Safety

The accidents that hydrogen ignites without ignition source are reported in several cases which phenomenon is called “auto-ignition.” Since the use of high pressure hydrogen will be increased for the hydrogen society it must be necessary to understand auto-ignition mechanism in detail to prevent such accidents. In this study we performed three-dimensional numerical simulations to clarify the autoignition mechanism using the three-dimensional compressive Navier-Stokes equations and a hydrogen chemical reaction model including nine species and twenty elementary reactions. We focus on the effects of the shape of the cross-section on the hydrogen auto-ignition mechanism applying for a rectangular and cylindrical tube. The results obtained indicate that the Richtmyer-Meshukov instability involves these auto-ignition.

Platinum metals dispersed on a porous carrier e.g. -Al2O3 are used as catalysts for removal of small amounts of hydrogen from the air where the excess of oxygen is significant.<br/>The recombination reaction of H2 and O2 on smooth platinum proceeds at a high rate only in gas mixes with an excess of hydrogen. When the concentration of oxygen exceeds that of hydrogen in terms of stoichiometric ratio the process slows down sharply and eventually stops completely. In research undertaken at the Karpov Institute of Physical Chemistry (Moscow) forty years ago the electrochemical mechanism of red-ox reactions was proposed as an explanation for this inhibition by excess oxygen. The results of ellipsometric analysis pointed to the formation of a protective monolayer of PtO molecules on the Pt surface in an oxygen-rich atmosphere. It was observed that the recombination reaction proceeds at a high rate with the use of a porous catalyst at any concentrations of reactant gases. The reason for that lies in the mechanism of the catalysis: the reaction proceeds at a certain depth in the porous body of the catalyst. Hydrogen which has higher mobility penetrates in larger quantity than oxygen thus creating there the stoichiometric excess. To test the proposed mechanism of recombination the catalytic reaction was studied ) with porous carriers of various thicknesses and b) with metal grids of various porosities covering the catalyst. The data obtained have confirmed unequivocally the earlier hypothesis of hydrogenation of a porous catalyst.<br/>Such insight has allowed the authors to develop more effective prototypes of catalyst for removal of hydrogen. In particular by using a porous grid cover to remove excess heat in the reaction zone of the catalyst plate we achieved a considerable expansion of the region of hydrogen concentrations where the catalyst is both effective and reliable.

For the emerging hydrogen-powered vehicles the safety concern is one of the most important barriers for their further development and commercialization. The safety of commercial natural gas vehicles has been well accepted and the total number of natural gas vehicles operating worldwide was approximately 23 million by November 2016. Hydrogen vehicles would be more acceptable for the general public if their safety is comparable to that of commercialized CNG vehicles. A comparison study is conducted to reveal the differences of hazard distances and accident durations between hydrogen vehicles and CNG vehicles during a representative accident in an open environment. The tank blowdown time for hydrogen and CNG are calculated separately to compare the accident durations. CFD simulations for real world situations are performed to study the hazard distances from impinging jet fires under vehicle. Results show that the release duration for CNG vehicle is over two times longer than that for hydrogen vehicle indicating that CNG vehicle jet fire accident is more timeconsuming and firefighters have to wait a longer time before they can safely approach the vehicle. For both hydrogen vehicle and CNG vehicle the longest hazard distance near the ground occur about 1 to 4 seconds after the initiation of the thermally-activated pressure relief devices. Afterwards the flames will shrink and the hazard distances will decrease. For firefighters with bunker gear they must stand 6 m and 14 m away from the hydrogen vehicle and CNG vehicle respectively. For general public a perimeter of 12 m and 29 m should be set around the accident scene for hydrogen vehicle and CNG vehicle respectively.

A methodology for explosion and fire risk analyses in enclosed rooms is presented. The objectives of this analysis are to accurately predict the risks associated with hydrogen leaks in maritime applications and to use the approach to provide decision support regarding design and risk-prevention and risk mitigating measures. The methodology uses CFD tools and simpler consequence models for ventilation dispersion and explosion scenarios as well as updated frequency for leaks and ignition. Risk is then efficiently calculated with a Monte Carlo routine capturing the transient behavior of the leak. This makes it possible to efficiently obtain effects of sensitivities and design options maintaining safety and reducing costs.

Hydrogen infrastructures are important for the commercialization of fuel cell vehicles. Hydrogen storage and transportation are significant topics because it is difficult to safely and effectively treat large amounts of hydrogen because of hydrogen hazards. An organic chemical hydride method keeps and provides hydrogen using hydrogenation and dehydrogenation chemical reactions with aromatic compounds. This method has advantages in that the conventional petrochemical products are used as a hydrogen carrier and petrochemicals are more easily treated than hydrogen because of low hazards. Hydrogen fueling stations are also crucial infrastructures for hydrogen supply. In Japan hybrid gasoline-hydrogen fuelling stations are needed for effective space utilization in urban areas. It is essential to address the safety issues of hybrid fueling stations for inherently safer station construction. We focused on a hybrid gasoline-hydrogen fuelling station with an on-site hydrogen production system using methylcyclohexane as an organic chemical hydride. The purpose of this study is to reveal unique hybrid risks in the station with a hazard identification study (HAZID study). As a result of the HAZID study we identified 314 accident scenarios involving gasoline and organic chemical hydride systems. In addition we suggested improvement safety measures for uniquely worst-case accident scenarios to prevent and mitigate the scenarios.

It is important to understand and quantify the potential risk resulting from accidental environmental exposure of condensed phase hydrogen storage materials under differing environmental exposure scenarios. This paper describes a modelling and experimental study with the aim of predicting consequences of the accidental release of 2LiBH₄+MgH₂ from hydrogen storage systems. The methodology and results developed in this work are directly applicable to any solid hydride material and/or accident scenario using appropriate boundary conditions and empirical data.

The ability to predict hydride behaviour for hypothesized accident scenarios facilitates an assessment of the risk associated with the utilization of a particular hydride. To this end an idealized finite volume model was developed to represent the behaviour of dispersed hydride from a breached system. Semi-empirical thermodynamic calculations and substantiating calorimetric experiments were performed in order to quantify the energy released energy release rates and to quantify the reaction products resulting from water and air exposure of a lithium borohydride and magnesium hydride combination.

The hydrides LiBH₄ and MgH₂ were studied individually in the as-received form and in the 2:1 “destabilized” mixture. Liquid water hydrolysis reactions were performed in a Calvet calorimeter equipped with a mixing cell using neutral water. Water vapor and oxygen gas phase reactivity measurements were performed at varying relative humidities and temperatures by modifying the calorimeter and utilizing a gas circulating flow cell apparatus. The results of these calorimetric measurements were compared with standardized United Nations (UN) based test results for air and water reactivity and used to develop quantitative kinetic expressions for hydrolysis and air oxidation in these systems. Thermodynamic parameters obtained from these tests were then inputted into a computational fluid dynamics model to predict both the hydrogen generation rates and concentrations along with localized temperature distributions. The results of these numerical simulations can be used to predict ignition events and the resultant conclusions will be discussed.

In the Fukushima Daiichi Nuclear Power Station (NPS) accident hydrogen generated by oxidation reaction of the cladding and water etc. was leaked into the NPS building and finally led to occurrence of hydrogen explosion in the building. This resulted in serious damage to the environment. To improve the safety performance of the NPS especially on the hydrogen safety under severe accident conditions a simulation code system has been developed to analyze hydrogen behaviour including diffusion combustion explosion and structural integrity evaluation. This developing system consists of CFD and FEM tools in order to support various hydrogen user groups consisting of students researchers and engineers. Preliminary analytical results obtained with above mentioned tools especially with open source codes including buoyancy turbulent model and condensation model agreed well with the existing test data.

The higher rate of component failure and downtime during initial operation in hydrogen stations is not well understood. The National Renewable Energy Laboratory (NREL) has been collecting failed components from retail and research hydrogen fuelling stations in California and Colorado and analyzing them using an optical zoom and scanning electron microscope. The results show stainless steel metal particulate contamination. While it is difficult to definitively know the origin of the contaminants a possible source of the metal particulates is improper tube cleaning practices. To understand the impact of different cleaning procedures NREL performed an experiment to quantify the particulates introduced from newly cut tubes. The process of tube cutting threading and bevelling which is performed most often during station fabrication is shown to introduce metal contaminants and thus is an area that could benefit from improved cleaning practices. This paper shows how these particulates can be reduced which could prevent station downtime and costly repair. These results are from the initial phase of a project in which NREL intends to further investigate the sources of particulate contamination in hydrogen stations.

The Brazilian Fuel Cell Bus Project is being developed by a consortium comprising 14 national and international partners. The project was initially supported by the GEF/UNDP and MME/FINEP Brazil. The national coordination is under responsibility of MME and EMTU/SP the São Paulo Metropolitan Urban Transport Company that also controls the bus operation and bus routes. This work reports the efforts done in order to obtain the necessary licenses to operate the first fuel cell buses for regular service in Brazil as well as the first commercial hydrogen fueling station to attend the vehicles.

The hydrogen detection system is a key component of the hydrogen safety systems (HSS). Any HSS forms a second layer of protection for the assets under accidental conditions when a first layer of protection - passive protection systems (separation at “safe” distance natural ventilation) are inoperable or failed. In this report a performance-based risk-informed methodology for establishing of the explicit quantitative requirements for hydrogen detectors allocation and actuation is proposed. The main steps of the proposed methodology are described. It is suggested (as a first approximation) to use in a process of quantification of a hydrogen detection system performance (from safety viewpoint) a five-tiered hierarchy namely 1) safety goals 2) risk-informed safety objectives 3) performance goal and metrics 4) rational safety criteria 5) safety factors. Unresolved issues of the proposed methodology of Safety Performance Analysis for development of the risk-informed and performance based standards on the hydrogen detection systems are synopsized.<br/><br/>