Russian Federation
Hydrogen Safety Aspects Related to High Pressure - PEM Water Electrolysis
Sep 2007
Publication
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.
Experimental Study of Hydrogen Releases Combustion
Sep 2009
Publication
The objectives of the presented experimental work were investigation of hydrogen release distribution and combustion modelling possible emergency situation at industry scale. Results of large scale experiments on distribution and combustion in an open and congested area are presented. The mass of hydrogen in experiments varied from 50g to 1000g with release rate from 180 to 220 g/s. Qualitative characteristics of high momentum hydrogen jet releases distribution and subsequent combustion were obtained. It is shown that obstacles slow down jet speed promote combustible mixture formation in a large volume and accelerate combustion process. The maximum overpressure in experiments with additional congested area reached ΔР = 0.4 atm. Using partial confinement of congested area turbulent combustion regime with the maximum overpressure more than 10 atm. was obtained.
Decarbonizing Russia: Leapfrogging from Fossil Fuel to Hydrogen
Jan 2022
Publication
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.
Experimental Study of Explosion Wave Propagation in Hydrogen-Air Mixtures of Variable Compositions
Sep 2009
Publication
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.
Syngas Explosion Reactivity in Steam Methane Reforming Process
Sep 2013
Publication
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.
Hydrogen Storage Performance of the Multi-principal-component CoFeMnTiVZr Alloy in Electrochemical and Gas–solid Reactions
Jun 2020
Publication
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.
Estimation of Uncertainty in Risk Assessment of Hydrogen Applications
Sep 2011
Publication
Hydrogen technologies such as hydrogen fuelled vehicles and refuelling stations are being tested in practice in a number of projects (e.g. HyFleet-Cute and Whistler project) giving valuable information on the reliability and maintenance requirements. In order to establish refuelling stations the permitting authorities request qualitative and quantitative risk assessments to show the safety and acceptability in terms of failure frequencies and respective consequences. For new technologies not all statistical data can be established or are available in good quality causing assumptions and extrapolations to be made. Therefore the risk assessment results contain varying degrees of uncertainty as some components are well established while others are not. The paper describes a methodology to evaluate the degree of uncertainty in data for hydrogen applications based on the bias concept of the total probability and the NUSAP concept to quantify uncertainties of new not fully qualified hydrogen technologies and implications to risk management.
Hydrogen-Air Explosive Envelope Behaviour in Confined Space at Different Leak Velocities
Sep 2009
Publication
The report summarizes experimental results on the mechanisms and kinetics of hydrogen-air flammable gas cloud formation and evolution due to foreseeable (less than 10-3 kg/sec) hydrogen leaks into confined spaces with different shapes sizes and boundary conditions. The goals were - 1) to obtain qualitative information on the basic gas-dynamic patterns of flammable cloud formation at different leak velocities (between 935 and 905 m/sec) for a fixed leak flowrate and 2) to collect quantitative data on spatial and temporal characteristics of the revealed patterns. Data acquisition was performed using a spatially distributed reconfigurable net of 24 hydrogen gauges with short response time. This experimental innovation permits to study spatial features of flammable cloud evolution in detail which previously was attainable only from CFD computations. Two qualitatively different gas dynamic patterns were documented for the same leak flowrate. In one limiting case (sufficiently low speed of leak) the overall gas-dynamic pattern can be described by the well-known “filling box” model. In another limited case (high velocity of leak) it is proposed to describe the peculiarities of gas-dynamic behavior of flammable cloud by the term of a “fading up box” model. From the safety view point the “fading up box” case is more hazardous than the “filling box” case. Differences in macroscopic and kinetic behavior which are essential for safety provision are presented. Empirical non-dimensional criterion for discrimination of the two revealed basic patterns for hydrogen leaks into confined spaces with comparable length scale is proposed. The importance of the revealed “fading up box” gas-dynamic pattern is discussed for development of an advanced hydrogen gauges system design and safety criteria.
Catalysts for Hydrogen Removal: Kinetic Paradox and Functioning at High Concentration of Hydrogen
Sep 2009
Publication
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.
A Comparison Exercise on the CFD Detonation Simulation in Large Scale Confined Volumes
Sep 2009
Publication
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.
Improvements in Two-Step Model of Hydrogen Detonative Combustion: Model Description and Sensitivity to its Parameters
Sep 2009
Publication
In the present paper the two-stage model of detonative combustion of hydrogen is presented. The following improvements are described: accurate description of the heat release stage of combustion; the clear physics-based procedure for calculation of the parameters of the proposed model; sample calculations of the detonation wave in hydrogen/air mixtures in wide range of conditions showing that the proposed model performs well in a wide range of conditions (pressures temperatures mixture compositions). The results of the 2D simulations of the detonation cell are presented for the hydrogen/oxygen/argon mixture as example to show the performance and accuracy of the model presented in this paper.
Full Suppression of Hydrogen Explosion Using Phlegmatization Additives- Experimental Results
Sep 2011
Publication
The paper presents results of experimental investigations of different phlegmatizator substances and its binary compounds used for full hydrogen combustion suppression. The work was performed in experimental facilities of three different scales (small medium and large) at normal initial pressure and temperature range 20 ⎯ 120 °С. Ten individual substances and six binary compounds were tested in a small scale experiments. Three individual halogen containing substances capable of full suppression of hydrogen combustion were found in a series of small scale experiments (tube length – 1 m ID – 66 mm). The minimum concentration of the most effective substance was 11% at 20°С and 14% at 120°С in a small scale experiments. Medium scale confined and large scale unconfined experiments confirmed the possibility of full combustion suppression. The minimum concentration of the most effective binary mixture was found to be 12 % at 20°С in a large scale experiments.
Safe Testing of Catalytic Devices in Hydrogen-Air Flow
Sep 2009
Publication
Any experimental study of catalysts and catalytic recombining devices for removal of hydrogen gas from industrial environments is known to carry a risk of ignition of hydrogen. Experiments conducted in an atmosphere with a high concentration of hydrogen present a particular danger. Here a technique is reported that allows conducting such experiments with relative safety. This technique has been developed and applied by the company ‘Russian Energy Technologies’ for the last five years without any significant incident.<br/>A “Gas stream method” for testing and analysis of the characteristics of a catalyst for hydrogen/oxygen recombination is proposed. Tests with a variety of catalysts in a passive recombining device were carried out in a climatic chamber (86 l in volume) with a hydrogen/air mixture containing up to 20% (v/v) hydrogen flowing through it. The balance equation for hydrogen and oxygen flows entering reacting and exiting the chamber led to a formula for calculating the efficiency of a catalyst or a catalytic device under stationary conditions.<br/>Fluctuations in local temperatures of the catalyst and other parts of the chamber along with variation in the concentration of hydrogen gave the authors an insight into the thermal regime of an active catalyst. This enabled them to develop new catalysts for removal of hydrogen from the environment using industrial recombining devices.
Hydrogen Self-Ignition In Pressure Relief Devices
Sep 2009
Publication
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.
High-pressure PEM Water Electrolysis and Corresponding Safety Issues
Sep 2009
Publication
In this paper safety considerations related to the operation of proton-exchange membrane (PEM) water electrolysers (hydrogen production capacity up to 1 Nm3/h and operating pressure up to 130 bars) are presented. These results were obtained in the course of the GenHyPEM project a research program on high-pressure PEM water electrolysis supported by the European Commission. Experiments were made using a high-pressure electrolysis stack designed for operation in the 0–130 bars pressure range at temperatures up to 90 °C. Besides hazards related to the pressure itself hydrogen concentration in the oxygen gas production and vice-versa (resulting from membrane crossover permeation effects) have been identified as the most significant risks. Results show that the oxygen concentration in hydrogen at 130 bars can be as high as 2.66 vol %. This is a value still outside the flammability limit for hydrogen–oxygen mixtures (3.9–95.8 vol %) but safety measures are required to prevent explosion hazards. A simple model based on the diffusion of dissolved gases is proposed to account for gas cross-permeation effects. To reduce contamination levels different solutions are proposed. First thicker membranes can be used. Second modified or composite membranes with lower gas permeabilities can be used. Third as reported earlier external catalytic gas recombiners can be used to promote H2/O2 recombination and reduce contamination levels in the gas production. Finally other considerations related to cell and stack design are also discussed to further reduce operation risks.
Performance-Based Requirements for Hydrogen Detection Allocation and Actuation
Sep 2009
Publication
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/>
Failure of PEM Water Electrolysis Cells: Case Study Involving Anode Dissolution and Membrane Thinning
Sep 2013
Publication
Polymer electrolyte membrane (PEM) water electrolysis is an efficient and environmental friendly method that can be used for the production of molecular hydrogen of electrolytic grade using zero-carbon power sources such as renewable and nuclear. However market applications are asking for cost reduction and performances improvement. This can be achieved by increasing operating current density and lifetime of operation. Concerning performance safety reliability and durability issues the membrane-electrode assembly (MEA) is the weakest cell component. Most performance losses and most accidents occurring during PEM water electrolysis are usually due to the MEA. The purpose of this communication is to report on some specific degradation mechanisms that have been identified as a potential source of performance loss and membrane failure. An accelerated degradation test has been performed on a MEA by applying galvanostatic pulses. Platinum has been used as electrocatalyst at both anode and cathode in order to accelerate degradation rate by maintaining higher cell voltage and higher anodic potential that otherwise would have occurred if conventional Ir/IrOx catalysts had been used. Experimental evidence of degradation mechanisms have been obtained by post-mortem analysis of the MEA using microscopy and chemical analysis. Details of these degradation processes are presented and discussed.
Effect of Hydrogen on the Deformation Behavior and Localization of Plastic Deformation of the Ultrafine-Grained Zr–1Nb Alloy
Oct 2020
Publication
In this paper comparison studies of the hydrogen effect on the structural and phase state deformation behavior and mechanical properties of the fine- (average grain size 4 µm) and ultrafine-grained (average element size 0.3 and 0.4 µm) Zr–1wt.%Nb (hereinafter Zr–1Nb) alloy under tension at temperatures in the range of 293–873 K were conducted. The formation of an ultrafine-grained structure is established to increase the strength characteristics of the Zr–1Nb alloy by a factor of 1.5–2 with a simultaneous reduction of its resistance to the localization of plastic deformation at the macro level and the value of deformation to failure. The presence of hydrogen in the Zr–1Nb alloy in the form of a solid solution and hydride precipitates increases its resistance to the localization of plastic deformation at the macro level if the alloy has an ultrafine-grained structure and decreases if the structure of the alloy is fine-grained. In the studied temperature range the Zr–1Nb alloy in the ultrafine-grained state has a higher resistance to hydrogen embrittlement than the alloy in the fine-grained state.
Integration of Experimental Facilities: A Joint Effort for Establishing a Common Knowledge Base in Experimental Work on Hydrogen Safety
Sep 2009
Publication
With regard to the goals of the European HySafe Network research facilities are essential for the experimental investigation of relevant phenomena for testing devices and safety concepts as well as for the generation of validation data for the various numerical codes and models. The integrating activity ‘Integration of Experimental Facilities (IEF)’ has provided basic support for jointly performed experimental work within HySafe. Even beyond the funding period of the NoE HySafe in the 6th Framework Programme IEF represents a long lasting effort for reaching sustainable integration of the experimental research capacities and expertise of the partners from different research fields. In order to achieve a high standard in the quality of experimental data provided by the partners emphasis was put on the know-how transfer between the partners. The strategy for reaching the objectives consisted of two parts. On the one hand a documentation of the experimental capacities has been prepared and analysed. On the other hand a communication base has been established by means of biannual workshops on experimental issues. A total of 8 well received workshops has been organised covering topics from measurement technologies to safety issues. Based on the information presented by the partners a working document on best practice including the joint experimental knowledge of all partners with regard to experiments and instrumentation was created. Preserving the character of a working document it was implemented in the IEF wiki website which was set up in order to provide a central communication platform. The paper gives an overview of the IEF network activities over the last 5 years.
On the Use of Hydrogen in Confined Spaces: Results from the Internal Project InsHyde
Sep 2009
Publication
Alexandros G. Venetsanos,
Paul Adams,
Inaki Azkarate,
A. Bengaouer,
Marco Carcassi,
Angunn Engebø,
E. Gallego,
Olav Roald Hansen,
Stuart J. Hawksworth,
Thomas Jordan,
Armin Keßler,
Sanjay Kumar,
Vladimir V. Molkov,
Sandra Nilsen,
Ernst Arndt Reinecke,
M. Stöcklin,
Ulrich Schmidtchen,
Andrzej Teodorczyk,
D. Tigreat,
N. H. A. Versloot and
L. Boon-Brett
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.
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