Germany
Hydrogen Release from a High-Pressure Gh2 Reservoir in Case of a Small Leak
Sep 2009
Publication
High-pressure GH2 systems are of interest for storage and distribution of hydrogen. The dynamic blow-down process of a high-pressure GH2 reservoir in case of a small leak is a complex process involving a chain of distinct flow regimes and gas states which needs to be understood for safety investigations.<br/>This paper presents models to predict the hydrogen concentration and velocity field in the vicinity of a postulated small leak. An isentropic expansion model with a real gas equation of state for normal hydrogen is used to calculate the time dependent gas state in the reservoir and at the leak position. The subsequent gas expansion to 0.1 MPa is predicted with a zero-dimensional model. The gas conditions after expansion serve as input to a newly developed integral model for a round free turbulent H2-jet into ambient air. The model chain was evaluated by jet experiments with sonic hydrogen releases from different reservoir pressures and temperatures.<br/>Predictions are made for the blow-down of hydrogen reservoirs with 10 30 and 100 MPa initial pressure. The evolution of the pressure in the reservoir and of the H2 mass flux at the orifice are presented in dimensionless form which allows scaling to other system dimensions and initial gas conditions. Computed hydrogen concentrations and masses in the jet are given for the 100 MPa case. A normalized hydrogen concentration field in the free jet is presented which allows for a given leak scenario the prediction of the axial and radial range of burnable H2-air mixtures.
Effects of Radiation on the Flame Front of Hydrogen-air Explosions
Oct 2015
Publication
The flame velocities of unconfined gas explosions depend on the cloud size and the distance from the initiating source. The mechanisms for this effect are not fully understood; a possible explanation is turbulence generated by the propagating flame front. The molecular bands in the flame front are exposed to continuously increasing radiation intensity of water bands in the interior of the reaction product ball. A first approach to verifying this assumption is described in this paper. The flame propagation was observed by high speed video techniques including time resolved spectroscopy in the UV-Vis-NIR spectral range with a time resolution up to 3000 spectra/s. Ignition flame head velocity flame contours reacting species and temperatures were evaluated. The evaluation used video brightness subtraction and 1-dimensional image contraction to obtain traces of the movements perpendicular to the direction of propagation. Flame front velocities are found to be between 16m/s and 25 m/s. Analysis focused in particular on the flame front which is not smooth. Salients emerge on the surface to result in the well-known cellular structures. The radiation of various bands from the fire ball on the reacting species is estimated to have an influence on the flame velocity depending on the distance from initiation. Evaluation of OH-band and water band spectra might indicate might indicate higher temperatures of the flame front induced by radiation of the fireball. But it is difficult to verify the effect relative to competing flame acceleration mechanisms.
Hyper Experiments on Catastrophic Hydrogen Releases Inside a Fuel Cell Enclosure
Sep 2009
Publication
As a part of the experimental work of the EC-funded project HYPER Pro-Science GmbH performed experiments to evaluate the hazard potential of a severe hydrogen leakage inside a fuel cell cabinet. During this study hydrogen distribution and combustion experiments were performed using a generic enclosure model with the dimensions of the fuel cell "Penta H2" provided by ARCOTRONICS (now EXERGY Fuel Cells) to the project partner UNIPI for their experiments on small foreseeable leaks. Hydrogen amounts of 1.5 to 15 g H2 were released within one second into the enclosure through a nozzle with an internal diameter of 8 mm. In the distribution experiments the effects of different venting characteristics and different amounts of internal enclosure obstruction on the hydrogen concentrations measured at fixed positions in- and outside the model were investigated. Based on the results of these experiments combustion experiments with ignition positions in- and outside the enclosure and two different ignition times were performed. BOS (Background-Oriented-Schlieren) observation combined with pressure and light emission measurements were performed to describe the characteristics and the hazard potential of the induced hydrogen combustions. The experiments provide new experimental data on the distribution and combustion behaviour of hydrogen that is released into a partly vented and partly obstructed enclosure with different venting characteristics.
Spontaneous Ignition Processes Due To High-Pressure Hydrogen Release in Air
Sep 2011
Publication
Spontaneous ignition processes due to the high-pressure hydrogen releases into air were investigated both experimentally and theoretically. Such processes reproduce accident scenarios of sudden expansion of pressurized hydrogen into the ambient atmosphere in cases of tube or valve rupture. High-pressure hydrogen releases in the range of initial pressures from 20 to 275 bar and with nozzle diameters of 0.5 – 4 mm have been investigated. Glass tubes and high-speed CCD camera were used for experimental study of self-ignition process. The problem was theoretically considered in terms of contact discontinuity for the case when spontaneous ignition of pressurized hydrogen due to the contact with hot pressurized air occurs. The effects of boundary layer and material properties are discussed in order to explain the minimum initial pressure of 25 bar leading to the self-ignition of hydrogen with air.
A New Technology for Hydrogen Safety: Glass Structures as a Storage System
Sep 2011
Publication
The storage of hydrogen poses inherent weight volume and safety obstacles. An innovative technology which allows for the storage of hydrogen in thin sealed glass capillaries ensures the safe infusion storage and controlled release of hydrogen gas under pressures up to 100 MPa. Glass is a non-flammable material which also guarantees high burst pressures. The pressure resistance of single and multiple capillaries has been determined for different glass materials. Borosilicate capillaries have been proven to have the highest pressure resistance and have therefore been selected for further series of advanced testing. The innovative storage system is finally composed of a variable number of modules. As such in the case of the release of hydrogen this modular arrangement allows potential hazards to be reduced to a minimum. Further advantage of a modular system is the arrangement of single modules in every shape and volume dependent on the final application. Therefore the typical locations of storage systems e.g. the rear of cars can be modified or shifted to places of higher safety and not directly involved in crashes. The various methods of refilling and releasing capillaries with compressed hydrogen the increase of burst pressures through pre-treatment as well as the theoretical analysis and experimental results of the resistance of glass capillaries will further be discussed in detail.
Hydrogen Combustion Experiments in a Vertical Semi-confined Channel
Sep 2017
Publication
Experiments in an obstructed semi-confined vertical combustion channel with a height of 6 m (cross-section 0.4 × 0.4 m) inside a safety vessel of the hydrogen test center HYKA at the Karlsruhe Institute of Technology (KIT) are reported. In the work homogeneous hydrogen-air-mixtures as well as mixtures with different well-defined H2-concentration gradients were ignited either at the top or at the bottom end of the channel. The combustion characteristics were recorded using pressure sensors and sensors for the detection of the flame front that were distributed along the complete channel length. In the tests slow subsonic and fast sonic deflagrations as well as detonations were observed and the conditions for the flame acceleration (FA) to speed of sound and deflagration-to-detonation transition (DDT) are compared with the results of similar experiments performed earlier in a larger semi-confined horizontal channel.
Visualisation of Jet Fires from Hydrogen Release
Sep 2009
Publication
In order to achieve a high level of safety while using hydrogen as a vehicle fuel the possible hazards must be estimated. Especially hydrogen release tests with defined ignition represent a very important way to characterize the basics of hydrogen combustion in a potential accident. So ICT participated on a hydrogen jet release campaign at HSL (Buxton) in 2008 to deploy their measurement techniques and evaluation methods to visualize jets ignition and subsequent flames. The following paper shows the application of high speed cinematography in combination with image processing techniques the Background Oriented Schlieren (BOS) and a difference method to visualize the shape of hydrogen jet. In addition these methods were also used to observe ignition and combustion zone after defined initiation. In addition the combustion zone was recorded by a fast spectral radiometer and a highspeed-IR-camera. The IR-camera was synchronized with a rotating filter wheel to generate four different motion pictures at 100Hz each on a defined spectral range. The results of this preliminary evaluation provide some detailed information that might be used for improving model predictions.
Evaluation of an Improved Vented Deflagration CFD Model Against Nine Experimental Cases
Sep 2019
Publication
In the present work a newly developed CFD deflagration model incorporated into the ADREA-HF code is evaluated against hydrogen vented deflagrations experiments carried out by KIT and FM-Global in a medium (1 m3) and a real (63.7 m3) scale enclosure respectively. A square vent of 0.5 m2 and 5.4 m2 respectively is located in the center of one of side walls. In the case of the medium scale enclosure the 18% v/v homogeneous hydrogen-air mixture and back-wall ignition case is examined. In the case of the real scale enclosure the examined cases cover different homogeneous mixture concentrations (15% and 18% v/v) different ignition locations (back-wall and center) and different levels of initial turbulence. The CFD model accounts for flame instabilities that develop as the flame propagates inside the chamber and turbulence that mainly develops outside the vent. Pressure predictions are compared against experimental measurements revealing a very good performance of the CFD model for the back-wall ignition cases. For the center ignition cases the model overestimates the maximum overpressure. The opening of the vent cover is identified as a possible reason for the overprediction. The analysis indicates that turbulence is the main factor which enhances external explosion strength causing the sudden pressure increase confirming previous findings.
HYDRIDE4MOBILITY: An EU HORIZON 2020 Project on Hydrogen Powered Fuel Cell Utility Vehicles Using Metal Hydrides in Hydrogen Storage and Refuelling Systems
Feb 2021
Publication
Volodymyr A. Yartys,
Mykhaylo V. Lototskyy,
Vladimir Linkov,
Sivakumar Pasupathi,
Moegamat Wafeeq Davids,
Gojmir Radica,
Roman V. Denys,
Jon Eriksen,
José Bellosta von Colbe,
Klaus Taube,
Giovanni Capurso,
Martin Dornheim,
Fahmida Smith,
Delisile Mathebula,
Dana Swanepoel,
Suwarno Suwarno and
Ivan Tolj
The goal of the EU Horizon 2020 RISE project 778307 “Hydrogen fuelled utility vehicles and their support systems utilising metal hydrides” (HYDRIDE4MOBILITY) is in addressing critical issues towards a commercial implementation of hydrogen powered forklifts using metal hydride (MH) based hydrogen storage and PEM fuel cells together with the systems for their refuelling at industrial customers facilities. For these applications high specific weight of the metallic hydrides has an added value as it allows counterbalancing of a vehicle with no extra cost. Improving the rates of H2 charge/discharge in MH on the materials and system level simplification of the design and reducing the system cost together with improvement of the efficiency of system “MH store-FC” is in the focus of this work as a joint effort of consortium uniting academic teams and industrial partners from two EU and associated countries Member States (Norway Germany Croatia) and two partner countries (South Africa and Indonesia).<br/>The work within the project is focused on the validation of various efficient and cost-competitive solutions including (i) advanced MH materials for hydrogen storage and compression (ii) advanced MH containers characterised by improved charge-discharge dynamic performance and ability to be mass produced (iii) integrated hydrogen storage and compression/refuelling systems which are developed and tested together with PEM fuel cells during the collaborative efforts of the consortium.<br/>This article gives an overview of HYDRIDE4MOBILITY project focused on the results generated during its first phase (2017–2019).
Modeling of the Flame Acceleration in Flat Layer for Hydrogen-air Mixtures
Sep 2011
Publication
The flame propagation regimes for the stoichiometric hydrogen-air mixtures in an obstructed semiconfined flat layer have been numerically investigated in this paper. Conditions defining fast or sonic propagation regime were established as a function of the main dimensions characterizing the system and the layout of the obstacles. It was found that the major dependencies were the following: the thickness of the layer of H2-air mixture the blockage ratio and the distance between obstacles and the obstacle size. A parametric study was performed to determine the combination of the above variables prone to produce strong combustions. Finally a criterion that separates experiments resulting in slow subsonic from fast sonic propagations regimes was proposed.
Mechanism of Action of Polytetrafluoroethylene Binder on the Performance and Durability of High-temperature Polymer Electrolyte Fuel Cells
Feb 2021
Publication
In this work new insights into impacts of the polytetrafluoroethylene (PTFE) binder on high temperature polymer electrolyte fuel cells (HT-PEFCs) are provided by means of various characterizations and accelerated stress tests. Cathodes with PTFE contents from 0 wt% to 60 wt% were fabricated and compared using electrochemical measurements. The results indicate that the cell with 10 wt% PTFE in the cathode catalyst layer (CCL) shows the best performance due to having the lowest mass transport resistance and cathode protonic resistance. Moreover cyclic voltammograms show that Pt (100) edge and corner sites are significantly covered by PTFE and phosphate anions when the PTFE content is higher than 25 wt%. Open-circuit and low load-cycling conditions are applied to accelerate degradation processes of the HT-PEFCs. The PTFE binder shows a network structure in the pores of the catalyst layer which reduces phosphoric acid leaching during the aging tests. In addition the high binder HT-PEFCs more easily suffer from a mass transport problem leading to more severe performance degradation.
Experiments on Flame Acceleration and DDT for Stoichiometric Hydrogen/Air Mixture in a Thin Layer Geometry
Sep 2017
Publication
A series of experiments in a thin layer geometry performed at the HYKA test site of the KIT. The experiments on different combustion regimes for lean and stoichiometric H2/air mixtures were performed in a rectangular chamber with dimensions of 20 x 90 x h cm3 where h is the thickness of the layer (h = 1 2 4 6 8 10 mm). Three different layer geometries:
- a smooth channel without obstructions;
- the channel with a metal grid filled 25% of length and
- a metal grid filled 100% of length.
Numerical Study on the Influence of Different Boundary Conditions on the Efficiency of Hydrogen Recombiners Inside a Car Garage
Oct 2015
Publication
Passive auto-catalytic recombiners (PARs) have the potential to be used in the future for the removal of accidentally released hydrogen inside confined areas. PARs could be operated both as stand-alone or backup safety devices e.g. in case of active ventilation failure.
Recently computational fluid dynamics (CFD) simulations have been performed in order to demonstrate the principal performance of a PAR during a postulated hydrogen release inside a car garage. This fundamental study has now been extended towards a variation of several boundary conditions including PAR location hydrogen release scenario and active venting operation. The goal of this enhanced study is to investigate the sensitivity of the PAR operational behaviour for changing boundary conditions and to support the identification of a suitable PAR positioning strategy. For the simulation of PAR operation the in-house code REKO-DIREKT has been implemented in the CFD code ANSYS-CFX 15.
In a first step the vertical position of the PAR and the thermal boundary conditions of the garage walls have been modified. In a subsequent step different hydrogen release modes have been simulated which result either in a hydrogen-rich layer underneath the ceiling or in a homogeneous hydrogen distribution inside the garage. Furthermore the interaction of active venting and PAR operation has been investigated.
As a result of this parameter study the optimum PAR location was identified to be close underneath the garage ceiling. In case of active venting failure the PAR efficiently reduces the flammable gas volume (hydrogen concentration > 4 vol.%) for both stratified and homogeneous distribution. However the simulations indicate that the simultaneous operation of active venting and PAR may in some cases reduce the overall efficiency of hydrogen removal. Consequently a well-matched arrangement of both safety systems is required in order to optimize the overall efficiency. The presented CFD-based approach is an appropriate tool to support the assessment of the efficiency of PAR application for plant design and safety considerations with regard to the use of hydrogen in confined areas.
Recently computational fluid dynamics (CFD) simulations have been performed in order to demonstrate the principal performance of a PAR during a postulated hydrogen release inside a car garage. This fundamental study has now been extended towards a variation of several boundary conditions including PAR location hydrogen release scenario and active venting operation. The goal of this enhanced study is to investigate the sensitivity of the PAR operational behaviour for changing boundary conditions and to support the identification of a suitable PAR positioning strategy. For the simulation of PAR operation the in-house code REKO-DIREKT has been implemented in the CFD code ANSYS-CFX 15.
In a first step the vertical position of the PAR and the thermal boundary conditions of the garage walls have been modified. In a subsequent step different hydrogen release modes have been simulated which result either in a hydrogen-rich layer underneath the ceiling or in a homogeneous hydrogen distribution inside the garage. Furthermore the interaction of active venting and PAR operation has been investigated.
As a result of this parameter study the optimum PAR location was identified to be close underneath the garage ceiling. In case of active venting failure the PAR efficiently reduces the flammable gas volume (hydrogen concentration > 4 vol.%) for both stratified and homogeneous distribution. However the simulations indicate that the simultaneous operation of active venting and PAR may in some cases reduce the overall efficiency of hydrogen removal. Consequently a well-matched arrangement of both safety systems is required in order to optimize the overall efficiency. The presented CFD-based approach is an appropriate tool to support the assessment of the efficiency of PAR application for plant design and safety considerations with regard to the use of hydrogen in confined areas.
Hydrogen Storage Using a Hot Pressure Swing Reactor
Jun 2017
Publication
Our contribution demonstrates that hydrogen storage in stationary Liquid Organic Hydrogen Carrier (LOHC) systems becomes much simpler and significantly more efficient if both the LOHC hydrogenation and the LOHC dehydrogenation reaction are carried out in the same reactor using the same catalyst. The finding that the typical dehydrogenation catalyst for hydrogen release from perhydro dibenzyltoluene (H18-DBT) Pt on alumina turns into a highly active and very selective dibenzyltoluene hydrogenation catalyst at temperatures above 220 °C paves the way for our new hydrogen storage concept. Herein hydrogenation of H0-DBT and dehydrogenation of H18-DBT is carried out at the same elevated temperature between 290 and 310 °C with hydrogen pressure being the only variable for shifting the equilibrium between hydrogen loading and release. We demonstrate that the heat of hydrogenation can be provided at a temperature level suitable for effective dehydrogenation catalysis. Combined with a heat storage device of appropriate capacity or a high pressure steam system this heat could be used for dehydrogenation.
The Slow Burst Test as a Method for Probabilistic Quantification of Cylinder Degradation
Sep 2013
Publication
"The current practise of focusing the periodic retesting of composite cylinders primarily on the hydraulic pressure test has to be evaluated as critical - with regard to the damage of the specimen as well as in terms of their significance. This is justified by micro damages caused to the specimen by the test itself and by a lack of informative values. Thus BAM Federal Institute of Materials Research and Testing (Germany) uses a new approach of validation of composite for the determination of re-test periods. It enables the description of the state of a population of composite cylinders based on destructive tests parallel to operation.<br/>An essential aspect of this approach is the prediction of residual safe service life. In cases where it cannot be estimated by means of hydraulic load cycle tests as a replacement the creep or burst test remains. As a combination of these two test procedures BAM suggests the ""slow burst test SBT"". On this a variety of about 150 burst test results on three design types of cylinders with plastic liners are presented. For this purpose both the parameters of the test protocol as well as the nature and intensity of the pre-damage artificially aged test samples are analysed statistically. This leads first to an evaluation of the different types of artificial ageing but also to the clear recommendation that conventional burst tests be substituted totally if indented for assessment of composite pressure receptacles."
Review and Assessment of the Effect of Hydrogen Gas Pressure on the Embrittlement of Steels in Gaseous Hydrogen Environment
Apr 2021
Publication
Hydrogen gas pressure is an important test parameter when considering materials for high-pressure hydrogen applications. A large set of data on the effect of hydrogen gas pressure on mechanical properties in gaseous hydrogen experiments was reviewed. The data were analyzed by converting pressures into fugacities (f) and by fitting the data using an f|n| power law. For 95% of the data sets |n| was smaller than 0.37 which was discussed in the context of (i) rate-limiting steps in the hydrogen reaction chain and (ii) statistical aspects. This analysis might contribute to defining the appropriate test fugacities (pressures) to qualify materials for gaseous hydrogen applications.
Safety Criteria for the Transport of Hydrogen in Permanently Mounted Composite Pressure Vessels
Sep 2019
Publication
The recent growth of the net of hydrogen fuelling stations increases the demands to transport compressed hydrogen on road by battery vehicles or tube-trailers both in composite pressure vessels. As a transport regulation the ADR is applicable in Europe and adjoined regions and is used for national transport in the EU. This regulation provides requirements based on the behaviour of each individual pressure vessel regardless of the pressure of the transported hydrogen and relevant consequences resulting from generally possible worst case scenarios such as sudden rupture. In 2012 the BAM (German Federal Institute for Materials Research and Testing) introduced consequence-dependent requirements and established them in national transport requirements concerning the “UN service life checks” etc. to consider the transported volume and pressure of gases. This results in a requirement that becomes more restrictive as the product of pressure and volume increases. In the studies presented here the safety measures for hydrogen road transport are identified and reviewed through a number of safety measures from countries including Japan the USA and China. Subsequently the failure consequences of using trailer vehicles the related risk and the chance are evaluated. A benefit-related risk criterion is suggested to add to regulations and to be defined as a safety goal in standards for hydrogen transport vehicles and for mounted pressure vessels. Finally an idea is given for generating probabilistic safety data and for highly efficient evaluation without a significant increase of effort.
Single-catalyst High-weight% Hydrogen Storage in an N-heterocycle Synthesized from Lignin Hydrogenolysis Products and Ammonia
Oct 2016
Publication
Large-scale energy storage and the utilization of biomass as a sustainable carbon source are global challenges of this century. The reversible storage of hydrogen covalently bound in chemical compounds is a particularly promising energy storage technology. For this compounds that can be sustainably synthesized and that permit high-weight% hydrogen storage would be highly desirable. Herein we report that catalytically modified lignin an indigestible abundantly available and hitherto barely used biomass can be harnessed to reversibly store hydrogen. A novel reusable bimetallic catalyst has been developed which is able to hydrogenate and dehydrogenate N-heterocycles most efficiently. Furthermore a particular N-heterocycle has been identified that can be synthesized catalytically in one step from the main lignin hydrogenolysis product and ammonia and in which the new bimetallic catalyst allows multiple cycles of high-weight% hydrogen storage.
Optimizing Mixture Properties for Accurate Laminar Flame Speed Measurement from Spherically Expanding Flame: Application to H2/O2/N2/He Mixtures
Sep 2019
Publication
The uncertainty on the laminar flame speed extracted from spherically expanding flames can be minimized by using large flame radius data for the extrapolation to zero stretch-rate. However at large radii the hydrodynamic and thermo-diffusive instabilities induce the formation of a complex cellular flame front and limit the range of usable data. In the present study we have employed the flame stability theory of Matalon to optimize the properties of the initial mixture so that transition to cellularity may occur at a pre-determined large radius. This approach was employed to measure the laminar flame speeds of H2/O2/N2/He mixtures with equivalence ratios from 0.6 to 2.0 at pressures of 50/80/100 kPa and a temperature of 300 K. For all the performed experiments the uncertainty related to the extrapolation to zero stretch-rate (performed with the linear curvature model) was below 2% as shown by the position of the data points in the (Lb/Rf;U Lb/Rf;L) plan where Lb is the burned Markstein length; and Rf;L and Rf;U are the flame radii at the lower and upper bounds of the extrapolation range. Comparison of the predictions of four chemical mechanisms with the present unstretched laminar flame speed data indicated an error below 10% for most conditions. In addition unsteady 1-D simulations performed with A-SURF demonstrated that the flame dynamical response to stretch rate could not be captured by the mechanisms. The present work indicates that although the stability theory of Matalon provides a well defined framework to optimize the mixture properties for improved flame speed measurement the uncertainty of some of the required parameters can result in largely over-estimated critical radius for cellularity onset which compromise the accuracy of the optimization procedure.
Modelling and Optimization of a Flexible Hydrogen-fueled Pressurized PEMFC Power Plant for Grid Balancing Purposes
Feb 2021
Publication
In a scenario characterized by an increasing penetration of non-dispatchable renewable energy sources and the need of fast-ramping grid-balancing power plants the EU project GRASSHOPPER aims to setup and demonstrate a highly flexible PEMFC Power Plant hydrogen fueled and scalable to MW-size designed to provide grid support.<br/>In this work different layouts proposed for the innovative MW-scale plant are simulated to optimize design and off-design operation. The simulation model details the main BoP components performances and includes a customized PEMFC model validated through dedicated experiments.<br/>The system may operate at atmospheric or mild pressurized conditions: pressurization to 0.7 barg allows significantly higher net system efficiency despite the increasing BoP consumptions. The additional energy recovery from the cathode exhaust with an expander gives higher net power and net efficiency adding up to 2%pt and reaching values between 47%LHV and 55%LHV for currents between 100% and 20% of the nominal value.
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