Italy
Effect of Hot Mill Scale on Hydrogen Embrittlement of High Strength Steels for Pre-Stressed Concrete Structures
Mar 2018
Publication
The presence of a conductive layers of hot-formed oxide on the surface of bars for pre or post-compressing structures can promote localized attacks as a function of pH. The aggressive local environment in the occluded cells inside localized attacks has as consequence the possibility of initiation of stress corrosion cracking. In this paper the stress corrosion cracking behavior of high strength steels proposed for tendons was studied by means of Constant Load (CL) tests and Slow Strain Rate (SSR) tests. Critical ranges of pH for cracking were verified. The promoting role of localized attack was confirmed. Further electrochemical tests were performed on bars in as received surface conditions in order to evaluate pitting initiation. The adverse effect of mill scale was recognized.
Investigation of Mechanical Tests for Hydrogen Embrittlement in Automotive PHS Steels
Aug 2019
Publication
The problem of hydrogen embrittlement in ultra-high-strength steels is well known. In this study slow strain rate four-point bending and permeation tests were performed with the aim of characterizing innovative materials with an ultimate tensile strength higher than 1000 MPa. Hydrogen uptake in the case of automotive components can take place in many phases of the manufacturing process: during hot stamping due to the presence of moisture in the furnace atmosphere high-temperature dissociation giving rise to atomic hydrogen or also during electrochemical treatments such as cataphoresis. Moreover possible corrosive phenomena could be a source of hydrogen during an automobile’s life. This series of tests was performed here in order to characterize two press-hardened steels (PHS)—USIBOR 1500® and USIBOR 2000®—to establish a correlation between ultimate mechanical properties and critical hydrogen concentration.
Experimental Characterization of an Alkaline Electrolyser and a Compression System for Hydrogen Production and Storage
Aug 2021
Publication
Storing renewable energy in chemicals like hydrogen can bring various benefits like high energy density seasonal storability possible cost reduction of the final product and the potential to let renewable power penetrate other markets and to overcome their intermittent availability. In the last year’s production of this gas from renewable energy sources via electrolysis has grown its reputation as one feasible solution to satisfy future zero-emission energy demand. To extend the exploitation of Renewable Energy Source (RES) small-scale conversion plants seem to be an interesting option. In view of a possible widespread adoption of these types of plants the authors intend to present the experimental characterization of a small-scale hydrogen production and storage plant. The considered experimental plant is based on an alkaline electrolyser and an air-driven hydrogen compression and storage system. The results show that the hydrogen production-specific consumption is on average 77 kWh/kgH2 . The hydrogen compressor energy requirement is on average 15 kWh/kgH2 (data referred to the driving compressed air). The value is higher than data found in literature (4.4–9.3 kWh/kgH2 ) but the difference can be attributed to the small size of the considered compressor and the choice to limit the compression stages.
Graphene Oxide/metal Nanocrystal Multilaminates as the Atomic Limit for Safe and Selective Hydrogen Storage
Mar 2016
Publication
Interest in hydrogen fuel is growing for automotive applications; however safe dense solid-state hydrogen storage remains a formidable scientific challenge. Metal hydrides offer ample storage capacity and do not require cryogens or exceedingly high pressures for operation. However hydrides have largely been abandoned because of oxidative instability and sluggish kinetics. We report a new environmentally stable hydrogen storage material constructed of Mg nanocrystals encapsulated by atomically thin and gas-selective reduced graphene oxide (rGO) sheets. This material protected from oxygen and moisture by the rGO layers exhibits exceptionally dense hydrogen storage (6.5 wt% and 0.105 kg H2 per litre in the total composite). As rGO is atomically thin this approach minimizes inactive mass in the composite while also providing a kinetic enhancement to hydrogen sorption performance. These multilaminates of rGO-Mg are able to deliver exceptionally dense hydrogen storage and provide a material platform for harnessing the attributes of sensitive nanomaterials in demanding environments.
Tetrahydroborates: Development and Potential as Hydrogen Storage Medium
Oct 2017
Publication
The use of fossil fuels as an energy supply becomes increasingly problematic from the point of view of both environmental emissions and energy sustainability. As an alternative hydrogen is widely regarded as a key element for a potential energy solution. However differently from fossil fuels such as oil gas and coal the production of hydrogen requires energy. Alternative and intermittent renewable energy sources such as solar power wind power etc. present multiple advantages for the production of hydrogen. On the one hand the renewable sources contribute to a remarkable reduction of pollutants released to the air and on the other hand they significantly enhance the sustainability of energy supply. In addition the storage of energy in form of hydrogen has a huge potential to balance an effective and synergetic utilization of renewable energy sources. In this regard hydrogen storage technology is a key technology towards the practical application of hydrogen as “energy carrier”. Among the methods available to store hydrogen solid-state storage is the most attractive alternative from both the safety and the volumetric energy density points of view. Because of their appealing hydrogen content complex hydrides and complex hydride-based systems have attracted considerable attention as potential energy vectors for mobile and stationary applications. In this review the progresses made over the last century on the synthesis and development of tetrahydroborates and tetrahydroborate-based systems for hydrogen storage purposes are summarized.
Study of Hydrogen Enriched Premixed Flames
Sep 2005
Publication
In the present paper the theoretical study of the un-stretched laminar premixed flames of hydrogen-methane mixtures is carried out by using the detailed reaction mechanism GRI-Mech 3.0 implemented in the CHEMKIN software to find out the effect of hydrogen addition on the hybrid fuel burning velocity. The model results show that the laminar burning velocity of the hydrogen-methane mixtures is not the linear regression of those of the pure fuels since it results substantially less than the proportional averaging of the values for the fuel constituents. Moreover the effect of hydrogen addition in terms of enhancement of the mixture laminar burning velocity with respect to the methane is relevant only at very high values of the hydrogen content in the hybrid mixtures (> 70 % mol.). The performed sensitivity analysis shows that these results can be attributed to kinetics and in particular to the concentration of H radicals: depending on the hydrogen content in the fuels mixture the production of the H radicals can affect the limiting reaction step for methane combustion. Two regimes are identified in the hydrogen-methane combustion. The first regime is controlled by the methane reactivity the hydrogen being not able to significantly affect the laminar burning velocity (< 70 % mol.). In the second regime the hydrogen combustion has a relevant role as its high content in the hybrid fuel leads to a significant H radicals pool thus enhancing the reaction rate of the more slowly combusting methane.
Risk Analysis of the Storage Unit in Hydrogen Refuelling Station
Sep 2007
Publication
Nowadays consumer demand for local and global environmental quality in terms of air pollution and in particular greenhouse gas emissions reduction may help to drive to the introduction of zero emission vehicles. At this regard the hydrogen technology appears to have future market valuablepotential. On the other hand the use of hydrogen vehicles which requires appropriate infrastructures for production storage and refuelling stages presents a lot of safety problems due to the peculiar chemicophysical hydrogen characteristics. Therefore safe at the most practices are essential for the successful proliferation of hydrogen vehicles. Indeed to avoid limit hazards it is necessary to implement practices that if early adopted in the development of a fuelling station project can allow very low environmental impact safety being incorporated in the project itself. Such practices generally consist in the integrated use of Failure Mode and Effect Analysis (FMEA) HAZard OPerability (HAZOP) and Fault Tree Analysis (FTA) which constitute well established standards in reliability engineering. At this regard however a drawback is the lack of experience and the scarcity of the relevant data collection. In this work we present the results obtained by the integrated use of FMEA HAZOP and FTA analyses relevant for the moment the high-pressure storage equipment in a hydrogen gas refuelling station. The study that is intended to obtain elements for improving safety of the system can constitute a basis for further more refined works.
Inhomogeneous Hydrogen Deflagrations in the Presence of Obstacles in 25 m3 Enclosure. Experimental Results
Sep 2019
Publication
Explosion venting is a frequently used measure to mitigate the consequence of gas deflagrations in closed environments. Despite the effort to predict the vent area needed to achieved the protection through engineering formulas and CFD tools work has still to be done to reliably predict the outcome of a vented gas explosion. Blind-prediction exercises recently published show a large spread in the prediction of both engineering formula than CFD tools. University of Pisa performed experimental tests in a 25 m3 facility in inhomogeneous conditions and with the presence of simple obstacles constituted by plates bolted to HEB beams. The present paper is aimed to share the results of hydrogen dispersion and deflagration tests and discuss the comparison of maximum peak overpressure generated with different blockage ratio and repeated obstacles sets. Description of the experimental set-up includes all the details deemed necessary to reproduce the phenomenon with a CFD tool.
Integrating IT-SOFC and Gasification Combined Cycle with Methanation Reactor and Hydrogen Firing for Near Zero-emission Power Generation from Coal
Apr 2011
Publication
Application of Solid Oxide Fuel Cells (SOFC) in gasification-based power plants would represent a turning point in the power generation sector allowing to considerably increase the electric efficiency of coal-fired power stations while reducing CO2 and other pollutant emissions. The aim of this paper is the thermodynamic assessment of a SOFC-based IGFC plant with methanation reactor hydrogen post-firing and CO2 capture by physical absorption. The configuration proposed allows to obtain a very high net efficiency (51.6%) overcoming the main limits of configurations assessed in previous works.
Material Testing and Design Recommendations for Components Exposed to Hydrogen Enhanced Fatigue – the Mathryce Project
Sep 2013
Publication
The three years European MATHRYCE project dedicated to material testing and design recommendations for components exposed to hydrogen enhanced fatigue started in October 2012. Its main goal is to provide an “easy” to implement methodology based on lab-scale experimental tests under hydrogen gas to assess the service life of a real scale component taking into account fatigue loading under hydrogen gas. Dedicated experimental tests will be developed for this purpose. In the present paper the proposed approach is presented and compared to the methodologies currently developed elsewhere in the world.
Experimental Study of Hydrogen Releases in the Passenger Compartment of a Piaggio Porter
Sep 2011
Publication
There are currently projects and demonstration programs aiming at introducing Hydrogen powered Fuel Cell (HFC) vehicles into the market. Regione Toscana has been cofounder of the project “H2 Filiera Idrogeno” whose goal is to achieve a clean and sustainable mobility through HFC vehicle studies covering their production storage and use. Among the goals of the project was the substitution of the electric propulsion system with a hydrogen fuel cells propulsion system. This work presents a brief overview of the necessary modifications of the electric propulsion version of a Piaggio Porter to host a H2 fuel cell and experimental studies of realistic H2 releases from the vehicle. The scenarios covered H2 unintended releases underneath the vehicle when at rest and focused on three types of releases diffusive major and minor that might reach the interior of the vehicle and potentially pose a direct risk to the passengers.
Trends in Gas Sensor Development for Hydrogen Safety
Sep 2013
Publication
Gas sensors are applied for facilitating the safe use of hydrogen in for example fuel cell and hydrogen fuelled vehicles. New sensor developments aimed at meeting the increasingly stringent performance requirements in emerging applications are presented based on in-house technical developments and a literature study. The strategy of combining different detection principles i.e. sensors based on electrochemical cells semiconductors or field effects in combination with thermal conductivity sensor or catalytic combustion elements in one new measuring system is reported. This extends the dynamic measuring range of the sensor while improving sensor reliability to achieve higher safety integrity through diverse redundancy. The application of new nanoscaled materials nano wires carbon tubes and graphene as well as the improvements in electronic components of field-effect resistive-type and optical systems are evaluated in view of key operating parameters such as sensor response time low energy consumption and low working temperature.
CFD Simulations on Small Hydrogen Releases Inside a Ventilated Facility and Assessment of Ventilation Efficiency
Sep 2009
Publication
The use of stationary H2 and fuel cell systems is expected to increase rapidly in the future. In order to facilitate the safe introduction of this new technology the HyPer project funded by the EC developed a public harmonized Installation Permitting Guidance (IPG) document for the installation of small stationary H2 and fuel cell systems for use in various environments. The present contribution focuses on the safety assessment of a facility inside which a small H2 fuel cell system (4.8 kWe) is installed and operated. Dispersion experiments were designed and performed by partner UNIPI. The scenarios considered cover releases occurring inside the fuel cell at the valve of the inlet gas pipeline just before the pressure regulator which controls the H2 flow to the fuel cell system. H2 was expected to leak out of the fuel cell into the facility and then outdoors through the ventilation system. The initial leakage diameter was chosen based on the Italian technical guidelines for the enforcement of the ATEX European directive. Several natural ventilation configurations were examined. The performed tests were simulated by NCSRD using the ADREA-HF code. The numerical analysis took into account the full interior of the fuel cell in order to investigate for any potential accumulation effects. Comparisons between predicted and experimental H2 concentrations at 4 sensor locations inside the facility are reported. Finally an overall assessment of the ventilation efficiency was made based on the simulations and experiments.
Recent Developments in Pd-CeO2 Nano-composite Electrocatalysts for Anodic Reactions in Anion Exchange Membrane Fuel Cells
Jan 2022
Publication
In 2016 for the first time a polymer electrolyte fuel cell free of Pt electrocatalysts was shown to deliver more than 0.5 W cm-2 of peak power density from H2 and air (CO2 free). This was achieved with a silver-based oxygen reduction (ORR) cathode and a Pd-CeO2 hydrogen oxidation reaction (HOR) anodic electrocatalyst. The poor kinetics of the HOR under alkaline conditions is a considerable challenge to Anion Exchange Membrane Fuel Cell (AEMFC) development as high Pt loadings are still required to achieve reasonable performance. Previously the ameliorative combination of Pd and CeO2 nanocomposites has been exploited mostly in heterogeneous catalysis where the positive interaction is well documented. Carbon supported PdCeO2 HOR catalysts have now been prepared by different synthetic techniques and employed in AEMFCs as alternative to Pt and PtRu standards. Important research has also been recently reported delving into the origin of the HOR enhancement on Pd-CeO2. Such work has highlighted the importance of the bifunctional mechanism of the HOR at high pHs. Carefully prepared nano-structures of Pd and CeO2 that promote the formation of the Pd-O-Ce interface provide optimal binding of both Had and OHad species aspects which are crucial for enhanced HOR kinetics. This review paper discusses the recent advances in Pd-CeO2 electrocatalysts for AEMFC anodes.
Homogeneous and Inhomogeneous Hydrogen Deflagrations in 25 m3 Enclosure
Sep 2019
Publication
Explosion venting is a frequently used measure to mitigate the consequence of gas deflagrations in closed environments. Despite the effort to predict the vent area needed to achieved the protection through engineering formulas and CFD tools work has still to be done to reliably predict the outcome of a vented gas explosion. Most of available data derived from experimental campaigns performed in the past involved homogeneous conditions while especially in the case of a very buoyant gas such as hydrogen the most probable scenario that can follow and unintended release in a closed environment foresee the ignition of a stratified inhomogeneous mixture. University of Pisa performed experimental tests in a 25 m3 facility in homogeneous and inhomogeneous conditions. The present paper is aimed to share the results of hydrogen dispersion and deflagration tests and discuss the comparison of maximum peak overpressure generated in the two scenarios. Description of the experimental set-up includes all the details deemed necessary to reproduce the phenomenon with a CFD tool.
Safety Distances: Comparison of the Methodologies for Their Determination
Sep 2011
Publication
In this paper a study on the comparison between the different methodologies for the determination of the safety distances proposed by Standard Organizations and national Regulations is presented. The application of the risk-informed approach is one of the methodologies used for the determination of safety distances together with the risk-based approach. One of the main differences between the various methodologies is the risk criterion chosen. In fact a critical point is which level of risk should be used and then which are the harm events that must be considered. The harm distances are evaluated for a specified leak diameter that is a consequence of some parameters used in the various methodologies. The values of the safety distances proposed by Standard Organizations and national Regulations are a demonstration of the different approaches of the various methodologies especially in the choice of the leak diameter considered.
Integration of Open Slag Bath Furnace with Direct Reduction Reactors for New‐Generation Steelmaking
Jan 2022
Publication
The present paper illustrates an innovative steel processing route developed by employing hydrogen direct reduced pellets and an open slag bath furnace. The paper illustrates the direct reduction reactor employing hydrogen as reductant on an industrial scale. The solution allows for the production of steel from blast furnace pellets transformed in the direct reduction reactor. The reduced pellets are then melted in open slag bath furnaces allowing carburization for further refining. The proposed solution is clean for the decarbonization of the steel industry. The kinetic chemical and thermodynamic issues are detailed with particular attention paid to the slag conditions. The proposed solution is also supported by the economic evaluation compared to traditional routes.
Non-monotonic Overpressure vs. H2 Concentration Behaviour During Vented Deflagration. Experimental Results
Oct 2015
Publication
Explosion relief panels or doors are often used in industrial buildings to reduce damages caused by gas explosions. Decades of research have contributed to the understanding of the phenomena involved in gas explosions in order to establish an effective method to predict reliably the explosion overpressure. All the methods predict a monotonic increase of the overpressure with the concentration of the gas in the range from the lower explosion limit to the stoichiometric one. Nevertheless in few cases a non-monotonic behaviour of the maximum developed pressure as a function of hydrogen concentration was reported in the literature. The non-monotonic behaviour was also observed during experimental tests performed at the Scalbatraio laboratory at the University of Pisa in a 25 m3 vented combustion test facility with a vent area of 112 m2. This paper presents the results obtained during the tests and investigates the possible explanations of the phenomena.
Green H2 Production by Water Electrolysis Using Cation Exchange Membrane: Insights on Activation and Ohmic Polarization Phenomena
Dec 2021
Publication
Low-temperature electrolysis by using polymer electrolyte membranes (PEM) can play an important role in hydrogen energy transition. This work presents a study on the performance of a proton exchange membrane in the water electrolysis process at room temperature and atmospheric pressure. In the perspective of applications that need a device with small volume and low weight a miniaturized electrolysis cell with a 36 cm2 active area of PEM over a total surface area of 76 cm2 of the device was used. H2 and O2 production rates electrical power energy efficiency Faradaic efficiency and polarization curves were determined for all experiments. The effects of different parameters such as clamping pressure and materials of the electrodes on polarization phenomena were studied. The PEM used was a catalyst-coated membrane (Ir-Pt-Nafion™ 117 CCM). The maximum H2 production was about 0.02 g min−1 with a current density of 1.1 A cm−2 and a current power about 280 W. Clamping pressure and the type of electrode materials strongly influence the activation and ohmic polarization phenomena. High clamping pressure and electrodes in titanium compared to carbon electrodes improve the cell performance and this results in lower ohmic and activation resistances.
European Hydrogen Safety Training Programme for First Responders: Hyresponse Outcomes and Perspectives
Sep 2017
Publication
The paper presents the outcomes of the HyResponse project i.e. the European Hydrogen Safety Training Programme for first responders. The threefold training is described: the content of the educational training is presented the operational training platform and its mock-up real scale transport and hydrogen stationary installations are detailed and the innovative virtual tools and training exercises are highlighted. The paper underlines the outcomes the three pilot sessions as well as the Emergency Response Guide available on the HyResponse’s public website. The next steps for widespread dissemination into the community are discussed.
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