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A new spinelized Ni catalyst (Ni-UGSO) using Ni(NO₃)₂·6H₂O as the Ni precursor was prepared according to a less material intensive protocol. The support of this catalyst is a negative-value mining residue UpGraded Slag Oxide (UGSO) produced from a TiO2 slag production unit. Applied to dry reforming of methane (DRM) at atmospheric pressure T = 810 °C space velocity of 3400 mL/(h·g) and molar CO₂/CH₄ = 1.2 Ni-UGSO gives a stable over 168 h time-on-stream methane conversion of 92%. In this DRM reaction optimization study: (1) the best performance is obtained with the 10–13 wt% Ni load; (2) the Ni-UGSO catalysts obtained from two different batches of UGSO demonstrated equivalent performances despite their slight differences in composition; (3) the sulfur-poisoning resistance study shows that at up to 5.5 ppm no Ni-UGSO deactivation is observed. In steam reforming of methane (SRM) Ni-UGSO was tested at 900 °C and a molar ratio of H₂O/CH₄ = 1.7. In this experimental range CH4 conversion rapidly reached 98% and remained stable over 168 h time-on-stream (TOS). The same stability is observed for H₂ and CO yields at around 92% and 91% respectively while H₂/CO was close to 3. In mixed (dry and steam) methane reforming using a ratio of H₂O/CH₄ = 0.15 and CO2/CH4 = 0.97 for 74 h and three reaction temperature levels (828 °C 847 °C and 896 °C) CH₄ conversion remains stable; 80% at 828 °C (26 h) 85% at 847 °C (24 h) and 95% at 896 °C (24 h). All gaseous streams have been analyzed by gas chromatography. Both fresh and used catalysts are analyzed by scanning electron microscopy-electron dispersive X-ray spectroscopy (SEM-EDXS) X-ray diffraction (XRD) and thermogravimetric analysis (TGA) coupled with mass spectroscopy (MS) and BET Specific surface. In the reducing environment of reforming such catalytic activity is mainly attributed to (a) alloys such as FeNi FeNi3 and Fe3Ni2 (reduction of NiFe2O4 FeNiAlO4) and (b) to the solid solution NiO-MgO. The latter is characterized by a molecular distribution of the catalytically active Ni phase while offering an environment that prevents C deposition due to its alkalinity.

Currently hydrogen production is based on the reforming process leading to the emission of pollutants; therefore a substitute production method is imminently required. Water electrolysis is an ideal alternative for large-scale hydrogen production as it does not produce any carbon-based pollutant byproducts. The production of green hydrogen from water electrolysis using intermittent sources (e.g. solar and eolic sources) would facilitate clean energy storage. However the electrocatalysts currently required for water electrolysis are noble metals making this potential option expensive and inaccessible for industrial applications. Therefore there is a need to develop electrocatalysts based on earth-abundant and low-cost metals. Nickel-based electrocatalysts are a fitting alternative because they are economically accessible. Extensive research has focused on developing nickel-based electrocatalysts for hydrogen and oxygen evolution. Theoretical and experimental work have addressed the elucidation of these electrochemical processes and the role of heteroatoms structure and morphology. Even though some works tend to be contradictory they have lit up the path for the development of efficient nickel-based electrocatalysts. For these reasons a review of recent progress is presented herein.

When hydrogen flows through a small finite length constant exit area nozzle the viscous effects create a fluid throat which acts as a converging-diverging nozzle and lead to Mach number greater than one at the exit if the jet is under-expanded. This phenomenon influences the mass flow rate and the dispersion cloud size. In this study the boundary layer effect on the unsteady hydrogen sonic jet flow through a 1 mm diameter pipe from a high pressure reservoir (up to 70 MPa) is studied using computational fluid dynamics with a large eddy simulation turbulence model. This viscous flow simulation is compared with a non-viscous simulation to demonstrate that the velocity is supersonic at the exit of a small exit nozzle and that the mass flow is reduced.

The use of high-fidelity simulation methods based on large-eddy simulation (LES) are proving useful for understanding and mitigating the safety hazards associated with hydrogen releases from nuclear power plants. However accurate modelling of turbulent premixed hydrogen flames via LES can require very high resolution to capture both the large-scale turbulence and its interaction with the flame fronts. Standard meshing strategies can result in impractically high computational costs especially for the thin fronts of hydrogen flames. For these reasons the use of a recently formulated integral length scale approximation (ILSA) subfilter-scale model in combination with an efficient anisotropic block-based adaptive mesh refinement (AMR) technique is proposed and examined herein for performing LES of turbulent premixed hydrogen flames. The anisotropic AMR method allows dynamic and solution-dependent resolution of flame fronts and the grid-independent properties of the ILSA model ensure that numerical errors associated with implicitly-filtered LES techniques in regions with varying resolution are avoided. The combined approach has the potential to allow formally converged LES solutions (direct numerical simulation results are typically reached in the limit of very fine meshes with standard subgrid models). The proposed LES methodology is applied to combustion simulations of lean premixed hydrogen-air mixtures within closed vessels: a problem relevant to hydrogen safety applications in nuclear facilities. A progress variable-based method with a multi-phenomena burning velocity model is used as the combustion model. The present simulation results are compared to the available experiment data for several previously studied THAI vessel cases and the capabilities of the proposed LES approach are assessed.

During the early phase of the transient process following a hydrogen leak into the atmosphere a contact surface appears separating air heated by the leading shock from hydrogen cooled by expansion. Locally the interface is approximately planar. Diffusion leads to a temperature decrease on the air side and an increase in the hydrogen-filled region and mass diffusion of hydrogen into air and of air into hydrogen potentially resulting in ignition. This process was analyzed by Li ˜nan and Crespo [1] for unity Lewis number and Li ˜nan and Williams [2] for Lewis number less than unity. We included in the analysis the effect of a slow expansion [3 4] leading to a slow drop in temperature which occurs in transient jets. Chemistry being very temperature-sensitive the reaction rate peaks close to the hot side of the interface where only a small fuel concentration present close to the warm air-rich side which depends crucially upon the fuel Lewis number. For Lewis number unity the fuel concentration due to diffusion is comparable to the rate of consumption by chemistry. If the Lewis number is less than unity diffusion brings in more fuel than temperature-controlled chemistry consumes. For a Lewis number greater than unity diffusion is not strong enough to bring in as much fuel as chemistry would burn; combustion is controlled by fuel diffusion. If the temperature drop due to expansion associated with the multidimensional jet does not lower significantly the reaction rate up to that point analysis shows that ignition in the jet takes place. For fuel Lewis number greater than unity chemistry does not lead to a defined explosion so that eventually expansion will affect the process; ignition does not take place [3 4]. In the current paper these results are extended to consider multistep chemical kinetics but for otherwise similar assumptions. High activation energy is no longer applicable. Instead results are obtained in the short time limit still as a perturbation superimposed to the self-similar solution to the chemically frozen diffusion solution. In that approximation the initiation step which consumes fuel and oxidant is taken to be slow compared with steps that consume one of the reactants and an intermediate species. The formulation leads to a two point boundary value problem for set of coupled rate equations plus an energy equation for perturbations. These equations are linear with variable co-effcients. The coupled problem is solved numerically using a split algorithm in which chemical reaction is solved for frozen diffusion while diffusion is solved for frozen chemistry. At each time step the still coupled linear problem is solved exactly by projecting onto the eigenmodes of the stiff matrix so that the solution is unaffected by stiffness. Since in the short time limit temperature is only affected at the perturbation level the matrix depends only on the similarity variable x t but it is otherwise time-independent. As a result determination of the eigenvalues and eigenvectors is only done once (using Maple) for the entire range of discretized values of the similarity variable. The diffusion problem consists of a set of independent equations for each species. Each of these is solved using orthogonal decomposition onto Hermite polynomials for the homogeneous part plus a particular solution proportional to time for the non-homogeneous (source) terms. That approach can be implemented for different kinetic schemes.

On October 16-17 2012 the International Association for Hydrogen Safety (HySafe) in cooperation with the Institute for Energy and Transport of the Joint Research Centre of the European Commission (JRC IET Petten) held a two-day workshop dedicated to Hydrogen Safety Research Priorities. The workshop was hosted by Federal Institute for Materials Research and Testing (BAM) in Berlin Germany. The main idea of the Workshop was to bring together stakeholders who can address the existing knowledge gaps in the area of the hydrogen safety including identification and prioritization of such gaps from the standpoint of scientific knowledge both experimental and theoretical including numerical. The experience highlighting these gaps which was obtained during both practical applications (industry) and risk assessment should serve as reference point for further analysis. The program included two sections: knowledge gaps as they are addressed by industry and knowledge gaps and state-of-the-art by research. In the current work the main results of the workshop are summarized and analysed.

The heat transfer analysis in the filling process of compressed on-board hydrogen storage tank has been the focus of hydrogen storage research. The initial conditions mass flow rate and heat transfer coefficient have certain influence on the hydrogen filling performance. In this paper the effects of mass flow rate and heat transfer coefficient on hydrogen filling performance are mainly studied. A thermodynamic model of the compressed hydrogen storage tank was established by Matlab/Simulink. This 0D model is utilized to predict the hydrogen temperature hydrogen pressure tank wall temperature and SOC (State of Charge) during filling process. Comparing the simulated results with the experimental data the practicability of the model can be verified. The simulated results have certain meaning for improving the hydrogenation parameters in real filling process. And the model has a great significance to the study of hydrogen filling and purification.

This paper describes experimental and numerical modelling results from an investigation into the flammability profiles associated with high pressure hydrogen jets released in close proximity to surfaces. This work was performed under a Transnational Access Agreement activity funded by the European Research Infrastructure project H2FC.<br/>The experimental programme involved ignited and unignited releases of hydrogen at pressures of 150 and 425 barg through nozzles of 1.06 and 0.64 mm respectively. The proximity of the release to a ceiling or the ground was varied and the results compared with an equivalent free-jet test. During the unignited experiments concentration profiles were measured using hydrogen sensors. During the ignited releases thermal radiation was measured using radiometers and an infra-red camera. The results show that the flammable volume and flame length increase when the release is in close proximity to a surface. The increases are quantified and the safety implications discussed.<br/>Selected experiments were modelled using the CFD model FLACS for validation purposes and a comparison of the results is also included in this paper. Similarly to experiments the CFD results show an increase in flammable volume when the release is close to a surface. The unstable atmospheric conditions during the experiments are shown to have a significant impact on the results.

The current study addresses the spontaneous ignition of hydrogen jets released into a confined oxidizer environment experimentally. The experiments are conducted in a shock tube where hydrogen gas is shock-accelerated into oxygen across a perforated plate. The operating conditions and hole dimension of the plate were varied in order to identify different flow field and ignition scenarios. Time resolved Schlieren visualization permitted to reconstruct the gasdynamic evolution of the release and different shock interactions. Time resolved self-luminosity records permitted us to record whether ignition was achieved and also to record the dimension of the turbulent mixing layer. The ignition limits determined experimentally in good agreement with the 1D diffusion ignition model proposed by Maxwell and Radulescu. Nevertheless the experiments demonstrated that the mixing layer is two to three orders of magnitude thicker than predicted by molecular diffusion which can be attributed to the observed mixing layer instabilities and shock-mixing layer interactions which provide a much more intense mixing rate than anticipated from previous and current numerical predictions. These observations further clarify why releases through partly confined geometries are more conducive to jet ignition of the jets.

The scenario of detonative ignition in shocked mixture is significant because it is a contributor to deflagration to detonation transition for example following shock reflections. However even in one dimension simulation of ignition between a contact surface or a flame and a shock moving into a combustible mixture is difficult because of the singular nature of the initial conditions. Initially as the shock starts moving into reactive mixture the region filled with reactive mixture has zero thickness. On a fixed grid the number of grid points between the shock and the contact surface increases as the shock moves away from the latter. Due to initial lack of resolution in the region of interest staircasing may occur whereby the resulting plots consist of jumps between few values a few grid points and these numerical artifacts are amplified by the chemistry which is very sensitive to temperature leading to unreliable results. The formulation is transformed replacing time and space by time and space over time as the independent variables. This frame of reference corresponds to the self-similar formulation in which the non-reactive problem remains stationary and the initial conditions are well-resolved. Additionally a solution obtained from short time perturbation is used as initial condition at a time still short enough for the perturbation to be very accurate but long enough so that there is sufficient resolution. The numerical solution to the transformed problem is obtained using an essentially non-oscillatory algorithm which is adequate not only for the early part of the process but also for the latter part when chemistry leads to appearance of a shock and eventually a detonation wave is formed. A validation study was performed and the results were compared with the literature for single step Arrhenius chemistry. The method and its implementation were found to be effective. Results are presented for values of activation energy ranging from mild to stiff.