hydrogen Through Gypsum
Sep 2011
Publication
An experimental apparatus which was based on the ¼-scale garage previously used for studying helium release and dispersion in our laboratory was used to obtain effective diffusion coefficients of helium and hydrogen (released as forming gas for safety reasons) through gypsum panel. Two types of gypsum panel were used in the experiments. Helium or forming gas was released into the enclosure from a Fischer burner1 located near the enclosure floor for a fixed duration and then terminated. Eight thermal-conductivity sensors mounted at different vertical locations above the enclosure floor were used to monitor the temporal and spatial gas concentrations. An electric fan was used inside the enclosure to mix the released gas to ensure a spatially uniform gas concentration to minimize stratification. The temporal variations of the pressure difference between the enclosure interior and the ambience were also measured. An analytical model was developed to extract the effective diffusion coefficients from the experimental data.
Use of Hydrogen Safety Sensors Under Anaerobic Conditions – Impact of Oxygen Content on Sensor Performance
Sep 2011
Publication
In any application involving the production storage or use of hydrogen sensors are important devices for alerting to the presence of leaked hydrogen. Hydrogen sensors should be accurate sensitive and specific as well as resistant to long term drift and varying environmental conditions. Furthermore as an integral element in a safety system sensor performance should not be compromised by operational parameters. For example safety sensors may be required to operate at reduced oxygen levels relative to air. In this work we evaluate and compare a number of sensor technologies in terms of their ability to detect hydrogen under conditions of varying oxygen concentration.
Real-size Calculation of High-pressure Hydrogen Flow and its Auto-ignition in Cylindrical Tube
Sep 2013
Publication
A real-size calculation is performed for high-pressure hydrogen release in a tube using the axisymmetric Navier–Stokes equations with the full hydrogen chemistry. A Harten–Yee-type total variation diminishing scheme and point-implicit method are used to integrate the governing equations. The calculated real-size results show that the leading shock wave velocity is similar to that calculated using a smaller tube. The mixing process and ignition behaviour of high-pressure hydrogen are explained in detail; the velocity shear layer and Kelvin–Helmholtz instability are the main causes of mixing of hydrogen with air and ignition in the high-temperature region behind the leading shock wave.
No more items...