Publications

Underground or partial underground tunnels form a very important part of modern road transportation systems. As the development of hydrogen cars advancing into the markets it is unavoidable in the near future that hydrogen cars would become the users of ordinary road tunnels. This paper discusses potential fire scenarios and fire hazards of hydrogen cars in road tunnels and implications on the fire safety measures and ventilation systems in existing tunnels. The information needed for carry out risk assessment of hydrogen cars in road tunnels are discussed. hydrogen has a low ignition energy and wide flammable range suggesting that leaks have a high probability of ignition and result hydrogen flame. CFD simulations of hydrogen fires in a full scale 5m by 5m square cross-section tunnel were carried out. The effect of the ventilation on controlling the back-layering and the downstream flame are discussed.

The paper presents an overview of the main results of the EC NOE HySafe activity to estimate an allowable hydrogen permeation rate for automotive legal requirements and standards. The work was undertaken as part of the HySafe internal project InsHyde.<br/>A slow long term hydrogen release such as that due to permeation from a vehicle into an inadequately ventilated enclosed structure is a potential risk associated with the use of hydrogen in automotive applications. Due to its small molecular size hydrogen permeates through the containment materials found in compressed gaseous hydrogen storage systems and is an issue that requires consideration for containers with non-metallic (polymer) liners. Permeation from compressed gaseous hydrogen storage systems is a current hydrogen safety topic relevant to regulatory and standardisation activities at both global and regional levels.<br/>Various rates have been proposed in different draft legal requirements and standards based on different scenarios and the assumption that hydrogen dispenses homogeneously. This paper focuses on the development of a methodology by HySafe Partners (CEA NCSRD. University of Ulster and Volvo Technology) to estimate an allowable upper limit for hydrogen permeation in automotive applications by investigating the behaviour of hydrogen when released at small rates with a focus on European scenario. The background to the activity is explained. reasonable scenarios are identified a methodology proposed and a maximum hydrogen permeation rate from road vehicles into enclosed structures is estimated The work is based on conclusions from the experimental and numerical investigations described by CEA NCSRD and the University of Ulster in related papers.

The ignition limits of hydrogen/air mixtures in turbulent jets are necessary to establish safety distances based on ignitable hydrogen location for safety codes and standards development. Studies in turbulent natural gas jets have shown that the mean fuel concentration is insufficient to determine the flammable boundaries of the jet. Instead integration of probability density functions (PDFs) of local fuel concentration within the quiescent flammability limits termed the flammability factor (FF) was shown to provide a better representation of ignition probability (PI). Recent studies in turbulent hydrogen jets showed that the envelope of ignitable gas composition (based on the mean hydrogen concentration) did not correspond to the known flammability limits for quiescent hydrogen/air mixtures. The objective of this investigation is to validate the FF approach to the prediction of ignition in hydrogen leak scenarios. The PI within a turbulent hydrogen jet was determined using a pulsed Nd:YAG laser as the ignition source. Laser Rayleigh scattering was used to characterize the fuel concentration throughout the jet. Measurements in methane and hydrogen jets exhibit similar trends in the ignition contour which broadens radially until an axial location is reached after which the contour moves inward to the centerline. Measurements of the mean and fluctuating hydrogen concentration are used to characterize the local composition statistics conditional on whether the laser spark results in a local ignition event or complete light-up of a stable jet flame. The FF is obtained through direct integration of local PDFs. A model was developed to predict the FF using a presumed PDF with parameters obtained from experimental data and computer simulations. Intermittency effects that are important in the shear layer are incorporated in a composite PDF. By comparing the computed FF with the measured PI we have validated the flammability factor approach for application to ignition of hydrogen jets.

A series of experiments are described in which helium was released at a constant rate into a 1.5 m × 1.5 m × 0.75 m enclosure designed as a ¼-scale model of a two car garage. The purpose was to provide reference data sets for testing and validating computational fluid dynamics (CFD) models and to experimentally characterize the effects of a number of variables on the mixing behaviour within an enclosure and the exchange of helium with the surroundings. Helium was used as a surrogate for hydrogen and the total volume released was scaled as the amount that would be released by a typical hydrogen fuelled automobile with a full tank. Temporal profiles of helium were measured at seven vertical locations within the enclosure during and following one hour and four hour releases. Idealized vents in one wall sized to provide air exchange rates typical of actual garages were used. The effects of vent size number and location were investigated using three different vent combinations. The dependence on leak location was considered by releasing helium from three different points within the enclosure. It is shown that the National Institute of Standards and Technology (NIST) CFD code Fire Dynamics Simulator (FDS) provides time resolved predictions for helium concentrations that agree well with the experimental measurements.

It has been suggested that separation or safety distances for pressurised hydrogen storage can be reduced by the inclusion of walls or barriers between the hydrogen storage and vulnerable plant or other items. Various NFPA codes (1) suggest the use of 60° inclined fire barriers for protection against jet flames in preference to vertical ones.<br/>This paper describes a series of experiments performed in order to compare the performance of 60° barriers with that of 90° barriers. Their relative efficiency at protecting from thermal radiation and blast overpressure was measured together with the propensity for the thermal radiation and blast overpressure to be reflected back to the source of the leak. The work was primarily focused on compressed H2 storage for stationary fuel cell systems which may be physically separated from a fuel cell system or could be on board such a system. Different orifice sizes were used to simulate different size leaks and all releases were made were from storage at 200 bar.<br/>Overall conclusions on barrier performance were made based on the recorded measurements.

A techno-economic analysis has been used to evaluate three processes for hydrogen production from advanced steam reforming (SR) of bio-oil as an alternative route to hydrogen with BECCS: conventional steam reforming (C-SR) C-SR with CO2 capture (C-SR-CCS) and sorption-enhanced chemical looping (SE-CLSR). The impacts of feed molar steam to carbon ratio (S/C) temperature pressure the use of hydrodesulphurisation pretreatment and plant production capacity were examined in an economic evaluation and direct CO2 emissions analysis. Bio-oil C-SR-CC or SE-CLSR may be feasible routes to hydrogen production with potential to provide negative emissions. SE-CLSR can improve process thermal efficiency compared to C-SR-CCS. At the feed molar steam to carbon ratio (S/C) of 2 the levelised cost of hydrogen (USD 3.8 to 4.6 per kg) and cost of carbon avoided are less than those of a C-SR process with amine-based CCS. However at higher S/C ratios SE-CLSR does not have a strong economic advantage and there is a need to better understand the viability of operating SE-CLSR of bio-oil at high temperatures (>850 ◦C) with a low S/C ratio (e.g. 2) and whether the SE-CLSR cycle can sustain low carbon deposition levels over a long operating period.

In our society the use of hydrogen is continually growing and there will be a widespread installation of plants with high capacity storages in our towns as automotive refuelling stations. For this reason it is necessary to make accurate studies on the safety of these kinds of plants to protect our town inhabitants Moreover hydrogen is a highly flammable chemical that can be particularly dangerous in case of release since its mixing with air in the presence of an ignition source could lead to fires or explosions. Generally most simulation models whether or not concerned with fluid dynamics used in safety and risk studies are not validated for hydrogen use. This aspect may imply that the results of studies on safety cannot be too accurate and realistic. This paper introduces an experimental activity which was performed by the Department of Energetics of Politecnico of Torino with the collaboration of the University of Pisa. Accidental hydrogen release and dispersion were studied in order to acquire a set of experimental data to validate simulation models for such studies. At the laboratories of the Department of Mechanical Nuclear and Production Engineering of the University of Pisa a pilot plant called Hydrogen Pipe Break Test was built. The apparatus consisted of a 12 m3 tank which was fed by high pressure cylinders. A 50 m long pipe moved from the tank to an open space and at the far end of the pipe there was an automatic release system that could be operated by remote control. During the experimental activity data was acquired regarding hydrogen concentration as a function of distance from the release hole also lengthwise and vertically. In this paper some of the experimental data acquired during the activity have been compared with the integral models Effects and Phast. In the future experimental results will be used to calibrate a more sophisticated model to atmospheric dispersion studies.

Photocatalysis for “green” hydrogen production is a technology of increasing importance that has been studied using both TiO2–based and heterojunction composite-based semiconductors. Different irradiation sources and reactor units can be considered for the enhancement of photocatalysis. Current approaches also consider the use of electron/hole scavengers organic species such as ethanol that are “available” in agricultural waste in communities around the world. Alternatively organic pollutants present in wastewaters can be used as organic scavengers reducing health and environmental concerns for plants animals and humans. Thus photocatalysis may help reduce the carbon footprint of energy production by generating H2 a friendly energy carrier and by minimizing water contamination. This review discusses the most up-to-date and important information on photocatalysis for hydrogen production providing a critical evaluation of: (1) The synthesis and characterization of semiconductor materials; (2) The design of photocatalytic reactors; (3) The reaction engineering of photocatalysis; (4) Photocatalysis energy efficiencies; and (5) The future opportunities for photocatalysis using artificial intelligence. Overall this review describes the state-of-the-art of TiO2–based and heterojunction composite-based semiconductors that produce H2 from aqueous systems demonstrating the viability of photocatalysis for “green” hydrogen production.

The UK has committed to significantly reduce greenhouse gas emissions by 2050 to help address climate change. Decarbonising heating is a key part of this and using hydrogen (H2) as a replacement to natural gas (NG) can help in achieving this. The objective of current research including HyDeploy is to demonstrate that NG containing levels of H2 beyond those currently allowed of 0.1 vol% (1000 ppm) [1] can be distributed and utilised safely and efficiently. Initial projects such as HyDeploy are studying the effects of introducing up to 20 vol% H2 in NG but later projects are considering using up to 100 vol% H2.

A key element in the safe operation of a modern gas distribution system is gas detection. However the addition of hydrogen to NG will alter the characteristics of the gas and the impact on gas detection must be considered. It is important that sensors remain sufficiently sensitive to the presence of hydrogen natural gas carbon monoxide (CO) and oxygen (O2) deficiency and that they don’t lead to false positive or false negative readings. The aim of this document is to provide a summary of the requirements for gas detection of hydrogen enriched natural gas for the gas distribution industry and other potentially interested parties. As such it is based on gas detectors presently used by the industry with the only major differences being the effects of hydrogen on the sensitivity of flammable gas sensors and the cross sensitivity of carbon monoxide gas sensors to hydrogen.

There is further information of gas detector concepts and technologies in the appendices.

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Hydrogen is a notoriously difficult substance to store yet has endless energy applications. Thus the study of long-term hydrogen storage and high-pressure bulk hydrogen storage have been the subject of much research in the last several years. To create a research path forward it is important to know what research has already been done and what is already known about hydrogen storage. In this review several approaches to hydrogen storage are addressed including high-pressure storage cryogenic liquid hydrogen storage and metal hydride absorption. Challenges and advantages are offered based on reported research findings. Since the project looks closely at advanced manufacturing techniques for the same are outlined as well. There are seven main categories into which most rapid prototyping styles fall. Each is briefly explained and illustrated as well as some generally accepted advantages and drawbacks to each style. An overview of hydrogen adsorption on metal hydrides carbon fibers and carbon nanotubes are presented. The hydrogen storage capacities of these materials are discussed as well as the differing conditions in which the adsorption was performed under. Concepts regarding storage shape and materials accompanied by smaller-scale advanced manufacturing options for hydrogen storage are also presented.

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.

For hydrogen fuelled vehicles to attain significant market penetration it is essential that any potential risks be controlled within acceptable levels. To achieve this goal on-board vehicle hydrogen storage systems should undergo risk analyses during early concept development and design phases. By so doing the process of eliminating safety-critical failure modes will help guide storage system development and be more efficient to implement than if undertaken after the design-freeze stage. The focus of this paper is the development of quantitative risk analyses of storage systems which use onboard reversible materials such as conventional AB5 metal hydrides the complex hydride NaAlH4 or other material candidates currently being researched. Collision of a vehicle having such a hydrogen storage system was selected as a dominant accident initiator and a probabilistic event tree model has been developed for this initiator. The event tree model contains a set of comprehensive mutually exclusive accident sequences. The event tree represents chronological ordering of key events that are postulated to occur sequentially in time during the accident progression. Each event may represent occurrence of a phenomenon (e.g. hydride chemical reaction and dust cloud explosion) or a hardware failure (e.g. hydride storage vessel rupture). Event tree branch probabilities can be quantified using fault tree models or basic events with probability distributions. A fault tree model for hydride dust cloud explosion is provided as an example. Failure probabilities assigned to the basic events in the fault tree can be estimated from test results published data or expert opinion elicitation. To account for variabilities in the probabilities assigned to fault tree basic events and hence to propagate uncertainties in event tree sequences Monte Carlo sampling and Latin Hypercube sampling were employed and the statistics of the results from both techniques were compared.

Previous experiments demonstrated that the accidental release of high pressure hydrogen into air can lead to the possibility of spontaneous ignition. It is believed that this ignition is due to the heating of the mixing layer between hydrogen and air that is caused by the shock wave driven by the pressurized hydrogen during the release. Currently this problem is poorly understood and not amenable to direct numerical simulation. This is due to the presence of a wide range of scales between the sizes of the blast wave driven and the very thin mixing layer. The present study addresses this fundamental ignition problem and develops a solution framework in order to predict the ignition event for given hydrogen storage pressures and dimension of the release hole. In this problem only the mixing layer between the hydrogen and air is considered. This permits us to use much higher resolution than previous studies. This mixing layer at the jet head is advected as a Lagrangian fluid particle. The key physical processes in the problem are identified to be the mixing of the two gases at the mixing layer the initial heating by the shock wave and a cooling effect due to the expansion of the mixing layer. The results of the simulations indicate that for every storage pressure there exists a critical hole size below which ignition is prevented during the release process. Close inspection of the results indicate that this limit is due to the competition between the heating provided by the shock wave and the cooling due to expansion. Furthermore the results also indicate that the details of the mixing process do not play a significant role to leading order. The limiting ignition criteria were found to be well approximated by the Homogeneous Ignition Model of Cuenot and Poinsot supplemented by a heat loss term due to expansion. Therefore turbulent mixing occurring in reality is not likely to affect the ignition limits derived in the present study. Comparison with existing experiments showed very good agreement.

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/>

Transport by pipe is one the most usual way to carry liquid or gaseous energies from their extraction point until their final field sites. To limit explosion risk or escape to avoid pollution problems and human risks it is necessary to assess nocivity of defect promoting fracture. This need to know the mechanical properties of the pipes steels. Hydrogen is considered to day as a new energy vector and its transport in one of the key problems to extension of its use. Within the European project NATURALHY it has been proposed to transport a mixture of natural gas and hydrogen. 39 European partners have combined their efforts to assess the effects of hydrogen presence on the existing gas network. Key issues are durability of pipeline material integrity management safety aspects life cycle and socio-economic assessment and end-use. The work described in this paper was performed within the NATURALHY work package on ’Durability of pipeline material’. This study makes it possible to emphasize the hydrogen effect on mechanical properties of several pipe steels as X52 X70 or X100 in fatigue and fracture and in two different environments: air and hydrogen electrolytic.

Computational fluid dynamics (CFD) is used to numerically solve the sudden release of hydrogen from a high pressure tank (up to 70MPa) into air. High pressure tanks increase the risk of failure of the joints and pipes connected to the tank which results in release of Hydrogen. The supersonic flow caused by high pressure ratio of reservoir to ambient generates a strong Mach disk. A three dimensional in-house code is developed to simulate the flow. High pressure Hydrogen requires a real gas law because it deviates from ideal gas law. Firstly Beattie-Bridgeman and Abel-Noble real gas equation of states are applied to simulate the release of hydrogen in hydrogen. Then Abel-Noble is implied to simulate the release of hydrogen in air. Beattie-Bridgeman has stability problems in the case of hydrogen in air. A transport equation is used to solve the concentration of Hydrogen-air mixture. The code is second order accurate in space and first order in time and uses a modified Van Leer limiter. The fast release of Hydrogen from a small rupture needs a very small mesh therefore parallel computation is applied to overcome memory problems and to decrease the solution time. The high pressure ratio of the reservoir to ambient causes a very fast release which is accurately modelled by the code and all the shocks and Mach disk happening are observed in the results. The results show that the difference between real gas and ideal gas models cannot be ignored.

The scenario of ignition of fuels by the passage of shock waves is relevant from the perspective of safety primarily because shock ignition potentially plays an important role in deflagration to detonation transition. Even in one dimension simulation of ignition between a contact surface or a flame and a shock moving into combustible mixture is difficult because of the singular nature of the initial conditions. Indeed initially as the shock starts moving away from the contact surface the region filled with shocked reactive mixture does not exist. In the current work the formulation is transformed using time and length over time as the independent variables. This transformation yields a finite domain from t = 0. In this paper the complete spatial and temporal ignition evolution of hydrogen combustible mixtures of different concentrations is studied numerically. Integration of the governing equations is performed using an Essentially Non-Oscillatory (ENO) algorithm in space and Runge-Kutta in time while the chemistry is modeled by a three-step chain-branching mechanism which appropriately mimics hydrogen combustion.

Experiments with a hydrogen jet were performed at two different pressures 96 psig (6.6 bars) and 237 psig (16.3 bars). The hydrogen leak was generated at two different hole sizes 1/16 inch (1.6 mm) and 1/32 inch (0.79 mm). The flammable shape of the plume was characterised by numerous measurements of the hydrogen concentration inside of the jet. The effect of the nearby horizontal surface on the shape of the plume was measured and compared with results of CFD numerical simulations. The paper will present results and an interpretation on the nature of the plume shape.

The United States has 11 distinct natural gas pipeline corridors: five originate in the Southwest four deliver natural gas from Canada and two extend from the Rocky Mountain region. This study assesses the potential to deliver hydrogen through the existing natural gas pipeline network as a hydrogen and natural gas mixture to defray the cost of building dedicated hydrogen pipelines.

Plasmonic Ni nanoparticles were incorporated into LaFeO₃ photocathode (LFO-Ni) to excite the surface plasmon resonances (SPR) for enhanced light harvesting for enhancing the photoelectrochemical (PEC) hydrogen evolution reaction. The nanostructured LFO photocathode was prepared by spray pyrolysis method and Ni nanoparticles were incorporated on to the photocathode by spin coating technique. The LFO-Ni photocathode demonstrated strong optical absorption and higher current density where the untreated LFO film exhibited a maximum photocurrent of 0.036 mA/cm² at 0.6 V vs RHE and when incorporating 2.84 mmol Ni nanoparticles the photocurrent density reached a maximum of 0.066 mA/cm² at 0.6 V vs RHE due to the SPR effect. This subsequently led to enhanced hydrogen production where more than double (2.64 times) the amount of hydrogen was generated compared to the untreated LFO photocathode. Ni nanoparticles were modelled using Finite Difference Time Domain (FDTD) analysis and the results showed optimal particle size in the range of 70–100 nm for Surface Plasmon Resonance (SPR) enhancement.

Operating chemical looping process at mid-temperatures (550-750 oC) presents exciting potential for the stable production of hydrogen. However the reactivity of oxygen carriers is compromised by the detrimental effect of the relatively low temperatures on the redox kinetics. Although the reactivity at mid-temperature can be improved by the addition of noble metals the high cost of these noble metal containing materials significantly hindered their scalable application. In the current work we propose to incorporate earth-abundant metals into the iron-based spinel for hydrogen production in a chemical looping scheme at mid-temperatures. Mn0.2Co0.4Fe2.4O4 shows a high hydrogen production rate at the average rate of ∼0.62 mmol.g-1.min-1 and a hydrogen yield of ∼9.29 mmol.g-1 with satisfactory stability over 20 cycles at 550 oC. The mechanism studies manifest that the enhanced hydrogen production performance is a result of the improved oxygen-ion conductivity to enhance reduction reaction and high reactivity of reduced samples with steam. The performance of the oxygen carriers in this work is comparable to those noble-metal containing materials enabling their potential for industrial applications.

Searching for efficient and robust non-noble electrocatalysts for hydrogen generation is extremely desirable for future green energy systems. Here we present the synthesis of integrated Ni-P-S nanosheets array including Ni2P and NiS on nickel foam by a simple simultaneous phosphorization and sulfurization strategy. The resultant sample with optimal composition exhibits superior electrocatalytic performance for hydrogen evolution reaction (HER) in a wide pH range. In alkaline media it can generate current densities of 10 20 and 100 mA cm−2 at low overpotentials of only −101.9 −142.0 and −207.8 mV with robust durability. It still exhibits high electrocatalytic activities even in acid or neutral media. Such superior electrocatalytic performances can be mainly attributed to the synergistic enhancement of the hybrid Ni-P-S nanosheets array with integration microstructure. The kind of catalyst gives a new insight on achieving efficient and robust hydrogen generation.

Hydrogen and fuel cell technologies have experienced cycles of high expectations followed by impractical realities. This time around however falling renewable energy and fuel cell prices stringent climate change requirements and the discrete involvement of China are step changes. The combination of these factors is leading to realistic potential for hydrogen’s role in the Grand Transition.<br/>Having conducted exploratory interviews with leaders from all around the globe the World Energy Council is featuring eight use cases which illustrate hydrogen’s potential. These range from decarbonising hard-to-abate sectors such as heat industry and transport to supporting the integration of renewables and providing an energy storage solution.<br/>Dr Angela Wilkinson Secretary General and former Senior Director Scenarios and Business Insights: “Green and blue hydrogen can refresh those parts of the energy system transition that electrification cannot reach.”<br/>This Innovation Insights Brief is part of a series of publications by the World Energy Council focused on Innovation. In a fast-paced era of disruptive changes this brief aims at facilitating strategic sharing of knowledge between the Council’s members and the other energy stakeholders and policy shapers.

To identify the safety issues associated with hydrogen fuelling stations incidents at such stations in Japan and the USA were analyzed considering the regulations in these countries. Leakage due to the damage and fracture of main bodies of apparatuses and pipes in Japan and the USA is mainly caused by design error that is poorly planned fatigue. Considering the present incidents in these countries adequate consideration of the usage environment in the design is very important. Leakage from flanges valves and seals in Japan is mainly caused by screw joints. If welded joints are to be used in hydrogen fuelling stations in Japan strength data for welded parts should be obtained and pipe thicknesses should be reduced. Leakage due to other factors e.g. external impact in Japan and the USA is mainly caused by human error. To realize self-serviced hydrogen fuelling stations safety measures should be developed to prevent human error by fuel cell vehicle users.

The purpose of this research was to derive promising technologies for the transport of hydrogen fuel cells thereby supporting the development of research and development policy and presenting directions for investment. We also provide researchers with information about technology that will lead the technology field in the future. Hydrogen energy as the core of carbon neutral and green energy is a major issue in changing the future industrial structure and national competitive advantage. In this study we derived promising technology at the core of future hydrogen fuel cell transportation using the published US patent and paper databases (DB). We first performed text mining and data preprocessing and then discovered promising technologies through generative topographic mapping analysis. We analyzed both the patent DB and treatise DB in parallel and compared the results. As a result two promising technologies were derived from the patent DB analysis and five were derived from the paper DB analysis.