Austria
Methodology for Efficient Parametrisation of Electrochemical PEMFC Model for Virtual Observers: Model Based Optimal Design of Experiments Supported by Parameter Sensitivity Analysis
Nov 2020
Publication
Determination of the optimal design of experiments that enables efficient parametrisation of fuel cell (FC) model with a minimum parametrisation data-set is one of the key prerequisites for minimizing costs and effort of the parametrisation procedure. To efficiently tackle this challenge the paper present an innovative methodology based on the electrochemical FC model parameter sensitivity analysis and application of D-optimal design plan. Relying on this consistent methodological basis the paper answers fundamental questions: a) on a minimum required data-set to optimally parametrise the FC model and b) on the impact of reduced space of operational points on identifiability of individual calibration parameters. Results reveal that application of D-optimal DoE enables enhancement of calibration parameters information resulting in up to order of magnitude lower relative standard errors on smaller data-sets. In addition it was shown that increased information and thus identifiability inherently leads to improved robustness of the FC electrochemical model.
The Future Potential Hydrogen Demand in Energy-intensive Industries - A Site-specific Approach Applied to Germany
Dec 2021
Publication
Hydrogen when based on renewable electricity can play a key role in the transition towards CO2-neutral industrial production since its use as an energy carrier as well as a feedstock in various industrial process routes is promising. At the same time a large-scale roll-out of hydrogen for industrial use would entail substantial impacts on the energy system which can only be assessed if the regional distribution of future hydrogen demand is considered. Here we assess the technical potential of hydrogen-based technologies for energy-intensive industries in Germany. The site-specific and process-specific bottom-up calculation considers 615 individual plants at 367 sites and results in a total potential hydrogen demand of 326 TWh/a. The results are available as an open dataset. Using hydrogen for non-energy-intensive sectors as well increases the potential hydrogen demand to between 482 and 534 TWh/a for Germany - based on today’s industrial structure and production output. This assumes that fossil fuels are almost completely replaced by hydrogen for process heating and feedstocks. The resulting hydrogen demand is very unevenly distributed: a few sites account for the majority of the overall potential and similarly the bulk of demand is concentrated in a few regions with steel and chemical clusters.
Asymmetric Solvation of the Zinc Dimer Cation Revealed by Infrared Multiple Photon Dissociation Spectroscopy of Zn2+(H2O)n (n = 1–20)
Jun 2021
Publication
Investigating metal-ion solvation—in particular the fundamental binding interactions—enhances the understanding of many processes including hydrogen production via catalysis at metal centers and metal corrosion. Infrared spectra of the hydrated zinc dimer (Zn2+(H2O)n; n = 1–20) were measured in the O–H stretching region using infrared multiple photon dissociation (IRMPD) spectroscopy. These spectra were then compared with those calculated by using density functional theory. For all cluster sizes calculated structures adopting asymmetric solvation to one Zn atom in the dimer were found to lie lower in energy than structures adopting symmetric solvation to both Zn atoms. Combining experiment and theory the spectra show that water molecules preferentially bind to one Zn atom adopting water binding motifs similar to the Zn+(H2O)n complexes studied previously. A lower coordination number of 2 was observed for Zn2+(H2O)3 evident from the highly red-shifted band in the hydrogen bonding region. Photodissociation leading to loss of a neutral Zn atom was observed only for n = 3 attributed to a particularly low calculated Zn binding energy for this cluster size.
The Influence of Hydrogen Sulfide Contaminations on Hydrogen Production in Chemical Looping Processes
Aug 2021
Publication
Chemical looping with iron-based oxygen carriers enables the production of hydrogen from various fossil and biogenic primary energy sources. In applications with real producer gases such as biogas or gasified biomass hydrogen sulfide represents one of the most challenging contaminants. The impact of H2S on the reactivity of a Fe2O3/Al2O3 oxygen carrier material in chemical looping hydrogen production was investigated in the present work. First potential sulfur deactivation mechanisms are discussed in detail on the basis of thermodynamic data. Afterwards an experimental study in a fixed-bed reactor system gave experimental evidence on the fate of sulfur in chemical looping hydrogen systems. The chemisorption of hydrogen sulfide (H2S) was identified as the main cause for the accumulative adsorption of H2S in the reduction phase and was confirmed by ex-situ ICP-EOS analysis. In the subsequent steam oxidation step significant quantities of H2S were released resulting in an undesirable contamination of the hydrogen product gas. The reason was found as weakened sulfur bonds through increasing reactor temperatures caused by the exothermic oxidation reactions. In additional air oxidation steps no further contaminants as sulfur dioxide were identified. A profound interpretation was achieved through the fulfillment of the overall sulfur mass balance within a mean deviation of 3.7%. Quantitative investigations showed that the hydrogen consumption decreased by 12% throughout the reduction phase in the event of 100 ppm H2S in the feed gas
Critical Review of Models for H2-permeation Through Polymers with Focus on the Differential Pressure Method
May 2021
Publication
To reduce loss of hydrogen in storage vessels with high energy-to-weight-ratio new materials especially polymers have to be developed as barrier materials. Very established methods for characterization of barrier materials with permeation measurements are the time-lag and flow rate method along with the differential pressure method which resembles the nature of hydrogen vessel systems very well. Long measurement durations are necessary to gain suitable measurement data for these evaluation methods and often restrictive conditions have to be fulfilled. For these reasons common models for hydrogen permeation through single-layer and multi-layer membranes as well as models for hydrogen gas properties were collected and reviewed. Using current computer power together with these models can reduce measurement time for characterization of the barrier properties of materials while additional information about the quality of the measurement results is obtained.
Validation of Selected Optical Methods for Assessing Polyethylene (PE) Liners Used in High Pressure Vessels for Hydrogen Storage
Jun 2021
Publication
A polyethylene (PE) liner is the basic element in high-pressure type 4 composite vessels designed for hydrogen or compressed natural gas (CNG) storage systems. Liner defects may result in the elimination of the whole vessel from use which is very expensive both at the manufacturing and exploitation stage. The goal is therefore the development of efficient non-destructive testing (NDT) methods to test a liner immediately after its manufacturing before applying a composite reinforcement. It should be noted that the current regulations codes and standards (RC&S) do not specify liner testing methods after manufacturing. It was considered especially important to find a way of locating and assessing the size of air bubbles and inclusions and the field of deformations in liner walls. It was also expected that these methods would be easily applicable to mass-produced liners. The paper proposes the use of three optical methods namely visual inspection digital image correlation (DIC) and optical fiber sensing based on Bragg gratings (FBG). Deformation measurements are validated with finite element analysis (FEA). The tested object was a prototype of a hydrogen liner for high-pressure storage (700 bar). The mentioned optical methods were used to identify defects and measure deformations.
Magnesium Gasar as a Potential Monolithic Hydrogen Absorbent
Feb 2021
Publication
The study focuses on the aspect of using the structure of gasars i.e. materials with directed open porosity as a potential hydrogen storage. The structure of the tested gasar is composed of a large number of thin open tubular pores running through the entire longitudinal section of the sample. This allows hydrogen to easily penetrate into the entire sample volume. The analysis of pore distribution showed that the longest diffusion path needed for full penetration of the metal structure with hydrogen is about L = 50–70 μm regardless of the external dimensions of the sample. Attempts to hydrogenate the magnesium gasar structure have shown its ability to accumulate hydrogen at a level of 1 wt%. The obtained results were compared with the best result was obtained for the ZK60 alloy after equal channel angular pressing (ECAP) and crushed to a powder form. The result obtained exceeded 4 wt% of hydrogen accumulated in the metal structure at theoretical 6.9 wt% maximum capacity. A model analysis of the theoretic absorption capacity of pure magnesium was also carried out based on the concentration of vacancies in the metal structure. The theoretical results obtained correlate well with experimental data.
Critical Assessment of the Effect of Atmospheric Corrosion Induced Hydrogen on Mechanical Properties of Advanced High Strength Steel
Dec 2020
Publication
Hydrogen absorption into steel during atmospheric corrosion has been of a strong concern during last decades. It is technically important to investigate if hydrogen absorbed under atmospheric exposure conditions can significantly affect mechanical properties of steels. The present work studies changes of mechanical properties of dual phase (DP) advanced high strength steel specimens with sodium chloride deposits during corrosion in humid air using Slow Strain Rate Test (SSRT). Additional annealed specimens were used as reference in order to separate the possible effect of absorbed hydrogen from that of corrosion deterioration. Hydrogen entry was monitored in parallel experiments using hydrogen electric resistance sensor (HERS) and thermal desorption mass spectrometry (TDMS). SSRT results showed a drop in elongation and tensile strength by 42% and 6% respectively in 27 days of atmospheric exposure. However this decrease cannot be attributed to the effect of absorbed hydrogen despite the increase in hydrogen content with time of exposure. Cross-cut analysis revealed considerable pitting which was suggested to be the main reason for the degradation of mechanical properties
High-pressure Hydrogen Production with Inherent Sequestration of a Pure Carbon Dioxide Stream Via Fixed Bed Chemical Looping
Feb 2019
Publication
The proof of concept for the production of pure pressurized hydrogen from hydrocarbons in combination with the sequestration of a pure stream of carbon dioxide with the reformer steam iron cycle is presented. The iron oxide based oxygen carrier (95% Fe2O3 5% Al2O3) is reduced with syngas and oxidized with steam at 1023 K. The carbon dioxide separation is achieved via partial reduction of the oxygen carrier from Fe2O3 to Fe3O4 yielding thermodynamically to a product gas only containing CO2 and H2O. By the subsequent condensation of steam pure CO2 is sequestrated. After each steam oxidation phase an air oxidation was applied to restore the oxygen carrier to hematite level. Product gas pressures of up to 30.1 bar and hydrogen purities exceeding 99% were achieved via steam oxidations. The main impurities in the product gas are carbon monoxide and carbon dioxide which originate from solid carbon depositions or from stored carbonaceous molecules inside the pores of the contact mass. The oxygen carrier samples were characterized using elemental analysis BET surface area measurement XRD powder diffraction SEM and light microscopy. The maximum pressure of 95 bar was demonstrated for hydrogen production in the steam oxidation phase after the full oxygen carrier reduction significantly reducing the energy demand for compressors in mobility applications.
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.
Accelerated Degradation for Solid Oxide Electrolysers: Analysis and Prediction of Performance for Varying Operating Environments
Jan 2022
Publication
Solid oxide electrolysis cells (SOECs) are an efficient technology for the production of green hydrogen that has great potential to contribute to the energy transition and decarbonization of industry. To date however time- and resource-intensive experimental campaigns slow down the development and market penetration of the technology. In order to speed-up the evaluation of SOEC performance and durability accelerated testing protocols are required. This work provides the results of experimental studies on the performance of a SOEC stack operated under accelerated degradation conditions. In order to initiate and accelerate degradation experiments were performed with high steam partial pressures at the gas inlet higher voltages and lower temperatures and high steam conversion rates. Thereby different types and degrees of impact on performance were observed which were analyzed in detail and linked to the underlying processes and degradation mechanisms. In this context significantly higher degradation rates were found compared to operation under moderate operating conditions with the different operating strategies varying in their degradation acceleration potential. The results also suggest that a few hundred hours of operation may be sufficient to predict long-term performance with the proposed operating strategies providing a solid basis for accelerated assessment of SOEC performance evolution and lifetime.
Characterization of Materials in Pressurized Hydrogen Under Cyclic Loading at Service Conditions in Hydrogen Powered Engines
Sep 2005
Publication
A new testing device for cyclic loading of specimens with a novel shape design is presented. The device was applied for investigations of fatigue of metallic specimens under pressurized hydrogen up to 300 bar at temperatures up to 200 °C. Main advantage of the specimen design is the very small amount of medium here hydrogen used for testing. This allows experiments with hazardous substances at lower safety level. Additionally no gasket for the load transmission is required. Woehler curves which show the influence of hydrogen on the fatigue behaviour of austenitic steel specimens at relevant service conditions in hydrogen powered engines are presented. Material and test conditions are in agreement with the cooperating industry.
Data-driven Parameterization of Polymer Electrolyte Membrane fuel Cell Models Via Simultaneous Local Linear Structured State Space Identification
Feb 2021
Publication
In order to mitigate the degradation and prolong the lifetime of polymer electrolyte membrane fuel cells advanced model-based control strategies are becoming indispensable. Thereby the availability of accurate yet computationally efficient fuel cell models is of crucial importance. Associated with this is the need to efficiently parameterize a given model to a concise and cost-effective experimental data set. A challenging task due to the large number of unknown parameters and the resulting complex optimization problem. In this work a parameterization scheme based on the simultaneous estimation of multiple structured state space models obtained by analytic linearization of a candidate fuel cell stack model is proposed. These local linear models have the advantage of high computational efficiency regaining the desired flexibility required for the typically iterative task of model parameterization. Due to the analytic derivation of the local linear models the relation to the original parameters of the non-linear model is retained. Furthermore the local linear models enable a straight-forward parameter significance and identifiability analysis with respect to experimental data. The proposed method is demonstrated using experimental data from a 30 kW commercial polymer electrolyte membrane fuel cell stack.
Recent Advancements in Chemical Looping Water Splitting for the Production of Hydrogen
Oct 2016
Publication
Chemical looping water splitting or chemical looping hydrogen is a very promising technology for the production of hydrogen. In recent years extensive research has enabled remarkable leaps towards a successful integration of the chemical looping technology into a future hydrogen infrastructure. Progress has been reported with iron based oxygen carriers for stable hydrogen production capacity over consecutive cycles without significant signs of degradation. The high stability improvements were achieved by adding alien metal oxides or by integrating the active component into a mineral structure which offers excellent resistance towards thermal stress. Prototype systems from small μ-systems up to 50 kW have been operated with promising results. The chemical looping water splitting process was broadened in terms of its application area and utilization of feedstocks using a variety of renewable and fossil resources. The three-reactor system was clearly advantageous due to its flexibility heat integration capabilities and possibility to produce separate pure streams of hydrogen CO2 and N2. However two-reactor and single fixed-bed reactor systems were successfully operated as well. This review aims to survey the recently presented literature in detail and systematically summarize the gathered data.
Hydrocarbon Production by Continuous Hydrodeoxygenation of Liquid Phase Pyrolysis Oil with Biogenous Hydrogen Rich Synthesis Gas
Feb 2019
Publication
This paper presents a beneficial combination of biomass gasification and pyrolysis oil hydrodeoxygenation for advanced biofuel production. Hydrogen for hydrodeoxygenation (HDO) of liquid phase pyrolysis oil (LPP oil) was generated by gasification of softwood. The process merges dual fluidized bed (DFB) steam gasification which produces a hydrogen rich product gas and the HDO of LPP oil. Synthesis gas was used directly without further cleaning and upgrading by making use of the water gas-shift (WGS) reaction. The water needed for the water gas-shift reaction was provided by LPP oil. HDO was successfully performed in a lab scale over 36 h time on stream (TOS). Competing reactions like the Boudouard reaction and Sabatier reaction were not observed. Product quality was close to Diesel fuel specification according to EN 590 with a carbon content of 85.4 w% and a residual water content of 0.28 w%. The water-gas shift reaction was confirmed by CO/CO2-balance high water consumption and 28% less hydrogen consumption during HDO.
Sustainable Hydrogen Society - Vision, Findings and Development of a Hydrogen Economy Using the Example of Austria
Oct 2021
Publication
Based on technical environmental economic and social facts and recent findings the feasibility of the transition from our current fossil age to the new green age is analyzed in detail at both global and local level. To avert the threats of health problems environmental pollution and climate change to our quality and standard of life a twofold radical paradigm shift is outlined: Green Energy Revolution means the complete change from fossil-based to green primary energy sources such as sun wind water environmental heat and biomass; Green Hydrogen Society means the complete change from fossil-based final energy to green electricity and green hydrogen in all areas of mobility industries households and energy services. Renewable energies offer a green future and are in combination with electrochemical machines such as electrolysers batteries and fuel cells able to achieve higher efficiencies and zero emissions.
Safety Demands for Automotive Hydrogen Storage Systems
Sep 2005
Publication
Fuel storage systems for vehicles require a fail-safe design strategy. In case of system failures or accidents the control electronics have to switch the system into a safe operation mode. Failure Mode and Effect Analysis (FMEA) or Failure Tree Analysis (FTA) are performed already in the early design phase in order to minimize the risk of design failures in the fuel storage system. Currently the specifications of requirements for pressurized and liquid hydrogen fuel tanks are based on draft UN-ECE Regulations developed by the European Integrated Hydrogen Project (EIHP). Used materials and accessories shall be compatible with hydrogen. A selection of metallic and non-metallic materials will be presented. Complex components have to be optimised by FEM simulations in order to determine weak spots in the design which will be overstressed in case of pressure thermal expansion or dynamic vibrations. According to automotive standards the performance of liquid hydrogen fuel tank systems has to be verified in various destructive and non-destructive tests.
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.
Prospects of Enhancing the Understanding of Material-hydrogen Interaction by Novel In-situ and In-operando Methods
Jan 2022
Publication
A main scientific and technical challenge facing the implementation of new and sustainable energy sources is the development and improvement of materials and components. In order to provide commercial viability of these applications an intensive research in material-hydrogen (H) interaction is required. This work provides an overview of recently developed in-situ and in-operando H-charging methods and their applicability to investigate mechanical properties H-absorption characteristics and H embrittlement (HE) susceptibility of a wide range of materials employed in H-related technologies such as subsea oil and gas applications nuclear fusion and fuel cells.
Combination of b-Fuels and e-Fuels—A Technological Feasibility Study
Aug 2021
Publication
The energy supply in Austria is significantly based on fossil natural gas. Due to the necessary decarbonization of the heat and energy sector a switch to a green substitute is necessary to limit CO2 emissions. Especially innovative concepts such as power-to-gas establish the connection between the storage of volatile renewable energy and its conversion into green gases. In this paper different methanation strategies are applied on syngas from biomass gasification. The investigated syngas compositions range from traditional steam gasification sorption-enhanced reforming to the innovative CO2 gasification. As the producer gases show different compositions regarding the H2/COx ratio three possible methanation strategies (direct sub-stoichiometric and over-stoichiometric methanation) are defined and assessed with technological evaluation tools for possible future large-scale set-ups consisting of a gasification an electrolysis and a methanation unit. Due to its relative high share of hydrogen and the high technical maturity of this gasification mode syngas from steam gasification represents the most promising gas composition for downstream methanation. Sub-stoichiometric operation of this syngas with limited H2 dosage represents an attractive methanation strategy since the hydrogen utilization is optimized. The overall efficiency of the sub-stoichiometric methanation lies at 59.9%. Determined by laboratory methanation experiments a share of nearly 17 mol.% of CO2 needs to be separated to make injection into the natural gas grid possible. A technical feasible alternative avoiding possible carbon formation in the methanation reactor is the direct methanation of sorption-enhanced reforming syngas with an overall process efficiency in large-scale applications of 55.9%.
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