Publications

This paper gives a historical and technical overview of hydrogen storage vessels and details the specific issues and constraints of hydrogen energy uses. Hydrogen as an industrial gas is stored either as a compressed or as a refrigerated liquefied gas. Since the beginning of the last century hydrogen is stored in seamless steel cylinders. At the end of the 60s tubes also made of seamless steels were used; specific attention was paid to hydrogen embrittlement in the 70s. Aluminum cylinders were also used for hydrogen storage since the end of the 60s but their cost was higher compared to steel cylinders and smaller water capacity. To further increase the service pressure of hydrogen tanks or to slightly decrease the weight metallic cylinders can be hoop-wrapped. Then with specific developments for space or military applications fully-wrapped tanks started to be developed in the 80s. Because of their low weight they started to be used in for portable applications for vehicles (on-board storages of natural gas) for leisure applications (paint-ball) etc… These fully-wrapped composite tanks named types III and IV are now developed for hydrogen energy storage; the requested pressure is very high (from 700 to 1 000 bar) leads to specific issues which are discussed. Each technology is described in term of materials manufacturing technologies and approval tests. The specific issues due to very high pressure are depicted. Hydrogen can also be stored in liquid form (refrigerated liquefied gases). The first cryogenic vessels were used in the 60s. In the following the main characteristics of this type of storage will be indicated.

Efficient storage of hydrogen is crucial for the success of hydrogen energy markets (early markets as well as transportation market). Hydrogen can be stored either as a compressed gas a refrigerated liquefied gas a cryo-compressed gas or in hydrides. This paper gives an overview of hydrogen storage technologies and details the specific issues and constraints related to the materials behaviour in hydrogen and conditions representative of hydrogen energy uses. It is indeed essential for the development of applications requiring long-term performance to have good understanding of long-term behaviour of the materials of the storage device and its components under operational loads.

Cell immobilization and co-culture techniques have gained attention due to its potential to obtain high volumetric hydrogen productivities (Q_H2). Chitosan retained biomass in the fermentation of co-cultures of Caldicellulosiruptor saccharolyticus and C. owensensis efficiently up to a maximum dilution rate (D) of 0.9 h⁻¹. Without chitosan wash out of the co-culture occurred earlier accompanied with approximately 50% drop in Q_H2 (D > 0.4 h⁻¹). However butyl rubber did not show as much potential as carrier material; it did neither improve Q_H2 nor biomass retention in continuous culture. The population dynamics revealed that C. owensensis was the dominant species (95%) in the presence of chitosan whereas C. saccharolyticus was the predominant (99%) during cultivation without chitosan. In contrast the co-culture with rubber as carrier maintained the relative population ratios around 1:1. This study highlighted chitosan as an effective potential carrier for immobilization thereby paving the way for cost – effective hydrogen production.

The separation storage and recovery of hydrogen are key requirements for the efficient development of advanced hydrogen fuel technologies. The ideal hydrogen separation membrane should have high hydrogen permeability and good mechanical properties at a range of temperatures and pressures. Tantalum is a potential candidate with highest permeability to hydrogen among pure materials for hydrogen separation membrane. Isothermal as well as isobaric PCT equilibrium studies have been done in the temperature range of 673 – 873 K and hydrogen pressure range of 0.60 – 1.20 atmospheres for pure Ta and its solid solution alloys with Fe in different compositions. Results are presented.

Thermal hazards from an under-expanded (900 bar) hydrogen jet fire have been numerically investigated. The simulation results have been compared with the flame length and radiative heat flux measured for the horizontal jet fire experiment conducted at INERIS. The release blowdown characteristics have been modelled using the volumetric source as an expanded implementation of the notional nozzle concept. The CFD study employs the realizable k-ε model for turbulence and the Eddy Dissipation Concept for combustion. Radiation has been taken into account through the Discrete Ordinates (DO) model. The results demonstrated good agreement with the experimental flame length. Performance of the model shall be improved to reproduce the radiative properties dynamics during the first stage of the release (time < 10 s) whereas during the remaining blowdown time the simulated radiative heat flux at five sensors followed the trend observed in the experiment.

Fast depletion of fossil fuels and their detrimental effect to the environment is demanding an urgent need of alternative fuels for meeting sustainable energy demand with minimum environmental impact.  Expert studies indicate hydrogen is one of the most promising energy carriers for the future due to its superior combustion qualities and availability. The use of hydrogen in spark ignition internal combustion engine may be part of an integrated solution to the problem of depletion of fossil fuels and pollution of the environment. The broader flammability limits and fast flame propagation velocity of hydrogen ensures complete combustion of fuel and allows engine to be operated at lean ranges. Lean burn operation comparatively maintains NOx CO and HC emissions at a very low level. In the present work oxyhydrogen (HHO) gas is produced in leak proof plexiglass reactor by electrolysis of water using potassium hydroxide as electrolyte.  The HHO gas generator is attached to a spark ignition engine currently operating on the road without any modifications of the engine. The HHO gas produced is then added to the air which is being drawn into the engine.  Experiments were conducted on a 4-stroke single cylinder natural air cooled spark ignition engine to determine total fuel consumption specific fuel consumption air fuel ratio brake power and brake thermal efficiency and emissions CO CO₂ O2 NOx HC at different loads with and without addition of HHO gas to gasoline for lower speeds ranging from 700 rpm to 1500 rpm. Also mileage tests were conducted to find the speed at which the fuel consumption is optimum.

A possible consequence of pressurized hydrogen release is an under-expanded jet fire. Knowledge of the flame length radiative heat flux and fraction as well as the effects of variations in ground reflectance is important for safety assessment. The present study applies an open source CFD code FireFOAM to study the radiation characteristics of hydrogen and hydrogen/methane jet fires. For combustion the eddy dissipation concept for multi-component fuels recently developed by the authors in the large eddy simulation (LES) framework is used. The radiative heat is computed with the finite volume discrete ordinates model in conjunction with the weighted-sum-of-gray-gases model for the absorption/emission coefficient. The pseudo-diameter approach is used in which the corresponding parameters are calculated using the correlations of Birch et al. [22]. The predicted flame length and radiant fraction are in good agreement with the measurements of Schefer et al. [2] Studer et al. [3] and Ekoto et al. [6]. In order to account for the effects of variation in ground surface reflectance the emissivity of hydrogen flames was modified following Ekoto et al. [6]. Four cases with different ground reflectance are computed. The predictions show that the ground surface reflectance only has minor effect on the surface emissive power of the hydrogen jet fire. The radiant fractions fluctuate from 0.168 to 0.176 close to the suggested value of 0.16 by Ekoto et al.[6] based on the analysis of their measurements.

In this paper we analyze the potential factors affecting the hydrogen sulfide type of stress corrosion cracking in C110 casing pipes. In order to further study these cracking factors the methods of material property testing scanning electron microscopy XRD TEM and 3D ultra-depth-of-field were applied in the experiments. Besides that an HTHP autoclave was independently designed by the laboratory to simulate the actual corrosion environment and the potential factors affecting the stress corrosion cracking of C110 casing pipes were determined. The test results showed that the chemical composition metallographic structure hardness and non-metallic inclusions of the two types of C110 casing pipes were all qualified. In fact there remains a risk of stress corrosion cracking when the two kinds of C110 casing pipes serve under long-term field-working conditions. It is considered in this paper that the precipitates on the material surface stress damage and pitting corrosion are all critical factors affecting the stress corrosion cracking of casing pipes.

A key element in the safe operation of a modern gas distribution system is gas detection. The addition of hydrogen to natural gas will alter the characteristics of the fuel and therefore its impact on gas detection must be considered. It is important that gas detectors remain sufficiently sensitive to the presence of hydrogen and natural gas mixtures and that they do not lead to false readings. This paper presents analyses of work performed as part of the Office for Gas and Energy Markets (OFGEM) funded HyDeploy project on the response of various natural gas industry detectors to blended mixtures up to 20 volume percent (vol%) of hydrogen in natural gas. The scope of the detectors under test included survey instruments and personal monitors that are used in the gas industry. Four blend ratios were analysed (0 10 15 and 20 vol% hydrogen in natural gas). The laboratory testing undertaken investigated the following:

• Flammable response to blends in the ppm range (0-0.2 vol%);
• Flammable response to blends in the lower explosion limit range (0.2-5 vol%);
• Flammable response to blends in the volume percent range (5-100 vol%);
• Oxygen response to blends in the volume percent range (0-25 vol%); and
• Carbon monoxide response to blends in the ppm range (0-1000 ppm).

Catalytic and thermal conductivity based flammable detectors in the volume percent range are as expected affected in the form of a relative increase in output. All of the carbon monoxide detectors tested were found to be cross-sensitive to hydrogen in the blended mixtures tested at levels which have the potential to cause false alarms at current permissible leakage rates. In summary a number of measurement ranges across multiple detectors commonly used in the gas industry have been found to be cross-sensitive to hydrogen in natural gas blends to differing degrees. This required the HyDeploy project to select alternative instruments for the purpose of gas detection as part of the trial. This paper relates to the preparatory work to introduce hydrogen into the Keele closed network.

This paper describes validation of the computational fluid dynamics tool FLACS-Hydrogen. The validation study focuses on concentration and pressure data from vented deflagration experiments performed in 20-foot shipping containers as part of the project Improving hydrogen safety for energy applications through pre-normative research on vented deflagrations (HySEA) funded by the Fuel Cells and Hydrogen 2 Joint Undertaking (FCH 2 JU). The paper presents results for tests involving inhomogeneous hydrogen-air clouds generated from realistic releases performed during the HySEA project. For both experiments and simulations the peak overpressures obtained for the stratified mixtures are higher than those measured for lean homogeneous mixtures with the same amount of hydrogen. Using an in-house version of FLACS-Hydrogen with the numerical solver Flacs3 and improved physics models results in significantly improved predictions of the peak overpressures compared to the predictions by the standard Flacs2 solver. The paper includes suggestions for further improvements to the model system.