Publications

Increasingly car manufacturers are turning to high pressure hydrogen storage for on-board power applications. Many prototypes use costly materials and fabrication methods such as Type 316L austenitic stainless steel and processes such as TIG (GTA) welding. There is a need to move to less expensive options without compromising safety to assist in developing economic vehicles. It is important that the behaviour of new/modified materials and joints (including those fabricated by new technologies) is understood at anticipated service temperatures and hydrogen pressure as the consequences of poor material choice could be severe. The greatest detrimental effect of gaseous hydrogen on the mechanical properties of metallic materials is commonly observed under conditions of dynamic plastic strain. Under such conditions an atomically clean surface is produced where hydrogen molecules will dissociate and penetrate the material. Thus static load test methods with hydrogen charging are not reliable for engineering data generation. To meet the need for dynamically straining material in a pressurised hydrogen environment TWI has developed a facility to load specimens in a high pressure environment for tensile toughness and fatigue testing. The design of this has involved a number of innovative steps. This paper outlines the requirements and the design and construction issues that were encountered when installing a facility which can not only perform tests at up to 1000bar (100MPa) but also for temperatures between –150°C to +85°C.

The development and promulgation of codes and standards are essential to establish a market-receptive environment for commercial hydrogen-based products and systems. The focus of the U.S. Department of Energy (DOE) is to conduct the research and development (R&D) needed to strengthen the scientific basis for technical requirements incorporated in national and international standards codes and regulations. In the U.S. the DOE and its industry partners have formed a Codes and Standards Tech Team (CSTT) to help guide the R&D. The CSTT has adopted an R&D Roadmap to achieve a substantial and verified database of the properties and behaviour of hydrogen and the performance characteristics of emerging hydrogen technology applications sufficient to enable the development of effective codes and standards for these applications. However to develop a more structured approach to the R&D described above the CSTT conducted a workshop on Risk Assessment for Hydrogen Codes and Standards in March 2005. The purpose of the workshop was to attain a consensus among invited experts on the protocols and data needed to address the development of risk-informed standards codes and regulations for hydrogen used as an energy carrier by consumers. Participants at the workshop identified and assessed requirements methodologies and applicability of risk assessment (RA) tools to develop a framework to conduct RA activities to address for example hydrogen fuel distribution delivery on-site storage and dispensing and hydrogen vehicle servicing and parking. The CSTT was particularly interested in obtaining the advice of RA experts and representatives of standards and model code developing organizations and industry on how data generated by R&D can be turned into information that is suitable for hydrogen codes and standards development. The paper reports on the results of the workshop and the RA activities that the DOE’s program on hydrogen safety codes and standards will undertake. These RA activities will help structure a comprehensive R&D effort that the DOE and its industry partners are undertaking to obtain the data and conduct the analysis and testing needed to establish a scientific and technical basis for hydrogen standards codes and regulations.

In order to facilitate the introduction of a new technology as it is the utilization of hydrogen as an energy carrier development of safety codes and standards besides the conduction of demonstrative projects becomes a very important action to be realized. Useful tools of work could be the existing gaseous fuel codes (natural gas and propane) regulating the stationary and automotive applications. Some safety codes have been updated to include hydrogen but they have been based on criteria and/or data applicable for large industrial facilities making the realization of public hydrogen infrastructures prohibitive in terms of space. In order to solve the above mentioned problems others questions come out: how these safety distances have been defined? Which hazard events have been taken as reference for calculation? Is it possible to reduce the safety distances through an appropriate design of systems and components or through the predisposition of adequate mitigation measures? This paper presents an analysis of the definitions of “safety distances” and “hazardous locations” as well as a synoptic analysis of the different values in force in several States for hydrogen and natural gas. The above mentioned synoptic table will highlight the lacks and so some fields that need to be investigated in order to produce a suitable hydrogen standard.

Under government funded project: "Development for Safe Utilization and Infrastructure of Hydrogen" entrusted by New Energy and Industrial Technology Development Organization (NEDO) special material testing equipment with heavy walled pressure vessel under 45MPa gaseous hydrogen is facilitated. Tensile properties strain controlled low-cycle and high-cycle fatigue and fatigue crack growth tests on CrMo steel (SCM435 (JIS G 4105)) which will be applied for the storage gas cylinders in Japanese hydrogen fuel stations are investigated. The results of the tensile tests under 45MPa ultra high purity hydrogen gas (O2<1ppm) at room temperature shows that there are no difference in yield and maximum tensile strength with those tested in air. However the reduced ductilities with brittle fracture surface were observed which indicates the occurrence of hydrogen environment embrittlement. It was also found by tensile tests that the embrittling origin is not only caused by machined traces on surface but also by the non-metallic inclusions dispersed on surface. Further discussions on surface treatment effects will be presented. In low cycle fatigue tests considerable reductions in cycles to failure in 45MPa ultra high purity hydrogen gas were observed. However there are tendencies that the effect of hydrogen environment embrittlement becomes not so significant as the plastic strain range decreases. It was demonstrated that there was no effect of hydrogen on fatigue limit and this implies that CrMo gas cylinders can be operated in limited fatigue safe condition. Another series of hydrogen test results temperature effect fatigue crack growth rate delayed fracture test using wedge opening loaded specimens and fatigue test of CrMo gas cylinders under repeated internal pressure with artificial crack will be presented.

A quantitative risk analysis to a central pressurized storage tank for gaseous hydrogen has been performed to attend requirements of licensing procedures established by the State Environment Agency of São Paulo State Brazil. Gaseous hydrogen is used to feed the reactor to promote hydrogenation at the surfactant unit. HAZOP was the hazard identification technique selected. System components failures were defined by event and fault tree analysis. Quantitative risk analysis was complied to define the acceptability concepts on societal and individual risks required by the State Environmental Agency to approve the installation operation license. Acceptable levels to public society from the analysis were reached. Safety recommendations to the gaseous hydrogen central were proposed to assure minimization of risk to the near-by community operators environment and property.

As a part of a broader project on hydrogen production by reforming of methane in a membrane catalytic reactor this paper outlines the research activity performed at the University of Pisa Department of Chemical Engineering aimed at developing and testing composite panels that can operate as thermal protective shields against hydrogen jet fires. The shield design criterion that appears to give a more practical and convenient solution for the type of installation to be protected is the one that suggest to realize composite panels. Composite material are made of two elements fiber and matrix. In this study composite panels will be realized with basalt fabric as fiber and epoxy-phenolic resins as matrix. Therefore following the indications given by norms as UNI 9174 and ASTM E 1321-93 a test method has been studied to obtain temperature data from a specimen impinged by an hydrogen flame. Thanks to thermocouples applied on backside of the sample and an infrared video camera to realize thermal images of specimen surface impinged by flame this type of test try to characterize the behaviour of composite materials under the action of hydrogen flame simulating in a simple way the action of hydrogen jet fires.

The current work is devoted to problems connected with application of CFD tools for safety analysis of large-scale industrial structures. With the aim to preserve conservatism of overall process of multistage procedure of such analysis special efforts are required. A strategy which has to lead to obtaining of reliable results in CFD analysis is discussed. Different aspects of proposed strategy including: adequate choice of physical and numerical models procedure of validation simulations and problem of ‘under-resolved’ simulations are considered. For physical phenomena which could cause significant uncertainties in the course of scenario simulation an approach which complements CFD simulations by application of auxiliary criteria is presented. Physical basis and applicability of strong flame acceleration and detonation-to-deflagration transition criteria are discussed. In concluding part two examples of application of presented approach for nuclear power plant and workshop cell for hydrogen driven vehicles are presented.

The present work proposes a novel safe method for obtaining metallic hydrides. The method is called SHS (Self-Propagating High temperature synthesis). A novel high pressure gas reactor governed by an electromechanical control device has been designed and built up in order to synthesise metallic hydrides. This system is provided with a control system that allows calculating the amount of gas coming into the reaction vessel at every stage of the process. The main feature of this method is that metallic hydrides can be safely synthesised using low gas reaction pressures. In order to validate the assessing system the main kinetic regularities of SHS in Ti-H2 system were studied. In addition phase analysis (by means of X ray diffraction) as well as chemical analysis have been performed.

Experimental studies were carried out to examine the lift-off and blow-out stability of H2/CO2 H2/Ar H2/C3H8 and H2/CH4 jet flames. The experiments were carried out using a burner with a 2mm inner diameter. The flame structures were recorded by direct filming and also by a schlieren apparatus. The experiments showed that the four gases affected the lift-off and blow-out stability of the hydrogen differently. The experiments showed that propane addition to an initially attached flame always produced lifted flame and the flame was blown out at higher jet velocity. The blow-out velocity decreased as the increasing in propane concentration. Direct blow-off of hydrogen/propane was never observed. Methane addition resulted in a relatively stable flame comparing with the carbon dioxide and propane addition. Comparisons of the stability of H2/C3H8 H2/CH4 and H2/CO2 flames showed that H2/C3H8 produced the highest lift-off height. Propane is much more effective in lift-off and blow out hydrogen flames. The study carried out a chemical kinetic analysis of H2/CO2 H2/Ar H2/C3H8 and H2/CH4 flames for a comparison of effect of chemical kinetics on flame stability.

When hydrogen gas is used or stored within a building as with a hydrogen-powered vehicle parked in a residential garage any leakage of unignited H2 will mix with indoor air and may form a flammable mixture. One approach to safety engineering relies on buoyancy-driven passive ventilation of H2 from the building through vents to the outside. To discover relationships between design variables we combine two types of analysis: (1) a simplified 1-D steady-state analysis of buoyancy-driven ventilation and (2) CFD modelling using FLUENT 6.3. The simplified model yields a closed-form expression relating the H2 concentration to vent area height and discharge coefficient; leakage rate; and a stratification factor. The CFD modelling includes 3-D geometry; H2 cloud formation; diffusion momentum convection and thermal effects; and transient response. We modelled a typical residential two-car garage with 5 kg of H2 stored in a fuel tank; leakage rates of 5.9 to 82 L/min (tank discharge times of 12 hours to 1 week); a variety of vent sizes and heights; and both isothermal and nonisothermal conditions. This modelling indicates a range of the stratification factor needed to apply the simplified model for vent sizing as well as a more complete understanding of the dynamics of H2 movement within the building. A significant thermal effect occurs when outdoor temperature is higher than indoor temperature so that thermocirculation opposes the buoyancy-driven ventilation of H2. This circumstance leads to higher concentrations of H2 in the building relative to an isothermal case. In an unconditioned space such as a residential garage this effect depends on the thermal coupling of indoor air to outdoor air the ground (under a concrete slab floor) and an adjacent conditioned space in addition to temperatures. We use CFD modelling to explore the magnitude of this effect under rather extreme conditions.

Design of hydrogen fueling components is critical for safety and reliability. Intensive usage of such components in urban public environment is expected in the near future. Any leakage of gas or failure of equipment will create potential hazards. Materials for such category of equipment must have specific mechanical characteristics including hardness (influence on the durability of the equipment and on the resistance to hydrogen) and be easy to machine. Air Liquide has developed a test program for qualifying equipment representing the present state of the art. Studies on the susceptibility of various steels to hydrogen embrittlement have been done. Test specimens were exposed to static and cyclic loads with hydrogen and an inert gas the inert gas representing a reference. Various tests are described here. As a result the importance of further development in the design and selection of appropriate materials for critical hydrogen components is required. Various options are presented and discussed.

Safety is a high priority for a hydrogen refueling station. Here we propose a method to safely refuel a vehicle at optimised speed of filling with minimum information about it. Actually we identify two major risks during a vehicle refuelling: over filling and overheating. These two risks depend on the temperature increase in the tank during refuelling. But the inside temperature is a difficult information to get from the station point of view. It assumes a temperature sensor in a representative place of the tank and an additional connection between the vehicle and the station for data exchange. The refuelling control may not depend on this parameter only. Therefore out objective was to effectively control the filling particularly to avoid the two identified risks independently of optional and safety redundant information from the vehicle. For that purpose we defined a maximum filling pressure which corresponds to the most severe following conditions: if the maximum temperature is reached in the tank or if the maximum capacity is reached in the tank. This maximum pressure depends on a few filling parameters which are easily available. The method and its practical applications are depicted.

This paper presents a compilation and discussion of the results supplied by HySafe partners participating in the Standard Benchmark Exercise Problem (SBEP) V1 which is based on an experiment on hydrogen release mixing and distribution inside a vessel. Each partner has his own point of view of the problem and uses a different approach to the solution. The main characteristics of the models employed for the calculations are compared. The comparison between results together with the experimental data when available is made. Relative deviations of each model from the experimental values are also included. Explanations and interpretations of the results are presented together with some useful conclusions for future work.

Microgrid with hydrogen storage is an effective way to integrate renewable energy and reduce carbon emissions. This paper proposes an optimal operation method for a microgrid with hydrogen storage. The electrolyzer efficiency characteristic model is established based on the linear interpolation method. The optimal operation model of microgrid is incorporated with the electrolyzer efficiency characteristic model. The sequential decision-making problem of the optimal operation of microgrid is solved by a deep deterministic policy gradient algorithm. Simulation results show that the proposed method can reduce about 5% of the operation cost of the microgrid compared with traditional algorithms and has a certain generalization capability.

A method for determination of hazardous zones for hydrogen installations has been studied. This work has been carried out within the NoE HySafe. The method is based on the Italian Method outlined in Guide 31-30(2004) Guide 31–35(2001) Guide 31-35/A(2001) and Guide 31-35/A; V1(2003). Hazardous zones for a “generic hydrogen refuelling station”(HRS) are assessed based on this method. The method is consistent with the EU directive 1999/92/EC “Safety and Health Protection of Workers potentially at risk from explosive atmospheres” which is the basis for determination of hazardous zones in Europe. This regulation is focused on protection of workers and is relevant for hydrogen installations such as hydrogen refuelling stations repair shops and other stationary installations where some type of work operations will be involved. The method is also based on the IEC standard and European norm IEC/EN60079-10 “Electrical apparatus for explosive gas atmospheres. Part 10 Classification of hazardous areas”. This is a widely acknowledged international standard/norm and it is accepted/approved by Fire and Safety Authorities in Europe and also internationally. Results from the HySafe work and other studies relevant for hydrogen and hydrogen installations have been included in the case study. Sensitivity studies have been carried out to examine the effect of varying equipment failure frequencies and leak sizes as well as environmental condition (ventilation obstacles etc.). The discharge and gas dispersion calculations in the Italian Method are based on simple mathematical formulas. However in this work also CFD (Computational Fluid Dynamics) and other simpler numerical tools have been used to quantitatively estimate the effect of ventilation and of different release locations on the size of the flammable gas cloud. Concentration limits for hydrogen to be used as basis for the extent of the hazardous zones in different situations are discussed.

A simple approximate method for evaluation of blast effects and safety distances for unconfined hydrogen explosions is presented. The method includes models for flame speeds hydrogen distribution blast parameters and blast damage criteria. An example of the application of this methodology for hydrogen releases in three hypothetical obstructed areas with different levels of congestion is presented. The severity of the blast effect of unconfined hydrogen explosions is shown to depend strongly on the level of congestion for relatively small releases. Extremely large releases of hydrogen are predicted to be less sensitive to the congestion level.

Hydrogen energy is very promising as it ensures a high efficiency and ecological cleanliness of energy conversion. The goal of the present work is to provide the analysis of hydrogen safety aspects and to prescribe methods of safety operation with hydrogen. The authors conducted a hazard analysis of hydrogen operation and storage in comparison with other fuels. Good ventilation is the main hydrogen operation requirement. Besides an effective way of protection against propagation of hazards (for instance leaks) is neutralization of dangerous hydrogen-air mixtures by a method of controlled catalytic combustion inside special devices so-called recombiners [1-3]. The basis of these devices is a high porosity cell material (HPCM) activated by platinum deposition. Apart from recombiners HPCM was also applied for development of hydrogen detectors intended for measurement and analysis of hydrogen concentration for hydrogen-driven transport and objects of hydrogen infrastructure (including vapor-air media at high pressure and  temperatures). A system of hydrogen safety based on hydrogen detectors and hydrogen catalytic recombiners was developed. Experimental and theoretical studies of hydrogen combustion processes heat- and mass transfer and also gas flows in catalytic-activated HPCM allowed for a design optimization of recombiners and their location. Pilot hydrogen detectors and hydrogen catalytic recombiners were fabricated and their laboratory tests were successfully performed. Thus it was indicated that on condition of following the  appropriate passive and active safety measures hydrogen is just as safe as the other fuels. This conclusion represents another incentive for a transition to the hydrogen energy.

Hydrogen is increasingly receiving a primary role as an energy vector in ensuring the achievement of the European decarbonization goals by 2050. In fact Hydrogen could be produced also by electrolysis of water using renewable sources such as photovoltaic and wind power being able to perform the energy storage function as well as through injection into natural gas infrastructures. However hydrogen injection directly impacts thermodynamic properties of the gas itself such as density calorific value Wobbe index sound speed etc. Consequently this practice leads to changes in metrological behavior especially in terms of volume and gas quality measurements. In this paper the authors present an overview on the impact of hydrogen injection in natural gas measurements. In particular the changes in thermodynamic properties of the gas mixtures with different H2 contents have been evaluated and the effects on the accuracy of volume conversion at standard conditions have been investigated both on the theoretical point of view and experimentally. To this end the authors present and discuss the effect of H2 injection in gas networks on static ultrasonic domestic gas meters both from a theoretical and an experimental point of view. Experimental tests demonstrated that ultrasonic gas meters are not significantly affected by H2 injection up to about 10%.

The response of a typical steel-lined reinforced concrete nuclear reactor containment to postulated internal hydrogen detonations is investigated by detailed axisymetric non-linear dynamic finite element analysis. The wall pressure histories are calculated for hydrogen detonations using a technique that reproduces the sharp discontinuity at the shock front. The pressure results can be applied to geometrically similar vessels. The analysis indicates that the response is more sensitive to the point of initiation than to the strength of the detonation. Approximate solutions based on a pure impulse assumption where the containment is modelled as a single-degree-of freedom (SDOF) system may be seriously unconservative. This work becomes relevant because new nuclear reactors are foreseen as a primary of source of hydrogen supply.<br/><br/>

Nowadays 4 type hydrogen stations have been demonstrated in Korea for preparing hydrogen economy. This simulator is consists of virtual experience modules and virtual accident scenarios of 4 type hydrogen stations. Virtual experience modules show the performance properties through a movie or a virtual reality technology. Also they provide an explanation of hydrogen station equipment and a guide for operators immediately after the accident. Virtual accident scenario modules show accident simulations based on modelling equations as 3D virtual reality. These modules could choose the sham accident for every kind of a station after categorizing all possible accidents in a station A Commercialized CFD program based on hydrogen dispersion model theory shows a movie of accident simulations. The result of a simulator has been developed as web applications. And will be applied to training materials and public relations for a user concerned about hydrogen stations.

The influence of environmental temperatures on the fatigue strength of compressed-hydrogen tanks for vehicles was investigated. The fatigue strength of Type-3 tanks was found to decrease in a low temperature environment and increase in a high-temperature environment. The Type-3 tank has been subjected to autofrettage to improve fatigue strength. The investigation clarified that the effect of autofrettage changes according to the environmental temperature due to the difference between the coefficients of thermal expansion of carbon fiber reinforced plastic (CFRP) and aluminum alloy. This causes life strength to change with changes in temperature. These results indicate that the service life of the Type-3 tank is influenced by the environmental temperature. The Type-4 tank has a very long fatigue life and did not break after 45000 cycles in a room-temperature or low-temperature environment. In a high-temperature environment however the tank broke in fewer than 45000 cycles. The fatigue of CFRP was promoted in the high-temperature environment resulting in breakage of the tank.

A total of 12 ventilation experiments with various combinations of hydrogen release rates and ventilation speeds were performed in order to study how ventilation speed and release rate effect the hydrogen concentration in a closed system. The experiential facility was constructed out of steel plates and beams in the shape of a rectangular enclosure. The volume of the test facility was about 60m3. The front face of the enclosure was covered by a plastic film in order to allow visible and infrared cameras to capture images of the flame. The inlet and outlet vents were located on the lower front face and the upper backside panel respectively. Hydrogen gas was released toward the ceiling from the center of the floor. The hydrogen gas was released at constant rate in each test. The hydrogen release rate ranged from 0.002 m3/s to 0.02 m3/s. Ventilation speeds were 0.1 0.2 and 0.4 m3/s respectively. Ignition was attempted at the end of the hydrogen release by using multiple continuous spark ignition modules on the ceiling and next to the release point. Time evolution of hydrogen concentration was measured using evacuated sample bottles. Overpressure and impulse inside and outside the facility were also measured. The mixture was ignited by a spark ignition module mounted on the ceiling in eight of eleven tests. In the other three tests the mixture was ignited by spark ignition modules mounted next to the nozzle. Overpressures generated by the hydrogen deflagration in most of these tests were low and represented a small risk to people or property. The primary risk associated with the hydrogen deflagrations studied in these tests was from the fire. The maximum concentration is proportional to the ratio of the hydrogen release rate to the ventilation speed within the range of parameters tested. Therefore a required ventilation speed can be estimated from the assumed hydrogen leak rate within the experimental conditions described in this paper.

For the sake of the increasing demand of hydrogen fuel cell vehicles there are more concerns on the safety of hydrogen refueling stations. As one of the key pieces of equipment the hydrogen dispenser has drawn attention on this aspect since it involves massive manual operations and may be bothered by a high probability of failure. In this paper a numerical study is conducted to simulate the possible leakage events of the hydrogen dispenser based on a prototype in China whose working pressure is 70 MPa. The leakage accident is analyzed with respect to leakage sizes leak directions and the time to stop the leakage. It is found that due to the large mass flow rate under such high pressure the leak direction and the layout of the components inside the dispenser become insignificant and the ignitable clouds will form inside the dispenser in less than 1 s if there is a leakage of 1% size of the main tube. The ignitable clouds will form near the vent holes outside the dispenser which may dissipate quickly if the leakage is stopped. On the other hand the gas inside the dispenser will remain ignitable for a long time which asks for a design with no possible ignition source inside. The results can be useful in optimizing the design of the dispenser regarding the reaction time and sensitivity requirements of the leakage detector the size and amount of vent holes etc.

In recent years federal and state safety authorities have worked to bring emergency planners and responders together with industry the scientific community and consumers to ensure high levels of safety with gas and liquid pipelines and more recently with liquefied natural gas terminals. The U.S. Department of Transportation (DOT) is the federal authority on the safe transportation of energy and the National Association of State Fire Marshals (NASFM) represents state-level safety authorities. Together they have produced firefighter safety training materials technical guidance and information for use in communities considering new energy infrastructure and conducted research to support these activities. In 2004 the DOT-NASFM partnership established the Hydrogen Executive Leadership Panel (HELP) to ensure a safe transition from fossil fuels to hydrogen fuel cells. HELP brings together senior policy-level experts from all sectors to understand and recommend mitigation strategies for the risks associated with the transportation and use of hydrogen in motor vehicles. The initial group includes experts from the United States Canada and Europe. HELP will be supported by an advisory committee of emergency planners and responders—individuals well-equipped to describe real-world scenarios of greatest concern—and by a second advisory committee of engineers and scientists who will help translate the real-world scenarios into useful technical solutions. By September 2005 HELP expects to define the initial real-world scenarios of greatest concern and bring together teams of experts to collaborate with automakers energy producers government authorities consumers and public safety officials. Much work lies ahead including creating guidance for hydrogen powered automobiles emergency response safety training establishing test methods to reflect real-world incident scenarios and modifying state and local building and fire codes. The HELP leadership will present its strategic plan and first report at the International Conference on Hydrogen Safety in September 2005.

In this paper a case of hydrogen release in a typical research laboratory for the characterisation of hydrogen solid-state storage materials has been considered. The laboratory is equipped with various testing equipments for the assessment of hydrogen capacity in materials typically in the 1 to 200 bar pressure range and temperatures up to 500°C. Hydrogen is delivered at 200 bar by a 50 l gas bottle and a compressor located outside the laboratory. The safety measures directly related to hydrogen hazard consist in a distributed ventilation of the laboratory and air extraction fume hoods located on top of each instrument. Goal of this work is the modelling of hydrogen accidental release in a real laboratory case in order to provide a more fundamental basis for the laboratory safety design and assist the decision on the number and position of the safety sensors. The computational fluid dynamics code (CFD) ANSYS-CFX has been selected in order to perform the numerical investigations. Two basic accidental release scenarios have been assumed both at 200 bar:  a major leak corresponding to a guillotine breaking of the hydrogen distribution line and a smaller leak typical for a not properly tight junction.