Russian Federation

The use of hydrogen as an energy carrier is going to widen exponentially in the next years. In order to ensure the public acceptance of the new fuel not only the environmental impact has to be excellent but also the risk management of its handling and storage must be improved. As a part of modern risk assessment procedure CFD modeling of the accident scenario development must provide reliable data on the possible pressure loads resulted from explosion processes. The expected combustion regimes can be ranged from slow flames to deflagration-to-detonation transition and even to detonation. In the last case the importance of the reliability of simulation results is particularly high since detonation is usually considered as a worst case state of affairs. A set of large-scale detonation experiments performed in Kurchatov Institute at RUT facility was selected as benchmark. RUT has typical industry-relevant characteristic dimensions. The CFD codes possibilities to correctly describe detonation in mixtures with different initial and boundary conditions were surveyed. For the modeling two detonation tests HYD05 and HYD09 were chosen; both tests were carried out in uniform hydrogen/air mixtures; first one with concentration of 20.0% vol. and the second one with 25.5% vol. In the present exercise three CFD codes using a number of different models were used to simulate these experiments. A thorough inter-comparison between the CFD results including codes models and obtained pressure predictions was carried out and reported. The results of this inter comparison should provide a solid basis for the further code development and detonation models’ validation thus improving CFD predictive capabilities.

Results are given of experimental study of propagation of explosion waves in hydrogen-air mixtures of different compositions under conditions of cumulation. The investigations are performed in a setup consisting of two parts namely the upper part in the form of a metal cone and the lower part in the form of a rubber envelope hermetically attached to the cone. The upper and lower parts of the experimental setup are separated by a thin rubber film and may be filled with hydrogen-air mixtures of different compositions.

High susceptibility to cold cracking induced by diffusible hydrogen and hydrogen embrittlement are major obstacles to greater utilization of underwater wet welding for high-strength steels. The aim of the research was to develop gas–slag systems for flux-cored wires that have high metallurgical activity in removal of hydrogen and hydroxyl groups. Thermodynamic modeling and experimental research confirmed that a decrease in the concentration of diffusible hydrogen can be achieved by reducing the partial pressure of hydrogen and water vapor in the vapor–gas bubble and by increasing the hydroxyl capacity of the slag system in metallurgical reactions leading to hydrogen fluoride formation and ionic dissolution of hydroxyl groups in the basic fluorine-containing slag of a TiO2–CaF₂–Na₃AlF₆ system.

Bamboo-like nitrogen-doped carbon nanotubes (N-CNTs) were used to synthesize supported palladium catalysts (0.2–2 wt.%) for hydrogen production via gas phase formic acid decomposition. The beneficial role of nitrogen centers of N-CNTs in the formation of active isolated palladium ions and dispersed palladium nanoparticles was demonstrated. It was shown that although the surface layers of N-CNTs are enriched with graphitic nitrogen palladium first interacts with accessible pyridinic centers of N-CNTs to form stable isolated palladium ions. The activity of Pd/N-CNTs catalysts is determined by the ionic capacity of N-CNTs and dispersion of metallic nanoparticles stabilized on the nitrogen centers. The maximum activity was observed for the 0.2% Pd/N-CNTs catalyst consisting of isolated palladium ions. A ten-fold increase in the concentration of supported palladium increased the contribution of metallic nanoparticles with a mean size of 1.3 nm and decreased the reaction rate by only a factor of 1.4.

The liquid organic hydrogen carriers (LOHC) are aromatic molecules which can be considered as an attractive option for the storage and transport of hydrogen. A considerable amount of hydrogen up to 7–8% wt. can be loaded and unloaded with a reversible chemical reaction. Substituted quinolines and pyridines are available from petroleum coal processing and wood preservation or they can be synthesized from aniline. Quinolines and pyridines can be considered as potential LOHC systems provided they have favorable thermodynamic properties which were the focus of this current study. The absolute vapor pressures of methyl-quinolines were measured using the transpiration method. The standard molar enthalpies of vaporization of alkyl-substituted quinolines and pyridines were derived from the vapor pressure temperature dependencies. Thermodynamic data on vaporization and formation enthalpies available in the literature were collected evaluated and combined with our own experimental results. The theoretical standard molar gas-phase enthalpies of formation of quinolines and pyridines calculated using the quantum-chemical G4 methods agreed well with the evaluated experimental data. Reliable standard molar enthalpies of formation in the liquid phase were derived by combining high-level quantum chemistry values of gas-phase enthalpies of formation with experimentally determined enthalpies of vaporization. The liquid-phase hydrogenation/dehydrogenation reaction enthalpies of alkyl-substituted pyridines and quinolines were calculated and compared with the data for other potential liquid organic hydrogen carriers. The comparatively low enthalpies of reaction make these heteroaromatics a seminal LOHC system.

Today it is not known – neither qualitatively not quantitatively - how large the impact can be of the promoters on sensitivity to hydrogen-air detonation in hypothetical accidents at hydrogen-containing installations transport or storage facilities. Report goal is to estimate theoretically an effect of hydrogen-peroxide (as representative promoter) on sensitivity to detonation of the stoichiometric hydrogen-oxygen gas mixtures. The classical H₂-O2-Ar (2:1:7) gas mixture was chosen as reference system with the well established and unambiguously interpreted experimental data. In kinetic simulations it was found that the ignition delay time is sensitive to H₂O₂addition for small initial H₂O₂concentrations and is nearly constant for the large ones. Parametric reactive CFD studies of two dimensional cellular structure of 2H₂-O₂-7Ar-H₂O₂ detonations with variable hydrogen peroxide concentration (up to 10 vol.%) were also performed. Two un-expected results were obtained. First result: detonation cell size is practically independent upon variation of initial hydrogen peroxide concentration. For practical applications it means that presence of hydrogen-peroxide did not change drastically sensitivity of the stoichiometric hydrogen-oxygen gas mixtures. These theoretical speculations require an experimental verification. Second result: for large enough initial H₂O₂concentrations (> 1 vol.% at least) a new element of cellular structure of steady detonation wave was revealed. It is a system of multiple secondary longitudinal shock waves (SLSW) which propagates in the direction opposite to that of the leading shock wave. Detailed mechanism of SLSW formation is proposed.

PEM water electrolysis offers an efficient and flexible way to produce “green-hydrogen” from renewable (intermittent) energy sources. Most research papers published in the open literature on the subject are addressing performances issues and to date very few information is available concerning the mechanisms of performance degradation and the associated consequences. Results reported in this communication have been used to analyze the failure mechanisms of PEM water electrolysis cells which can ultimately lead to the destruction of the electrolyzer. A two-step process involving firstly the local perforation of the solid polymer electrolyte followed secondly by the catalytic recombination of hydrogen and oxygen stored in the electrolysis compartments has been evidenced. The conditions leading to the onset of such mechanism are discussed and some preventive measures are proposed to avoid accidents.

We examine a different approach to complete the decarbonization of the Russian economy in a world where climate policy increasingly requires the radical reduction of emissions wherever possible. We propose an energy system that can supply solar and wind-generated electricity to fulfill demand and which accounts for intermittency problems. This is instead of the common approach of planning for expensive carbon capture and storage and a massive increase in energy efficiency and therefore a drastic reduction in energy use per unit of Gross Domestic Product (GDP). Coupled with this massive increase in alternative energy we also propose using excess electricity to generate green hydrogen. Hydrogen technology can function as storage for future electricity needs or for potential fuel use. Importantly green hydrogen can potentially be used as a replacement export for Russia’s current fossil fuel exports. The analysis was carried out using the highly detailed modeling framework the High-Resolution Renewable Energy System for Russia (HIRES-RUS) representative energy system. The modeling showed that there are a number of feasible combinations of wind and solar power generation coupled with green hydrogen production to achieve 100% decarbonization of the Russian economy.

In future pressure relief devices (PRDs) should be installed on hydrogen vehicles to prevent a hydrogen container burst in the event of a nearby fire. Weakening of the container at elevated temperature could result in such burst. In this case the role of a PRD is to release some or all of the system fluid in the event of an abnormally high pressure. The paper analyzes the possibility of hydrogen self-ignition at PRD operation and ways of its prevention.

The single-phase multi-principal-component CoFeMnTiVZr alloy was obtained by rapid solidification and examined by a combination of electrochemical methods and gas–solid reactions. X-ray diffraction and high-resolution transmission electron microscopy analyses reveal a hexagonal Laves-phase structure (type C14). Cyclic voltammetry and electrochemical impedance spectroscopy investigations in the hydrogen absorption/desorption region give insight into the absorption/desorption kinetics and the change in the desorption charge in terms of the applied potential. The thickness of the hydrogen absorption layer obtained by the electrochemical reaction is estimated by high-resolution transmission electron microscopy. The electrochemical hydrogen storage capacity for a given applied voltage is calculated from a series of chronoamperometry and cyclic voltammetry measurements. The selected alloy exhibits good stability for reversible hydrogen absorption and demonstrates a maximum hydrogen capacity of ∼1.9 wt% at room temperature. The amount of hydrogen absorbed in the gas–solid reaction reaches 1.7 wt% at 298 K and 5 MPa evidencing a good correlation with the electrochemical results.

This paper describes hydrogen self-ignition as a result of the formation of a shock wave in front of a high-pressure hydrogen gas propagating in the tube and the semi-confined space for which the numerical and experimental investigation was done. An increase in the temperature behind the shock wave leads to the ignition on the contact surface of the mixture of combustible gas with air. The required condition of combustible self-ignition is to maintain the high temperature in the mixture for a time long enough for inflammation to take place. Experimental technique was based on a high-pressure chamber inflating with hydrogen burst disk failure and pressurized hydrogen discharge into tube of round or rectangular cross section filled with air. A physicochemical model involving the gas dynamic transport of a viscous gas the detailed kinetics of hydrogen oxidation k-ω differential turbulence model and the heat exchange was used for calculations of the self-ignition of high-pressure hydrogen. The results of our experiments and model calculations show that self-ignition in the emitted jet takes place. The stable development of self-ignition naturally depends on the orifice size and the pressure in the vessel a decrease in which leads to the collapse of the ignition process. The critical conditions are obtained.

We use a detailed solid oxide fuel cell (SOFC) model for micro-grid applications to analyze the effect of failure and degradation on system performance. Design and operational constraints on a component and system level are presented. A degrees of freedom analysis identifies controlled and manipulated system variables which are important for control. Experimental data are included to model complex degradation phenomena of the SOFC unit. Rather than using a constant value a spatially distributed degradation rate as function of temperature and current density is used that allows to study trajectory based performance deterioration. The SOFC unit is assumed to consist of multiple stacks. The failure scenario studied is the loss of one individual SOFC stack e.g. due to breakage of sealing or a series of fuel cells. Simulations reveal that degradation leads to significant drifts from the design operating point. Moreover failure of individual stacks may bring the still operating power generation unit into a regime where further failures and accelerated degradation is more likely. It is shown that system design dimensioning operation and control are strongly linked. Apart from specific quantitative results perhaps the main practical contribution are the collected constraints and the degrees of freedom analysis.

Polymer electrolyte membrane (PEM) water electrolysis has demonstrated its potentialities in terms of cell efficiency (energy consumption ≈ 4.0-4.2 kW/Nm3 H2) and gas purity (> 99.99% H2). Current research activities are aimed at increasing operating pressure up to several hundred bars for direct storage of hydrogen in pressurized vessels. Compared to atmospheric pressure electrolysis high-pressure operation yields additional problems especially with regard to safety considerations. In particular the rate of gases (H2 and O2) cross-permeation across the membrane and their water solubility both increase with pressure. As a result gas purity is affected in both anodic and cathodic circuits and this can lead to the formation of explosive gas mixtures. To prevent such risks two different solutions reported in this communication have been investigated. First the chemical modification of the solid polymer electrolyte in order to reduce cross-permeation phenomena. Second the use of catalytic H2/O2 recombiners to maintain H2 levels in O2 and O2 levels in H2 at values compatible with safety requirements.

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

Hydrogen energy is very promising as it ensures a high efficiency and ecological cleanliness of energy conversion. The goal of the present work is to provide the analysis of hydrogen safety aspects and to prescribe methods of safety operation with hydrogen. The authors conducted a hazard analysis of hydrogen operation and storage in comparison with other fuels. Good ventilation is the main hydrogen operation requirement. Besides an effective way of protection against propagation of hazards (for instance leaks) is neutralization of dangerous hydrogen-air mixtures by a method of controlled catalytic combustion inside special devices so-called recombiners [1-3]. The basis of these devices is a high porosity cell material (HPCM) activated by platinum deposition. Apart from recombiners HPCM was also applied for development of hydrogen detectors intended for measurement and analysis of hydrogen concentration for hydrogen-driven transport and objects of hydrogen infrastructure (including vapor-air media at high pressure and  temperatures). A system of hydrogen safety based on hydrogen detectors and hydrogen catalytic recombiners was developed. Experimental and theoretical studies of hydrogen combustion processes heat- and mass transfer and also gas flows in catalytic-activated HPCM allowed for a design optimization of recombiners and their location. Pilot hydrogen detectors and hydrogen catalytic recombiners were fabricated and their laboratory tests were successfully performed. Thus it was indicated that on condition of following the  appropriate passive and active safety measures hydrogen is just as safe as the other fuels. This conclusion represents another incentive for a transition to the hydrogen energy.

The paper presents an overview of the main achievements of the internal project InsHyde of the HySafe NoE. The scope of InsHyde was to investigate realistic small-medium indoor hydrogen leaks and provide recommendations for the safe use/storage of indoor hydrogen systems. Additionally InsHyde served to integrate proposals from HySafe work packages and existing external research projects towards a common effort. Following a state of the art review InsHyde activities expanded into experimental and simulation work. Dispersion experiments were performed using hydrogen and helium at the INERIS gallery facility to evaluate short and long term dispersion patterns in garage like settings. A new facility (GARAGE) was built at CEA and dispersion experiments were performed there using helium to evaluate hydrogen dispersion under highly controlled conditions. In parallel combustion experiments were performed by FZK to evaluate the maximum amount of hydrogen that could be safely ignited indoors. The combustion experiments were extended later on by KI at their test site by considering the ignition of larger amounts of hydrogen in obstructed environments outdoors. An evaluation of the performance of commercial hydrogen detectors as well as inter-lab calibration work was jointly performed by JRC INERIS and BAM. Simulation work was as intensive as the experimental work with participation from most of the partners. It included pre-test simulations validation of the available CFD codes against previously performed experiments with significant CFD code inter-comparisons as well as CFD application to investigate specific realistic scenarios. Additionally an evaluation of permeation issues was performed by VOLVO CEA NCSRD and UU by combining theoretical computational and experimental approaches with the results being presented to key automotive regulations and standards groups. Finally the InsHyde project concluded with a public document providing initial guidance on the use of hydrogen in confined spaces.

Some aspects of damage accumulation modelling and brittle fracture processes mechanisms under the combined effect of mechanical loading and hydrogen has been discussed in the article. New mechanism of brittle fracture for metallic materials based on dislocation and phonon structure fingerprints and lattice hydrogen content under the static and dynamic loading at low temperature condition has been proposed. The mechanism based on theoretical research and experimental and numerical studies. The experiments include the energy spectrum of internal friction determination and impact toughness testing for low-temperature brittle-ductile transition revealing. The numerical study based on damage accumulation modeling under the influence of up-hill diffusion in the elastic-plastic problem of solid state by finite element method. A new simple activation model of low temperature and hydrogen influence on damage accumulation process has been proposed. The model shows the rate of damage strong dependence of stress level and hydrogen content and test temperature. The combination of low temperature and high hydrogen content is most dangerous so the weld structures in extreme environment such as the Arctic and Subarctic regions have a high risk of breakage. So it is possible to estimate the energy and phonon spectrum of crystal lattice and predict the properties of microcrystalline and nanostructured materials with the high cold-short threshold on the base of such the approach. There are the recommendations propose to improve the cold resistance of steels and alloys by controlling the characteristics of the dislocation structure of new materials with polycrystalline and ultrafine-grained structure.

Regularities of steel structure degradation of the “Novopskov-Aksay-Mozdok” gas main pipelines (Nevinnomysskaya CS) as well as the “Gorky-Center” pipelines (Gavrilovskaya CS) were studied. The revealed peculiarities of their degradation after long-term operation are suggested to be treated as a particular case of the damage accumulation classification (scheme) proposed by prof. H.M. Nykyforchyn. It is shown that the fracture surface consists of sections of ductile separation and localized zones of micro-spalling. The presence of the latter testifies to the hydrogen-induced embrittlement effect. However the steels under investigation possess sufficiently high levels of the mechanical properties required for their further safe exploitation both in terms of durability and cracking resistance.

Pipeline failure caused by Hydrogen-Induced Cracking (HIC) also known as Hydrogen Embrittlement (HE) is a pressing issue for the oil and natural gas industry. Bursts in pipelines are devastating and extremely costly. The explosive force of a bursting pipe can inflict fatal injuries to workers while the combined loss of product and effort to repair are highly costly to producers. Further pipeline failures due to HIC have a long lasting impact on the surrounding environment. Safe use and operation of such pipelines depend on a good understanding of the underlying forces that cause HIC. Specifically a reliable way to predict the growth rate of hydrogen-induced cracks is needed to establish a safe duration of service for each length of pipeline. Pipes that have exceeded or are near the end of their service life can then be retired before the risk of HIC-related failures becomes too high. However little is known about the mechanisms that drive HIC. To date no model has been put forth that accurately predicts the growth rate of fractures due to HIC under extreme pressures such as in the context of natural gas and petroleum pipelines. Herein a mathematical model for the growth of fractures by HIC under extreme pressures is presented. This model is derived from first principles and the results are compared with other models. The implications of these findings are discussed and a description of future work based on these findings is presented.

We have demonstrated that the strength of produced flexible quartz capillaries can be high enough to withstand the internal hydrogen pressure up to 233 MPa at normal and cryogenic temperature. According to the experimental results the cryo-compressed storage of hydrogen in the capillaries at moderate pressure can enable one to reach DOE 2015 aims for the gravimetric and volumetric capacities of vessels for the safe mobile hydrogen storage. Furthermore flexible capillaries in a bundle can probably serve as a high-pressure pipes for the transportation of gases over long distances. The developed technology of hydrogen storage can be applied to methane and hythane (H₂ - CH₄ mixture) which bridge the gap between conventional fossil fuels and the clean future of a hydrogen economy. It can be also applied to other gases i.e. air oxygen and helium-oxygen mixtures widely used in autonomic breathing devices.

During the synthesis of hydrogen by methane steam reforming mixtures composed of H2 CH4 CO and CO2 are produced in the process. In this work the explosion reactivity of these mixtures on the basis of detonation cell size and laminar flame speed is calculated using a reactant assimilation simplification and a kinetic approach. The detonation cells width are calculated using the Cell_CH Kurchatov institute method and the laminar flame velocities are calculated with Chemkin Premix using different detailed chemical kinetic mechanisms. These calculations are used to define if these mixtures could be considered having a medium or a high reactivity for risk assessment in case of leak in the hydrogen plants.

This study focuses on structural imperfections caused by hydrogen impurities in AlN thin films obtained using atomic layer deposition method (ALD). Currently there is a severe lack of studies regarding the presence of hydrogen in the bulk of AlN films. Fourier-transform infrared spectroscopy (FTIR) is one of the few methods that allow detection bonds of light elements in particular - hydrogen. Hydrogen is known to be a frequent contaminant in AlN films grown by ALD method it may form different bonds with nitrogen e.g. amino (–NH2) or imide (–NH) groups which impair the quality of the resulting film. Which is why it is important to investigate the phenomenon of hydrogen as well as to search for the suitable methods to eliminate or at least reduce its quantity. In this work several samples have been prepared using different precursors substrates and deposition parameters and characterized using FTIR and additional techniques such as AFM XPS and EDS to provide a comparative and comprehensive analysis of topography morphology and chemical composition of AlN thin films.

At the present stage of electric power industry development special attention is being paid to the development and research of new efficient energy sources. The use of hydrogen fuel cells is promising for remote autonomous power supply systems. The authors of the paper have developed the structure and determined the optimal composition of a hybrid generation system based on hydrogen fuel cells and battery storage and have conducted studies of its operating modes and for remote consumers’ power supply efficiency. A simulation of the electromagnetic processes was carried out to check the operability of the proposed hybrid generation system structure. The simulation results confirmed the operability of the structure under consideration the calculation of its parameters reliability and the high quality of the output voltage. The electricity cost of a hybrid generation system was estimated according to the LCOE (levelized cost of energy) indicator its value being 1.17 USD/kWh. The factors influencing the electricity cost of a hydrogen generation system have been determined and ways for reducing its cost identified.

In this research we conducted water electrolysis experiments of a carbon black (CB) based sodium sulfate electrolyte using a Hoffman voltameter. The main objective was to investigate hydrogen production in such systems as well as analyse the electrical properties and thermal properties of nanofluids. A halogen lamp mimicking solar energy was used as a radiation source and a group of comparative tests were also conducted with different irradiation areas. The results showed that by using CB and light it was possible to increase the hydrogen production rate. The optimal CB concentration was 0.1 wt %. At this concentration the hydrogen production rate increased by 30.37% after 20 min of electrolysis. Hence we show that using CB in electrolytes irradiated by solar energy could save the electrical energy necessary for electrolysis processes.