Germany
Scale-up of Milling in a 100 L Device for Processing of TiFeMn Alloy for Hydrogen Storage Applications: Procedure and characterization
Feb 2019
Publication
In this work the mechanical milling of a FeTiMn alloy for hydrogen storage purposes was performed in an industrial milling device. The TiFe hydride is interesting from the technological standpoint because of the abundance and the low cost of its constituent elements Ti and Fe as well as its high volumetric hydrogen capacity. However TiFe is difficult to activate usually requiring a thermal treatment above 400 °C. A TiFeMn alloy milled for just 10 min in a 100 L industrial milling device showed excellent hydrogen storage properties without any thermal treatment. The as-milled TiFeMn alloy did not need any activation procedure and showed fast kinetic behavior and good cycling stability. Microstructural and morphological characterization of the as-received and as-milled TiFeMn alloys revealed that the material presents reduced particle and crystallite sizes even after such short time of milling. The refined microstructure of the as-milled TiFeMn is deemed to account for the improved hydrogen absorption-desorption properties.
Study on Hydrogen from Renewable Resources in the EU
Feb 2016
Publication
Hydrogen can be produced from a broad range of renewable energy sources acting as a unique energy hub providing low or zero emission energy to all energy consuming sectors. Technically and efficiently producing hydrogen from renewable sources is a key enabler for these developments.<br/>Traditionally hydrogen has been produced from fossil sources by steam methane reforming of natural gas. At present the technology of choice to produce renewable ‘green’ hydrogen is water electrolysis using renewable electricity. The FCH JU has been supporting research and development of electrolyser technology and application projects aiming to increase the energy efficiency of electrolytic hydrogen production from renewable sources and to reduce costs.<br/>This study complements these activities by focusing on renewable hydrogen generation other than electrolysis. In this report these alternative hydrogen generation technologies are described characterized by their technical capabilities maturity and economic performance and assessed for their future potential.<br/>A methodology has been devised to first identify and structure a set of relevant green hydrogen pathways (eleven pathways depicted in the figure below) analyse them at a level of detail allowing a selection of those technologies which fit into and promise early commercialization in the framework of FCH 2 JU’s funding program.<br/>These originally proposed eleven pathways use solar thermal energy sunlight or biomass as major energy input.
A Novel Emergency Gas-to-Power System Based on an Efficient and Long-Lasting Solid-State Hydride Storage System: Modeling and Experimental Validation
Jan 2022
Publication
In this paper a gas-to-power (GtoP) system for power outages is digitally modeled and experimentally developed. The design includes a solid-state hydrogen storage system composed of TiFeMn as a hydride forming alloy (6.7 kg of alloy in five tanks) and an air-cooled fuel cell (maximum power: 1.6 kW). The hydrogen storage system is charged under room temperature and 40 bar of hydrogen pressure reaching about 110 g of hydrogen capacity. In an emergency use case of the system hydrogen is supplied to the fuel cell and the waste heat coming from the exhaust air of the fuel cell is used for the endothermic dehydrogenation reaction of the metal hydride. This GtoP system demonstrates fast stable and reliable responses providing from 149 W to 596 W under different constant as well as dynamic conditions. A comprehensive and novel simulation approach based on a network model is also applied. The developed model is validated under static and dynamic power load scenarios demonstrating excellent agreement with the experimental results.
Enabling Large-scale Hydrogen Storage in Porous Media – The Scientific Challenges
Jan 2021
Publication
Niklas Heinemann,
Juan Alcalde,
Johannes M. Miocic,
Suzanne J. T. Hangx,
Jens Kallmeyer,
Christian Ostertag-Henning,
Aliakbar Hassanpouryouzband,
Eike M. Thaysen,
Gion J. Strobel,
Cornelia Schmidt-Hattenberger,
Katriona Edlmann,
Mark Wilkinson,
Michelle Bentham,
Stuart Haszeldine,
Ramon Carbonell and
Alexander Rudloff
Expectations for energy storage are high but large-scale underground hydrogen storage in porous media (UHSP) remains largely untested. This article identifies and discusses the scientific challenges of hydrogen storage in porous media for safe and efficient large-scale energy storage to enable a global hydrogen economy. To facilitate hydrogen supply on the scales required for a zero-carbon future it must be stored in porous geological formations such as saline aquifers and depleted hydrocarbon reservoirs. Large-scale UHSP offers the much-needed capacity to balance inter-seasonal discrepancies between demand and supply decouple energy generation from demand and decarbonise heating and transport supporting decarbonisation of the entire energy system. Despite the vast opportunity provided by UHSP the maturity is considered low and as such UHSP is associated with several uncertainties and challenges. Here the safety and economic impacts triggered by poorly understood key processes are identified such as the formation of corrosive hydrogen sulfide gas hydrogen loss due to the activity of microbes or permeability changes due to geochemical interactions impacting on the predictability of hydrogen flow through porous media. The wide range of scientific challenges facing UHSP are outlined to improve procedures and workflows for the hydrogen storage cycle from site selection to storage site operation. Multidisciplinary research including reservoir engineering chemistry geology and microbiology more complex than required for CH4 or CO2 storage is required in order to implement the safe efficient and much needed large-scale commercial deployment of UHSP.
Response Time Measurement of Hydrogen Sensors
Sep 2017
Publication
The efficiency of gas sensor application for facilitating the safe use of hydrogen depends considerably on the sensor response to a change in hydrogen concentration. Therefore the response time has been measured for five different-type commercially available hydrogen sensors. Experiments showed that all these sensors surpass the ISO 26142 standard; for the response times t90 values of 2 s to 16 s were estimated. Results can be fitted with an exponential or sigmoidal function. It can be demonstrated that the results on transient behaviour depend on both the operating parameters of sensors and investigation methods as well as on the experimental conditions: gas change rate and concentration jump.
Radiation Damage of Reactor Pressure Vessel Steels Studied by Positron Annihilation Spectroscopy—A Review
Oct 2020
Publication
Safe and long term operation of nuclear reactors is one of the most discussed challenges in nuclear power engineering. The radiation degradation of nuclear design materials limits the operational lifetime of all nuclear installations or at least decreases its safety margin. This paper is a review of experimental PALS/PLEPS studies of different nuclear reactor pressure vessel (RPV) steels investigated over last twenty years in our laboratories. Positron annihilation lifetime spectroscopy (PALS) via its characteristics (lifetimes of positrons and their intensities) provides useful information about type and density of radiation induced defects. The new results obtained on neutron-irradiated and hydrogen ions implanted German steels were compared to those from the previous studies with the aim to evaluate different processes (neutron flux/fluence thermal treatment or content of selected alloying elements) to the microstructural changes of neutron irradiated RPV steel specimens. The possibility of substitution of neutron treatment (connected to new defects creation) via hydrogen ions implantation was analyzed as well. The same materials exposed to comparable displacement damage (dpa) introduced by neutrons and accelerated hydrogen ions shown that in the results interpretation the effect of hydrogen as a vacancy-stabilizing gas must be considered too. This approach could contribute to future studies of nuclear fission/fusion design steels treated by high levels of neutron irradiation.
Irreproducibility in Hydrogen Storage Material Research
Sep 2016
Publication
The storage of hydrogen in materials has received a significant amount of attention in recent years because this approach is widely thought to be one of the most promising solutions to the problem of storing hydrogen for use as an alternative energy carrier in a safe compact and affordable form. However there have been a number of high profile cases in which erroneous or irreproducible data have been published. Meanwhile the irreproducibility of research results in a wide range of disciplines has been the subject of an increasing amount of attention due to problems with some of the data in the literature. In this Perspective we provide a summary of the problems that have affected hydrogen storage material research. We also discuss the reasons behind them and possible ways of reducing the likelihood of further problems occurring in the future.
Anchoring of Turbulent Premixed Hydrogen/Air Flames at Externally Heated Walls
Oct 2020
Publication
A joint experimental and numerical investigation of turbulent flame anchoring at externally heated walls is presented. The phenomenon has primarily been studied for laminar flames and micro-combustion while this study focuses on large-scale applications and elevated Reynolds number flows. Therefore a novel burner design is developed and examined for a diverse set of operating conditions. Hydroxyl radical chemiluminescence measurements are employed to validate the numerical method. The numerical investigation evaluates the performance of various hydrogen/air kinetics Reynolds-averaged turbulence models and the eddy dissipation concept (EDC) as a turbulence-chemistry interaction model. Simulation results show minor differences between detailed chemical mechanisms but pronounced deviations for a reduced kinetic. The baseline k-ω turbulence model is assessed to most accurately predict flame front position and shape. Universal applicability of EDC modelling constants is contradicted. Conclusively the flame anchoring concept is considered a promising approach for pilot flames in continuous combustion devices.
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.
Numerical study of the release and dispersion of a light gas using 3D CFD code GASFLOW-MPI
Sep 2017
Publication
With the development of the hydrogen economy it requires a better understanding of the potential for fires and explosions associated with the unintended release of hydrogen within a partially confined space. In order to mitigate the hydrogen fire and explosion risks effectively accurate predictions of the hydrogen transport and mixing processes are crucial. It is well known that turbulence modelling is one of the key elements for a successful simulation of gas mixing and transport. GASFLOW-MPI is a scalable CFD software solution used to predict fluid dynamics conjugate heat and mass transfer chemical kinetics aerosol transportation and other related phenomena. In order to capture more turbulence information the Large Eddy Simulation (LES) model and LES/RANS hybrid model Detached Eddy Simulation (DES) have been implemented and validated in 3-D CFD code GASFLOW-MPI. The standard Smagorisky SGS model is utilized in LES turbulence model. And the k-epsilon based DES model is employed. This paper assesses the capability of algebraic k-epsilon DES and LES turbulence model to simulate the mixing and transport behavior of highly buoyant gases in a partially confined geometry. Simulation results agree well with the overall trend measured in experiments conducted in a reduced scale enclosure with idealized leaks which shows that all these four turbulent models are validated and suitable for the simulation of light gas behavior. Furthermore the numerical results also indicate that the LES and DES model could be used to analysis the turbulence behavior in the hydrogen safety problems.
Hydrogen and Hydrogen-derived Fuels through Methane Decomposition of Natural Gas – GHG Emissions and Costs
May 2020
Publication
Hydrogen can be produced from the decomposition of methane (also called pyrolysis). Many studies assume that this process emits few greenhouse gas (GHG) because the reaction from methane to hydrogen yields only solid carbon and no CO2. This paper assesses the life-cycle GHG emissions and the levelized costs for hydrogen provision from methane decomposition in three configurations (plasma molten metal and thermal gas). The results of these configurations are then compared to electrolysis and steam methane reforming (SMR) with and without CO2capture and storage (CCS). Under the global natural gas supply chain conditions hydrogen from methane decomposition still causes significant GHG emissions between 43 and 97 g CO2-eq./MJ. The bandwidth is predominately determined by the energy source providing the process heat i.e. the lowest emissions are caused by the plasma system using renewable electricity. This configuration shows lower GHG emissions compared to the “classical” SMR (99 g CO2-eq./MJ) but similar emissions to the SMR with CCS (46 g CO2-eq./MJ). However only electrolysis powered with renewable electricity leads to very low GHG emissions (3 g CO2-eq./MJ). Overall the natural gas supply is a decisive factor in determining GHG emissions. A natural gas supply with below-global average GHG emissions can lead to lower GHG emissions of all methane decomposition configurations compared to SMR. Methane decomposition systems (1.6 to 2.2 €/kg H2) produce hydrogen at costs substantially higher compared to SMR (1.0 to 1.2 €/kg) but lower than electrolyser (2.5 to 3.0 €/kg). SMR with CCS has the lowest CO2abatement costs (24 €/t CO2-eq. other > 141 €/t CO2-eq.). Finally fuels derived from different hydrogen supply options are assessed. Substantially lower GHG emissions compared to the fossil reference (natural gas and diesel/gasoline) are only possible if hydrogen from electrolysis powered by renewable energy is used (>90% less). The other hydrogen pathways cause only slightly lower or even higher GHG emissions.
Production of H2-rich Syngas from Excavated Landfill Waste through Steam Co-gasification with Biochar
Jun 2020
Publication
Gasification of excavated landfill waste is one of the promising options to improve the added-value chain during remediation of problematic old landfill sites. Steam gasification is considered as a favorable route to convert landfill waste into H2-rich syngas. Co-gasification of such a poor quality landfill waste with biochar or biomass would be beneficial to enhance the H2 concentration in the syngas as well as to improve the gasification performance. In this work steam co-gasification of landfill waste with biochar or biomass was carried out in a lab-scale reactor. The effect of the fuel blending ratio was investigated by varying the auxiliary fuel content in the range of 15e35 wt%. Moreover co-gasification tests were carried out at temperatures between 800 and 1000°C. The results indicate that adding either biomass or biochar enhances the H2 yield where the latter accounts for the syngas with the highest H2 concentration. At 800°C the addition of 35 wt% biochar can enhance the H2 concentration from 38 to 54 vol% and lowering the tar yield from 0.050 to 0.014 g/g-fuel-daf. No apparent synergetic effect was observed in the case of biomass co-gasification which might cause by the high Si content of landfill waste. In contrast the H2 production increases non-linearly with the biochar share in the fuel which indicates that a significant synergetic effect occurs during co-gasification due to the reforming of tar over biochar. Increasing the temperature of biochar co-gasification from 800 to 1000°C elevates the H2 concentration but decreases the H2/CO ratio and increases the tar yield. Furthermore the addition of biochar also enhances the gasification efficiency as indicated by increased values of the energy yield ratio.
Using the Jet Stream for Sustainable Airship and Balloon Transportation of Cargo and Hydrogen
Jul 2019
Publication
The maritime shipping sector is a major contributor to CO2 emissions and this figure is expected to rise in coming decades. With the intent of reducing emissions from this sector this research proposes the utilization of the jet stream to transport a combination of cargo and hydrogen using airships or balloons at altitudes of 10–20 km. The jet streams flow in the mid-latitudes predominantly in a west–east direction reaching an average wind speed of 165 km/h. Using this combination of high wind speeds and reliable direction hydrogen-filled airships or balloons could carry hydrogen with a lower fuel requirement and shorter travel time compared to conventional shipping. Jet streams at different altitudes in the atmosphere were used to identify the most appropriate circular routes for global airship travel. Round-the-world trips would take 16 days in the Northern Hemisphere and 14 in the Southern Hemisphere. Hydrogen transport via the jet stream due to its lower energy consumption and shorter cargo delivery time access to cities far from the coast could be a competitive alternative to maritime shipping and liquefied hydrogen tankers in the development of a sustainable future hydrogen economy.
Atomistic Modelling of Light-element Co-segregation at Structural Defects in Iron
Dec 2018
Publication
Studying the behaviour of hydrogen in the vicinity of extended defects such as grain boundaries dislocations nanovoids and phase boundaries is critical in understanding the phenomenon of hydrogen embrittlement. A key complication in this context is the interplay between hydrogen and other segregating elements. Modelling the competition of H with other light elements requires an efficient description of the interactions of compositionally complex systems with the system sizes needed to appropriately describe extended defects often precluding the use of direct ab initio approaches. In this regard we have developed novel electronic structure approaches to understand the energetics and mutual interactions of light elements at representative structural features in high-strength ferritic steels. Using this approach we examine the co-segregation of hydrogen with carbon at chosen grain boundaries in α-iron. We find that the strain introduced by segregated carbon atoms at tilt grain boundaries increases the solubility of hydrogen close to the boundary plane giving a higher H concentration in the vicinity of the boundary than in a carbon-free case. Via simulated tensile tests we find that the simultaneous presence of carbon and hydrogen at grain boundaries leads to a significant decrease in the elongation to fracture compared with the carbon-free case.
Towards an Understanding of Hydrogen Supply Chains: A Structured Literature Review Regarding Sustainability Evaluation
Oct 2021
Publication
Hydrogen technologies have received increased attention in research and development to foster the shift towards carbon-neutral energy systems. Depending on the specific production techniques transportation concepts and application areas hydrogen supply chains (HSCs) can be anything from part of the energy transition problem to part of the solution: Even more than battery-driven electric mobility hydrogen is a polyvalent technology and can be used in very different contexts with specific positive or negative sustainability impacts. Thus a detailed sustainability evaluation is crucial for decision making in the context of hydrogen technology and its diverse application fields. This article provides a comprehensive structured literature review in the context of HSCs along the triple bottom line dimensions of environmental economic and social sustainability analyzing a total of 288 research papers. As a result we identify research gaps mostly regarding social sustainability and the supply chain stages of hydrogen distribution and usage. We suggest further research to concentrate on these gaps thus strengthening our understanding of comprehensive sustainability evaluations for HSCs especially in social sustainability evaluation. In addition we provide an additional approach for discussion by adding literature review results from neighboring fields highlighting the joint challenges and insights regarding sustainability evaluation.
Origin of the Catalytic Activity at Graphite Electrodes in Vanadium Flow Batteries
Jun 2021
Publication
For many electrochemical devices that use carbon-based materials such as electrolyzers supercapacitors and batteries oxygen functional groups (OFGs) are considered essential to facilitate electron transfer. Researchers implement surface-active OFGs to improve the electrocatalytic properties of graphite felt electrodes in vanadium flow batteries. Herein we show that graphitic defects and not OFGs are responsible for lowering the activation energy barrier and thus enhance the charge transfer properties. This is proven by a thermal deoxygenation procedure in which specific OFGs are removed before electrochemical cycling. The electronic and microstructural changes associated with deoxygenation are studied by quasi in situ X-ray photoelectron and Raman spectroscopy. The removal of oxygen groups at basal and edge planes improves the activity by introducing new active edge sites and carbon vacancies. OFGs hinder the charge transfer at the graphite–electrolyte interface. This is further proven by modifying the sp2 plane of graphite felt electrodes with oxygen-containing pyrene derivatives. The electrochemical evolution of OFGs and graphitic defects are studied during polarization and long-term cycling conditions. The hypothesis of increased activity caused by OFGs was refuted and hydrogenated graphitic edge sites were identified as the true reason for this increase.
Energetics of LOHC: Structure-Property Relationships from Network of Thermochemical Experiments and in Silico Methods
Feb 2021
Publication
The storage of hydrogen is the key technology for a sustainable future. We developed an in silico procedure which is based on the combination of experimental and quantum-chemical methods. This method was used to evaluate energetic parameters for hydrogenation/dehydrogenation reactions of various pyrazine derivatives as a seminal liquid organic hydrogen carriers (LOHC) that are involved in the hydrogen storage technologies. With this in silico tool the tempo of the reliable search for suitable LOHC candidates will accelerate dramatically leading to the design and development of efficient materials for various niche applications.
Decarbonizing Copper Production by Power-to-Hydrogen A Techno-Economic Analysis
Apr 2021
Publication
Electrifying energy-intensive processes is currently intensively explored to cut greenhouse gas (GHG) emissions through renewable electricity. Electrification is particularly challenging if fossil resources are not only used for energy supply but also as feedstock. Copper production is such an energy-intensive process consuming large quantities of fossil fuels both as reducing agent and as energy supply.
Here we explore the techno-economic potential of Power-to-Hydrogen to decarbonize copper production. To determine the minimal cost of an on-site retrofit with Power-to-Hydrogen technology we formulate and solve a mixed-integer linear program for the integrated system. Under current techno-economic parameters for Germany the resulting direct CO2 abatement cost is 201 EUR/t CO2-eq for Power-to-Hydrogen in copper production. On-site utilization of the electrolysis by-product oxygen has a substantial economic benefit. While the abatement cost vastly exceeds current European emission certificate prices a sensitivity analysis shows that projected future developments in Power-to-Hydrogen technologies can greatly reduce the direct CO2 abatement cost to 54 EUR/t CO2-eq. An analysis of the total GHG emissions shows that decarbonization through Power-to-Hydrogen reduces the global GHG emissions only if the emission factor of the electricity supply lies below 160 g CO2-eq/kWhel.
The results suggest that decarbonization of copper production by Power-to-Hydrogen could become economically and environmentally beneficial over the next decades due to cheaper and more efficient Power-to-Hydrogen technology rising GHG emission certificate prices and further decarbonization of the electricity supply.
Here we explore the techno-economic potential of Power-to-Hydrogen to decarbonize copper production. To determine the minimal cost of an on-site retrofit with Power-to-Hydrogen technology we formulate and solve a mixed-integer linear program for the integrated system. Under current techno-economic parameters for Germany the resulting direct CO2 abatement cost is 201 EUR/t CO2-eq for Power-to-Hydrogen in copper production. On-site utilization of the electrolysis by-product oxygen has a substantial economic benefit. While the abatement cost vastly exceeds current European emission certificate prices a sensitivity analysis shows that projected future developments in Power-to-Hydrogen technologies can greatly reduce the direct CO2 abatement cost to 54 EUR/t CO2-eq. An analysis of the total GHG emissions shows that decarbonization through Power-to-Hydrogen reduces the global GHG emissions only if the emission factor of the electricity supply lies below 160 g CO2-eq/kWhel.
The results suggest that decarbonization of copper production by Power-to-Hydrogen could become economically and environmentally beneficial over the next decades due to cheaper and more efficient Power-to-Hydrogen technology rising GHG emission certificate prices and further decarbonization of the electricity supply.
Techno-economic Analysis of Hydrogen Enhanced Methanol to Gasoline Process from Biomass-derived Synthesis Gas
Mar 2021
Publication
In this paper the implications of the use of hydrogen on product yield and conversion efficiency as well as on economic performance of a hydrogen enhanced Biomass-to-Liquid (BtL) process are analyzed. A process concept for the synthesis of fuel (gasoline and LPG) from biomass-derived synthesis gas via Methanol-to-Gasoline (MtG) route with utilization of carbon dioxide from gasification by feeding additional hydrogen is developed and modeled in Aspen Plus. The modeled process produces 0.36 kg fuel per kg dry straw. Additionally 99 MW electrical power are recovered from purge and off gases from fuel synthesis in CCGT process covering the electricity consumption of fuel synthesis and synthesis gas generation. The hydrogen enhanced BtL procces reaches a combined chemical and electrical efficiency of 48.2% and overall carbon efficiency of 69.5%. The total product costs (TPC) sum up to 3.24 €/kg fuel. Raw materials (hydrogen and straw) make up the largest fraction of TPC with a total share of 75%. The hydrogen enhanced BtL process shows increased chemical energy and carbon efficiencies and thus higher product yields. However economic analysis shows that the process is unprofitable under current conditions due to high costs for hydrogen provision.
Effect of Corrosion-induced Hydrogen Embrittlement and its Degradation Impact on Tensile Properties and Fracture Toughness of (Al-Cu-Mg) 2024 Alloy
Jul 2016
Publication
In the present work the effect of artificial ageing of AA2024-T3 on the tensile mechanical properties and fracture toughness degradation due to corrosion exposure will be investigated. Tensile and fracture toughness specimens were artificially aged to tempers that correspond to Under-Ageing (UA) Peak-Ageing (PA) and Over-Ageing (OA) conditions and then were subsequently exposed to exfoliation corrosion environment. The corrosion exposure time was selected to be the least possible according to the experimental work of Alexopoulos et al. (2016) so as to avoid the formation of large surface pits trying to simulate the hydrogen embrittlement degradation only. The mechanical test results show that minimum corrosion-induced decrease in elongation at fracture was achieved for the peak-ageing condition while maximum was noticed at the under-ageing and over-ageing conditions. Yield stress decrease due to corrosion is less sensitive to tempering; fracture toughness decrease was sensitive to ageing heat treatment thus proving that the S΄ particles play a significant role on the corrosion-induced degradation.
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