Safety

The properties of hydrogen compared to conventional fuels such as gasoline and diesel are substantially different requiring adaptations to the design and layout of test cells for hydrogen fuelled engines and vehicles. A comparison of hydrogen fuel properties versus conventional fuels in this paper provides identification of requirements that need to be adapted to design a safe test cell. Design examples of actual test cells are provided to showcase the differences in overall layout and ventilation safety features fuel supply and metering and emissions measurements. Details include requirements for ventilation patterns the necessity for engine fume hoods as well as hydrogen specific intake and exhaust design. The unique properties of hydrogen in particular the wide flammability limits and nonvisible flames also require additional safety features such as hydrogen sensors and flame cameras. A properly designed and implemented fuel supply system adds to the safety of the test cell by minimizing the amount of hydrogen that can be released. Apart from this the properties of hydrogen also require different fuel consumption measurement systems pressure levels of the fuel supply system additional ventilation lines strategically placed safety solenoids combined with appropriate operational procedures. The emissions measurement for hydrogen application has to be expanded to include the amount of unburned hydrogen in the exhaust as a measurement of completeness of combustion. This measurement can also be used as a safety feature to avoid creation of ignitable hydrogen-air mixtures in the engine exhaust. The considerations provided in this paper lead to the conclusion that hydrogen IC engines can be safely tested however properly designed test cell and safety features have to be included to mitigate the additional hazards related to the change in fuel characteristics.

Fault trees and event trees have for decades been the most commonly applied modelling tools in both risk analysis in general and the risk analysis of hydrogen applications including infrastructure in particular. It is sometimes found challenging to make traditional Quantitative Risk Analyses sufficiently transparent and it is frequently challenging for outsiders to verify the probabilistic modelling. Bayesian Networks (BN) are a graphical representation of uncertain quantities and decisions that explicitly reveal the probabilistic dependence between the variables and the related information flow. It has been suggested that BN represent a modelling tool that is superior to both fault trees and event trees with respect to the structuring and modelling of large complex systems. This paper gives an introduction to BN and utilises a case study as a basis for discussing and demonstrating the suitability of BN for modelling the risks associated with the introduction of hydrogen as an energy carrier. In this study we explore the benefits of modelling a hydrogen refuelling station using BN. The study takes its point of departure in input from a traditional detailed Quantitative Risk Analysis conducted by DNV during the HyApproval project. We compare and discuss the two analyses with respect to their advantages and disadvantages. We especially focus on a comparison of transparency and the results that may be extracted from the two alternative procedures.

Experimental data obtained for hydrogen mixtures in a room-size enclosure are presented and compared with data for propane and methane mixtures. This set of data was also used to develop a three-dimensional gas dynamic model for the simulation of gaseous combustion in vented enclosures. The experiments were performed in a 64 m3 chamber with dimensions of 4.6 × 4.6 × 3.0 m and a vent opening on one side and vent areas of either 2.7 or 5.4 m2 were used. Tests were performed for three ignition locations at the wall opposite the vent at the center of the chamber or at the center of the wall containing the vent. Hydrogen–air mixtures with concentrations close 18% vol. were compared with stoichiometric propane–air and methane–air mixtures. Pressure data as function of time and flame time-of-arrival data were obtained both inside and outside the chamber near the vent. Modelling was based on a Large Eddy Simulation (LES) solver created using the OpenFOAM CFD toolbox using sub-grid turbulence and flame wrinkling models. A comparison of these simulations with experimental data is discussed.

Performing research in the interest of providing relevant safety requirements is a valuable and essential endeavor but translating research results into enforceable requirements adopted into codes and standards a process sometimes referred to as codification can be a separate and challenging task. This paper discusses the process utilized to successfully translate research results related to bulk gaseous hydrogen storage separation (or stand-off) distances into code requirements in NFPA 55:Storage Use and Handling of Compressed Gases and Cryogenic Fluids in Portable and StationaryContainers Cylinders and Tanks and NFPA 2: Hydrogen Technologies. The process utilized can besummarized as follows: First the technical committees for the documents to be revised were engaged to confirm that the codification process was endorsed by the committee. Then a sub-committee referred to as a task group was formed. A chair must be elected or appointed. The chair should be a generalist with code enforcement or application experience. The task group was populated with several voting members of each technical committee. By having voting members as part of the task group the group becomes empowered and uniquely different from any other code proposal generating body. The task group was also populated with technical experts as needed but primarily the experts needed are the researchers involved. Once properly populated and empowered the task group must actively engage its members. The researchers must educate the code makers on the methods and limitations of their work and the code makers must take the research results and fill the gaps as needed to build consensus and create enforceable code language and generate a code change proposal that will be accepted. While this process seems simple there are pitfalls along the way that can impede or nullify the desired end result – changes to codes and standards. A few of these pitfalls include: wrong task group membership task group not empowered task group not supported in-person meetings not possible consensus not achieved. This paper focuses on the process used and how pitfalls can be avoided for future efforts.

Discrete Event Simulation (DES) environments are rapidly developing and they appear to be promising tools for developing reliability and risk analysis models of safety-critical systems. DES models are an alternative to the conventional methods such as fault and event trees Bayesian networks and cause-consequence diagrams that could be used to assess the reliability of fuel supply. DES models can rather easily account for the dynamic dimensions and other important features that can hardly be captured by the conventional models. The paper describes a novel approach to estimate gas supply security and the reliability/safety of gas installations and argues that this approach can be transferred to estimate future hydrogen supply reliability. The core of the approach is a DES model of gas or other fuel propulsion through a pipeline to the customers and failures of the components of the pipeline. We will argue in the paper that the experience gained in the modelling of gas supply reliability is very relevant to the security and safety of a future hydrogen supply and worth being employed in this area.

If the ‘Hydrogen Economy’ is to progress more hydrogen fuelling stations are required. In the short term and in the absence of a hydrogen distribution network these fuelling stations will have to be supplied by liquid hydrogen (LH2) road tankers. Such a development will increase the number of tanker offloading operations significantly and these may need to be performed in close proximity to the general public. LH2 was first investigated experimentally as large-scale spills of LH2 at a rate of 60 litres per minute. Measurements were made on un-ignited releases which included the concentration of hydrogen in air thermal gradients in the concrete substrate liquid pool formation and temperatures within the pool. Computational modelling on the un-ignited spills was also performed. The experimental work on ignited releases of LH2 detailed in this paper is a continuation of the work performed by Royle and Willoughby. The experimental findings presented are split into three phenomena; jet-fires in high and low wind conditions ‘burn-back’ of ignited clouds and secondary explosions post ‘burn-back’. The aim of this work was to determine the hazards and severity of a realistic ignited spill of LH2 focussing on; flammability limits of an LH2 vapour cloud flame speeds through an LH2 vapour cloud and subsequent radiative heat levels after ignition. An attempt was made to estimate the magnitude of an explosion that occurred during one of the releases. The results of these experiments will inform the wider hydrogen community and contribute to the development of more robust modelling tools. The resulting data were used to propose safety distances for LH2 offloading facilities which will help to update and develop guidance for codes and standards.

Knowledge of the concentration field and flammability envelope from small-scale leaks is important for the safe use of hydrogen. These small-scale leaks may occur from leaky fittings or o-ring seals on liquid hydrogen-based systems. The present study focuses on steady-state leaks with large amounts of pressure drop along the leak path such that hydrogen enters the atmosphere at near atmospheric pressure (i.e. Very low Mach number). A three-stage buoyant turbulent entrainment model is developed to predict the properties (trajectory hydrogen concentration and temperature) of a jet emanating from the leak. Atmospheric hydrogen properties (temperature and quality) at the leak plane depend on the storage pressure and whether the leak occurs from the saturated vapor space or saturated liquid space. In the first stage of the entrainment model ambient temperature air (295 K) mixes with the leaking hydrogen (20–30 K) over a short distance creating an ideal gas mixture at low temperature (∼65 K). During this process states of hydrogen and air are determined from equilibrium thermodynamics using models developed by NIST. In the second stage of the model (also relatively short in distance) the radial distribution of hydrogen concentration and velocity in the jet develops into a Gaussian profile characteristic of free jets. The third and by far the longest stage is the part of the jet trajectory where flow is fully developed. Results show that flammability envelopes for cold hydrogen jets are generally larger than those of ambient temperature jets. While trajectories for ambient temperature jets depend solely on the leak densimetric Froude number results from the present study show that cold jet trajectories depend on the Froude number and the initial jet density ratio. Furthermore the flammability envelope is influenced by the hydrogen concentration in the jet at the beginning of fully developed flow.

In searching for high gravimetric and volumetric density hydrogen storage systems it is inevitable that higher energy density materials will be used. In order to make safe and commercially acceptable condensed phase hydrogen storage systems it is important to understand quantitatively the hazards involved in using and handling these materials and to develop appropriate mitigation strategies to handle potential material exposure events. A crucial aspect of the development of risk identification and mitigation strategies is the development of rigorous environmental reactivity testing standards and procedures. This will allow for the identification of potential hazards and implementation of risk mitigation strategies. Modified testing procedures for shipping air and/or water sensitive materials as codified by the United Nations have been used to evaluate two potential hydrogen storage materials 2LiBH4·MgH2 and NH3BH3. The modified U.N. procedures include identification of self-reactive substances pyrophoric substances and gas-emitting substances with water contact. The results of these tests for air and water contact sensitivity will be compared to the pure material components where appropriate (e.g. LiBH4 and MgH2). The water contact tests are divided into two scenarios dependent on the hydride to water mole ratio and heat transport characteristics. Air contact tests were run to determine whether a substance will spontaneously react with air in a packed or dispersed form. Relative to 2LiBH4·MgH2 the chemical hydride NH3BH3 was observed to be less environmentally reactive.

This paper describes a combined experimental analytical and numerical modelling investigation into hydrogen jet fires in a passively ventilated enclosure. The work was funded by the EU Fuel Cells and Hydrogen Joint Undertaking project Hyindoor. It is relevant to situations where hydrogen is stored or used indoors. In such situations passive ventilation can be used to prevent the formation of a flammable atmosphere following a release of hydrogen. Whilst a significant amount of work has been reported on unignited releases in passively ventilated enclosures and on outdoor hydrogen jet fires very little is known about the behaviour of hydrogen jet fires in passively ventilated enclosures. This paper considers the effects of passive ventilation openings on the behaviour of hydrogen jet fires. A series of hydrogen jet fire experiments were carried out using a 31 m3 passively ventilated enclosure. The test programme included subsonic and chocked flow releases with varying hydrogen release rates and vent configurations. In most of the tests the hydrogen release rate was sufficiently low and the vent area sufficiently large to lead to a well-ventilated jet fire. In a limited number of tests the vent area was reduced allowing under-ventilated conditions to be investigated. The behaviour of a jet fire in a passively ventilated enclosure depends on the hydrogen release rate the vent area and the thermal properties of the enclosure. An analytical model was used to quantify the relative importance of the hydrogen release rate and vent area whilst the influence of the thermal properties of the enclosure were investigated using a CFD model. Overall the results indicate that passive ventilation openings that are sufficiently large to safely ventilate an unignited release will tend to be large enough to prevent a jet fire from becoming under-ventilated.

Refueling infrastructure for use in gaseous hydrogen powered vehicles requires extensive manifolding for delivering the hydrogen from the stationary fuel storage at the refueling station to the vehicle as well as from the mobile storage on the vehicle to the fuel cell or combustion engine. Manifolds for gas handling often use welded construction (as opposed to compression fittings) to minimize gas leaks. Therefore it is important to understand the effects of hydrogen on tubing and tubing welds. This paper provides a brief overview of on-going studies on the effects of hydrogen precharging on the tensile properties of austenitic stainless tubing and orbital tube welds of several austenitic stainless steels.

For the general public to use hydrogen as a vehicle fuel they must be able to handle hydrogen with the same degree of confidence as conventional liquid and gaseous fuels. The hazards associated with jet releases from accidental leaks in a vehicle-refuelling environment must be considered if hydrogen is stored and used as a high-pressure gas since a jet release can result in a fire or explosion. This paper describes the work done by us in modelling some of the consequences of accidental releases of hydrogen implemented in our Fire Explosion Release Dispersion (FRED) software. The new dispersion model is validated against experimental data available in the open literature. The model predictions of hydrogen gas concentration as a function of distance are in good agreement with experiments. In addition FRED has been used to model the consequence of the bursting of a vessel containing compressed hydrogen. The results obtained from FRED i.e. overpressure as a function of distance match well in comparison to experiments. Overall it is concluded that FRED can model the consequences of an accidental release of hydrogen and the blast waves generated from bursting of vessel containing compressed hydrogen

The International Maritime Organization under the United Nations has developed safety requirements for seaborne transportation of hydrogen fuel cell vehicles in consideration of a recent increase in such transportation. Japan has led the development of new regulations in the light of some research outcomes including numerical simulations on hydrogen dispersion in a cargo space of a vehicle carrier in case of accidental leakage of hydrogen from the vehicle. Numerical results indicate that the region of space occupied by flammable hydrogen/air mixture strongly depends on the direction of ventilation openings. These findings have contributed to the development of new international regulations.

The three years European MATHRYCE project dedicated to material testing and design recommendations for components exposed to hydrogen enhanced fatigue started in October 2012. Its main goal is to provide an “easy” to implement methodology based on lab-scale experimental tests under hydrogen gas to assess the service life of a real scale component taking into account fatigue loading under hydrogen gas. Dedicated experimental tests will be developed for this purpose. In the present paper the proposed approach is presented and compared to the methodologies currently developed elsewhere in the world.

In order to achieve a high level of safety while using hydrogen as a vehicle fuel the possible hazards must be estimated. Especially hydrogen release tests with defined ignition represent a very important way to characterize the basics of hydrogen combustion in a potential accident. So ICT participated on a hydrogen jet release campaign at HSL (Buxton) in 2008 to deploy their measurement techniques and evaluation methods to visualize jets ignition and subsequent flames. The following paper shows the application of high speed cinematography in combination with image processing techniques the Background Oriented Schlieren (BOS) and a difference method to visualize the shape of hydrogen jet. In addition these methods were also used to observe ignition and combustion zone after defined initiation. In addition the combustion zone was recorded by a fast spectral radiometer and a highspeed-IR-camera. The IR-camera was synchronized with a rotating filter wheel to generate four different motion pictures at 100Hz each on a defined spectral range. The results of this preliminary evaluation provide some detailed information that might be used for improving model predictions.

Storing a hydrogen fuel-cell vehicle in a garage poses a potential safety hazard because of the accidents that could arise from a hydrogen leak. A series of tests examined the risk involved with hydrogen releases and deflagrations in a structure built to simulate a one-car garage. The experiments involved igniting hydrogen gas that was released inside the structure and studying the effects of the deflagrations. The “garage” measured 2.72 m high 3.64 m wide and 6.10 m long internally and was constructed from steel using a reinforced design capable of withstanding a detonation. The front face of the garage was covered with a thin transparent plastic film. Experiments were performed to investigate extended-duration (20–40 min) hydrogen leaks. The effect that the presence of a vehicle in the garage has on the deflagration was also studied. The experiments examined the effectiveness of different ventilation techniques at reducing the hydrogen concentration in the enclosure. Ventilation techniques included natural upper and lower openings and mechanical ventilation systems. A system of evacuated sampling bottles was used to measure hydrogen concentration throughout the garage prior to ignition and at various times during the release. All experiments were documented with standard and infrared (IR) video. Flame front propagation was monitored with thermocouples. Pressures within the garage were measured by four pressure transducers mounted on the inside walls of the garage. Six free-field pressure transducers were used to measure the pressures outside the garage.

In order to ensure safe operation of hydrogen storage cylinders under adverse conditions one should be able to predict the extremities under which these cylinders are capable of operating without failing catastrophically. It is therefore necessary to develop a comprehensive model which can predict the behavior and failure of composite storage cylinders when subjected to various types of loading conditions and operating environments. In the present work a finite element model has been developed to analyze composite hydrogen storage cylinders subjected to transient localized thermal loads and internal pressure. The composite cylinder consists of an aluminium liner that serves as a hydrogen gas permeation barrier. A filament-wound carbon/epoxy composite laminate placed over the liner provides the desired load bearing capacity. A glass/epoxy layer or other material is placed over the carbon/epoxy laminate to provide damage resistance for the carbon/epoxy laminates. A doubly curved composite shell element accounting for transverse shear deformation and geometric nonlinearity is used. A temperature dependent material model has been developed and implemented in ABAQUS using user subroutine. A failure model based on Hashin's failure theory is used to predict the various types of failure in the cylinder. A progressive damage model has also been implemented to account for reduction in modulus due to failure. A sublaminate model has been developed to save computational time and reduce the complications in the analysis. A numerical study is conducted to analyze a typical hydrogen storage cylinder and possible failure trends due to localized thermal loading and internal pressure is presented.

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.

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.

The aim in the CEP-Berlin project was to follow the guidelines from the European Integrated Hydrogen Project phase 2 (EIHP2) [1] when planning and designing a new hydrogen fuelling station. These guidelines focus on installation and operation of hydrogen refuelling stations and were based upon best practice and knowledge from the industrial partners in EIHP 2. The explosion risk analysis for the CEP-Berlin facility demonstrated that the safety risk was acceptable if certain design modifications were carried out. Both Aral/BP and Hydro accepted the results from the quantitative risk assessments. These companies have also their own standards regarding safety acceptance criteria which have to be complied with. The fuelling station was opened November 12 2004 and was put in normal operation during winter 2005.

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.

The modelling of Rayleigh–Taylor instability during premixed combustion scenarios is presented. Experimental data obtained from experiments undertaken by FM Global using their large-scale vented deflagration chamber was used to develop the modelling approach. Rayleigh–Taylor instability is introduced as an additional time-dependent combustion enhancing mechanism. It is demonstrated that prior to the addition of this mechanism the LES deflagration model under-predicted the experimental pressure transients. It is confirmed that the instability plays a significant role throughout the coherent deflagration process. The addition of the mechanism led to the model more closely replicating the pressure peak associated with the external deflagration.

The development of hydrogen as energy carrier is promoted by the increasing in energy demand depletion of fossil resources and the global warming. However this issue relies primarily on the safety aspect which requires the knowledge in the case of gas release of the quantities such as the flammable cloud size release path and the location of the lower flammability limit of the mixture. The integral models for predicting the atmospheric dispersion were extensively used in previous works for low pressure releases such as pollutant and  flammable gas transport. In the present investigation this approach is extended to the high pressure gas releases. The model is developed in the non-Boussinesq approximation and is based on Gaussian profiles for buoyant variable density jet or plume in stratified atmosphere with a crossflow. Validations have been performed on a broad range of hydrogen methane and air dispersion cases including vertical or horizontal jets or plumes into a quiescent atmosphere or with crosswind.

Burning hydrogen emits thermal radiation in UV NIR and IR spectral range. Especially in the case of large cloud explosion the risk of heat radiation is commonly underestimated due to the non-visible flame of hydrogen-air combustion. In the case of a real explosion accident organic substances or inert dust might be entrained from outer sources to produce soot or heated solids to substantially increase the heat release by continuum radiation. To investigate the corresponding combustion phenomena different hydrogen-air mixtures were ignited in a closed vessel and the combustion was observed with fast scanning spectrometers using a sampling rate up to 1000 spectra/s. In some experiments to take into account the influence of organic co-combustion a spray of a liquid glycol-ester and milk powder was added to the mixture. The spectra evaluation uses the BAM code of ICT to model bands of reaction products and thus to get the temperatures. The code calculates NIR/IR-spectra (1 - 10 μm) of non-homogenous gas mixtures of H2O CO2 CO NO and HCl taking into consideration also emission of soot particles. It is based on a single line group model and makes also use of tabulated data of H2O and CO2 and a Least Squares Fit of calculated spectra to experimental ones enables the estimation of flame temperatures. During hydrogen combustion OH emits an intense spectrum at 306 nm. This intermediary radical allows monitoring the reaction progress. Intense water band systems between 1.2 and 3 μm emit remarkable amounts of heat radiation according to a measured flame temperature of 2000 K. At this temperature broad optically-thick water bands between 4.5 μm and 10 μm contribute only scarcely to the total heat output. In case of co-combustion of organic materials additional emission bands of CO and CO2 as well as a continuum radiation of soot and other particles occur and particularly increase the total thermal output drastically.

The first part of the present work is to validate a detailed kinetic mechanism for the oxidation of hydrogen – methane – air mixtures in a detonation waves. A series of experiments on auto-ignition delay times have been performed by shock tube technique coupled with emission spectrometry for H2 / CH4 / O2 mixtures highly diluted in argon. The CH4/H2 ratio was varied from 0 to 4 and the equivalence ratio from 0.4 up to 1. The temperature range was from 1250 K to 2000 K and the pressure behind reflected shock waves was between 0.15 and 1.6 MPa. A correlation was proposed between temperature (K) concentration of chemical species (mol m-3) and ignition delay times. The experimental auto-ignition delay times were compared to the modelled ones using four different mechanisms from the literature: GRI [22] Marinov et al. [23] Hughes et al. [24] Konnov [25]. A large discrepancy was generally found between the different models. The Konnov’s model that predicted auto-ignition delay times close to the measured ones has been selected to calculate the ignition delay time in the detonation waves. The second part of the study concerned the experimental determination of the detonation properties namely the detonation velocity and the cell size. The effect of the initial composition hydrogen to methane ratio and the amount of oxygen in the mixture as well as the initial pressure on the detonation velocity and on the cell size were investigated. The ratio of methane / (methane + hydrogen) varied between 0 and 0.6 for 2 different equivalence ratio (0.75 and 1) while the initial pressure was fixed to 10 kPa. A correlation was established between the characteristic cell size and the ignition delay time behind the leading shock of the detonation. It was clearly showed that methane has an important inhibitor effect on the detonation of these combustible mixtures.

This paper shows the experimental results and findings of field explosion tests conducted to obtain fundamental data concerning the explosion of hydrogen-air mixtures. A tent covered with thin plastic sheets was filled with hydrogen/air mixed gas and subsequently ignited by an electric-spark or explosives to induce deflagration and/or detonation. Several experiments with different concentrations and/or volumes of mixture were carried out. The static overpressure of blast waves was measured using piezoelectric pressure sensors. The recorded data show that the shape of the pressure-time histories of the resulting blast waves depends on the difference in the ignition method used. The pictures of the explosion phenomenon (deflagration and/or detonation) were taken by high-speed cameras.

A phenomenological approach is developed to calculate the velocity of flame propagation and to estimate the value of pressure peak when igniting gaseous combustible mixtures in a congested space. The basic idea of this model is afterburning of the remanent fuel in pockets of congested space behind the flame front. The estimation of probable overpressure peak is based on solution of one-dimensional problem of the piston (having corresponding symmetry) moving with given velocity in polytropic gas. Submitted work is the first representation of such phenomenological approach and is realized for the simplest situation close to one-dimensional.