Austria
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.
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.
Hydrogen-assisted Cracking of GMA Welded 960 & A Grade High-strength Steels
Jan 2020
Publication
High-strength steels with yield strength of 960 MPa are susceptible to hydrogen-assisted cracking (HAC) during welding processing. In the present paper the implant test is used to study HAC in a quenched and tempered steel S960QL and a high-strength steel produced by thermo-mechanical controlled process S960MC. Welding is performed using the gas-metal arc welding process. Furthermore diffusible hydrogen concentration (HD) in arc weld metal is determined. Based on the implant test results lower critical stress (LCS) for complete fracture critical implant stress (σkrit) for crack initiation and embrittlement index (EI) are determined. At HD of 1.66 ml/100 g LCS is 605 MPa and 817 MPa for S960QL and S960MC respectively. EI is 0.30 and 0.46 for S960QL and S960MC respectively. Fracture surfaces of S960QL show higher degradation with reduced deformation. Both higher EI of S960MC and fractography show better resistance to HAC in the HAZ of S960MC compared to S960QL.
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.
Interlinking the Renewable Electricity and Gas Sectors: A Techno-Economic Case Study for Austria
Oct 2021
Publication
Achieving climate neutrality requires a massive transformation of current energy systems. Fossil energy sources must be replaced with renewable ones. Renewable energy sources with reasonable potential such as photovoltaics or wind power provide electricity. However since chemical energy carriers are essential for various sectors and applications the need for renewable gases comes more and more into focus. This paper determines the Austrian green hydrogen potential produced exclusively from electricity surpluses. In combination with assumed sustainable methane production the resulting renewable gas import demand is identified based on two fully decarbonised scenarios for the investigated years 2030 2040 and 2050. While in one scenario energy efficiency is maximised in the other scenario significant behavioural changes are considered to reduce the total energy consumption. A techno-economic analysis is used to identify the economically reasonable national green hydrogen potential and to calculate the averaged levelised cost of hydrogen (LCOH2) for each scenario and considered year. Furthermore roll-out curves for the necessary expansion of national electrolysis plants are presented. The results show that in 2050 about 43% of the national gas demand can be produced nationally and economically (34 TWh green hydrogen 16 TWh sustainable methane). The resulting national hydrogen production costs are comparable to the expected import costs (including transport costs). The most important actions are the quick and extensive expansion of renewables and electrolysis plants both nationally and internationally
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.
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.
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.
Porosity and Thickness Effect of Pd–Cu–Si Metallic Glasses on Electrocatalytic Hydrogen Production and Storage
Aug 2021
Publication
This contribution places emphasis on tuning pore architecture and film thickness of mesoporous Pd–Cu–Si thin films sputtered on Si/SiO2 substrates for enhanced electrocatalytic and hydrogen sorption/desorption activity and their comparison with the state-of-the-art thin film electrocatalysts. Small Tafel slope of 43 mV dec–1 for 1250 nm thick coatings with 2 µm diameter pores with 4.2 µm interspacing (H2) electrocatalyst with comparable hydrogen overpotentials to the literature suggests its use for standard fuel cells. The largest hydrogen sorption has been attained for the 250 nm thick electrocatalyst on 5 µm pore diameter and 12 µm interspacing (2189 µC cm–2 per CV cycle) making it possible for rapid storage systems. Moreover the charge transfer resistance described by an equivalent circuit model has an excellent correlation with Tafel slopes. Along with its very low Tafel slope of 42 mV dec–1 10 nm thick H2 pore design electrocatalyst has the highest capacitive response of ∼0.001 S sn cm–2 and is promising to be used as a nano-charger and hydrogen sensor.
Decarbonization of Australia’s Energy System: Integrated Modelling of the Transformation of Electricity, Transportation, and Industrial Sectors
Jul 2020
Publication
To achieve the Paris Agreement’s long-term temperature goal current energy systems must be transformed. Australia represents an interesting case for energy system transformation modelling: with a power system dominated by fossil fuels and specifically with a heavy coal component there is at the same time a vast potential for expansion and use of renewables. We used the multi-sectoral Australian Energy Modelling System (AUSeMOSYS) to perform an integrated analysis of implications for the electricity transport and selected industry sectors to the mid-century. The state-level resolution allows representation of regional discrepancies in renewable supply and the quantification of inter-regional grid extensions necessary for the physical integration of variable renewables. We investigated the impacts of different CO2 budgets and selected key factors on energy system transformation. Results indicate that coal-fired generation has to be phased out completely by 2030 and a fully renewable electricity supply achieved in the 2030s according to the cost-optimal pathway implied by the 1.5 °C Paris Agreement-compatible carbon budget. Wind and solar PV can play a dominant role in decarbonizing Australia’s energy system with continuous growth of demand due to the strong electrification of linked energy sectors.
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.
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.
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.
Characterization of the Inducible and Slow-Releasing Hydrogen Sulfide and Persulfide Donor P*: Insights into Hydrogen Sulfide Signaling
Jun 2021
Publication
Hydrogen sulfide (H2S) is an important mediator of inflammatory processes. However controversial findings also exist and its underlying molecular mechanisms are largely unknown. Recently the byproducts of H2S per-/polysulfides emerged as biological mediators themselves highlighting the complex chemistry of H2S. In this study we characterized the biological effects of P* a slow-releasing H2S and persulfide donor. To differentiate between H2S and polysulfide-derived effects we decomposed P* into polysulfides. P* was further compared to the commonly used fast-releasing H2S donor sodium hydrogen sulfide (NaHS). The effects on oxidative stress and interleukin-6 (IL-6) expression were assessed in ATDC5 cells using superoxide measurement qPCR ELISA and Western blotting. The findings on IL-6 expression were corroborated in primary chondrocytes from osteoarthritis patients. In ATDC5 cells P* not only induced the expression of the antioxidant enzyme heme oxygenase-1 via per-/polysulfides but also induced activation of Akt and p38 MAPK. NaHS and P* significantly impaired menadione-induced superoxide production. P* reduced IL-6 levels in both ATDC5 cells and primary chondrocytes dependent on H2Srelease. Taken together P* provides a valuable research tool for the investigation of H2S and per-/polysulfide signalling. These data demonstrate the importance of not only H2S but also per-/polysulfides as bioactive signaling molecules with potent anti-inflammatory and in particular antioxidant properties.
Achieving Carbon-neutral Iron and Steelmaking in Europe Through the Deployment of Bioenergy with Carbon Capture and Storage
Jan 2019
Publication
The 30 integrated steel plants operating in the European Union (EU) are among the largest single-point CO2 emitters in the region. The deployment of bioenergy with carbon capture and storage (bio-CCS) could significantly reduce their emission intensities. In detail the results demonstrate that CO2 emission reduction targets of up to 20% can be met entirely by biomass deployment. A slow CCS technology introduction on top of biomass deployment is expected as the requirement for emission reduction increases further. Bio-CCS could then be a key technology particularly in terms of meeting targets above 50% with CO2 avoidance costs ranging between €60 and €100 tCO2−1 at full-scale deployment. The future of bio-CCS and its utilisation on a larger scale would therefore only be viable if such CO2 avoidance cost were to become economically appealing. Small and medium plants in particular would economically benefit from sharing CO2 pipeline networks. CO2 transport however makes a relatively small contribution to the total CO2 avoidance cost. In the future the role of bio-CCS in the European iron and steelmaking industry will also be influenced by non-economic conditions such as regulations public acceptance realistic CO2 storage capacity and the progress of other mitigation technologies.
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.
Energy Management of Heavy-duty Fuel Cell Vehicles in Real-world Driving Scenarios: Robust Design of Strategies to Maximize the Hydrogen Economy and System Lifetime
Feb 2021
Publication
Energy management is a critical issue for the advancement of fuel cell vehicles because it significantly influences their hydrogen economy and lifetime. This paper offers a comprehensive investigation of the energy management of heavy-duty fuel cell vehicles for road freight transportation. An important and unique contribution of this study is the development of an extensive and realistic representation of the vehicle operation which includes 1750 hours of real-world driving data and variable truck loading conditions. This framework is used to analyze the potential benefits and drawbacks of heuristic optimal and predictive energy management strategies to maximize the hydrogen economy and system lifetime of fuel cell vehicles for road freight transportation. In particular the statistical evaluation of the effectiveness and robustness of the simulation results proves that it is necessary to consider numerous and realistic driving scenarios to validate energy management strategies and obtain a robust design. This paper shows that the hydrogen economy can be maximized as an individual target using the available driving information achieving a negligible deviation from the theoretical limit. Furthermore this study establishes that heuristic and optimal strategies can significantly reduce fuel cell transients to improve the system lifetime while retaining high hydrogen economies. Finally this investigation reveals the potential benefits of predictive energy management strategies for the multi-objective optimization of the hydrogen economy and system lifetime.
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.
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.
Hydrogen Uptake and Embrittlement of Carbon Steels in Various Environments
Aug 2020
Publication
To avoid failures due to hydrogen embrittlement it is important to know the amount of hydrogen absorbed by certain steel grades under service conditions. When a critical hydrogen content is reached the material properties begin to deteriorate. The hydrogen uptake and embrittlement of three different carbon steels (API 5CT L80 Type 1 P110 and 42CrMo4) was investigated in autoclave tests with hydrogen gas (H2) at elevated pressure and in ambient pressure tests with hydrogen sulfide (H2S). H2 gas with a pressure of up to 100 bar resulted in an overall low but still detectable hydrogen absorption which did not cause any substantial hydrogen embrittlement in specimens under a constant load of 90% of the specified minimum yield strength (SMYS). The amount of hydrogen absorbed under conditions with H2S was approximately one order of magnitude larger than under conditions with H2 gas. The high hydrogen content led to failures of the 42CrMo4 and P110 specimens.
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