Russian Federation

Simulation of hydrogen-air mixture explosions in a closed large-scale vessel with uniform and nonuniform mixture compositions was performed by the group of partners within the EC funded project “Hydrogen Safety as an Energy Carrier” (HySafe). Several experiments were conducted previously by Whitehouse et al. in a 10.7 m3 vertically oriented (5.7-m high) cylindrical facility with different hydrogen-air mixture compositions. Two particular experiments were selected for simulation and comparison as a Standard Benchmark Exercise (SBEP) problem: combustion of uniform 12.8% (vol.) hydrogen-air mixture and combustion of non-uniform hydrogen-air mixture with average 12.6% (vol.) hydrogen concentration across the vessel (vertical stratification 27% vol. hydrogen at the top of the vessel 2.5% vol. hydrogen at the bottom of the vessel); both mixtures were ignited at the top of the vessel. The paper presents modelling approaches used by the partners comparison of simulation results against the experiment data and conclusions regarding the non-uniform mixture combustion modelling in real-life applications.

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.

Hydrogen embrittlement has been intensively studied in the past. However its governing mechanism is still under debate. Particularly the details of the formation of specific cleavage-like or quasi-cleavage fracture surfaces related to hydrogen embrittled steels are unclear yet. Recently it has been found that the fracture surface of the hydrogen charged and tensile tested low-carbon steel exhibits quasi-cleavage facets having specific smoothly curved surface which is completely different from common flat cleavage facets. In the present contribution we endeavor to shed light on the origin of such facets. For this purpose the notched flat specimens of the commercial low carbon steel were tensile tested using ex- and in-situ hydrogen charging. It is found that in the ex-situ hydrogen charged specimens the cracks originate primarily inside the specimen bulk and expand radially form the origin to the specimen surface. This process results in formation of “fisheyes” – the round-shape areas with the surface composed of curved quasi-cleavage facets. In contrast during tensile testing with in-situ hydrogen charging the cracks initiate from the surface and propagate to the bulk. This process results in the formation of the completely brittle fracture surface with the quasi-cleavage morphology - the same as that in fisheyes. The examination of the side surface of the in-situ hydrogen charged specimens revealed the straight and S-shaped sharp cracks which path is visually independent of the microstructure and crystallography but is strongly affected by the local stress fields. Nano-voids are readily found at the tips of these cracks. It is concluded that the growth of such cracks occurs by the nano-void coalescence mechanism and is responsible for the formation of fisheyes and smoothly curved quasi-cleavage facets in hydrogen charged low-carbon steel.

The actual start of the full-scale hydrogen energy infrastructure operations is scheduled to 2020 in Japan. The scope of factors and policy for the hydrogen infrastructure development in Japan is made. The paper provides observation for the major undergoing and already done projects for each link within hydrogen infrastructure chain – from production to end-user applications. Implications for the Russian energy policy are provided.

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.

The simultaneous photocatalytic H2 evolution with environmental remediation over semiconducting metal oxides is a fascinating process for sustainable fuel production. However most of the previously reported photocatalytic reforming showed nonstoichiometric amounts of the evolved H2 when organic substrates were used. To explain the reasons for this phenomenon a careful analysis of the products and intermediates in gas and aqueous phases upon the photocatalytic hydrogen evolution from oxalic acid using Pt/TiO2 was performed. A quadrupole mass spectrometer (QMS) was used for the continuous flow monitoring of the evolved gases while high performance ion chromatography (HPIC) isotopic labeling and electron paramagnetic resonance (EPR) were employed to understand the reactions in the solution. The entire consumption of oxalic acid led to a ~30% lower H2 amount than theoretically expected. Due to the contribution of the photoKolbe reaction mechanism a tiny amount of formic acid was produced then disappeared shortly after the complete consumption of oxalic acid. Nevertheless a much lower concentration of formic acid was generated compared to the nonstoichiometric difference between the formed H2 and the consumed oxalic acid. Isotopic labeling measurements showed that the evolved H2 HD and/or D2 matched those of the solvent; however using D2O decreased the reaction rate. Interestingly the presence of KI as an additional hole scavenger with oxalic acid had a considerable impact on the reaction mechanism and thus the hydrogen yield as indicated by the QMS and the EPR measurements. The added KI promoted H2 evolution to reach the theoretically predictable amount and inhibited the formation of intermediates without affecting the oxalic acid degradation rate. The proposed mechanism by which KI boosts the photocatalytic performance is of great importance in enhancing the overall energy efficiency for hydrogen production via photocatalytic organic reforming.

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.

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.

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.

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.