Germany
Combustion Features of CH4/NH3/H2 Ternary Blends
Mar 2022
Publication
The use of so-called “green” hydrogen for decarbonisation of the energy and propulsion sectors has attracted considerable attention over the last couple of decades. Although advancements are achieved hydrogen still presents some constraints when used directly in power systems such as gas turbines. Therefore another vector such as ammonia can serve as a chemical to transport and distribute green hydrogen whilst its use in gas turbines can limit combustion reactivity compared to hydrogen for better operability. However pure ammonia on its own shows slow complex reaction kinetics which requires its doping by more reactive molecules thus ensuring greater flame stability. It is expected that in forthcoming years ammonia will replace natural gas (with ~ 90% methane in volume) in power and heat production units thus making the co-firing of ammonia/methane a clear path towards replacement of CH4 as fossil fuel. Hydrogen can be obtained from the precracking of ammonia thus denoting a clear path towards decarbonisation by the use of ammonia/hydrogen blends. Therefore ammonia/methane/hydrogen might be co-fired at some stage in current combustion units hence requiring a more intrinsic analysis of the stability emissions and flame features that these ternary blends produce. In return this will ensure that transition from natural gas to renewable energy generated e-fuels such as so-called “green” hydrogen and ammonia is accomplished with minor detrimentals towards equipment and processes. For this reason this work presents the analysis of combustion properties of ammonia/methane/hydrogen blends at different concentrations. A generic tangential swirl burner was employed at constant power and various equivalence ratios. Emissions OH*/NH*/NH2*/CH* chemiluminescence operability maps and spectral signatures were obtained and are discussed. The extinction behaviour has also been investigated for strained laminar premixed flames. Overall the change from fossils to e-fuels is led by the shift in reactivity of radicals such as OH CH CN and NH2 with an increase of emissions under low and high ammonia content. Simultaneously hydrogen addition improves operability when injected up to 30% (vol) an amount at which the hydrogen starts governing the reactivity of the blends. Extinction strain rates confirm phenomena found in the experiments with high ammonia blends showing large discrepancies between values at different hydrogen contents. Finally a 20/55/25% (vol) methane/ammonia/hydrogen blend seems to be the most promising at high equivalence ratios (1.2) with no apparent flashback low emissions and moderate formation of NH2/OH radicals for good operability.
A Concept to Support the Transformation from a Linear to Circular Carbon Economy: Net Zero emissions, Resource Efficiency and Conservation Through a Coupling of the Energy, Chemical and Waste Management Sectors
Dec 2017
Publication
Coal and carbon-containing waste are valuable primary and secondary carbon carriers. In the current dominant linear economy such carbon resources are generally combusted to produce electricity and heat and as a way to resolve a nation’s waste issue. Not only is this a wastage of precious carbon resources which can be chemically utilized as raw materials for production of other value-added goods it is also contrary to international efforts to reduce carbon emissions and increase resource efficiency and conservation. This article presents a concept to support the transformation from a linear ‘one-way cradle to grave manufacturing model’ toward a circular carbon economy. The development of new and sustainable value chains through the utilization of coal and waste as alternative raw materials for the chemical industry via a coupling of the energy chemical and waste management sectors offers a viable and future-oriented perspective for closing the carbon cycle. Further benefits also include a lowering of the carbon footprint and increasing resource efficiency and conservation of primary carbon resources. In addition technological innovations and developments that are necessary to support a successful sector coupling will be identified. To illustrate our concept a case analysis of domestic coal and waste as alternative feedstock to imported crude oil for chemical production in Germany will be presented. Last but not least challenges posed by path dependency along technological institutional and human dimensions in the sociotechnical system for a successful transition toward a circular carbon economy will be discussed.
A Homogeneous Non-equilibrium Two-phase Critical Flow Model
Sep 2011
Publication
A non-equilibrium two-phase single-component critical (choked) flow model for cryogenic fluids is developed from first principle thermodynamics. Modern equations-of-state (EOS) based upon the Helmholtz free energy concepts are incorporated into the methodology. Extensive validation of the model is provided with the NASA cryogenic data tabulated for hydrogen methane nitrogen and oxygen critical flow experiments performed with four different nozzles. The model is used to develop a hydrogen critical flow map for stagnation states in the liquid and supercritical regions.
Simulation and Techno-Economic Analysis of a Power-to-Hydrogen Process for Oxyfuel Glass Melting
Dec 2021
Publication
As an energy-intensive industry sector the glass industry is strongly affected by the increasingly stringent climate protection targets. As established combustion-based production systems ensure high process stability and glass quality an immediate switch to low greenhouse gas emission processes is difficult. To approach these challenges this work investigates a step-by-step integration of a Power-to-Hydrogen concept into established oxyfuel glass melting processes using a simulation approach. This is complemented by a case study for economic analysis on a selected German glass industry site by simulating the power production of a nearby renewable energy park and subsequent optimization of the power-to-hydrogen plant performance and capacities. The results of this study indicate that the proposed system can reduce specific carbon dioxide emissions by up to 60 % while increasing specific energy demand by a maximum of 25 %. Investigations of the impact of altered combustion and furnace properties like adiabatic flame temperature (+25 °C) temperature efficiency (∆ξ = −0.003) and heat capacity flow ratio (∆zHL = −0.009) indicate that pure hydrogen-oxygen combustion has less impact on melting properties than assumed so far. Within the case study high CO2 abatement costs of 295 €/t CO2-eq. were determined.. This is mainly due to the insufficient performance of renewable energy sources. The correlations between process scaling and economic parameters presented in this study show promising potential for further economic optimization of the proposed energy system in the future.
Explosion Characteristics of Hydrogen-air and Hydrogen-Oxygen Mixtures at Elevated Pressures
Sep 2005
Publication
An essential problem for the operation of high pressure water electrolyzers and fuel cells is the permissible contamination of hydrogen and oxygen. This contamination can create malfunction and in the worst case explosions in the apparatus and gas cylinders. In order to avoid dangerous conditions the exact knowledge of the explosion characteristics of hydrogen/air and hydrogen/oxygen mixtures is necessary. The common databases e.g. the CHEMSAFE® database published by DECHEMA BAM and PTB contains even a large number of evaluated safety related properties among other things explosion limits which however are mainly measured according to standard procedures under atmospheric conditions.<br/>Within the framework of the European research project “SAFEKINEX” and other research projects the explosion limits explosion pressures and rates of pressure rise (KG values) of H2/air and H2/O2 mixtures were measured at elevated conditions of initial pressures and temperatures by the Federal Institute of Materials Research and Testing (BAM). Empirical equations of the temperature influence could be deduced from the experimental values. An anomaly was found at the pressure influence on the upper explosion limits of H2/O2 and H2/air mixtures in the range of 20 bars. In addition explosion pressures and also rates of pressure rises have been measured for different hydrogen concentrations inside the explosion range. Such data are important for constructive explosion protection measures. Furthermore the mainly used standards for the determination of explosion limits have been compared. Therefore it was interesting to have a look at the systematic differences between the new EN 1839 tube and bomb method ASTM E 681-01 and German DIN 51649-1.
Safety of Hydrogen-fueled Motor Vehicles with IC Engines.
Sep 2005
Publication
Clarification of questions of safety represents a decisive contribution to the successful introduction of vehicles fuelled by hydrogen. At the moment the safety of hydrogen is being discussed and investigated by various bodies. The primary focus is on fuel-cell vehicles with hydrogen stored in gaseous form. This paper looks at the safety of hydrogen-fuelled vehicles with an internal combustion engine and liquefied hydrogen storage. The safety concept of BMW’s hydrogen vehicles is described and the specific aspects of the propulsion and storage concepts discussed. The main discussion emphasis is on the utilization of boil-off parking of the vehicles in an enclosed space and their crash behaviour. Theoretical safety observations are complemented by the latest experimental and test results. Finally reference is made to the topic-areas in the field of hydrogen safety in which cooperative research work could make a valuable contribution to the future of the hydrogen-powered vehicle.
Measuring and Modelling Unsteady Radiation of Hydrogen Combustion
Sep 2005
Publication
Burning hydrogen emits thermal radiation in UV NIR and IR spectral range. Especially in the case of large cloud explosion the risk of heat radiation is commonly underestimated due to the non-visible flame of hydrogen-air combustion. In the case of a real explosion accident organic substances or inert dust might be entrained from outer sources to produce soot or heated solids to substantially increase the heat release by continuum radiation. To investigate the corresponding combustion phenomena different hydrogen-air mixtures were ignited in a closed vessel and the combustion was observed with fast scanning spectrometers using a sampling rate up to 1000 spectra/s. In some experiments to take into account the influence of organic co-combustion a spray of a liquid glycol-ester and milk powder was added to the mixture. The spectra evaluation uses the BAM code of ICT to model bands of reaction products and thus to get the temperatures. The code calculates NIR/IR-spectra (1 - 10 μm) of non-homogenous gas mixtures of H2O CO2 CO NO and HCl taking into consideration also emission of soot particles. It is based on a single line group model and makes also use of tabulated data of H2O and CO2 and a Least Squares Fit of calculated spectra to experimental ones enables the estimation of flame temperatures. During hydrogen combustion OH emits an intense spectrum at 306 nm. This intermediary radical allows monitoring the reaction progress. Intense water band systems between 1.2 and 3 μm emit remarkable amounts of heat radiation according to a measured flame temperature of 2000 K. At this temperature broad optically-thick water bands between 4.5 μm and 10 μm contribute only scarcely to the total heat output. In case of co-combustion of organic materials additional emission bands of CO and CO2 as well as a continuum radiation of soot and other particles occur and particularly increase the total thermal output drastically.
Analysis Methodology for Hydrogen Behaviour in Accident Scenarios
Sep 2005
Publication
Hydrogen is not more dangerous than current fossil energy carriers but it behaves differently. Therefore hydrogen specific analyses and countermeasures will be needed to support the development of safe hydrogen technologies. A systematic step-by-step procedure for the mechanistic analysis of hydrogen behaviour and mitigation in accidents is presented. The procedure can be subdivided into four main parts:<br/>1) 3D modelling of the H2-air mixture generation<br/>2) hazard evaluation for this mixture based on specifically developed criteria for flammability flame acceleration and detonation on-set<br/>3) numerical simulation of the appropriate combustion regime using verified 3D-CFD codes and<br/>4) consequence analysis based on the calculated pressure and temperature loads.
Electrochemical and Mechanical Stability of Catalyst Layers in Anion Exchange Membrane Water Electrolysis
Dec 2021
Publication
Anion exchange membrane (AEM) water electrolysis is considered a promising solution to future cost reduction of electrochemically produced hydrogen. We present an AEM water electrolyzer with CuCoOx as the anode catalyst and Aemion as membrane and electrode binder. Full cell experiments in pure water and 0.1 M KOH revealed that the optimum binder content depended on the type of electrolyte employed. Online dissolution measurements suggested that Aemion alone was not sufficient to establish an alkaline environment for thermodynamically stabilizing the synthesized CuCoOx in a neutral electrolyte feed. A feed of base is thus indispensable to ensure the thermodynamic stability of such non-noble catalyst materials. Particle loss and delamination of the catalyst layer during MEA operation could be reduced by employing a heat treatment step after electrode fabrication. This work summarizes possible degradation pathways for low-cost anodes in AEMWE and mitigation strategies for enhanced system durability and performance.
Challenges and Important Considerations When Benchmarking Single-cell Alkaline Electrolyzers
Nov 2021
Publication
This study outlines an approach to identifying the difficulties associated with the bench-marking of alkaline single cells under real electrolyzer conditions. A challenging task in the testing and comparison of different catalysts is obtaining reliable and meaningful benchmarks for these conditions. Negative effects on reproducibility were observed due to the reduction in conditioning time. On the anode side a stable passivation layer of NiO can be formed by annealing of the Ni foams which is even stable during long-term operation. Electrical contact resistance and impedance measurements showed that most of the contact resistance derived from the annealed Ni foam. Additionally analysis of various overvoltages indicated that most of the total overvoltage comes from the anode and cathode activation overpotential. Different morphologies of the substrate material exhibited an influence on the performance of the alkaline single cell based on an increase in the ohmic resistance.
Decentral Hydrogen
Apr 2022
Publication
This concept study extends the power-to-gas approach to small combined heat and power devices in buildings that alternately operate fuel cells and electrolysis. While the heat is used to replace existing fossil heaters on-site the power is either fed into the grid or consumed via heatcoupled electrolysis to balance the grid power at the nearest grid node. In detail the power demand of Germany is simulated as a snapshot for 2030 with 100% renewable sourcing. The standard load profile is supplemented with additional loads from 100% electric heat pumps 100% electric cars and a fully electrified industry. The renewable power is then scaled up to match this demand with historic hourly yield data from 2018/2019. An optimal mix of photovoltaics wind biomass and hydropower is calculated in respect to estimated costs in 2030. Hydrogen has recently entered a large number of national energy roadmaps worldwide. However most of them address the demands of heavy industry and heavy transport which are more difficult to electrify. Hydrogen is understood to be a substitute for fossil fuels which would be continuously imported from non-industrialized countries. This paper focuses on hydrogen as a storage technology in an all-electric system. The target is to model the most cost-effective end-to-end use of local renewable energies including excess hydrogen for the industry. The on-site heat coupling will be the principal argument for decentralisation. Essentially it flattens the future peak from massive usage of electric heat pumps during cold periods. However transition speed will either push the industry or the prosumer approach in front. Batteries are tried out as supplementary components for short-term storage due to their higher round trip efficiencies. Switching the gas net to hydrogen is considered as an alternative to overcome the slow power grid expansions. Further decentral measures are examined in respect to system costs.
Local Degradation Effects in Automotive Size Membrane Electrode Assemblies Under Realistic Operating Conditions
Dec 2019
Publication
In automotive applications the operational parameters for fuel cell (FC) systems can vary over a wide range. To analyze their impact on fuel cell degradation an automotive size single cell was operated under realistic working conditions. The parameter sets were extracted from the FC system modelling based on on-road customer data. The parameter variation included simultaneous variation of the FC load gas pressures cell temperature stoichiometries and relative humidity. Current density distributions and the overall cell voltage were recorded in real time during the tests. The current densities were low at the geometric anode gas outlet and high at the anode gas inlet. After electrochemical tests post mortem analysis was conducted on the membrane electrode assemblies using scanning electron microscopy. The ex-situ analysis showed significant cathode carbon corrosion in areas associated with low current densities. This suggests that fuel starvation close to the anode outlet is the origin of the cathode electrode degradation. The results of the numerical simulations reveal high relative humidity at that region and therefore water flooding is assumed to cause local anode fuel starvation. Even though the hydrogen oxidation reaction has low kinetic overpotentials “local availability” of H2 plays a significant role in maintaining a homogeneous current density distribution and thereby in local degradation of the cathode catalyst layer. The described phenomena occurred while the overall cell voltage remained above 0.3 V. This indicates that only voltage monitoring of fuel cell systems does not contain straightforward information about this type of degradation.
Statistics, Lessons Learned and Recommendations from Analysis of HIAD 2.0 Database
Mar 2022
Publication
The manuscript firstly describes the data collection and validation process for the European Hydrogen Incidents and Accidents Database (HIAD 2.0) a public repository tool collecting systematic data on hydrogen-related incidents and near-misses. This is followed by an overview of HIAD 2.0 which currently contains 706 events. Subsequently the approaches and procedures followed by the authors to derive lessons learned and formulate recommendations from the events are described. The lessons learned have been divided into four categories including system design; system manufacturing installation and modification; human factors and emergency response. An overarching lesson learned is that minor events which occurred simultaneously could still result in serious consequences echoing James Reason's Swiss Cheese theory. Recommendations were formulated in relation to the established safety principles adapted for hydrogen by the European Hydrogen Safety Panel considering operational modes industrial sectors and human factors. This work provide an important contribution to the safety of systems involving hydrogen benefitting technical safety engineers emergency responders and emergency services. The lesson learned and the discussion derived from the statistics can also be used in training and risk assessment studies being of equal importance to promote and assist the development of sound safety culture in organisations.
A Coupled Transient Gas Flow Calculation with a Simultaneous Calorific-value-gradient Improved Hydrogen Tracking
Apr 2022
Publication
Gas systems can provide considerable flexibility in integrated energy systems to accommodate hydrogen produced from Power-to-Hydrogen units using excess volatile renewable energy generation. To use the flexibility in integrated energy systems while ensuring a secure and reliable system operation gas system operators need to accurately and easily analyze the effects of varying hydrogen levels on the dynamic gas behavior and vice versa. Existing methods for hydrogen tracking however either solve the hydrogen propagation and dynamic gas behavior separately or must cope with a large inaccuracy. Hence existing methods do not allow an accurate and coupled analysis of gas systems in integrated energy systems considering varying hydrogen levels. This paper proposes a calorific-value-gradient method which can accurately track the propagation of varying hydrogen levels in a gas system even with large simulation time increments of up to one hour. The new method is joined and simultaneously solved with an implicit finite difference scheme describing the transient gas behavior in a single equation system in a coupled Newton–Raphson gas flow calculation. As larger simulation time increments can be chosen without reducing the accuracy the computation time can be strongly reduced compared to existing Euler-based methods. With its high accuracy and its coupled approach this paper provides gas system operators a method to accurately analyze how the propagation of hydrogen affects the entire gas system. With its coupled approach the presented method can enhance the investigation of integrated energy systems as the transient gas behavior and varying hydrogen propagation of the gas system can be easily included in such analyses.
Addressing H-Material Interaction in Fast Diffusion Materials—A Feasibility Study on a Complex Phase Steel
Oct 2020
Publication
Hydrogen embrittlement (HE) is one of the main limitations in the use of advanced high-strength steels in the automotive industry. To have a better understanding of the interaction between hydrogen (H) and a complex phase steel an in-situ method with plasma charging was applied in order to provide continuous H supply during mechanical testing in order to avoid H outgassing. For such fast-H diffusion materials only direct observation during in-situ charging allows for addressing H effects on materials. Different plasma charging conditions were analysed yet there was not a pronounced effect on the mechanical properties. The H concentration was calculated while using a simple analytical model as well as a simulation approach resulting in consistent low H values below the critical concentration to produce embrittlement. However the dimple size decreased in the presence of H and with increasing charging time the crack propagation rate increased. The rate dependence of flow properties of the material was also investigated proving that the material has no strain rate sensitivity which confirmed that the crack propagation rate increased due to H effects. Even though the H concentration was low in the experiments that are presented here different technological alternatives can be implemented in order to increase the maximum solute concentration.
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.
The Role of Trust and Familiarity in Risk Communication
Sep 2009
Publication
In socio-economics it is well known that the success of an innovation process not only depends upon the technological innovation itself or the improvement of economic and institutional system boundaries but also on the public acceptance of the innovation. The public acceptance can as seen with genetic engineering for agriculture be an obstacle for the development and introduction of a new and innovative idea. In respect to hydrogen technologies this means that the investigation compilation and communication of scientific risk assessments are not sufficient to enhance or generate public acceptance. Moreover psychological social and cultural aspects of risk perception have to be considered when introducing new technologies. Especially trust and familiarity play an important role for risk perception and thus public acceptance of new technologies.
Ignition and Heat Radiation of Cryogenic Hydrogen Jets
Sep 2011
Publication
In the present work release and ignition experiments with horizontal cryogenic hydrogen jets at temperatures of 35–65 K and pressures from 0.7 to 3.5 MPa were performed in the ICESAFE facility at KIT. This facility is specially designed for experiments under steady-state sonic release conditions with constant temperature and pressure in the hydrogen reservoir. In distribution experiments the temperature velocity turbulence and concentration distribution of hydrogen with different circular nozzle diameters and reservoir conditions was investigated for releases into stagnant ambient air. Subsequent combustion experiments of hydrogen jets included investigations on the stability of the flame and its propagation behaviour as function of the ignition position. Furthermore combustion pressures and heat radiation from the sonic jet flame during the combustion process were measured. Safety distances were evaluated and an extrapolation model to other jet conditions was proposed. The results of this work provide novel data on cryogenic sonic hydrogen jets and give information on the hazard potential arising from leaks in liquid hydrogen reservoirs.
Regulations and Research on RC&S for Hydrogen Storage Relevant To Transport and Vehicle Issues with Special Focus on Composite Containments
Sep 2011
Publication
Developers interested in high pressure storage of hydrogen for mobile use increasingly rely on composite cylinders for onboard storage or transport of dangerous goods. Thus composite materials and systems deserve special consideration. History gives interesting background information important to the understanding of the current situation as to regulations codes and standards.<br/>Based on this review origins of different regulations for the storage of hydrogen as dangerous good and as propellant for vehicles will be examined. Both categories started out using steel and sometimes aluminium as cylinder material. With composite materials becoming more common a new problem emerged: vital input for regulations on composite pressure systems was initially derived from decades of experience with steel cylinders. As a result both regulatory fields suffer somewhat from this common basis. Only recent developments regarding requirements for composite cylinders have begun to go more and more separate ways. Thus these differences lead to some shortcomings in regulation with respect to composite storage systems.<br/>In principle in spite of separate development these deficits are in both applications very much the same: there are uncertainties in the prediction of safe service life in retesting procedures of composite cylinders and in their intervals. Hence different aspects of uncertainties and relevant approaches to solutions will be explained.
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.
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