Italy
Process Integration of Green Hydrogen: Decarbonization of Chemical Industries
Sep 2020
Publication
Integrated water electrolysis is a core principle of new process configurations for decarbonized heavy industries. Water electrolysis generates H2 and O2 and involves an exchange of thermal energy. In this manuscript we investigate specific traditional heavy industrial processes that have previously been performed in nitrogen-rich air environments. We show that the individual process streams may be holistically integrated to establish new decarbonized industrial processes. In new process configurations CO2 capture is facilitated by avoiding inert gases in reactant streams. The primary energy required to drive electrolysis may be obtained from emerging renewable power sources (wind solar etc.) which have enjoyed substantial industrial development and cost reductions over the last decade. The new industrial designs uniquely harmonize the intermittency of renewable energy allowing chemical energy storage. We show that fully integrated electrolysis promotes the viability of decarbonized industrial processes. Specifically new process designs uniquely exploit intermittent renewable energy for CO2 conversion enabling thermal integration H2 and O2 utilization and sub-process harmonization for economic feasibility. The new designs are increasingly viable for decarbonizing ferric iron reduction municipal waste incineration biomass gasification fermentation pulp production biogas upgrading and calcination and are an essential step forward in reducing anthropogenic CO2 emissions.
Expert Opinion Analysis on Renewable Hydrogen Storage Systems Potential in Europe
Nov 2016
Publication
Among the several typologies of storage technologies mainly on different physical principles (mechanical electrical and chemical) hydrogen produced by power to gas (P2G) from renewable energy sources complies with chemical storage principle and is based on the conversion of electrical energy into chemical energy by means of the electrolysis of water which does not produce any toxic or climate-relevant emission. This paper aims to pinpoint the potential uses of renewable hydrogen storage systems in Europe analysing current and potential locations regulatory framework governments’ outlooks economic issues and available renewable energy amounts. The expert opinion survey already used in many research articles on different topics including energy has been selected as an effective method to produce realistic results. The obtained results highlight strategies and actions to optimize the storage of hydrogen produced by renewables to face varying electricity demand and generation-driven fluctuations reducing the negative effects of the increasing share of renewables in the energy mix of European Countries.
Water Electrolysis for the Production of Hydrogen to Be Employed in the Ironmaking and Steelmaking Industry
Nov 2021
Publication
The way to decarbonization will be characterized by the huge production of hydrogen through sustainable routes. Thus the basic production way is water electrolysis sustained by renewable energy sources allowing for obtaining “green hydrogen”. The present paper reviews the main available technologies for the water electrolysis finalized to the hydrogen production. We describe the fundamental of water electrolysis and the problems related to purification and/or desalinization of water before electrolysis. As a matter of fact we describe the energy efficiency issues with particular attention to the potential application in the steel industry. The fundamental aspects related to the choice of high-temperature or low-temperature technologies are analyzed.
Electrolyzer Performance Analysis of an Integrated Hydrogen Power System for Greenhouse Heating. A Case Study
Jul 2016
Publication
A greenhouse containing an integrated system of photovoltaic panels a water electrolyzer fuel cells and a geothermal heat pump was set up to investigate suitable solutions for a power system based on solar energy and hydrogen feeding a self-sufficient geothermal-heated greenhouse. The electricity produced by the photovoltaic source supplies the electrolyzer; the manufactured hydrogen gas is held in a pressure tank. In these systems the electrolyzer is a crucial component; the technical challenge is to make it work regularly despite the irregularity of the solar source. The focus of this paper is to study the performance and the real energy efficiency of the electrolyzer analyzing its operational data collected under different operating conditions affected by the changeable solar radiant energy characterizing the site where the experimental plant was located. The analysis of the measured values allowed evaluation of its suitability for the agricultural requirements such as greenhouse heating. On the strength of the obtained result a new layout of the battery bank has been designed and exemplified to improve the performance of the electrolyzer. The evaluations resulting from this case study may have a genuine value therefore assisting in further studies to better understand these devices and their associated technologies.
Goal and Scope in Life Cycle Sustainability Analysis: The Case of Hydrogen Production from Biomass
Aug 2014
Publication
The framework for life cycle sustainability analysis (LCSA) developed within the project CALCAS (Co-ordination Action for innovation in Life-Cycle Analysis for Sustainability) is introducing a truly integrated approach for sustainability studies. However it needs to be further conceptually refined and to be made operational. In particular one of the gaps still hindering the adoption of integrated analytic tools for sustainability studies is the lack of a clear link between the goal and scope definition and the modeling phase. This paper presents an approach to structure the goal and scope phase of LCSA so as to identify the relevant mechanisms to be further detailed and analyzed in the modeling phase. The approach is illustrated with an on-going study on a new technology for the production of high purity hydrogen from biomass to be used in automotive fuel cells.
Integration of Gas Switching Combustion and Membrane Reactors for Exceeding 50% Efficiency in Flexible IGCC Plants with Near-zero CO2 Emissions
Jul 2020
Publication
Thermal power plants face substantial challenges to remain competitive in energy systems with high shares of variable renewables especially inflexible integrated gasification combined cycles (IGCC). This study addresses this challenge through the integration of Gas Switching Combustion (GSC) and Membrane Assisted Water Gas Shift (MAWGS) reactors in an IGCC plant for flexible electricity and/or H2 production with inherent CO2 capture. When electricity prices are high H2 from the MAWGS reactor is used for added firing after the GSC reactors to reach the high turbine inlet temperature of the H-class gas turbine. In periods of low electricity prices the turbine operates at 10% of its rated power to satisfy the internal electricity demand while a large portion of the syngas heating value is extracted as H2 in the MAWGS reactor and sold to the market. This product flexibility allows the inflexible process units such as gasification gas treating air separation unit and CO2 compression transport and storage to operate continuously while the plant supplies variable power output. Two configurations of the GSC-MAWGS plant are presented. The base configuration achieves 47.2% electric efficiency and 56.6% equivalent hydrogen production efficiency with 94.8–95.6% CO2 capture. An advanced scheme using the GSC reduction gases for coal-water slurry preheating and pre-gasification reached an electric efficiency of 50.3% hydrogen efficiency of 62.4% and CO2 capture ratio of 98.1–99.5%. The efficiency is 8.4%-points higher than the pre-combustion CO2 capture benchmark and only 1.9%-points below the unabated IGCC benchmark.
Improved Hydrogen-Production-Based Power Management Control of a Wind Turbine Conversion System Coupled with Multistack Proton Exchange Membrane Electrolyzers
Mar 2020
Publication
This paper deals with two main issues regarding the specific energy consumption in an electrolyzer (i.e. the Faraday efficiency and the converter topology). The first aspect is addressed using a multistack configuration of proton exchange membrane (PEM) electrolyzers supplied by a wind turbine conversion system (WTCS). This approach is based on the modeling of the wind turbine and the electrolyzers. The WTCS and the electrolyzers are interfaced through a stacked interleaved DC–DC buck converter (SIBC) due to its benefits for this application in terms of the output current ripple and reliability. This converter is controlled so that it can offer dynamic behavior that is faster than the wind turbine avoiding overvoltage during transients which could damage the PEM electrolyzers. The SIBC is designed to be connected in array configuration (i.e. parallel architecture) so that each converter operates at its maximum efficiency. To assess the performance of the power management strategy experimental tests were carried out. The reported results demonstrate the correct behavior of the system during transient operation.
Determination Of Hazardous Zones For A Generic Hydrogen Station – A Case Study
Sep 2007
Publication
A method for determination of hazardous zones for hydrogen installations has been studied. This work has been carried out within the NoE HySafe. The method is based on the Italian Method outlined in Guide 31-30(2004) Guide 31–35(2001) Guide 31-35/A(2001) and Guide 31-35/A; V1(2003). Hazardous zones for a “generic hydrogen refuelling station”(HRS) are assessed based on this method. The method is consistent with the EU directive 1999/92/EC “Safety and Health Protection of Workers potentially at risk from explosive atmospheres” which is the basis for determination of hazardous zones in Europe. This regulation is focused on protection of workers and is relevant for hydrogen installations such as hydrogen refuelling stations repair shops and other stationary installations where some type of work operations will be involved. The method is also based on the IEC standard and European norm IEC/EN60079-10 “Electrical apparatus for explosive gas atmospheres. Part 10 Classification of hazardous areas”. This is a widely acknowledged international standard/norm and it is accepted/approved by Fire and Safety Authorities in Europe and also internationally. Results from the HySafe work and other studies relevant for hydrogen and hydrogen installations have been included in the case study. Sensitivity studies have been carried out to examine the effect of varying equipment failure frequencies and leak sizes as well as environmental condition (ventilation obstacles etc.). The discharge and gas dispersion calculations in the Italian Method are based on simple mathematical formulas. However in this work also CFD (Computational Fluid Dynamics) and other simpler numerical tools have been used to quantitatively estimate the effect of ventilation and of different release locations on the size of the flammable gas cloud. Concentration limits for hydrogen to be used as basis for the extent of the hazardous zones in different situations are discussed.
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.
Guidelines for Fire Corps Standard Operating Procedures in the Event of Hydrogen Releases
Sep 2007
Publication
This paper presents a study on the Standard Operating Procedures (P.O.S.s) for the operation of the Fire Corps squads in the event of accidents with a hydrogen release fire or explosion. This study has been carried out by the Italian Working Group on the fire prevention safety issues as one of its main objectives. The Standard Operating Procedures proved to be a basic tool in order to improve the effectiveness of the Fire Corps rescue activity. The unique physical and chemical properties of the hydrogen its use without odorization and its almost invisible flame require a review of the already codified approaches to the rescue operations where conventional gases are involved. However this is only the first step; a Standard Operating Procedure puts together both the theoretical and practical experience achieved on the management of the rescue operations; therefore its arrangement is a cyclic process by nature always under continuous revision updating and improvement.
Potential Models For Stand-Alone And Multi-Fuel Gaseous Hydrogen Refuelling Stations- Assessment Of Associated Risk
Sep 2005
Publication
Air pollution and traffic congestion are two of the major issues affecting public authorities policy makers and citizens not only in Italy and European Union but worldwide; this is nowadays witnessed by always more frequent limitations to the traffic in most of Italian cities for instance. Hydrogen use in automotive appears to offer a viable solution in medium-long term; this new perspective involves the need to carry out adequate infrastructures for distribution and refuelling and consequently the need to improve knowledge on hydrogen technologies from a safety point of view. In the present work possible different configurations for gaseous hydrogen refuelling station has been compared: “stand-alone” and “multi-fuel”. These two alternative scenarios has been taken into consideration each of one with specific hypotheses: “stand-alone” configuration based on the hypothesis of a potential model consisting of a hydrogen refuelling station composed by on-site hydrogen production via electrolysis a trailer of compressed gas for back-up compressor unit intermediate storage unit and dispenser. In this model it is assumed that no other refuelling equipment and/or dispenser of traditional fuel is present in the same site. “multi-fuel” configuration where it is assumed that the same components for hydrogen refuelling station are placed in the same site beside one or more refuelling equipment and/or dispenser of traditional fuel. Comparisons have been carried out from the point of view of specific risk assessment which have been conducted on both the two alternative scenarios.
Comparative Life Cycle Assessment of Hydrogen-fuelled Passenger Cars
Feb 2021
Publication
In order to achieve gradual but timely decarbonisation of the transport sector it is essential to evaluate which types of vehicles provide a suitable environmental performance while allowing the use of hydrogen as a fuel. This work compares the environmental life-cycle performance of three different passenger cars fuelled by hydrogen: a fuel cell electric vehicle an internal combustion engine car and a hybrid electric vehicle. Besides two vehicles that use hydrogen in a mixture with natural gas or gasoline were considered. In all cases hydrogen produced by wind power electrolysis was assumed. The resultant life-cycle profiles were benchmarked against those of a compressed natural gas car and a hybrid electric vehicle fed with natural gas. Vehicle infrastructure was identified as the main source of environmental burdens. Nevertheless the three pure hydrogen vehicles were all found to be excellent decarbonisation solutions whereas vehicles that use hydrogen mixed with natural gas or gasoline represent good opportunities to encourage the use of hydrogen in the short term while reducing emissions compared to ordinary vehicles.
Fire Prevention Technical Rule for Gaseous Hydrogen Transport in Pipelines
Sep 2007
Publication
This paper presents the current results of the theoretical and experimental activity carried out by the Italian Working Group on the fire prevention safety issues in the field of the hydrogen transport in pipelines. From the theoretical point of view a draft document has been produced beginning from the regulations in force on the natural gas pipelines; these have been reviewed corrected and integrated with the instructions suitable to the use with hydrogen gas. From the experimental point of view a suitable apparatus has been designed and installed at the University of Pisa; this apparatus will allow the simulation of hydrogen releases from a pipeline with or without ignition of the hydrogen-air mixture. The experimental data will help the completion of the above-mentioned draft document with the instructions about the safety distances. However in the opinion of the Group the work on the text contents is concluded and the document is ready to be discussed with the Italian stakeholders involved in the hydrogen applications.
Modelling and Optimization of a Flexible Hydrogen-fueled Pressurized PEMFC Power Plant for Grid Balancing Purposes
Feb 2021
Publication
In a scenario characterized by an increasing penetration of non-dispatchable renewable energy sources and the need of fast-ramping grid-balancing power plants the EU project GRASSHOPPER aims to setup and demonstrate a highly flexible PEMFC Power Plant hydrogen fueled and scalable to MW-size designed to provide grid support.<br/>In this work different layouts proposed for the innovative MW-scale plant are simulated to optimize design and off-design operation. The simulation model details the main BoP components performances and includes a customized PEMFC model validated through dedicated experiments.<br/>The system may operate at atmospheric or mild pressurized conditions: pressurization to 0.7 barg allows significantly higher net system efficiency despite the increasing BoP consumptions. The additional energy recovery from the cathode exhaust with an expander gives higher net power and net efficiency adding up to 2%pt and reaching values between 47%LHV and 55%LHV for currents between 100% and 20% of the nominal value.
Green Hydrogen in Europe – A Regional Assessment: Substituting Existing Production with Electrolysis Powered by Renewables
Nov 2020
Publication
The increasing ambition of climate targets creates a major role for hydrogen especially in achieving carbon-neutrality in sectors presently difficult to decarbonise. This work examines to what extent the currently carbon-intensive hydrogen production in Europe could be replaced by water electrolysis using electricity from renewable energy resources (RES) such as solar photovoltaic onshore/offshore wind and hydropower (green hydrogen). The study assesses the technical potential of RES at regional and national levels considering environmental constraints land use limitations and various techno-economic parameters. It estimates localised clean hydrogen production and examines the capacity to replace carbon-intensive hydrogen hubs with ones that use RES-based water electrolysis. Findings reveal that -at national level- the available RES electricity potential exceeds the total electricity demand and the part for hydrogen production from electrolysis in all analysed countries. At regional level from the 109 regions associated with hydrogen production (EU27 and UK) 88 regions (81%) show an excess of potential RES generation after covering the annual electricity demand across all sectors and hydrogen production. Notably 84 regions have over 50% excess RES electricity potential after covering the total electricity demand and that for water electrolysis. The study provides evidence on the option to decarbonize hydrogen production at regional level. It shows that such transformation is possible and compatible with the ongoing transition towards carbon–neutral power systems in the EU. Overall this work aims to serve as a tool for designing hydrogen strategies in harmony with renewable energy policies.
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.
Helios- A New Method for Hydrogen Permeation Test
Sep 2013
Publication
Hydrogen induced cracking is still a severe and current threat for several industrial applications. With the aim of providing a simple and versatile device for hydrogen detection a new instrument was designed based on solid state sensor technology. New detection technique allows to execute hydrogen permeation measurement in short time and without material surface preparation. Thanks to this innovation HELIOS offers a concrete alternative to traditional experimental methods for laboratory permeability tests. In addition it is proposed as a new system for Non Destructive Testing of components in service in hydrogenating environment. Hydrogen flux monitoring is particularly relevant for risk mitigation of elements involved in hydrogen storage and transportation. Hydrogen permeation tests were performed by means of HELIOS instruments both on a plane membrane and on the wall of a gas cylinder. Results confirmed the extreme sensitivity of the detection system and its suitability to perform measurements even on non metallic materials by means of an easy-to-handle instrument.
Cylinders and Tubes Used as Buffers in Filling Stations
Oct 2015
Publication
Buffers are key components for hydrogen filling stations that are currently being developed. Type 1 or composite cylinders are used for this application. The type used depends on many parameters including pressure level cost and space available for the filling station. No international standards exist for such high pressure vessels whereas many standards exist covering Types 123 and 4 used for transport of gas or on-board fuel tanks. It is suggested to use the cylinders approved for transport or on-board applications as buffers. This solution appears to be safe if at least one issue is solved. The main difference is that transport or on-board cylinders are cycled from a low pressure to a high pressure during service whereas buffers are cycled from a relatively high pressure (corresponding to the vehicle’s filling pressure) to the MAWP. Another difference is that buffers are cycled many times per day. For standards developers requesting to systematically verify that buffers pass millions of cycles at low pressure amplitude would be impractical. Several standards and codes give formulae to estimate the number of shallow cycles when number of deep cycles are known. In this paper we describe tests performed on all types of composite cylinders to verify or determine the appropriate formulae.
Non-stoichiometric Methanation as Strategy to Overcome the Limitations of Green Hydrogen Injection into the Natural Gas Grid
Jan 2022
Publication
The utilization of power to gas technologies to store renewable electricity surpluses in the form of hydrogen enables the integration of the gas and electricity sectors allowing the decarbonization of the natural gas network through green hydrogen injection. Nevertheless the injection of significant amounts of hydrogen may lead to high local concentrations that may degrade materials (e.g. hydrogen embrittlement of pipelines) and in general be not acceptable for the correct and safe operation of appliances. Most countries have specific regulations to limit hydrogen concentration in the gas network. The methanation of hydrogen represents a potential option to facilitate its injection into the grid. However stoichiometric methanation will lead to a significant presence of carbon dioxide limited in gas networks and requires an accurate design of several reactors in series to achieve relevant concentrations of methane. These requirements are smoothed when the methanation is undertaken under non-stoichiometric conditions (high H/C ratio). This study aims to assess to influence of nonstoichiometric methanation under different H/C ratios on the limitations presented by the pure hydrogen injection. The impact of this injection on the operation of the gas network at local level has been investigated and the fluid-dynamics and the quality of gas blends have been evaluated. Results show that non-stoichiometric methanation could be an alternative to increase the hydrogen injection in the gas network and facilitates the gas and electricity sector coupling.
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.
Solid State Hydrogen Storage in Alanates and Alanate-Based Compounds: A Review
Jul 2018
Publication
The safest way to store hydrogen is in solid form physically entrapped in molecular form in highly porous materials or chemically bound in atomic form in hydrides. Among the different families of these compounds alkaline and alkaline earth metals alumino-hydrides (alanates) have been regarded as promising storing media and have been extensively studied since 1997 when Bogdanovic and Schwickardi reported that Ti-doped sodium alanate could be reversibly dehydrogenated under moderate conditions. In this review the preparative methods; the crystal structure; the physico-chemical and hydrogen absorption-desorption properties of the alanates of Li Na K Ca Mg Y Eu and Sr; and of some of the most interesting multi-cation alanates will be summarized and discussed. The most promising alanate-based reactive hydride composite (RHC) systems developed in the last few years will also be described and commented on concerning their hydrogen absorption and desorption performance.
Energy Saving in Public Transport Using Renewable Energy
Jan 2017
Publication
Hydrogen produced by renewable sources represents an interesting way to reduce the energetic dependence on fossil fuels in the transportation sector. This paper shows a feasibility study for the production storage and distribution of hydrogen in the western Sicilian context using three different renewable sources: wind biomass and sea wave. The objective of this study is the evaluation of the hydrogen demand needed to replace all diesel supplied buses with electrical buses equipped with fuel cells. An economic analysis is presented with the evaluation of the avoidable greenhouse gas emissions. Four different scenarios correlate the hydrogen demand for urban transport to the renewable energy resources present in the territories and to the modern technologies available for the production of hydrogen. The study focuses on the possibility of tapping into the potential of renewable energies (wind biomass and sea wave) for the production of hydrogen by electrolysis. The use of hydrogen would reduce significantly the emissions of particulate and greenhouse gases in the urban districts under analysis.
Willingness to Pay and Public Acceptance for Hydrogen Buses: A Case Study of Perugia
Sep 2015
Publication
Sustainability transportation is characterized by a positive externality on the environment health social security land use and social inclusion. The increasing interest in global warming has caused attention to be paid to the introduction of the hydrogen bus (H2B). When introducing new environmental technologies such as H2B it is often necessary to assess the environmental benefits related to this new technology. However such benefits are typically non-priced due to their public good nature. Therefore we have to address this problem using the contingent valuation (CV) method. This method has been developed within environmental economics as a means to economically assess environmental changes which are typically not traded in the market. So far several big cities have been analyzed to evaluate the perceived benefit related to H2B introduction but to the best of our knowledge no one has performed a CV analysis of a historical city where smog also damages historical buildings. This paper presents the results obtained using a multi-wave survey. We have investigated user preferences to elicit their willingness to pay for H2B introduction in Perugia taking into account all types of negative externalities due to the traffic pollution. The results confirm that residents in Perugia are willing to pay extra to support the introduction of H2B.
Optimal Integration of Hydrogen-Based Energy Storage Systems in Photovoltaic Microgrids: A Techno-Economic Assessment
Aug 2020
Publication
The feasibility and cost-effectiveness of hydrogen-based microgrids in facilities such as public buildings and small- and medium-sized enterprises provided by photovoltaic (PV) plants and characterized by low electric demand during weekends were investigated in this paper. Starting from the experience of the microgrid being built at the Renewable Energy Facility of Sardegna Ricerche (Italy) which among various energy production and storage systems includes a hydrogen storage system a modeling of the hydrogen-based microgrid was developed. The model was used to analyze the expected performance of the microgrid considering different load profiles and equipment sizes. Finally the microgrid cost-effectiveness was evaluated using a preliminary economic analysis. The results demonstrate that an effective design can be achieved with a PV system sized for an annual energy production 20% higher than the annual energy requested by the user and a hydrogen generator size 60% of the PV nominal power size. This configuration leads to a self-sufficiency rate of about 80% and without public grants a levelized cost of energy comparable with the cost of electricity in Italy can be achieved with a reduction of at least 25–40% of the current initial costs charged for the whole plant depending on the load profile shape.
Thermal Efficiency of On-site, Small-scale Hydrogen Production Technologies using Liquid Hydrocarbon Fuels in Comparison to Electrolysis a Case Study in Norway
Oct 2018
Publication
The main goal of this study was to assess the energy efficiency of a small-scale on-site hydrogen production and dispensing plant for transport applications. The selected location was the city of Narvik in northern Norway where the hydrogen demand is expected to be 100 kg/day. The investigated technologies for on-site hydrogen generation starting from common liquid fossil fuels such as heavy naphtha and diesel were based on steam reforming and partial oxidation. Water electrolysis derived by renewable energy was also included in the comparison. The overall thermal efficiency of the hydrogen station was computed including compression and miscellaneous power consumption.
Analysis of the Existing Barriers for the Market Development of Power to Hydrogen (P2H) in Italy
Sep 2020
Publication
New technological solutions are required to control the impact of the increasing presence of renewable energy sources connected to the electric grid that are characterized by unpredictable production (i.e. wind and solar energy). Energy storage is becoming essential to stabilize the grid when a mismatch between production and demand occurs. Among the available solutions Power to Hydrogen (P2H) is one of the most attractive options. However despite the potential many barriers currently hinder P2H market development. The literature reports general barriers and strategies to overcome them but a specific analysis is fundamental to identifying how these barriers concretely arise in national and regional frameworks since tailored solutions are needed to foster the development of P2H local market. The paper aims to identify and to analyze the existing barriers for P2H market uptake in Italy. The paper shows how several technical regulatory and economic issues are still unsolved resulting in a source of uncertainty for P2H investment. The paper also suggests possible approaches and solutions to address the Italian barriers and to support politics and decision-makers in the definition and implementation of the national hydrogen strategy.
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.
Macroeconomic Factors Influencing Public Policy Strategies for Blue and Green Hydrogen
Nov 2021
Publication
The aim of this paper is to analyze the factors affecting hydrogen and Carbon Capture and Storage Technologies (“CCS”) policies taking into consideration Fossil Fuel Consumption Oil Reserves the Debt/GDP Ratio the Trilemma Index and other variables with respect to OECD countries. STATA 17 was used for the analysis. The results confirm the hypothesis that countries with high fossil fuel consumption and oil reserves are investing in blue hydrogen and CCS towards a “zero-carbon-emission” perspective. Moreover countries with a good Debt/GDP ratio act most favorably to green policies by raising their Public Debt because Foreign Direct Investments are negatively correlated with those kinds of policies. Future research should exploit Green Finance policy decision criteria on green and blue hydrogen.
Innovative Passive Protection Systems For Hydrogen Production Plants
Sep 2005
Publication
As a part of a broader project on hydrogen production by reforming of methane in a membrane catalytic reactor this paper outlines the research activity performed at the University of Pisa Department of Chemical Engineering aimed at developing and testing composite panels that can operate as thermal protective shields against hydrogen jet fires. The shield design criterion that appears to give a more practical and convenient solution for the type of installation to be protected is the one that suggest to realize composite panels. Composite material are made of two elements fiber and matrix. In this study composite panels will be realized with basalt fabric as fiber and epoxy-phenolic resins as matrix. Therefore following the indications given by norms as UNI 9174 and ASTM E 1321-93 a test method has been studied to obtain temperature data from a specimen impinged by an hydrogen flame. Thanks to thermocouples applied on backside of the sample and an infrared video camera to realize thermal images of specimen surface impinged by flame this type of test try to characterize the behaviour of composite materials under the action of hydrogen flame simulating in a simple way the action of hydrogen jet fires.
Evaluation of Sorbents for High Temperature Removal of Tars, Hydrogen Sulphide, Hydrogen Chloride and Ammonia from Biomass-derived Syngas by Using Aspen Plus
Jan 2020
Publication
Biomass gasification is a promising technology to produce secondary fuels or heat and power offering considerable advantages over fossil fuels. An important aspect in the usage of producer gas is the removal of harmful contaminants from the raw syngas. Thus the object of this study is the development of a simulation model for a gasifier including gas clean-up for which a fluidized-bed gasifier for biomass-derived syngas production was considered based on a quasi-equilibrium approach through Gibbs free energy minimisation and including an innovative hot gas cleaning constituted by a combination of catalyst sorbents inside the gasification reactor catalysts in the freeboard and subsequent sorbent reactors by using Aspen Plus software. The gas cleaning chain simulates the raw syngas clean-up for several organic and inorganic contaminants i.e. toluene benzene naphthalene hydrogen sulphide hydrogen chloride and ammonia. The tar and inorganic contaminants final values achieved are under 1 g/Nm3 and 1 ppm respectively.
Safety Distances- Definition and Values
Sep 2005
Publication
In order to facilitate the introduction of a new technology as it is the utilization of hydrogen as an energy carrier development of safety codes and standards besides the conduction of demonstrative projects becomes a very important action to be realized. Useful tools of work could be the existing gaseous fuel codes (natural gas and propane) regulating the stationary and automotive applications. Some safety codes have been updated to include hydrogen but they have been based on criteria and/or data applicable for large industrial facilities making the realization of public hydrogen infrastructures prohibitive in terms of space. In order to solve the above mentioned problems others questions come out: how these safety distances have been defined? Which hazard events have been taken as reference for calculation? Is it possible to reduce the safety distances through an appropriate design of systems and components or through the predisposition of adequate mitigation measures? This paper presents an analysis of the definitions of “safety distances” and “hazardous locations” as well as a synoptic analysis of the different values in force in several States for hydrogen and natural gas. The above mentioned synoptic table will highlight the lacks and so some fields that need to be investigated in order to produce a suitable hydrogen standard.
Low-carbon Hydrogen Via Integration of Steam Methane Reforming with Molten Carbonate Fuel Cells at Low Fuel Utilization
Feb 2021
Publication
Hydrogen production is critical to many modern chemical processes – ammonia synthesis petroleum refining direct reduction of iron and more. Conventional approaches to hydrogen manufacture include steam methane reforming and autothermal reforming which today account for the lion's share of hydrogen generation. Without CO2 capture these processes emit about 8.7 kg of CO2 for each kg of H2 produced. In this study a molten carbonate fuel cell system with CO2 capture is proposed to retrofit the flue gas stream of an existing Steam Methane Reforming plant rated at 100000 Nm3 h−1 of 99.5% pure H2. The thermodynamic analysis shows direct CO2 emissions can be reduced by more than 95% to 0.4 to 0.5 kg CO2 /kg H2 while producing 17% more hydrogen (with an increase in natural gas input of approximately 37%). Because of the additional power and hydrogen generation of the carbonate fuel cell the efficiency debit associated with CO2 capture is quite small reducing the SMR efficiency from 76.6% without capture to 75.6% with capture. In comparison the use of standard amine technology for CO2 capture reduces the efficiency below 70%. This demonstrates the synergistic nature of the carbonate fuel cells which can reform natural gas to H2 while simultaneously capturing CO2 from the SMR flue gas and producing electricity giving rise to a total system with very low emissions yet high efficiency.
Control of Electrons’ Spin Eliminates Hydrogen Peroxide Formation During Water Splitting
Jul 2017
Publication
The production of hydrogen through water splitting in a photoelectrochemical cell suffers from an overpotential that limits the efficiencies. In addition hydrogen-peroxide formation is identified as a competing process affecting the oxidative stability of photoelectrodes. We impose spin-selectivity by coating the anode with chiral organic semiconductors from helically aggregated dyes as sensitizers; Zn-porphyrins and triarylamines. Hydrogen peroxide formation is dramatically suppressed while the overall current through the cell correlating with the water splitting process is enhanced. Evidence for a strong spin-selection in the chiral semiconductors is presented by magnetic conducting (mc-)AFM measurements in which chiral and achiral Zn-porphyrins are compared. These findings contribute to our understanding of the underlying mechanism of spin selectivity in multiple electron-transfer reactions and pave the way toward better chiral dye-sensitized photoelectrochemical cells.
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.
Life Cycle Performance of Hydrogen Production via Agro-Industrial Residue Gasification—A Small Scale Power Plant Study
Mar 2018
Publication
This study evaluates the environmental profile of a real biomass-based hydrogen production small-scale (1 MWth) system composed of catalytic candle indirectly heated steam gasifier coupled with zinc oxide (ZnO) guard bed water gas shift (WGS) and pressure swing absorber (PSA) reactors. Environmental performance from cradle-to-gate was investigated by life cycle assessment (LCA) methodology. Biomass production shows high influence over all impact categories. In the syngas production process the main impacts observed are global warming potential (GWP) and acidification potential (AP). Flue gas emission from gasifier burner has the largest proportion of total GWP. The residual off gas use in internal combustion engine (ICE) leads to important environmental savings for all categories. Hydrogen renewability score is computed as 90% due to over 100% decline in non-renewable energy demand. Sensitivity analysis shows that increase in hydrogen production efficiency does not necessarily result in decrease in environmental impacts. In addition economic allocation of environmental charges increases all impact categories especially AP and photochemical oxidation (POFP).
Mixing of Dense or Light Gases with Turbulent Air- a Fast-Running Model for Lumped Parameter Codes
Sep 2005
Publication
The release of gases heavier than air like propane at ground level or lighter than air like hydrogen close to a ceiling can both lead to fire and explosion hazards that must be carefully considered in safety analyses. Even if the simulation of accident scenarios in complex installations and long transients often appears feasible only using lumped parameter computer codes the phenomenon of denser or lighter gas dispersion is not implicitly accounted by these kind of tools. In the aim to set up an ad hoc model to be used in the computer code ECART fluid-dynamic simulations by the commercial FLUENT 6.0 CFD code are used. The reference geometry is related to cavities having variable depth (2 to 4 m) inside long tunnels filled with a gas heavier or lighter than air (propane or hydrogen). Three different geometrical configurations with a cavity width of 3 6 and 9 m are considered imposing different horizontal air stream velocities ranging from 1 to 5 m/s. A stably-stratified flow region is observed inside the cavity during gas shearing. In particular it is found that the density gradient tends to inhibit turbulent mixing thus reducing the dispersion rate. The obtained data are correlated in terms of main dimensionless groups by means of a least squares method. In particular the Sherwood number is correlated as a function of Reynolds a density ratio modified Froude numbers and in terms of the geometrical parameter obtained as a ratio between the depth of the air-dense gas interface and the length of the cavity. This correlation is implemented in the ECART code to add the possibility to simulate large installations during complex transients lasting many hours with reasonable computation time. An example of application to a typical case is presented.
Recent Progress and New Perspectives on Metal Amide and Imide Systems for Solid-State Hydrogen Storage
Apr 2018
Publication
Hydrogen storage in the solid state represents one of the most attractive and challenging ways to supply hydrogen to a proton exchange membrane (PEM) fuel cell. Although in the last 15 years a large variety of material systems have been identified as possible candidates for storing hydrogen further efforts have to be made in the development of systems which meet the strict targets of the Fuel Cells and Hydrogen Joint Undertaking (FCH JU) and U.S. Department of Energy (DOE). Recent projections indicate that a system possessing: (i) an ideal enthalpy in the range of 20–50 kJ/mol H2 to use the heat produced by PEM fuel cell for providing the energy necessary for desorption; (ii) a gravimetric hydrogen density of 5 wt. % H2 and (iii) fast sorption kinetics below 110 ◦C is strongly recommended. Among the known hydrogen storage materials amide and imide-based mixtures represent the most promising class of compounds for on-board applications; however some barriers still have to be overcome before considering this class of material mature for real applications. In this review the most relevant progresses made in the recent years as well as the kinetic and thermodynamic properties experimentally measured for the most promising systems are reported and properly discussed.
A Preliminary Assessment of the Potential of Low Percentage Green Hydrogen Blending in the Italian Natural Gas Network
Oct 2020
Publication
The growing rate of electricity generation from renewables is leading to new operational and management issues on the power grid because the electricity generated exceeds local requirements and the transportation or storage capacities are inadequate. An interesting option that is under investigation by several years is the opportunity to use the renewable electricity surplus to power electrolyzers that split water into its component parts with the hydrogen being directly injected into natural gas pipelines for both storage and transportation. This innovative approach merges together the concepts of (i) renewable power-to-hydrogen (P2H) and of (ii) hydrogen blending into natural gas networks. The combination of renewable P2H and hydrogen blending into natural gas networks has a huge potential in terms of environmental and social benefits but it is still facing several barriers that are technological economic legislative. In the framework of the new hydrogen strategy for a climate-neutral Europe Member States should design a roadmap moving towards a hydrogen ecosystem by 2050. The blending of “green hydrogen” that is hydrogen produced by renewable sources in the natural gas network at a limited percentage is a key element to enable hydrogen production in a preliminary and transitional phase. Therefore it is urgent to evaluate at the same time (i) the potential of green hydrogen blending at low percentage (up to 10%) and (ii) the maximum P2H capacity compatible with low percentage blending. The paper aims to preliminary assess the green hydrogen blending potential into the Italian natural gas network as a tool for policy makers grid and networks managers and energy planners.
Design and Costs Analysis of Hydrogen Refuelling Stations Based on Different Hydrogen Sources and Plant Configurations
Jan 2022
Publication
In this study the authors present a techno-economic assessment of on-site hydrogen refuelling stations (450 kg/day of H2 ) based on different hydrogen sources and production technologies. Green ammonia biogas and water have been considered as hydrogen sources while cracking autothermal reforming and electrolysis have been selected as the hydrogen production technologies. The electric energy requirements of the hydrogen refuelling stations (HRSs) are internally satisfied using the fuel cell technology as power units for ammonia and biogas-based configurations and the PV grid-connected power plant for the water-based one. The hydrogen purification where necessary is performed by means of a Palladium-based membrane unit. Finally the same hydrogen compression storage and distribution section are considered for all configurations. The sizing and the energy analysis of the proposed configurations have been carried out by simulation models adequately developed. Moreover the economic feasibility has been performed by applying the life cycle cost analysis. The ammonia-based configurations are the best solutions in terms of hydrogen production energy efficiency (>71% LHV) as well as from the economic point of view showing a levelized cost of hydrogen (LCOH) in the range of 6.28 EUR/kg to 6.89 EUR/kg a profitability index greater than 3.5 and a Discounted Pay Back Time less than five years.
Seasonal Energy Storage for Zero-emissions Multi-energy Systems Via Underground Hydrogen Storage
Jan 2020
Publication
The deployment of diverse energy storage technologies with the combination of daily weekly and seasonal storage dynamics allows for the reduction of carbon dioxide (CO2) emissions per unit energy provided. In particular the production storage and re-utilization of hydrogen starting from renewable energy has proven to be one of the most promising solutions for offsetting seasonal mismatch between energy generation and consumption. A realistic possibility for large-scale hydrogen storage suitable for long-term storage dynamics is presented by salt caverns. In this contribution we provide a framework for modelling underground hydrogen storage with a focus on salt caverns and we evaluate its potential for reducing the CO2 emissions within an integrated energy systems context. To this end we develop a first-principle model which accounts for the transport phenomena within the rock and describes the dynamics of the stored energy when injecting and withdrawing hydrogen. Then we derive a linear reduced order model that can be used for mixed-integer linear program optimization while retaining an accurate description of the storage dynamics under a variety of operating conditions. Using this new framework we determine the minimum-emissions design and operation of a multi-energy system with H2 storage. Ultimately we assess the potential of hydrogen storage for reducing CO2 emissions when different capacities for renewable energy production and energy storage are available mapping emissions regions on a plane defined by storage capacity and renewable generation. We extend the analysis for solar- and wind-based energy generation and for different energy demands representing typical profiles of electrical and thermal demands and different CO2 emissions associated with the electric grid.
Methanol Steam Reforming for Hydrogen Generation Via Conventional and Membrane Reactors: A Review
Sep 2013
Publication
Variable renewable energy (VRE) is expected to play a major role in the decarbonization of the electricity sector. However decarbonization via VRE requires a fleet of flexible dispatchable plants with low CO2 emissions to supply clean power during times with limited wind and sunlight. These plants will need to operate at reduced capacity factors with frequent ramps in electricity output posing techno-economic challenges. This study therefore presents an economic assessment of a new near-zero emission power plant designed for this purpose. The gas switching reforming combined cycle (GSR-CC) plant can produce electricity during times of low VRE output and hydrogen during times of high VRE output. This product flexibility allows the plant to operate continuously even when high VRE output makes electricity production uneconomical. Although the CO2 avoidance cost of the GSR-CC plant (€61/ton) was similar to the benchmark post-combustion CO2 capture plant under baseload operation GSR-CC clearly outperformed the benchmark in a more realistic scenario where continued VRE expansion forces power plants into mid-load operation (45% capacity factor). In this scenario GSR-CC promises a 5 %-point higher annualized investment return than the post-combustion benchmark. GSR-CC therefore appears to be a promising concept for a future scenario with high VRE market share and CO2 prices provided that a large market for clean hydrogen is established.
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.
Development of an Italian Fire Prevention Technical Rule For Hydrogen Pipelines
Sep 2011
Publication
This paper summarizes the current results of the theoretical and experimental activity carried out by the Italian Working Group on the fire prevention safety issues in the field of the hydrogen transport in pipelines. From the theoretical point of view a draft document has been produced beginning from the regulations in force on the natural gas pipelines; these have been reviewed corrected and integrated with the instructions suitable to the use of hydrogen. From the experimental point of view an apparatus has been designed and installed at the University of Pisa; this apparatus has allowed the simulation of hydrogen releases from a pipeline with and without ignition of hydrogen-air mixture. The experimental data have helped the completion of the above-mentioned draft document with the instructions about the safety distances. The document has been improved for example pipelines above ground (not buried) are allowed due to the knowledge acquired by means of the experimental campaign. The safety distances related to this kind of piping has been chosen on the base of risk analysis. The work on the text contents is concluded and the document is currently under discussion with the Italian stakeholders involved in the hydrogen applications.
Consequence Assessment of the BBC Hydrogen Refuelling Station, Using The Adrea-Hf Code
Sep 2009
Publication
Within the framework of the internal project HyQRA of the HYSAFE Network of Excellence (NoE) funded by the European Commission (EC) the participating partners were requested to apply their Quantitative Risk Assessment (QRA) methodologies on a predefined hypothetical gaseous H2 refuelling station named BBC (Benchmark Base Case). The overall aim of the HyQRA project was to perform an inter-comparison of the various QRA approaches and to identify the knowledge gaps on data and information needed in the QRA steps specifically related to H2. Partners NCSRD and UNIPI collaborated on a common QRA. UNIPI identified the hazards on site selected the most critical ones defined the events that could be the primary cause of an accident and provided to NCSRD the scenarios listed in risk order for the evaluation of the consequences. NCSRD performed the quantitative analysis using the ADREA-HF CFD code. The predicted risk assessment parameters (flammable H2 mass and volume time histories and maximum horizontal and vertical distances of the LFL from the source) were provided to UNIPI to analyze the consequences and to evaluate the risk and distances of damage. In total 15 scenarios were simulated. Five of them were H2 releases in confined ventilated spaces (inside the compression and the purification/drying buildings). The remaining 10 scenarios were releases in open/semi-confined spaces (in the storage cabinet storage bank and refuelling hose of one dispenser). This paper presents the CFD methodology applied for the quantitative analysis of the common UNIPI/NCSRD QRA and discusses the results obtained from the performed calculations.
Enhanced Performance and Durability of Low Catalyst Loading PEM Water Electrolyser Based on a Short-side Chain Perfluorosulfonic Ionomer
Sep 2016
Publication
Water electrolysis supplied by renewable energy is the foremost technology for producing ‘‘green” hydrogen for fuel cell vehicles. In addition the ability to rapidly follow an intermittent load makes electrolysis an ideal solution for grid-balancing caused by differences in supply and demand for energy generation and consumption. Membrane-electrode assemblies (MEAs) designed for polymer electrolyte membrane (PEM) water electrolysis based on a novel short-side chain (SSC) perfluorosulfonic acid (PFSA) membrane Aquivion with various cathode and anode noble metal loadings were investigated in terms of both performance and durability. Utilizing a nanosized Ir0.7Ru0.3O solid solution anode catalyst and a supported Pt/C cathode catalyst in combination with the Aquivion membrane gave excellent electrolysis performances exceeding 3.2 A cm-2 at 1.8 V terminal cell voltage ( 80% efficiency) at 90 ºC in the presence of a total catalyst loading of 1.6 mg cm−2. A very small loss of efficiency corresponding to 30 mV voltage increase was recorded at 3 A cm 2 using a total noble metal catalyst loading of less than 0.5 mg cm−2 (compared to the industry standard of 2 mg cm−2). Steady-state durability tests carried out for 1000 h at 1 A cm -2 showed excellent stability for the MEA with total noble metal catalyst loading of 1.6 mg cm−2 (cell voltage increase 5 lV/h). Moderate degradation rate (cell voltage increase 15 lV/h) was recorded for the low loading 0.5 mg cm-2 MEA. Similar stability characteristics were observed in durability tests at 3 A cm−2. These high performance and stability characteristics were attributed to the enhanced proton conductivity and good stability of the novel membrane the optimized structural properties of the the enhanced proton conductivity and good stability of the novel membrane the optimized structural properties of the the enhanced proton conductivity and good stability of the novel membrane the optimized structural properties of the Ir and Ru oxide solid solution and the enrichment of Ir species on the surface for the anodic catalyst.
Experimental Measurements of Structural Displacement During Hydrogen Vented Deflagrations for FE Model Validation
Sep 2017
Publication
Vented deflagration tests were conducted by UNIPI at B. Guerrini Laboratory during the experimental campaign for HySEA project. Experiments included homogeneous hydrogen-air mixture in a 10-18% vol. range of concentrations contained in an about 1 m3 enclosure called SSE (Small Scale Enclosure). Displacement measurements of a test plate were taken in order to acquire useful data for the validation of FE model developed by IMPETUS Afea. In this paper experimental facility displacement measurement system and FE model are briefly described then comparison between experimental data and simulation results is discussed.
Hydrogen and Fuel Cell Stationary Applications: Key Findings of Modelling and Experimental Work in the Hyper Project
Sep 2009
Publication
Síle Brennan,
A. Bengaouer,
Marco Carcassi,
Gennaro M. Cerchiara,
Andreas Friedrich,
O. Gentilhomme,
William G. Houf,
N. Kotchourko,
Alexei Kotchourko,
Sergey Kudriakov,
Dmitry Makarov,
Vladimir V. Molkov,
Efthymia A. Papanikolaou,
C. Pitre,
Mark Royle,
R. W. Schefer,
G. Stern,
Alexandros G. Venetsanos,
Anke Veser,
Deborah Willoughby,
Jorge Yanez and
Greg H. Evans
"This paper summarises the modelling and experimental programme in the EC FP6 project HYPER. A number of key results are presented and the relevance of these findings to installation permitting guidelines (IPG) for small stationary hydrogen and fuel cell systems is discussed. A key aim of the activities was to generate new scientific data and knowledge in the field of hydrogen safety and where possible use this data as a basis to support the recommendations in the IPG. The structure of the paper mirrors that of the work programme within HYPER in that the work is described in terms of a number of relevant scenarios as follows: 1. high pressure releases 2. small foreseeable releases 3. catastrophic releases and 4. the effects of walls and barriers. Within each scenario the key objectives activities and results are discussed.<br/>The work on high pressure releases sought to provide information for informing safety distances for high-pressure components and associated fuel storage activities on both ignited and unignited jets are reported. A study on small foreseeable releases which could potentially be controlled through forced or natural ventilation is described. The aim of the study was to determine the ventilation requirements in enclosures containing fuel cells such that in the event of a foreseeable leak the concentration of hydrogen in air for zone 2 ATEX is not exceeded. The hazard potential of a possibly catastrophic hydrogen leakage inside a fuel cell cabinet was investigated using a generic fuel cell enclosure model. The rupture of the hydrogen feed line inside the enclosure was considered and both dispersion and combustion of the resulting hydrogen air mixture were examined for a range of leak rates and blockage ratios. Key findings of this study are presented. Finally the scenario on walls and barriers is discussed; a mitigation strategy to potentially reduce the exposure to jet flames is to incorporate barriers around hydrogen storage equipment. Conclusions of experimental and modelling work which aim to provide guidance on configuration and placement of these walls to minimise overall hazards is presented. "
Risk Analysis of Complex Hydrogen Infrastructures
Oct 2015
Publication
Building a network of hydrogen refuelling stations is essential to develop the hydrogen economy within transport. Additional hydrogen is regarded a likely key component to store and convert back excess electrical power to secure future energy supply and to improve the quality of biomass-based fuels. Therefore future hydrogen supply and distribution chains will have to address several objectives. Such a complexity is a challenge for risk assessment and risk management of these chains because of the increasing interactions. Improved methods are needed to assess the supply chain as a whole. The method of “Functional modelling” is discussed in this paper. It will be shown how it could be a basis for other decision support methods for comprehensive risk and sustainability assessments.
Techno-economic Analysis of In-situ Production by Electrolysis, Biomass Gasification and Delivery Systems for Hydrogen Refuelling Stations: Rome Case Study
Oct 2018
Publication
Starting from the Rome Hydrogen Refuelling Station demand of 65 kg/day techno-economics of production systems and balance of plant for small scale stations have been analysed. A sensitivity analysis has been done on Levelised Cost of Hydrogen (LCOH) in the range of 0 to 400 kg/day varying capacity factor and availability hours or travel distance for alkaline electrolysers biomass gasification and hydrogen delivery. As expected minimum LCOH for electrolyser and gasifier is found at 400 kg/day and 24 h/day equal to 12.71 €/kg and 5.99 €/kg however for operating hours over 12 and 10 h/day the differential cost reaches a plateau (below 5%) for electrolyser and gasifier respectively. For the Rome station design 160 kWe of electrolysers 24 h/day and 100 kWth gasifier at 8 h/day LCOH (11.85 €/kg) was calculated considering the modification of the cost structure due to the existing equipment which is convenient respect the use of a single technology except for 24 h/day gasification.
Analysis of Acoustic Pressure Oscillation During Vented Deflagration
Oct 2015
Publication
In industrial buildings explosion relief panels or doors are often used to reduce damages caused by gas explosion. Decades of research produced a significant contribution to the understanding of the phenomena involved nevertheless among the aspects that need further research interaction between acoustic oscillation and the flame front is one of the more important. Interaction between the flame front and acoustic oscillation has raised technical problem in lots of combustion applications as well and had been studied theoretically and experimentally in such cases. Pressure oscillation had been observed in vented deflagration and in certain cases they are responsible for the highest pressure peak generated during the event. At Scalbatraio laboratory of Pisa University CVE test facility was built in order to investigate vented hydrogen deflagration. This paper is aimed to present an overview of the results obtained during several experimental campaigns which tests are analysed with the focus on the investigation of flame acoustic interaction phenomenon. Qualitative and quantitative analysis is presented and the possible physic generating the phenomenon investigated.
Impact Assessments on People and Buildings for Hydrogen Pipeline Explosions
Sep 2019
Publication
Hydrogen has the potential to act as the energy carrier of the future. It will be then produced in large amounts and will certainly need to be transported for long distances. The safest way to transport hydrogen is through pipelines. Failure of pipelines carrying gaseous hydrogen can have several effects some of which can pose a significant threat of damage to people and buildings in the immediate proximity of the failure location. This paper presents a probabilistic risk assessment procedure for the estimation of damage to people and buildings endangered by high-pressure hydrogen pipeline explosions. The procedure provides evaluation of annual probability of damage to people and buildings under an extreme event as a combination of the conditional probability of damage triggered by an explosion and the probability of occurrence of the explosion as a consequence of the pipeline failure. Physical features such as the gas jet release process flammable cloud size blast generation and explosion effects on people and buildings are considered and evaluated through the SLAB integral model TNO model Probit equations and Pressure-Impulse diagrams. For people both direct and indirect effects of overpressure events are considered. For buildings a comparison of the damage to different types of buildings (i.e. reinforced concrete buildings and tuff stone masonry buildings) is made. The probabilistic procedure presented may be used for designing a new hydrogen pipeline network and will be an advantageous tool for safety management of hydrogen gas pipelines.
Optimal Operations for Hydrogen-based Energy Storage Systems in Wind Farms via Model Predictive Control
Feb 2021
Publication
Efficient energy production and consumption are fundamental points for reducing carbon emissions that influence climate change. Alternative resources such as renewable energy sources (RESs) used in electricity grids could reduce the environmental impact. Since RESs are inherently unreliable during the last decades the scientific community addressed research efforts to their integration with the main grid by means of properly designed energy storage systems (ESSs). In order to highlight the best performance from these hybrid systems proper design and operations are essential. The purpose of this paper is to present a so-called model predictive controller (MPC) for the optimal operations of grid-connected wind farms with hydrogen-based ESSs and local loads. Such MPC has been designed to take into account the operating and economical costs of the ESS the local load demand and the participation to the electricity market and further it enforces the fulfillment of the physical and the system's dynamics constraints. The dynamics of the hydrogen-based ESS have been modeled by means of the mixed-logic dynamic (MLD) framework in order to capture different behaviors according to the possible operating modes. The purpose is to provide a controller able to cope both with all the main physical and operating constraints of a hydrogen-based storage system including the switching among different modes such as ON OFF STAND-BY and at the same time reduce the management costs and increase the equipment lifesaving. The case study for this paper is a plant under development in the north Norway. Numerical analysis on the related plant data shows the effectiveness of the proposed strategy which manages the plant and commits the equipment so as to preserve the given constraints and save them from unnecessary commutation cycles.
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.
The Role of the Flow Field Generated by Venting Process on the Pressure Time History of a Vented Deflagration
Sep 2017
Publication
Vented deflagrations are one of the most challenging phenomenon to be replicated numerically in order to predict its resulting pressure time history. As a matter of fact a number of different phenomena can contribute to modify the burning velocity of a gas mixture undergoing a deflagration especially when the flame velocity is considerably lower than the speed of sound. In these conditions acceleration generated by both the flow field induced by the expanding flame and from discontinuities as the vent opening and the venting of the combustion products affect the burning velocity and the burning behaviour of the flame. In particular the phenomena affecting the pressure time history of a deflagration after the flame front reaches the vent area such as flame acoustic interaction and local pressure peaks seem to be closely related to a change in the burning behaviour induced by the venting process. Flame acoustic interaction and local pressure peaks arise as a consequence of the change in the burning behaviour of the flame. This paper analyses the video recording of the flame front produced during the TP experimental campaign performed by UNIPI in the project HySEA to analyse qualitatively the contribution of the generated flow field in a vented deflagration in its pressure-time history.
Homogeneous Hydrogen Deflagrations in Small Scale Enclosure. Experimental Results
Sep 2017
Publication
University of Pisa performed experimental tests in a 1m3 facility which shape and dimensions resemble a gas cabinet for the HySEA project founded by the Fuel Cells and Hydrogen 2 Joint Undertaking with the aim to conduct pre-normative research on vented deflagrations in real-life enclosures and containers used for hydrogen energy applications in order to generate experimental data of high quality. The test facility named Small Scale Enclosure (SSE) had a vent area of 042m2 which location could be varied namely on the top or in front of the facility while different types of vent were investigated. Three different ignition location were investigated as well and the range of Hydrogen concentration ranged between 10 and 18% vol. This paper is aimed to summarize the main characteristics of the experimental campaign as well as to present its results.
Blind-prediction: Estimating the Consequences of Vented Hydrogen Deflagrations for Homogeneous Mixtures in a 20-foot ISO Container
Sep 2017
Publication
Trygve Skjold,
Helene Hisken,
Sunil Lakshmipathy,
Gordon Atanga,
Marco Carcassi,
Martino Schiavetti,
James R. Stewart,
A. Newton,
James R. Hoyes,
Ilias C. Tolias,
Alexandros G. Venetsanos,
Olav Roald Hansen,
J. Geng,
Asmund Huser,
Sjur Helland,
Romain Jambut,
Ke Ren,
Alexei Kotchourko,
Thomas Jordan,
Jérome Daubech,
Guillaume Lecocq,
Arve Grønsund Hanssen,
Chenthil Kumar,
Laurent Krumenacker,
Simon Jallais,
D. Miller and
Carl Regis Bauwens
This paper summarises the results from a blind-prediction study for models developed for estimating the consequences of vented hydrogen deflagrations. The work is part of the project Improving hydrogen safety for energy applications through pre-normative research on vented deflagrations (HySEA). The scenarios selected for the blind-prediction entailed vented explosions with homogeneous hydrogen-air mixtures in a 20-foot ISO container. The test program included two configurations and six experiments i.e. three repeated tests for each scenario. The comparison between experimental results and model predictions reveals reasonable agreement for some of the models and significant discrepancies for others. It is foreseen that the first blind-prediction study in the HySEA project will motivate developers to improve their models and to update guidelines for users of the models.
Fatigue and Fracture of High-hardenability Steels for Thick-walled Hydrogen Pressure Vessels
Sep 2017
Publication
Stationary pressure vessels for the storage of large volumes of gaseous hydrogen at high pressure (>70 MPa) are typically manufactured from Cr-Mo steels. These steels display hydrogen-enhanced fatigue crack growth but pressure vessels can be manufactured using defect-tolerant design methodologies. However storage volumes are limited by the wall thickness that can be reliably manufactured for quench and tempered Cr-Mo steels typically not more than 25-35 mm. High-hardenability steels can be manufactured with thicker walls which enables larger diameter pressure vessels and larger storage volumes. The goal of this study is to assess the fracture and fatigue response of high hardenability Ni-Cr-Mo pressure vessel steels for use in high-pressure hydrogen service at pressure in excess of 1000 bar. Standardized fatigue crack growth tests were performed in gaseous hydrogen at frequency of 1Hz and for R-ratios in the range of 0.1 to 0.7. Elastic-plastic fracture toughness measurements were also performed. The measured fatigue and fracture behavior is placed into the context of previous studies on fatigue and fracture of Cr-Mo steels for gaseous hydrogen.
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.
How Far Away is Hydrogen? Its Role in the Medium and Long-term Decarbonisation of the European Energy System
Nov 2015
Publication
Hydrogen is a promising avenue for decarbonising energy systems and providing flexibility. In this paper the JRC-EU-TIMES model – a bottom-up technology-rich model of the EU28 energy system – is used to assess the role of hydrogen in a future decarbonised Europe under two climate scenarios current policy initiative (CPI) and long-term decarbonisation (CAP). Our results indicate that hydrogen could become a viable option already in 2030 – however a long-term CO2 cap is needed to sustain the transition. In the CAP scenario the share of hydrogen in the final energy consumption of the transport and industry sectors reaches 5% and 6% by 2050. Low-carbon hydrogen production technologies dominate and electrolysers provide flexibility by absorbing electricity at times of high availability of intermittent sources. Hydrogen could also play a significant role in the industrial and transport sectors while the emergence of stationary hydrogen fuel cells for hydrogen-to-power would require significant cost improvements over and above those projected by the experts.
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.
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.
Fire Prevention Technical Rule for Gaseous Hydrogen Refuelling Stations
Sep 2005
Publication
In the last years different Italian hydrogen projects provided for gaseous hydrogen motor vehicles refuelling stations. Motivated by the lack of suitable set of rules in the year 2002 Italian National Firecorps (Institute under the Italian Ministry of the Interior) formed an Ad Hoc Working Group asked to regulate the above-said stations as regards fire prevention and protection safety. This Working Group consists of members coming from both Firecorps and academic world (Pisa University). Throughout his work this Group produced a technical rule covering the fire prevention requirements for design construction and operation of gaseous hydrogen refuelling stations. This document has been approved by the Ministry’s Technical Scientific Central Committee for fire prevention (C.C.T.S.) and now it has to carry out the “Community procedure for the provision of information”. This paper describes the main safety contents of the technical rule.
Hydrogen Transport Safety: Case of Compressed Gaseous Tube Trailer
Sep 2005
Publication
The following paper describes researches to evaluate the behaviour under various accidental conditions of systems of transport compressed hydrogen. Particularly have been considered gaseous tube trailer and the packages cylinders employed for the road transport which have an internal gas pressures up to 200 barg.<br/>Further to a verification of the actual safety conditions this analysis intends to propose a theme that in the next future if confirmed projects around the employment of hydrogen as possible source energetic alternative could become quite important. The general increase of the consumptions of hydrogen and the consequently probable increase of the transports of gaseous hydrogen in pressure they will make the problem of the safety of the gaseous tube trail particularly important. Gaseous tube trailers will also use as components of plant. for versatility easy availability' and inexpensiveness.<br/>The first part of the memory is related to the analysis of the accidents happened in the last year in Italy with compressed hydrogen transports and particularly an accurate study has been made on the behaviour of a gaseous tube trailer involved in fire following a motorway accident in March 2003. In the central part of the job has been done a safety analysis of the described events trying to make to also emerge the most critical elements towards the activities developed by the teams of help intervened.<br/>Finally in the last part you are been listed on the base of the picked data a series of proposals and indications of the possible structural and procedural changes that could be suggested with the purpose to guarantee more elevated safety levels.
Integration of Chemical Looping Combustion for Cost-effective CO2 Capture from State-of-the-art Natural Gas Combined Cycles
May 2020
Publication
Chemical looping combustion (CLC) is a promising method for power production with integrated CO2 capture with almost no direct energy penalty. When integrated into a natural gas combined cycle (NGCC) plant however CLC imposes a large indirect energy penalty because the maximum achievable reactor temperature is far below the firing temperature of state-of-the-art gas turbines. This study presents a techno-economic assessment of a CLC plant that circumvents this limitation via an added combustor after the CLC reactors. Without the added combustor the energy penalty amounts to 11.4%-points causing a high CO2 avoidance cost of $117.3/ton which is more expensive than a conventional NGCC plant with post-combustion capture ($93.8/ton) with an energy penalty of 8.1%-points. This conventional CLC plant would also require a custom gas turbine. With an added combustor fired by natural gas a standard gas turbine can be deployed and CO2 avoidance costs are reduced to $60.3/ton mainly due to a reduction in the energy penalty to only 1.4%-points. However due to the added natural gas combustion after the CLC reactor CO2 avoidance is only 52.4%. Achieving high CO2 avoidance requires firing with clean hydrogen instead increasing the CO2 avoidance cost to $96.3/ton when a hydrogen cost of $15.5/GJ is assumed. Advanced heat integration could reduce the CO2 avoidance cost to $90.3/ton by lowering the energy penalty to only 0.6%-points. An attractive alternative is therefore to construct the plant for added firing with natural gas and retrofit the added combustor for hydrogen firing when CO2 prices reach very high levels.
Dynamic Simulation and Thermoeconomic Analysis of a Hybrid Renewable System Based on PV and Fuel Cell Coupled with Hydrogen Storage
Nov 2021
Publication
The production of “green hydrogen” is currently one of the hottest topics in the field of renewable energy systems research. Hydrogen storage is also becoming more and more attractive as a flexible solution to mitigate the power fluctuations of solar energy systems. The most promising technology for electricity-to-hydrogen conversion and vice versa is the reversible solid-oxide cell (SOC). This device is still very expensive but it exhibits excellent performance under dynamic operating conditions compared to the competing devices. This work presents the dynamic simulation of a prototypal renewable plant combining a 50 kW photovoltaic (PV) field with a 50 kW solid-oxide electrolyzer cell (SOEC) and a compressed hydrogen tank. The electricity is used to meet the energy demand of a dwelling located in the area of Campi Flegrei (Naples). The SOC efficiency is simulated by developing a mathematical model in MATLAB®. The model also calculates the cell operating temperature as a function of the input current. Once the optimal values of the operating parameters of the SOC are calculated the model is integrated in the transient system simulation tool (TRNSYS) for dynamic analysis. Furthermore this work presents a parametric analysis of the hydrogen storage system (HSS). The results of the energy and environmental analyses show that the proposed system can reach a primary energy saving by 70% and an amount of saved CO2 of 28 tons/year. Some possible future market scenarios are considered for the economic analysis. In the most realistic case the optimal configuration shows a simple pay back lower than 10 years and a profit index of 46%.
Hydrogen Release and Atmospheric Dispersion- Experimental Studies and Comparison With Parametric Simulations
Sep 2009
Publication
In our society the use of hydrogen is continually growing and there will be a widespread installation of plants with high capacity storages in our towns as automotive refuelling stations. For this reason it is necessary to make accurate studies on the safety of these kinds of plants to protect our town inhabitants Moreover hydrogen is a highly flammable chemical that can be particularly dangerous in case of release since its mixing with air in the presence of an ignition source could lead to fires or explosions. Generally most simulation models whether or not concerned with fluid dynamics used in safety and risk studies are not validated for hydrogen use. This aspect may imply that the results of studies on safety cannot be too accurate and realistic. This paper introduces an experimental activity which was performed by the Department of Energetics of Politecnico of Torino with the collaboration of the University of Pisa. Accidental hydrogen release and dispersion were studied in order to acquire a set of experimental data to validate simulation models for such studies. At the laboratories of the Department of Mechanical Nuclear and Production Engineering of the University of Pisa a pilot plant called Hydrogen Pipe Break Test was built. The apparatus consisted of a 12 m3 tank which was fed by high pressure cylinders. A 50 m long pipe moved from the tank to an open space and at the far end of the pipe there was an automatic release system that could be operated by remote control. During the experimental activity data was acquired regarding hydrogen concentration as a function of distance from the release hole also lengthwise and vertically. In this paper some of the experimental data acquired during the activity have been compared with the integral models Effects and Phast. In the future experimental results will be used to calibrate a more sophisticated model to atmospheric dispersion studies.
A Techno-Economic Analysis of Solar Hydrogen Production by Electrolysis in the North of Chile and the Case of Exportation from Atacama Desert to Japan
Aug 2020
Publication
H2 production from solar electricity in the region of the Atacama Desert – Chile – has been identified as strategical for global hydrogen exportation. In this study the full supply chain of solar hydrogen has been investigated for 2018 and projected to scenarios for 2025-2030. Multi-year hourly electrical profiles data have been used from real operating PV plants and simulated Concentrated Solar Power “CSP” plants with Thermal Energy Storage “TES” as well as commercial electricity Power Purchase Agreement “PPA” prices reported in the Chilean electricity market were considered. The Levelized Cost of Hydrogen “LCOH” of each production pathway is calculated by a case-sensitive techno-economic MATLAB/Simulink model for utility scale (multi-MW) alkaline and PEM electrolyser technologies. Successively different distribution storage and transportation configurations are evaluated based on the 2025 Japanese case study according to the declared H2 demand. Transport in the form of liquefied hydrogen (LH2) and via ammonia (NH3) carrier is compared from the port of Antofagasta CL to the port of Osaka JP.
Hydrogen Embrittlement in a 2101 Lean Duplex Stainless Steel
Sep 2019
Publication
Duplex Stainless Steels (DSSs) are an attractive class of materials characterized by a strong corrosion resistance in many aggressive environments. Thanks to the high mechanical performances DSSs are widely used for many applications in petrochemical industry chemical and nuclear plants marine environment desalination etc.<br/>Among the DSSs critical aspects concerning the embrittlement process it is possible to remember the steel sensitization and the hydrogen embrittlement.<br/>The sensitization of the DSSs is due to the peculiar chemical composition of these grades which at high temperature are susceptible to carbide nitrides and second phases precipitation processes mainly at grains boundary and in the ferritic grains. The hydrogen embrittlement process is strongly influenced by the duplex (austenitic-ferritic) microstructure and by the loading conditions.<br/>In this work a rolled lean ferritic-austenitic DSS (2101) has been investigated in order to analyze the hydrogen embrittlement mechanisms by means of slow strain rate tensile tests considering the steel after different heat treatments. The damaging micromechanisms have been investigated by means of the scanning electron microscope observations on the fracture surfaces.
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.
Risk Assessment of the Large-Scale Hydrogen Storage in Salt Caverns
May 2021
Publication
Salt caverns are accepted as an ideal solution for high-pressure hydrogen storage. As well as considering the numerous benefits of the realization of underground hydrogen storage (UHS) such as high energy densities low leakage rates and big storage volumes risk analysis of UHS is a required step for assessing the suitability of this technology. In this work a preliminary quantitative risk assessment (QRA) was performed by starting from the worst-case scenario: rupture at the ground of the riser pipe from the salt cavern to the ground. The influence of hydrogen contamination by bacterial metabolism was studied considering the composition of the gas contained in the salt caverns as time variable. A bow-tie analysis was used to highlight all the possible causes (basic events) as well as the outcomes (jet fire unconfined vapor cloud explosion (UVCE) toxic chemical release) and then consequence and risk analyses were performed. The results showed that a UVCE is the most frequent outcome but its effect zone decreases with time due to the hydrogen contamination and the higher contents of methane and hydrogen sulfide.
Optimal Design of Multi-energy Systems with Seasonal Storage
Oct 2017
Publication
Optimal design and operation of multi-energy systems involving seasonal energy storage are often hindered by the complexity of the optimization problem. Indeed the description of seasonal cycles requires a year-long time horizon while the system operation calls for hourly resolution; this turns into a large number of decision variables including binary variables when large systems are analyzed. This work presents novel mixed integer linear program methodologies that allow considering a year time horizon with hour resolution while significantly reducing the complexity of the optimization problem. First the validity of the proposed techniques is tested by considering a simple system that can be solved in a reasonable computational time without resorting to design days. Findings show that the results of the proposed approaches are in good agreement with the full-scale optimization thus allowing to correctly size the energy storage and to operate the system with a long-term policy while significantly simplifying the optimization problem. Furthermore the developed methodology is adopted to design a multi-energy system based on a neighborhood in Zurich Switzerland which is optimized in terms of total annual costs and carbon dioxide emissions. Finally the system behavior is revealed by performing a sensitivity analysis on different features of the energy system and by looking at the topology of the energy hub along the Pareto sets.
Green Synthetic Fuels: Renewable Routes for the Conversion of Non-Fossil Feedstocks into Gaseous Fuels and Their End Uses
Jan 2020
Publication
Innovative renewable routes are potentially able to sustain the transition to a decarbonized energy economy. Green synthetic fuels including hydrogen and natural gas are considered viable alternatives to fossil fuels. Indeed they play a fundamental role in those sectors that are difficult to electrify (e.g. road mobility or high-heat industrial processes) are capable of mitigating problems related to flexibility and instantaneous balance of the electric grid are suitable for large-size and long-term storage and can be transported through the gas network. This article is an overview of the overall supply chain including production transport storage and end uses. Available fuel conversion technologies use renewable energy for the catalytic conversion of non-fossil feedstocks into hydrogen and syngas. We will show how relevant technologies involve thermochemical electrochemical and photochemical processes. The syngas quality can be improved by catalytic CO and CO2 methanation reactions for the generation of synthetic natural gas. Finally the produced gaseous fuels could follow several pathways for transport and lead to different final uses. Therefore storage alternatives and gas interchangeability requirements for the safe injection of green fuels in the natural gas network and fuel cells are outlined. Nevertheless the effects of gas quality on combustion emissions and safety are considered.
Hydrogen–methane Mixtures: Dispersion and Stratification Studies
Sep 2011
Publication
The study of hydrogen as an alternative fuel clean and “environment friendly” has been in the last years and continues to be object of many studies international projects and standard development. Hydrogen is a fundamental energy carrier to be developed together with other renewable resources for the transition to a sustainable energy system.<br/>But experience has shown how often the introduction and establishment of a new technology does not necessarily pass through radical changes but can be stimulated by slight modifications to the “present situation”.<br/>So the worldwide experience with natural gas as industrial automotive and domestic fuel has been the incentive to the present interest towards hydrogen–methane mixtures. The possible use of existing pipeline networks for mixtures of natural gas and hydrogen offers a unique and cost-effective opportunity to initiate the progressive introduction of hydrogen as part of the development of a full hydrogen system.<br/>The aim of the work presented in this paper is the investigation of the dispersion and stratification properties of hydrogen and methane mixtures. Experimental activities have been carried out in a large scale closed apparatus characterized by a volume of about 25 m3 both with and without natural ventilation. Mixtures of 10%vol. hydrogen – 90%vol. methane and 30%vol. hydrogen – 70%vol. methane have been studied with the help of oxygen sensors and gas chromatography.
Quantification of the Uncertainty of the Peak Pressure Value in the Vented Deflagrations of Air-Hydrogen Mixtures
Sep 2007
Publication
In the problem of the protection by the consequences of an explosion is actual for many industrial application involving storage of gas like methane or hydrogen refuelling stations and so on. A simple and economic way to reduce the peak pressure associated to a deflagration is to supply to the confined environment an opportune surface substantially less resistant then the protected structure typically in stoichiometric conditions the peak pressure reduction is around the 8 bars for a generic hydrocarbon combustion in an adiabatic system lacking of whichever mitigation system. In general the problem is the forecast of the peak pressure value (PMAX) of the explosion. This problem is faced using CFD codes modelling the structure in which the explosion is located and setting the main parameters like concentration of the gas in the mixture the volume available the size of vent area and obstacles (if included) and so on. In this work the idea is to start from empirical data to train a Neural Network (NN) in order to find the correlation among the parameters regulating the phenomenon. Associated to this prediction a fuzzy model will provide to quantify the uncertainty of the predicted value.
Micro-wrinkled Pd Surface for Hydrogen Sensing and Switched Detection of Lower Explosive Limit
Sep 2011
Publication
We report the development and testing of a novel hydrogen sensor that shows a very peculiar response to hydrogen exposure due to its micro-structured palladium surface. The fabrication of the wrinkled Pd surface is obtained using an innovative fast and cheap technique based on the deposition of a thin Pd film on to a thermo-retractable polystyrene sheet that shrinks to 40% of its original size when heated. The buckling of the Pd surface induced by shrinking of the substrate produces nano and micro-wrinkles on the sensor surface. The micro-structured sensor surface is very stable even after repeated hydrogen sorption/desorption cycles. The hydrogen sensing mechanism is based on the transitory absorption of hydrogen atoms into the Pd layer leading to the reversible change of its electrical resistance. Interestingly depending on hydrogen concentration the proposed sensor shows the concurrent effect of both the usually described behaviors of increase or decrease of resistance related to different phenomena occurring upon hydrogen exposure and formation of palladium hydride. The study reports and discusses evidences for an activation threshold of hydrogen concentration in air switching the behavior of sensor performances from e.g. poor negative to large positive sensitivity and from slow to fast detection.
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.
Experimental Study of Vented Hydrogen Deflagration with Ignition Inside and Outside the Vented Volume
Sep 2013
Publication
Experiments were carried out inside a 25 m3 vented combustion test facility (CVE) with a fixed vent area sealed by a plastic sheet vent. Inside the CVE a 0.64 m3 open vent box called RED-CVE was placed. The vent of the RED-CVE was left open and three different vent area were tested. Two different mixing fans one for each compartment were used to establish homogeneous H2 concentrations. This study examined H2 concentrations in the range between 8.5% vol. to 12.5% vol. and three different ignition locations (1) far vent ignition (2) inside the RED-CVE box ignition and (3) near vent ignition (the vent refers to the CVE vent). Peak overpressures generated inside the test facility and the smaller compartment were measured. The results indicate that the near vent ignition generates negligible peak overpressures inside the test facility as compared to those originated by far vent ignition and ignition inside the RED-CVE box. The experiments with far vent ignition showed a pressure increase with increasing hydrogen concentration which reached a peak value at 11% vol. concentration and then decreased showing a non-monotonic behaviour. The overpressure measured inside the RED-CVE was higher when the ignition was outside the box whereas the flame entered the box through the small vent.
Life Cycle Assessment of Substitute Natural Gas Production from Biomass and Electrolytic Hydrogen
Feb 2021
Publication
The synthesis of a Substitute Natural Gas (SNG) that is compatible with the gas grid composition requirements by using surplus electricity from renewable energy sources looks a favourable solution to store large quantities of electricity and to decarbonise the gas grid network while maintaining the same infrastructure. The most promising layouts for SNG production and the conditions under which SNG synthesis reduces the environmental impacts if compared to its fossil alternative is still largely untapped. In this work six different layouts for the production of SNG and electricity from biomass and fluctuating electricity are compared from the environmental point of view by means of Life Cycle Assessment (LCA) methodology. Global Warming Potential (GWP) Cumulative Energy Demand (CED) and Acidification Potential (AP) are selected as impact indicators for this analysis. The influence of key LCA methodological aspects on the conclusions is also explored. In particular two different functional units are chosen: 1 kg of SNG produced and 1 MJ of output energy (SNG and electricity). Furthermore different approaches dealing with co-production of electricity are also applied. The results show that the layout based on hydrogasification has the lowest impacts on all the considered cases apart from the GWP and the CED with SNG mass as the functional unit and the avoided burden approach. Finally the selection of the multifunctionality approach is found to have a significant influence on technology ranking.
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.
Hydrogen as a Clean and Sustainable Energy Vector for Global Transition from Fossil-Based to Zero-Carbon
Dec 2021
Publication
Hydrogen is recognized as a promising and attractive energy carrier to decarbonize the sectors responsible for global warming such as electricity production industry and transportation. However although hydrogen releases only water as a result of its reaction with oxygen through a fuel cell the hydrogen production pathway is currently a challenging issue since hydrogen is produced mainly from thermochemical processes (natural gas reforming coal gasification). On the other hand hydrogen production through water electrolysis has attracted a lot of attention as a means to reduce greenhouse gas emissions by using low-carbon sources such as renewable energy (solar wind hydro) and nuclear energy. In this context by providing an environmentally-friendly fuel instead of the currently-used fuels (unleaded petrol gasoline kerosene) hydrogen can be used in various applications such as transportation (aircraft boat vehicle and train) energy storage industry medicine and power-to-gas. This article aims to provide an overview of the main hydrogen applications (including present and future) while examining funding and barriers to building a prosperous future for the nation by addressing all the critical challenges met in all energy sectors.
Natural and Forced Ventilation Study In An Enclosure Hosting a Fuel Cell
Sep 2009
Publication
The purpose of the experimental work is to determine the conditions for which an enclosure can guest a fuel cell for civil use. Concerning the installation permitting guide this study allows the safe use of the fuel cell in case of small not catastrophic leakages. In fact the correct plan of the vents in the enclosure guarantees the low concentration of hydrogen (H2) below the LFL.
Experimental Studies on Wind Influence on Hydrogen Release from Low Pressure Pipelines
Sep 2009
Publication
At the DIMNP (Department of Mechanical Nuclear and Production Engineering) laboratories of University of Pisa (Italy) a pilot plant called HPBT (Hydrogen Pipe Break Test) was built in cooperation with the Italian Fire Brigade Department. The apparatus consists of a 12 m3 tank connected with a 50 m long pipe. At the far end of the pipeline a couple of flanges have been used to house a disc with a hole of the defined diameter. The plant has been used to carry out experiments of hydrogen release. During the experimental activity data have been acquired about the gas concentration and the length of release as function of internal pressure and release hole diameter. The information obtained by the experimental activity will be the basis for the development of a new specific normative framework arranged to prevent fire and applied to hydrogen. This study is focused on hydrogen concentration as function of wind velocity and direction. Experimental data have been compared with theoretical and computer models (such as CFD simulations)
Hydrogen as an Energy Vector to Optimize the Energy Exploitation of a Self-consumption Solar Photovoltaic Facility in a Dwelling House
Nov 2019
Publication
Solar photovoltaic (PV) plants coupled with storage for domestic self-consumption purposes seem to be a promising technology in the next years as PV costs have decreased significantly and national regulations in many countries promote their installation in order to relax the energy requirements of power distribution grids. However electrochemical storage systems are still unaffordable for many domestic users and thus the advantages of self-consumption PV systems are reduced. Thus in this work the adoption of hydrogen systems as energy vectors between a PV plant and the energy user is proposed. As a preliminary study in this work the design of a PV and hydrogen-production self-consumption plant for a single dwelling is described. Then a technical and economic feasibility study conducted by modeling the facility within the Homer Energy Pro energy systems analysis tool is reported. The proposed system will be able to provide back not only electrical energy but also thermal energy through a fuel cell or refined water covering the fundamental needs of the householders (electricity heat or cooling and water). Results show that although the proposed system effectively increases the energy local use of the PV production and reduces significantly the energy injections or demands into/from the power grid avoiding power grid congestions and increasing the nano-grid resilience operation and maintenance costs may reduce its economic attractiveness for a single dwelling.
Modelling and Experimental Analysis of a Polymer Electrolyte Membrane Water Electrolysis Cell at Different Operating Temperatures
Nov 2018
Publication
In this paper a simplified model of a Polymer Electrolyte Membrane (PEM) water electrolysis cell is presented and compared with experimental data at 60 ◦C and 80 ◦C. The model utilizes the same modelling approach used in previous work where the electrolyzer cell is divided in four subsections: cathode anode membrane and voltage. The model of the electrodes includes key electrochemical reactions and gas transport mechanism (i.e. H2 O2 and H2O) whereas the model of the membrane includes physical mechanisms such as water diffusion electro osmotic drag and hydraulic pressure. Voltage was modelled including main overpotentials (i.e. activation ohmic concentration). First and second law efficiencies were defined. Key empirical parameters depending on temperature were identified in the activation and ohmic overpotentials. The electrodes reference exchange current densities and change transfer coefficients were related to activation overpotentials whereas hydrogen ion diffusion to Ohmic overvoltages. These model parameters were empirically fitted so that polarization curve obtained by the model predicted well the voltage at different current found by the experimental results. Finally from the efficiency calculation it was shown that at low current densities the electrolyzer cell absorbs heat from the surroundings. The model is not able to describe the transients involved during the cell electrochemical reactions however these processes are assumed relatively fast. For this reason the model can be implemented in system dynamic modelling for hydrogen production and storage where components dynamic is generally slower compared to the cell electrochemical reactions dynamics.
How to Give a renewed Chance to Natural Gas as Feed for the Production of Hydrogen: Electric MSR Coupled with CO2 Mineralization
Sep 2021
Publication
Recent years have seen a growing interest in water electrolysis as a way to store renewable electric energy into chemical energy through hydrogen production. However today the share of renewable energy is still limited and there is the need to have a continuous use of H2 for industrial chemicals applications. Firstly the paper discusses the use of electrolysis - connected to a conventional grid - for a continuous H2 production in terms of associated CO2 emissions and compares such emissions with conventional methane steam reforming (MSR). Therefore it explores the possibility to use electrical methane steam reforming (eMSR) as a way to reduce the CO2 emissions. As a way to have zero emissions carbon mineralization of CO2 is coupled - instead of in-situ carbon capture and storage technology (CCS) - to eMSR; associated relevant cost of production is evaluated for different scenarios. It appears that to minimize such production cost carbonate minerals must be reused in the making of other industrial products since the amount of carbonates generated by the process is quite significant.
Hydrogen Embrittlement Evaluation of Micro Alloyed Steels by Means of J-Integral Curve
Jun 2019
Publication
The aim of this work is the evaluation of the hydrogen effect on the J-integral parameter. It is well-known that the micro alloyed steels are affected by Hydrogen Embrittlement phenomena only when they are subjected at the same time to plastic deformation and hydrogen evolution at their surface. Previous works have pointed out the absence of Hydrogen Embrittlement effects on pipeline steels cathodically protected under static load conditions. On the contrary in slow strain rate tests it is possible to observe the effect of the imposed potential and the strain rate on the hydrogen embrittlement steel behavior only after the necking of the specimens. J vs. Δa curves were measured on different pipeline steels in air and in aerated NaCl 3.5 g/L solution at free corrosion potential or under cathodic polarization at −1.05 and −2 V vs. SCE. The area under the J vs. Δa curves and the maximum crack propagation rate were taken into account. These parameters were compared with the ratio between the reduction of area in environment and in air obtained by slow strain rate test in the same environmental conditions and used to rank the different steels.
A Model-based Parametric and Optimal Sizing of a Battery/Hydrogen Storage of a Real Hybrid Microgrid Supplying a Residential Load: Towards Island Operation
Jun 2021
Publication
In this study the optimal sizing of a hybrid battery/hydrogen Energy Storage System “ESS” is assessed via a model-based parametric analysis in the context of a real hybrid renewable microgrid located in Huelva Spain supplying a real-time monitored residential load (3.5 kW; 5.6 MWh/year) in island mode. Four storage configurations (battery-only H2-only hybrid battery priority and hybrid H2 priority) are assessed under different Energy Management Strategies analysing system performance parameters such as Loss of Load “LL” (kWh;%) Over Production “OP” (kWh;%) round-trip storage efficiency ESS (%) and total storage cost (€) depending on the ESS sizing characteristics. A parallel approach to the storage optimal sizing via both multi-dimensional sensitivity analysis and PSO is carried out in order to address both sub-optimal and optimal regions respectively. Results show that a hybridised ESS capacity is beneficial from an energy security and efficiency point of view but can represent a substantial additional total cost (between 100 and 300 k€) to the hybrid energy system especially for the H2 ESS which presents higher costs. Reaching 100% supply from renewables is challenging and introducing a LL threshold induces a substantial relaxation of the sizing and cost requirements. Increase in battery capacity is more beneficial for the LL abatement while increasing H2 capacity is more useful to absorb large quantities of excess energy. The optimal design via PSO technique is complemented to the parametric study.
The Role of Green and Blue Hydrogen in the Energy Transition—A Technological and Geopolitical Perspective
Dec 2020
Publication
Hydrogen is currently enjoying a renewed and widespread momentum in many national and international climate strategies. This review paper is focused on analysing the challenges and opportunities that are related to green and blue hydrogen which are at the basis of different perspectives of a potential hydrogen society. While many governments and private companies are putting significant resources on the development of hydrogen technologies there still remains a high number of unsolved issues including technical challenges economic and geopolitical implications. The hydrogen supply chain includes a large number of steps resulting in additional energy losses and while much focus is put on hydrogen generation costs its transport and storage should not be neglected. A low-carbon hydrogen economy offers promising opportunities not only to fight climate change but also to enhance energy security and develop local industries in many countries. However to face the huge challenges of a transition towards a zero-carbon energy system all available technologies should be allowed to contribute based on measurable indicators which require a strong international consensus based on transparent standards and targets.
Numerical Evaluation of the Effect of Fuel Blending with CO2 and H2 on the Very Early Corona‐Discharge Behavior in Spark Ignited Engines
Feb 2022
Publication
Reducing green‐house gases emission from light‐duty vehicles is compulsory in order to slow down the climate change. The application of High Frequency Ignition systems based on the Corona discharge effect has shown the potential to extend the dilution limit of engine operating conditions promoting lower temperatures and faster combustion events thus higher thermal and indicating efficiency. Furthermore predicting the behavior of Corona ignition devices against new sustainable fuel blends including renewable hydrogen and biogas is crucial in order to deal with the short‐intermediate term fleet electric transition. The numerical evaluation of Corona‐induced discharge radius and radical species under those conditions can be helpful in order to capture local effects that could be reached only with complex and expensive optical investigations. Using an ex‐ tended version of the Corona one‐dimensional code previously published by the present authors the simulation of pure methane and different methane–hydrogen blends and biogas–hydrogen blends mixed with air was performed. Each mixture was simulated both for 10% recirculated exhaust gas dilution and for its corresponding dilute upper limit which was estimated by means of chemical kinetics simulations integrated with a custom misfire detection criterion.
Analysis of Standard and Innovative Methods for Allocating Upstream and Refinery GHG Emissions to Oil Products
Sep 2017
Publication
Alternative fuel policies need accurate and transparent methods to find the embedded carbon intensity of individual refinery products. This study investigates different ways of allocating greenhouse gases emissions deriving from refining and upstream crude oil supply. Allocation methods based on mass energy content economic value and innovatively added-value are compared with the marginal refining emissions calculated by CONCAWE’s linear-programming model to the average EU refinery which has been adopted as reference in EU legislation. Beside the most important transportation fuels (gasoline diesel kerosene/jet fuel and heavy fuel oil) the analysis extends to petroleum coke and refinery hydrogen. Moreover novel criteria based on the implications due to hydrogen usage by each fuel pathway have been introduced to test the consistency of the analyzed approaches. It is found that only two economic-based allocation methods are consistent with the introduced criteria. These two methods also give negative refinery emissions for heavy products which is coherent with the marginal emissions calculated through the CONCAWE refinery model. The recommended allocation methods are transparent and use only publicly available statistical data so they may be useful not only for future EU legislation but also in jurisdictions where a representative refinery model is not available.
Stress Corrosion Cracking of Gas Pipeline Steels of Different Strength
Jul 2016
Publication
With the development of the natural gas industry gas transmission pipelines have been developed rapidly in terms of safety economy and efficiency. Our recent studies have shown that an important factor of main pipelines serviceability loss under their long-term service is the in-bulk metal degradation of the pipe wall. This leads to the loss of the initial mechanical properties primarily resistance to brittle fracture which were set in engineering calculations at the pipeline design stage. At the same time stress corrosion cracking has been identified as one of the predominant failures in pipeline steels in humid environments which causes rupture of high-pressure gas transmission pipes as well as serious economic losses and disasters.
In the present work the low-carbon pipeline steels with different strength levels from the point of view of their susceptibility to stress corrosion cracking in the as-received state and after in-laboratory accelerated degradation under environmental conditions similar to those of an acidic soil were investigated. The main objectives of this study were to determine whether the development of higher strength materials led to greater susceptibility to stress corrosion cracking and whether degraded pipeline steels became more susceptible to stress corrosion cracking than in the as-received state. The procedure of accelerated degradation of pipeline steels was developed and introduced in laboratory under the combined action of axial loading and hydrogen charging. It proved to be reliable and useful to performed laboratory simulation of in-service degradation of pipeline steels with different strength. The in-laboratory degraded 17H1S and X60 pipeline steels tested in the NS4 solution saturated with CO2 under open circuit potential revealed the susceptibility to stress corrosion cracking reflected in the degradation of mechanical properties and at the same time the degraded X60 steel showed higher resistance to stress corrosion cracking than the degraded 17H1S steel. Fractographic observation confirmed the pipeline steels hydrogen embrittlement caused by the permeated hydrogen.
In the present work the low-carbon pipeline steels with different strength levels from the point of view of their susceptibility to stress corrosion cracking in the as-received state and after in-laboratory accelerated degradation under environmental conditions similar to those of an acidic soil were investigated. The main objectives of this study were to determine whether the development of higher strength materials led to greater susceptibility to stress corrosion cracking and whether degraded pipeline steels became more susceptible to stress corrosion cracking than in the as-received state. The procedure of accelerated degradation of pipeline steels was developed and introduced in laboratory under the combined action of axial loading and hydrogen charging. It proved to be reliable and useful to performed laboratory simulation of in-service degradation of pipeline steels with different strength. The in-laboratory degraded 17H1S and X60 pipeline steels tested in the NS4 solution saturated with CO2 under open circuit potential revealed the susceptibility to stress corrosion cracking reflected in the degradation of mechanical properties and at the same time the degraded X60 steel showed higher resistance to stress corrosion cracking than the degraded 17H1S steel. Fractographic observation confirmed the pipeline steels hydrogen embrittlement caused by the permeated hydrogen.
Life Cycle Assessment and Water Footprint of Hydrogen Production Methods: From Conventional to Emerging Technologies
Oct 2020
Publication
A common sustainability issue arising in production systems is the efficient use of resources for providing goods or services. With the increased interest in a hydrogen (H2) economy the life-cycle environmental performance of H2 production has special significance for assisting in identifying opportunities to improve environmental performance and to guide challenging decisions and select between technology paths. Life cycle impact assessment methods are rapidly evolving to analyze multiple environmental impacts of the production of products or processes. This study marks the first step in developing process-based streamlined life cycle analysis (LCA) of several H2 production pathways combining life cycle impacts at the midpoint (17 problem-oriented) and endpoint (3 damage-oriented) levels using the state-of-the-art impact assessment method ReCiPe 2016. Steam reforming of natural gas coal gasification water electrolysis via proton exchange membrane fuel cell (PEM) solid oxide electrolyzer cell (SOEC) biomass gasification and reforming and dark fermentation of lignocellulosic biomass were analyzed. An innovative aspect is developed in this study is an analysis of water consumption associated with H2 production pathways by life-cycle stage to provide a better understanding of the life cycle water-related impacts on human health and natural environment. For water-related scope Water scarcity footprint (WSF) quantified using Available Water Remaining (AWARE) method was applied as a stand-alone indicator. The paper discusses the strengths and weaknesses of each production pathway identify the drivers of environmental impact quantify midpoint environmental impact and its influence on the endpoint environmental performance. The findings of this study could serve as a useful theoretical reference and practical basis to decision-makers of potential environmental impacts of H2 production systems.
Detection, Characterization and Sizing of Hydrogen Induced Cracking in Pressure Vessels Using Phased Array Ultrasonic Data Processing
Jul 2016
Publication
Pressure vessels operating in sour service conditions in refinery environments can be subject to the risk of H₂S cracking resulting from the hydrogen entering into the material. This risk which is related to the specific working conditions and to the quality of the steel used shall be properly managed in order to maintain the highest safety at a cost-effective level.<br/>Nowadays the typical management strategy is based on a risk based inspection (RBI) evaluation to define the inspection plan used in conjunction with a fitness for service (FFS) approach in defining if the vessel although presenting dangerous defects such as cracks can still be considered “fit for purpose” for a given time window based on specific fracture mechanics analysis.<br/>These vessels are periodically subject to non-destructive evaluation typically ultrasonic testing. Phased Array (PA) ultrasonic is the latest technology more and more used for this type of application.<br/>This paper presents the design and development of an optimized Phased Array ultrasonic inspection technique for the detection and sizing of hydrogen induced cracking (HIC) type flaws used as reference for comparison. Materials used containing natural operational defects were inspected in “as-service” conditions.<br/>Samples have then been inspected by means of a “full matrix capture” (FMC) acquisition process followed by “total focusing method” (TFM) data post processing. FCM-TFM data have been further post-processed and then used to create a 3D geometrical reconstruction of the volume inspected. Results obtained show the significant improvement that FMC/TFM has over traditional PA inspection techniques both in terms of sensitivity and resolution for this specific type of defect. Moreover since the FMC allows for the complete time domain signal to be captured from every element of a linear array probe the full set of data is available for post-processing.<br/>Finally the possibility to reconstruct the geometry of the component from the scans including the defects present in its volume represents the ideal solution for a reliable data transferring process to the engineering function for the subsequent FFS analysis.
Investigation of an Intensified Thermo-Chemical Experimental Set-Up for Hydrogen Production from Biomass: Gasification Process Performance—Part I
Jun 2021
Publication
Biomass gasification for energy purposes has several advantages such as the mitigation of global warming and national energy independency. In the present work the data from an innovative and intensified steam/oxygen biomass gasification process integrating a gas filtration step directly inside the reactor are presented. The produced gas at the outlet of the 1 MWth gasification pilot plant was analysed in terms of its main gaseous products (hydrogen carbon monoxide carbon dioxide and methane) and contaminants. Experimental test sets were carried out at 0.25–0.28 Equivalence Ratio (ER) 0.4–0.5 Steam/Biomass (S/B) and 780–850 °C gasification temperature. Almond shells were selected as biomass feedstock and supplied to the reactor at approximately 120 and 150 kgdry/h. Based on the collected data the in-vessel filtration system showed a dust removal efficiency higher than 99%-wt. A gas yield of 1.2 Nm3dry/kgdaf and a producer gas with a dry composition of 27–33%v H2 23–29%v CO 31–36%v CO2 9–11%v CH4 and light hydrocarbons lower than 1%v were also observed. Correspondingly a Low Heating Value (LHV) of 10.3–10.9 MJ/Nm3dry and a cold gas efficiency (CGE) up to 75% were estimated. Overall the collected data allowed for the assessment of the preliminary performances of the intensified gasification process and provided the data to validate a simulative model developed through Aspen Plus software.
Hydrogen vs. Battery in the Long-term Operation. A Comparative Between Energy Management Strategies for Hybrid Renewable Microgrids
Apr 2020
Publication
The growth of the world’s energy demand over recent decades in relation to energy intensity and demography is clear. At the same time the use of renewable energy sources is pursued to address decarbonization targets but the stochasticity of renewable energy systems produces an increasing need for management systems to supply such energy volume while guaranteeing at the same time the security and reliability of the microgrids. Locally distributed energy storage systems (ESS) may provide the capacity to temporarily decouple production and demand. In this sense the most implemented ESS in local energy districts are small–medium-scale electrochemical batteries. However hydrogen systems are viable for storing larger energy quantities thanks to its intrinsic high mass-energy density. To match generation demand and storage energy management systems (EMSs) become crucial. This paper compares two strategies for an energy management system based on hydrogen-priority vs. battery-priority for the operation of a hybrid renewable microgrid. The overall performance of the two mentioned strategies is compared in the long-term operation via a set of evaluation parameters defined by the unmet load storage efficiency operating hours and cumulative energy. The results show that the hydrogen-priority strategy allows the microgrid to be led towards island operation because it saves a higher amount of energy while the battery-priority strategy reduces the energy efficiency in the storage round trip. The main contribution of this work lies in the demonstration that conventional EMS for microgrids’ operation based on battery-priority strategy should turn into hydrogen-priority to keep the reliability and independence of the microgrid in the long-term operation.
Influence of Thermal Treatment on SCC and HE Susceptibility of Supermartensitic Stainless Steel 16Cr5NiMo
Apr 2020
Publication
A 16Cr5NiMo supermartensitic stainless steel was subjected to different tempering treatments and analyzed by means of permeation tests and slow strain rate tests to investigate the effect of different amounts of retained austenite on its hydrogen embrittlement susceptibility. The 16Cr5NiMo steel class is characterized by a very low carbon content. It is the new variant of 13Cr4Ni. These steels are used in many applications for example compressors for sour environments offshore piping naval propellers aircraft components and subsea applications. The typical microstructure is a soft-tempered martensite very close to a body-centered cubic with a retained austenite fraction and limited δ ferrite phase. Supermartensitic stainless steels have high mechanical properties together with good weldability and corrosion resistance. The amount of retained austenite is useful to increase low temperature toughness and stress corrosion cracking resistance. Experimental techniques allowed us to evaluate diffusion coefficients and the mechanical behaviour of metals in stress corrosion cracking (SCC) conditions.
Magnesium Based Materials for Hydrogen Based Energy Storage: Past, Present and Future
Jan 2019
Publication
Volodymyr A. Yartys,
Mykhaylo V. Lototskyy,
Etsuo Akiba,
Rene Albert,
V. E. Antonov,
Jose-Ramón Ares,
Marcello Baricco,
Natacha Bourgeois,
Craig Buckley,
José Bellosta von Colbe,
Jean-Claude Crivello,
Fermin Cuevas,
Roman V. Denys,
Martin Dornheim,
Michael Felderhoff,
David M. Grant,
Bjørn Christian Hauback,
Terry D. Humphries,
Isaac Jacob,
Petra E. de Jongh,
Jean-Marc Joubert,
Mikhail A. Kuzovnikov,
Michel Latroche,
Mark Paskevicius,
Luca Pasquini,
L. Popilevsky,
Vladimir M. Skripnyuk,
Eugene I. Rabkin,
M. Veronica Sofianos,
Alastair D. Stuart,
Gavin Walker,
Hui Wang,
Colin Webb,
Min Zhu and
Torben R. Jensen
Magnesium hydride owns the largest share of publications on solid materials for hydrogen storage. The “Magnesium group” of international experts contributing to IEA Task 32 “Hydrogen Based Energy Storage” recently published two review papers presenting the activities of the group focused on magnesium hydride based materials and on Mg based compounds for hydrogen and energy storage. This review article not only overviews the latest activities on both fundamental aspects of Mg-based hydrides and their applications but also presents a historic overview on the topic and outlines projected future developments. Particular attention is paid to the theoretical and experimental studies of Mg-H system at extreme pressures kinetics and thermodynamics of the systems based on MgH2 nanostructuring new Mg-based compounds and novel composites and catalysis in the Mg based H storage systems. Finally thermal energy storage and upscaled H storage systems accommodating MgH2 are presented.
An Energy Autonomous House Equipped with a Solar PV Hydrogen Conversion System
Dec 2015
Publication
The use of RES in buildings is difficult for their random nature; therefore the plants using photovoltaic solar collectors must be connected to a power supply or interconnected with Energy accumulators if the building is isolated. The conversion of electricity into hydrogen technology is best suited to solve the problem and allows you to transfer the solar energy captured from day to night from summer to winter. This paper presents the feasibility study for a house powered by PV cogeneration solar collectors that reverse the electricity on the control unit that you command by a PC to power the household using a heat pump an electrolytic cell for the production of hydrogen to accumulate; control units sorting to the utilities the electricity produced by the fuel cell. The following are presented: The Energy analysis of the building the plant design economic analysis.
Electric Mobility in Portugal: Current Situation and Forecasts for Fuel Cell Vehicles
Nov 2021
Publication
In recent years the growing concern for air quality has led to the development of sustainable vehicles to replace conventional internal combustion engine (ICE) vehicles. Currently the most widespread technology in Europe and Portugal is that of Battery Electric Vehicles (BEV) or plug‐in HEV (PHEV) electric cars but hydrogen‐based transport has also shown significant growth in the commercialization of Fuel Cell Electric Vehicles (FCEV) and in the development of new infrastructural schemes. In the current panorama of EV particular attention should be paid to hydrogen technology i.e. FCEVs which is potentially a valid alternative to BEVs and can also be hybrid (FCHEV) and plug‐in hybrid (FCPHEV). Several sources cited show a positive trend of hydrogen in the transport sector identifying a growing trend in the expansion of hydrogen infrastructure although at this time it is still at an early stage of development. At the moment the cost of building the infrastructure is still high but on the basis of medium/long‐term scenarios it is clear that investments in hydrogen refueling stations will be profitable if the number of Fuel Cell vehicles increases. Conversely the Fuel Cell vehicle market is hampered if there is no adequate infrastructure for hydrogen development. The opportunity to use Fuel Cells to store electrical energy is quite fascinating and bypasses some obstacles encountered with BEVs. The advantages are clear since the charging times are reduced compared to charging from an electric charging post and the long‐distance voyage is made easier as the autonomy is much larger i.e. the psycho‐ sociological anxiety is avoided. Therefore the first part of the paper provides an overview of the current state of electric mobility in Portugal and the strategies adopted by the country. This is necessary to have a clear vision of how a new technology is accepted by the population and develops on the territory that is the propensity of citizens to technological change. Subsequently using current data on EV development and comparing information from recent years this work aims to investigate the future prospects of FCEVs in Portugal by adopting a dynamic model called SERA (Scenario Evaluation and Regionalization Analysis) with which it is possible to identify the Portuguese districts and cities where an FC charging infrastructure is expected to be most beneficial. From the results obtained the districts of Lisbon Porto and Aveiro seem to be the most interested in adopting FC technology. This analysis aims to ensure a measured view of the credible development of this market segment.
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