Italy
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.
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.
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.
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.
Investigation of Mechanical Tests for Hydrogen Embrittlement in Automotive PHS Steels
Aug 2019
Publication
The problem of hydrogen embrittlement in ultra-high-strength steels is well known. In this study slow strain rate four-point bending and permeation tests were performed with the aim of characterizing innovative materials with an ultimate tensile strength higher than 1000 MPa. Hydrogen uptake in the case of automotive components can take place in many phases of the manufacturing process: during hot stamping due to the presence of moisture in the furnace atmosphere high-temperature dissociation giving rise to atomic hydrogen or also during electrochemical treatments such as cataphoresis. Moreover possible corrosive phenomena could be a source of hydrogen during an automobile’s life. This series of tests was performed here in order to characterize two press-hardened steels (PHS)—USIBOR 1500® and USIBOR 2000®—to establish a correlation between ultimate mechanical properties and critical hydrogen concentration.
Achievements of European Projects on Membrane Reactor for Hydrogen Production
May 2017
Publication
Membrane reactors for hydrogen production can increase both the hydrogen production efficiency at small scale and the electric efficiency in micro-cogeneration systems when coupled with Polymeric Electrolyte Membrane fuel cells. This paper discusses the achievements of three European projects (FERRET FluidCELL BIONICO) which investigate the application of the membrane reactor concept to hydrogen production and micro-cogeneration systems using both natural gas and biofuels (biogas and bio-ethanol) as feedstock. The membranes used to selectively separate hydrogen from the other reaction products (CH4 CO2 H2O etc.) are of asymmetric type with a thin layer of Pd alloy (<5 μm) and supported on a ceramic porous material to increase their mechanical stability. In FERRET the flexibility of the membrane reactor under diverse natural gas quality is validated. The reactor is integrated in a micro-CHP system and achieves a net electric efficiency of about 42% (8% points higher than the reference case). In FluidCELL the use of bio-ethanol as feedstock for micro-cogeneration Polymeric Electrolyte Membrane based system is investigated in off-grid applications and a net electric efficiency around 40% is obtained (6% higher than the reference case). Finally BIONICO investigates the hydrogen production from biogas. While BIONICO has just started FERRET and FluidCELL are in their third year and the two prototypes are close to be tested confirming the potentiality of membrane reactor technology at small scale.
Hydrogen Embrittlement Behavior of 18Ni 300 Maraging Steel Produced by Selective Laser Melting
Jul 2019
Publication
A study was performed to investigate the hydrogen embrittlement behavior of 18-Ni 300 maraging steel produced by selective laser melting and subjected to different heat treatment strategies. Hydrogen was pre-charged into the tensile samples by an electro-chemical method at the constant current density of 1 A m−2 and 50 A m−2 for 48 h at room temperature. Charged and uncharged specimens were subjected to tensile tests and the hydrogen concentration was eventually analysed using quadrupole mass spectroscopy. After tensile tests uncharged maraging samples showed fracture surfaces with dimples. Conversely in H-charged alloys quasi-cleavage mode fractures occurred. A lower concentration of trapped hydrogen atoms and higher elongation at fracture were measured in the H-charged samples that were subjected to solution treatment prior to hydrogen charging compared to the as-built counterparts. Isothermal aging treatment performed at 460 °C for 8 h before hydrogen charging increased the concentration of trapped hydrogen giving rise to higher hydrogen embrittlement susceptibility.
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.
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.
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.
Impact of Hydrogen Injection on Natural Gas Measurement
Dec 2021
Publication
Hydrogen is increasingly receiving a primary role as an energy vector in ensuring the achievement of the European decarbonization goals by 2050. In fact Hydrogen could be produced also by electrolysis of water using renewable sources such as photovoltaic and wind power being able to perform the energy storage function as well as through injection into natural gas infrastructures. However hydrogen injection directly impacts thermodynamic properties of the gas itself such as density calorific value Wobbe index sound speed etc. Consequently this practice leads to changes in metrological behavior especially in terms of volume and gas quality measurements. In this paper the authors present an overview on the impact of hydrogen injection in natural gas measurements. In particular the changes in thermodynamic properties of the gas mixtures with different H2 contents have been evaluated and the effects on the accuracy of volume conversion at standard conditions have been investigated both on the theoretical point of view and experimentally. To this end the authors present and discuss the effect of H2 injection in gas networks on static ultrasonic domestic gas meters both from a theoretical and an experimental point of view. Experimental tests demonstrated that ultrasonic gas meters are not significantly affected by H2 injection up to about 10%.
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.
Effects of Steam Injection on the Permissible Hydrogen Content and Gaseous Emissions in a Micro Gas Turbine Supplied by a Mixture of CH4 and H2: A CFD Analysis
Apr 2022
Publication
The use of hydrogen in small scale gas turbines is currently limited by several issues. Blending hydrogen with methane or other gaseous fuels can be considered a low medium-term viable solution with the goal of reducing greenhouse gas emissions. In fact only small amounts can be mixed with methane in premixed combustors due to the risk of flashback. The aim of this article is to investigate the injection of small quantities of steam as a method of increasing the maximum permissible hydrogen content in a mixture with methane. The proposed approach involves introducing the steam directly into the combustion chamber into the main fuel feeding system of a Turbec T100. The study is carried out by means of CFD analysis of the combustion process. A thermodynamic analysis of the energy system is used to determine boundary conditions. The combustion chamber is discretized using a three-dimensional mesh consisting of 4.7 million nodes and the RANS RSM model is used to simulate the effects of turbulence. The results show that the addition of steam may triple the permissible percentage of hydrogen in the mixture for the considered MGT passing from 10% to over 30% by volume also leading to a reduction in NOx emissions without a significant variation in CO emissions.
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.
Recent Developments in Pd-CeO2 Nano-composite Electrocatalysts for Anodic Reactions in Anion Exchange Membrane Fuel Cells
Jan 2022
Publication
In 2016 for the first time a polymer electrolyte fuel cell free of Pt electrocatalysts was shown to deliver more than 0.5 W cm-2 of peak power density from H2 and air (CO2 free). This was achieved with a silver-based oxygen reduction (ORR) cathode and a Pd-CeO2 hydrogen oxidation reaction (HOR) anodic electrocatalyst. The poor kinetics of the HOR under alkaline conditions is a considerable challenge to Anion Exchange Membrane Fuel Cell (AEMFC) development as high Pt loadings are still required to achieve reasonable performance. Previously the ameliorative combination of Pd and CeO2 nanocomposites has been exploited mostly in heterogeneous catalysis where the positive interaction is well documented. Carbon supported PdCeO2 HOR catalysts have now been prepared by different synthetic techniques and employed in AEMFCs as alternative to Pt and PtRu standards. Important research has also been recently reported delving into the origin of the HOR enhancement on Pd-CeO2. Such work has highlighted the importance of the bifunctional mechanism of the HOR at high pHs. Carefully prepared nano-structures of Pd and CeO2 that promote the formation of the Pd-O-Ce interface provide optimal binding of both Had and OHad species aspects which are crucial for enhanced HOR kinetics. This review paper discusses the recent advances in Pd-CeO2 electrocatalysts for AEMFC anodes.
Inhomogeneous Hydrogen Deflagrations in the Presence of Obstacles in 25 m3 Enclosure. Experimental Results
Sep 2019
Publication
Explosion venting is a frequently used measure to mitigate the consequence of gas deflagrations in closed environments. Despite the effort to predict the vent area needed to achieved the protection through engineering formulas and CFD tools work has still to be done to reliably predict the outcome of a vented gas explosion. Blind-prediction exercises recently published show a large spread in the prediction of both engineering formula than CFD tools. University of Pisa performed experimental tests in a 25 m3 facility in inhomogeneous conditions and with the presence of simple obstacles constituted by plates bolted to HEB beams. The present paper is aimed to share the results of hydrogen dispersion and deflagration tests and discuss the comparison of maximum peak overpressure generated with different blockage ratio and repeated obstacles sets. Description of the experimental set-up includes all the details deemed necessary to reproduce the phenomenon with a CFD tool.
Integrating IT-SOFC and Gasification Combined Cycle with Methanation Reactor and Hydrogen Firing for Near Zero-emission Power Generation from Coal
Apr 2011
Publication
Application of Solid Oxide Fuel Cells (SOFC) in gasification-based power plants would represent a turning point in the power generation sector allowing to considerably increase the electric efficiency of coal-fired power stations while reducing CO2 and other pollutant emissions. The aim of this paper is the thermodynamic assessment of a SOFC-based IGFC plant with methanation reactor hydrogen post-firing and CO2 capture by physical absorption. The configuration proposed allows to obtain a very high net efficiency (51.6%) overcoming the main limits of configurations assessed in previous works.
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.
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.
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.
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.
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.
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.
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.
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. "
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.
Integration of Experimental Facilities: A Joint Effort for Establishing a Common Knowledge Base in Experimental Work on Hydrogen Safety
Sep 2009
Publication
With regard to the goals of the European HySafe Network research facilities are essential for the experimental investigation of relevant phenomena for testing devices and safety concepts as well as for the generation of validation data for the various numerical codes and models. The integrating activity ‘Integration of Experimental Facilities (IEF)’ has provided basic support for jointly performed experimental work within HySafe. Even beyond the funding period of the NoE HySafe in the 6th Framework Programme IEF represents a long lasting effort for reaching sustainable integration of the experimental research capacities and expertise of the partners from different research fields. In order to achieve a high standard in the quality of experimental data provided by the partners emphasis was put on the know-how transfer between the partners. The strategy for reaching the objectives consisted of two parts. On the one hand a documentation of the experimental capacities has been prepared and analysed. On the other hand a communication base has been established by means of biannual workshops on experimental issues. A total of 8 well received workshops has been organised covering topics from measurement technologies to safety issues. Based on the information presented by the partners a working document on best practice including the joint experimental knowledge of all partners with regard to experiments and instrumentation was created. Preserving the character of a working document it was implemented in the IEF wiki website which was set up in order to provide a central communication platform. The paper gives an overview of the IEF network activities over the last 5 years.
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.
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.
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.
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.
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.
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.
Benchmark Exercise on Risk Assessment Methods Applied to a Virtual Hydrogen Refuelling Station
Sep 2009
Publication
A benchmarking exercise on quantitative risk assessment (QRA) methodologies has been conducted within the project HyQRA under the framework of the European Network of Excellence (NoE) HySafe. The aim of the exercise was basically twofold: (i) to identify the differences and similarities in approaches in a QRA and their results for a hydrogen installation between nine participating partners representing a broad spectrum of background in QRA culture and history and (ii) to identify knowledge gaps in the various steps and parameters underlying the risk quantification. In the first step a reference case was defined: a virtual hydrogen refuelling station (HRS) in virtual surroundings comprising housing school shops and other vulnerable objects. All partners were requested to conduct a QRA according to their usual approach and experience. Basically participants were free to define representative release cases to apply models and frequency assessments according their own methodology and to present risk according to their usual format. To enable inter-comparison a required set of results data was prescribed like distances to specific thermal radiation levels from fires and distances to specific overpressure levels. Moreover complete documentation of assumptions base data and references was to be reported. It was not surprising that a wide range of results was obtained both in the applied approaches as well as in the quantitative outcomes and conclusions. This made it difficult to identify exactly which assumptions and parameters were responsible for the differences in results as the paper will show. A second phase was defined in which the QRA was determined by a more limited number of release cases (scenarios). The partners in the project agreed to assess specific scenarios in order to identify the differences in consequence assessment approaches. The results of this phase provide a better understanding of the influence of modelling assumptions and limitations on the eventual conclusions with regard to risk to on-site people and to the off-site public. This paper presents the results and conclusions of both stages of the exercise.
Integration of Open Slag Bath Furnace with Direct Reduction Reactors for New‐Generation Steelmaking
Jan 2022
Publication
The present paper illustrates an innovative steel processing route developed by employing hydrogen direct reduced pellets and an open slag bath furnace. The paper illustrates the direct reduction reactor employing hydrogen as reductant on an industrial scale. The solution allows for the production of steel from blast furnace pellets transformed in the direct reduction reactor. The reduced pellets are then melted in open slag bath furnaces allowing carburization for further refining. The proposed solution is clean for the decarbonization of the steel industry. The kinetic chemical and thermodynamic issues are detailed with particular attention paid to the slag conditions. The proposed solution is also supported by the economic evaluation compared to traditional routes.
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.
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.
Hydrogen Permeation in X65 Steel under Cyclic Loading
May 2020
Publication
This experimental work analyzes the hydrogen embrittlement mechanism in quenched and tempered low-alloyed steels. Experimental tests were performed to study hydrogen diffusion under applied cyclic loading. The permeation curves were fitted by considering literature models in order to evaluate the role of trapping—both reversible and irreversible—on the diffusion mechanism. Under loading conditions a marked shift to the right of the permeation curves was noticed mainly at values exceeding the tensile yield stress. In the presence of a relevant plastic strain the curve changes due to the presence of irreversible traps which efficiently subtract diffusible atomic hydrogen. A significant reduction in the apparent diffusion coefficient and a considerable increase in the number of traps were noticed as the maximum load exceeded the yield strength. Cyclic loading at a tensile stress slightly higher than the yield strength of the material increases the hydrogen entrapment phenomena. The tensile stress causes a marked and instant reduction in the concentration of mobile hydrogen within the metal lattice from 55% of the yield strength and it increases significantly in the plastic field.
Lock-In Effects on the Energy Sector: Evidence from Hydrogen Patenting Activities
Apr 2022
Publication
The aim of the paper is to analyze how regulatory design and its framework’s topics other than macroeconomic factors might impact green innovation by taking into consideration a brand-new renewable source of energy that is becoming more and more important in recent years: hydrogen and fuel cell patenting activities. Such activities have been used as a proxy for green technological change in a panel data of 52 countries over a 6-year period. A series of sectorial energy regulation and macroeconomic variables were tested to assess their impact on that technological frontier of green energy transition policy. As might have been expected the empirical analysis carried out with the model that was prefigured confirms significant evidence of lock-in effects on fossil fuel policies. The model confirms however another evidence: countries already investing in renewables might be willing to invest in hydrogen projects. A sort of reinforcement to the further development of green sustainable strategies seems to derive from having already concretely undertaken this direction. Future research should exploit different approaches to the research question and address the econometric criticalities mentioned in the paper along with exploiting results of the paper with further investigations.
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.
Application of Hydrides in Hydrogen Storage and Compression: Achievements, Outlook and Perspectives
Feb 2019
Publication
José Bellosta von Colbe,
Jose-Ramón Ares,
Jussara Barale,
Marcello Baricco,
Craig Buckley,
Giovanni Capurso,
Noris Gallandat,
David M. Grant,
Matylda N. Guzik,
Isaac Jacob,
Emil H. Jensen,
Julian Jepsen,
Thomas Klassen,
Mykhaylo V. Lototskyy,
Kandavel Manickam,
Amelia Montone,
Julian Puszkiel,
Martin Dornheim,
Sabrina Sartori,
Drew Sheppard,
Alastair D. Stuart,
Gavin Walker,
Colin Webb,
Heena Yang,
Volodymyr A. Yartys,
Andreas Züttel and
Torben R. Jensen
Metal hydrides are known as a potential efficient low-risk option for high-density hydrogen storage since the late 1970s. In this paper the present status and the future perspectives of the use of metal hydrides for hydrogen storage are discussed. Since the early 1990s interstitial metal hydrides are known as base materials for Ni – metal hydride rechargeable batteries. For hydrogen storage metal hydride systems have been developed in the 2010s [1] for use in emergency or backup power units i. e. for stationary applications.<br/>With the development and completion of the first submarines of the U212 A series by HDW (now Thyssen Krupp Marine Systems) in 2003 and its export class U214 in 2004 the use of metal hydrides for hydrogen storage in mobile applications has been established with new application fields coming into focus.<br/>In the last decades a huge number of new intermetallic and partially covalent hydrogen absorbing compounds has been identified and partly more partly less extensively characterized.<br/>In addition based on the thermodynamic properties of metal hydrides this class of materials gives the opportunity to develop a new hydrogen compression technology. They allow the direct conversion from thermal energy into the compression of hydrogen gas without the need of any moving parts. Such compressors have been developed and are nowadays commercially available for pressures up to 200 bar. Metal hydride based compressors for higher pressures are under development. Moreover storage systems consisting of the combination of metal hydrides and high-pressure vessels have been proposed as a realistic solution for on-board hydrogen storage on fuel cell vehicles.<br/>In the frame of the “Hydrogen Storage Systems for Mobile and Stationary Applications” Group in the International Energy Agency (IEA) Hydrogen Task 32 “Hydrogen-based energy storage” different compounds have been and will be scaled-up in the near future and tested in the range of 500 g to several hundred kg for use in hydrogen storage applications.
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.
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.
Soft-linking of a Behavioral Model for Transport with Energy System Cost optimization Applied to Hydrogen in EU
Sep 2019
Publication
Fuel cell electric vehicles (FCEV) currently have the challenge of high CAPEX mainly associated to the fuel cell. This study investigates strategies to promote FCEV deployment and overcome this initial high cost by combining a detailed simulation model of the passenger transport sector with an energy system model. The focus is on an energy system with 95% CO2 reduction by 2050. Soft-linking by taking the powertrain shares by country from the simulation model is preferred because it considers aspects such as car performance reliability and safety while keeping the cost optimization to evaluate the impact on the rest of the system. This caused a 14% increase in total cost of car ownership compared to the cost before soft-linking. Gas reforming combined with CO2 storage can provide a low-cost hydrogen source for FCEV in the first years of deployment. Once a lower CAPEX for FCEV is achieved a higher hydrogen cost from electrolysis can be afforded. The policy with the largest impact on FCEV was a purchase subsidy of 5 k€ per vehicle in the 2030–2034 period resulting in 24.3 million FCEV (on top of 67 million without policy) sold up to 2050 with total subsidies of 84 bln€. 5 bln€ of R&D incentives in the 2020–2024 period increased the cumulative sales up to 2050 by 10.5 million FCEV. Combining these two policies with infrastructure and fuel subsidies for 2030–2034 can result in 76 million FCEV on the road by 2050 representing more than 25% of the total car stock. Country specific incentives split of demand by distance or shift across modes of transport were not included in this study.
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.
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.
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.
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.
Life Cycle Environmental Analysis of a Hydrogen-based Energy Storage System for Remote Applications
Mar 2022
Publication
Energy storage systems are required to address the fluctuating behaviour of variable renewable energy sources. The environmental sustainability of energy storage technologies should be carefully assessed together with their techno-economic feasibility. In this work an environmental analysis of a renewable hydrogen-based energy storage system has been performed making use of input parameters made available in the framework of the European REMOTE project. The analysis is applied to the case study of the Froan islands (Norway) which are representative of many other insular microgrid sites in northern Europe. The REMOTE solution is compared with other scenarios based on fossil fuels and submarine connections to the mainland grid. The highest climate impacts are found in the dieselbased configuration (1090.9 kgCO2eq/MWh) followed by the REMOTE system (148.2 kgCO2eq/MWh) and by the sea cable scenario (113.7 kgCO2eq/MWh). However the latter is biased by the very low carbon intensity of the Norwegian electricity. A sensitivity analysis is then performed on the length of the sea cable and on the CO2 emission intensity of electricity showing that local conditions have a strong impact on the results. The REMOTE system is also found to be the most cost-effective solution to provide electricity to the insular community. The in-depth and comparative (with reference to possible alternatives) assessment of the renewable hydrogen-based system aims to provide a comprehensive overview about the effectiveness and sustainability of these innovative solutions as a support for off-grid remote areas.
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.
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.
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.
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.
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.
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.
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 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.
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 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.
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.
On the Use of Hydrogen in Confined Spaces: Results from the Internal Project InsHyde
Sep 2009
Publication
Alexandros G. Venetsanos,
Paul Adams,
Inaki Azkarate,
A. Bengaouer,
Marco Carcassi,
Angunn Engebø,
E. Gallego,
Olav Roald Hansen,
Stuart J. Hawksworth,
Thomas Jordan,
Armin Keßler,
Sanjay Kumar,
Vladimir V. Molkov,
Sandra Nilsen,
Ernst Arndt Reinecke,
M. Stöcklin,
Ulrich Schmidtchen,
Andrzej Teodorczyk,
D. Tigreat,
N. H. A. Versloot and
L. Boon-Brett
The paper presents an overview of the main achievements of the internal project InsHyde of the HySafe NoE. The scope of InsHyde was to investigate realistic small-medium indoor hydrogen leaks and provide recommendations for the safe use/storage of indoor hydrogen systems. Additionally InsHyde served to integrate proposals from HySafe work packages and existing external research projects towards a common effort. Following a state of the art review InsHyde activities expanded into experimental and simulation work. Dispersion experiments were performed using hydrogen and helium at the INERIS gallery facility to evaluate short and long term dispersion patterns in garage like settings. A new facility (GARAGE) was built at CEA and dispersion experiments were performed there using helium to evaluate hydrogen dispersion under highly controlled conditions. In parallel combustion experiments were performed by FZK to evaluate the maximum amount of hydrogen that could be safely ignited indoors. The combustion experiments were extended later on by KI at their test site by considering the ignition of larger amounts of hydrogen in obstructed environments outdoors. An evaluation of the performance of commercial hydrogen detectors as well as inter-lab calibration work was jointly performed by JRC INERIS and BAM. Simulation work was as intensive as the experimental work with participation from most of the partners. It included pre-test simulations validation of the available CFD codes against previously performed experiments with significant CFD code inter-comparisons as well as CFD application to investigate specific realistic scenarios. Additionally an evaluation of permeation issues was performed by VOLVO CEA NCSRD and UU by combining theoretical computational and experimental approaches with the results being presented to key automotive regulations and standards groups. Finally the InsHyde project concluded with a public document providing initial guidance on the use of hydrogen in confined spaces.
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.
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.
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.
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.
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.
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.
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.
The Deltah Lab, a New Multidisciplinary European Facility to Support the H2 Distribution & Storage Economy
Apr 2021
Publication
The target for European decarburization encourages the use of renewable energy sources and H2 is considered the link in the global energy system transformation. So research studies are numerous but only few facilities can test materials and components for H2 storage. This work offers a brief review of H2 storage methods and presents the preliminary results obtained in a new facility. Slow strain rate and fatigue life tests were performed in H2 at 80 MPa on specimens and a tank of AISI 4145 respectively. Besides the storage capacity at 30 MPa of a solid-state system they were evaluated on kg scale by adsorption test. The results have shown the H2 influence on mechanical properties of the steel. The adsorption test showed a gain of 26% at 12 MPa in H2 storage with respect to the empty condition. All samples have been characterized by complementary techniques in order to connect the H2 effect with material properties.
A Battery-Free Sustainable Powertrain Solution for Hydrogen Fuel Cell City Transit Bus Application
Apr 2022
Publication
The paper presents a sustainable electric powertrain for a transit city bus featuring an electrochemical battery-free power unit consisting of a hydrogen fuel cell stack and a kinetic energy storage system based on high-speed flywheels. A rare-earth free high-efficiency motor technology is adopted to pursue a more sustainable vehicle architecture by limiting the use of critical raw materials. A suitable dynamic energetic model of the full vehicle powertrain has been developed to investigate the feasibility of the traction system and the related energy management control strategy. The model includes losses characterisation as a function of the load of the main components of the powertrain by using experimental tests and literature data. The performance of the proposed solution is evaluated by simulating a vehicle mission on an urban path in real traffic conditions. Considerations about the effectiveness of the traction system are discussed.
Minimum Emissions Configuration of a Green Energy–Steel System: An Analytical Model
May 2022
Publication
The need to significantly reduce emissions from the steelmaking sector requires effective and ready-to-use technical solutions. With this aim different decarbonization strategies have been investigated by both researchers and practitioners. To this concern the most promising pathway is represented by the replacement of natural gas with pure hydrogen in the direct reduced iron (DRI) production process to feed an electric arc furnace (EAF). This solution allows to significantly reduce direct emissions of carbon dioxide from the DRI process but requires a significant amount of electricity to power electrolyzers adopted to produce hydrogen. The adoption of renewable electricity sources (green hydrogen) would reduce emissions by 95–100% compared to the blast furnace–basic oxygen furnace (BF–BOF) route. In this work an analytical model for the identification of the minimum emission configuration of a green energy–steel system consisting of a secondary route supported by a DRI production process and a renewable energy conversion system is proposed. In the model both technological features of the hydrogen steel plant and renewable energy production potential of the site where it is to be located are considered. Compared to previous studies the novelty of this work consists of the joint modeling of a renewable energy system and a steel plant. This allows to optimize the overall system from an environmental point of view considering the availability of green hydrogen as an inherent part of the model. Numerical experiments proved the effectiveness of the model proposed in evaluating the suitability of using green hydrogen in the steelmaking process. Depending on the characteristics of the site and the renewable energy conversion system adopted decreases in emissions ranging from 60% to 91% compared to the BF–BOF route were observed for the green energy–steel system considered It was found that the environmental benefit of using hydrogen in the secondary route is strictly related to the national energy mix and to the electrolyzers’ technology. Depending on the reference context it was found that there exists a maximum value of the emission factor from the national electricity grid below which is environmentally convenient to produce DRI by using only hydrogen. It was moreover found that the lower the electricity consumption of the electrolyzer the higher the value assumed by the emission factor from the electricity grid which makes the use of hydrogen convenient.
An Innovative and Comprehensive Approach for the Consequence Analysis of Liquid Hydrogen Vessel Explosions
Oct 2020
Publication
Hydrogen is one of the most suitable solutions to replace hydrocarbons in the future. Hydrogen consumption is expected to grow in the next years. Hydrogen liquefaction is one of the processes that allows for increase of hydrogen density and it is suggested when a large amount of substance must be stored or transported. Despite being a clean fuel its chemical and physical properties often arise concerns about the safety of the hydrogen technologies. A potentially critical scenario for the liquid hydrogen (LH2) tanks is the catastrophic rupture causing a consequent boiling liquid expanding vapour explosion (BLEVE) with consequent overpressure fragments projection and eventually a fireball. In this work all the BLEVE consequence typologies are evaluated through theoretical and analytical models. These models are validated with the experimental results provided by the BMW care manufacturer safety tests conducted during the 1990’s. After the validation the most suitable methods are selected to perform a blind prediction study of the forthcoming LH2 BLEVE experiments of the Safe Hydrogen fuel handling and Use for Efficient Implementation (SH2IFT) project. The models drawbacks together with the uncertainties and the knowledge gap in LH2 physical explosions are highlighted. Finally future works on the modelling activity of the LH2 BLEVE are suggested.
Feasibility Investigation of Hydrogen Refuelling Infrastructure for Heavy‐Duty Vehicles in Canada
Apr 2022
Publication
A potentially viable solution to the problem of greenhouse gas emissions by vehicles in the transportation sector is the deployment of hydrogen as alternative fuel. A limitation to the diffusion of the hydrogen‐fuelled vehicles option is the intricate refuelling stations that vehicles will require. This study examines the practical use of hydrogen fuel within the internal combustion engine (ICE)‐powered long‐haul heavy‐duty trucking vehicles. Specifically it appraises the techno‐ economic feasibility of constructing a network of long‐haul truck refuelling stations using hydrogen fuel across Canada. Hydrogen fuel is chosen as an option for this study due to its low carbon emissions rate compared to diesel. This study also explores various operational methods including variable technology integration levels and truck traffic flows truck and pipeline delivery of hydrogen to stations and the possibility of producing hydrogen onsite. The proposed models created for this work suggest important parameters for economic development such as capital costs for station construction the selling price of fuel and the total investment cost for the infrastructure of a nation‐ wide refuelling station. Results showed that the selling price of hydrogen gas pipeline delivery op‐ tion is more economically stable. Specifically it was found that at 100% technology integration the range in selling prices was between 8.3 and 25.1 CAD$/kg. Alternatively at 10% technology integration the range was from 12.7 to 34.1 CAD$/kg. Moreover liquid hydrogen which is delivered by trucks generally had the highest selling price due to its very prohibitive storage costs. However truck‐delivered hydrogen stations provided the lowest total investment cost; the highest is shown by pipe‐delivered hydrogen and onsite hydrogen production processes using high technology integration methods. It is worth mentioning that once hydrogen technology is more developed and deployed the refuelling infrastructure cost is likely to decrease considerably. It is expected that the techno‐economic model developed in this work will be useful to design and optimize new and more efficient hydrogen refuelling stations for any ICE vehicles or fuel cell vehicles.
Statistics, Lessons Learned and Recommendations from Analysis of HIAD 2.0 Database
Mar 2022
Publication
The manuscript firstly describes the data collection and validation process for the European Hydrogen Incidents and Accidents Database (HIAD 2.0) a public repository tool collecting systematic data on hydrogen-related incidents and near-misses. This is followed by an overview of HIAD 2.0 which currently contains 706 events. Subsequently the approaches and procedures followed by the authors to derive lessons learned and formulate recommendations from the events are described. The lessons learned have been divided into four categories including system design; system manufacturing installation and modification; human factors and emergency response. An overarching lesson learned is that minor events which occurred simultaneously could still result in serious consequences echoing James Reason's Swiss Cheese theory. Recommendations were formulated in relation to the established safety principles adapted for hydrogen by the European Hydrogen Safety Panel considering operational modes industrial sectors and human factors. This work provide an important contribution to the safety of systems involving hydrogen benefitting technical safety engineers emergency responders and emergency services. The lesson learned and the discussion derived from the statistics can also be used in training and risk assessment studies being of equal importance to promote and assist the development of sound safety culture in organisations.
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.
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.
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.
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.
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.
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.
Optimisation-based System Designs for Deep Offshore Wind Farms including Power to Gas Technologies
Feb 2022
Publication
A large deployment of energy storage solutions will be required by the stochastic and non-controllable nature of most renewable energy sources when planning for higher penetration of renewable electricity into the energy mix. Various solutions have been suggested for dealing with medium- and long-term energy storage. Hydrogen and ammonia are two of the most frequently discussed as they are both carbon-free fuels. In this paper the authors analyse the energy and cost efficiency of hydrogen and ammonia-based pathways for the storage transportation and final use of excess electricity from an offshore wind farm. The problem is solved as a linear programming problem simultaneously optimising the size of each problem unit and the respective time-dependent operational conditions. As a case study we consider an offshore wind farm of 1.5 GW size located in a reference location North of Scotland. The energy efficiency and cost of the whole chain are evaluated and compared with competitive alternatives namely batteries and liquid hydrogen storage. The results show that hydrogen and ammonia storage can be part of the optimal solution. Moreover their use for long-term energy storage can provide a significant cost-effective contribution to an extensive penetration of renewable energy sources in national energy systems.
Photoelectrochemical Hydrogen Production by Screen-Printed Copper Oxide Electrodes
May 2021
Publication
In this work copper oxides-based photocathodes for photoelectrochemical cells (PEC) were produced for the first time by screen printing. A total 7 × 10−3 g/m2 glycerine trioleate was found as optimum deflocculant amount to assure stable and homogeneous inks based on CuO nano-powder. The inks were formulated considering different binder amounts and deposited producing films with homogenous thickness microstructure and roughness. The as-produced films were thermally treated to obtain Cu2O- and Cu2O/CuO-based electrodes. The increased porosity obtained by adding higher amounts of binder in the ink positively affected the electron transfer from the surface of the electrode to the electrolyte thus increasing the corresponding photocurrent values. Moreover the Cu2O/CuO system showed a higher charge carrier and photocurrent density than the Cu2O-based one. The mixed Cu2O/CuO films allowed the most significant hydrogen production especially in slightly acid reaction conditions.
Different Scenarios of Electric Mobility: Current Situation and Possible Future Developments of Fuel Cell Vehicles in Italy
Jan 2020
Publication
The diffusion of electric vehicles in Italy has started but some complications weight its spread. At present hybrid technology is the most followed by users due particularly to socioeconomic factors such as cost of investment and range anxiety. After a deep discussion of the Italian scenario the aim of the paper is to recognize whether fuel cell technology may be an enabling solution to overcome pollution problems and respect for the environment. The opportunity to use fuel cells to store electric energy is quite fascinating—the charging times will be shortened and heavy passenger transport should be effortless challenged. On the basis of the present history and by investigating the available information this work reports the current e-mobility state in Italy and forecasts the cities in which a fuel cell charging infrastructure should be more profitable with the intention of granting a measured outlook on the plausible development of this actual niche market.
Hydrogen and Oxygen Production via Water Splitting in a Solar-Powered Membrane Reactor—A Conceptual Study
Jan 2021
Publication
Among the processes for producing hydrogen and oxygen from water via the use of solar energy water splitting has the advantage of being carried out in onestep. According to thermodynamics this process exhibits conversions of practical interest at very high temperatures and needs efficient separation systems in order to separate the reaction products hydrogen and oxygen. In this conceptual work the behaviour of a membrane reactor that uses two membranes perm-selective to hydrogen and oxygen is investigated in the temperature range 2000–2500 °C of interest for coupling this device with solar receivers. The effect of the reaction pressure has been evaluated at 0.5 and 1 bar while the permeate pressure has been fixed at 100 Pa. As a first result the use of the membrane perm-selective to oxygen in addition to the hydrogen one has improved significantly the reaction conversion that for instance at 0.5 bar and 2000 °C moves from 9.8% up to 18.8%. Based on these critical data a preliminary design of a membrane reactor consisting of a Ta tubular membrane separating the hydrogen and a hafnia camera separating the oxygen is presented: optimaloperating temperature of the reactor results in being around 2500 °C a value making impracticable its coupling with solar receivers even in view of an optimistic development of this technology. The study has verified that at 2000 °C with a water feed flow rate of 1000 kg h−1 about 200 and 100 m3 h−1 of hydrogen and oxygen are produced. In this case a surface of the hafnia membrane of the order of hundreds m2 is required: the design of such a membrane device may be feasible when considering special reactor configurations.
Delivering Net-zero Carbon Heat: Technoeconomic and Whole-system Comparisons of Domestic Electricity- and Hydrogen-driven Technologies in the UK
Apr 2022
Publication
Proposed sustainable transition pathways for moving away from natural gas in domestic heating focus on two main energy vectors: electricity and hydrogen. Electrification would be implemented by using vapourcompression heat pumps which are currently experiencing market growth in many countries. On the other hand hydrogen could substitute natural gas in boilers or be used in thermally–driven absorption heat pumps. In this paper a consistent thermodynamic and economic methodology is developed to assess the competitiveness of these options. The three technologies along with the option of district heating are for the first time compared for different weather/ambient conditions and fuel-price scenarios first from a homeowner’s and then from a wholeenergy system perspective. For the former two-dimensional decision maps are generated to identify the most cost-effective technologies for different combinations of fuel prices. It is shown that in the UK hydrogen technologies are economically favourable if hydrogen is supplied to domestic end-users at a price below half of the electricity price. Otherwise electrification and the use of conventional electric heat pumps will be preferred. From a whole-energy system perspective the total system cost per household (which accounts for upstream generation and storage as well as technology investment installation and maintenance) associated with electric heat pumps varies between 790 and 880 £/year for different scenarios making it the least-cost decarbonisation pathway. If hydrogen is produced by electrolysis the total system cost associated with hydrogen technologies is notably higher varying between 1410 and 1880 £/year. However this total system cost drops to 1150 £/year with hydrogen produced cost-effectively by methane reforming and carbon capture and storage thus reducing the gap between electricity- and hydrogen-driven technologies.
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.
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.
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.
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.
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.
Direct Route from Ethanol to Pure Hydrogen through Autothermal Reforming in a Membrane Reactor: Experimental Demonstration, Reactor Modelling and Design
Nov 2020
Publication
This work reports the integration of thin (~3e4 mm thick) Pd-based membranes for H2 separation in a fluidized bed catalytic reactor for ethanol auto-thermal reforming. The performance of a fluidized bed membrane reactor has been investigated from an experimental and numerical point of view. The demonstration of the technology has been carried out over 50 h under reactive conditions using 5 thin Pd-based alumina-supported membranes and a 3 wt%Pt-10 wt%Ni catalyst deposited on a mixed CeO2/SiO2 support. The results have confirmed the feasibility of the concept in particular the capacity to reach a hydrogen recovery factor up to 70% while the operation at different fluidization regimes oxygen-to-ethanol and steam-to-ethanol ratios feed pressures and reactor temperatures have been studied. The most critical part of the system is the sealing of the membranes where most of the gas leakage was detected. A fluidized bed membrane reactor model for ethanol reforming has been developed and validated with the obtained experimental results. The model has been subsequently used to design a small reactor unit for domestic use showing that 0.45 m2 membrane area is needed to produce the amount of H2 required for a 5 kWe PEM fuel-cell based micro-CHP system.
Hydrogen Production as a Clean Energy Carrier through Heterojunction Semiconductors for Environmental Remediation
Apr 2022
Publication
Today as a result of the advancement of technology and increasing environmental problems the need for clean energy has considerably increased. In this regard hydrogen which is a clean and sustainable energy carrier with high energy density is among the well-regarded and effective means to deliver and store energy and can also be used for environmental remediation purposes. Renewable hydrogen energy carriers can successfully substitute fossil fuels and decrease carbon dioxide (CO2 ) emissions and reduce the rate of global warming. Hydrogen generation from sustainable solar energy and water sources is an environmentally friendly resolution for growing global energy demands. Among various solar hydrogen production routes semiconductor-based photocatalysis seems a promising scheme that is mainly performed using two kinds of homogeneous and heterogeneous methods of which the latter is more advantageous. During semiconductor-based heterogeneous photocatalysis a solid material is stimulated by exposure to light and generates an electron–hole pair that subsequently takes part in redox reactions leading to hydrogen production. This review paper tries to thoroughly introduce and discuss various semiconductor-based photocatalysis processes for environmental remediation with a specific focus on heterojunction semiconductors with the hope that it will pave the way for new designs with higher performance to protect the environment.
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.
Comprehensive Review on Fuel Cell Technology for Stationary Applications as Sustainable and Efficient Poly-Generation Energy Systems
Aug 2021
Publication
Fuel cell technologies have several applications in stationary power production such as units for primary power generation grid stabilization systems adopted to generate backup power and combined-heat-and-power configurations (CHP). The main sectors where stationary fuel cells have been employed are (a) micro-CHP (b) large stationary applications (c) UPS and IPS. The fuel cell size for stationary applications is strongly related to the power needed from the load. Since this sector ranges from simple backup systems to large facilities the stationary fuel cell market includes few kWs and less (micro-generation) to larger sizes of MWs. The design parameters for the stationary fuel cell system differ for fuel cell technology (PEM AFC PAFC MCFC and SOFC) as well as the fuel type and supply. This paper aims to present a comprehensive review of two main trends of research on fuel-cell-based poly-generation systems: tracking the market trends and performance analysis. In deeper detail the present review will list a potential breakdown of the current costs of PEM/SOFC production for building applications over a range of production scales and at representative specifications as well as broken down by component/material. Inherent to the technical performance a concise estimation of FC system durability efficiency production maintenance and capital cost will be presented.
Flammability Reduction in a Pressurised Water Electrolyser Based on a Thin Polymer Electrolyte Membrane through a Pt-alloy Catalytic Approach
Jan 2019
Publication
Various Pt-based materials (unsupported Pt PtRu PtCo) were investigated as catalysts for recombining hydrogen and oxygen back into water. The recombination performance correlated well with the surface Pt metallic state. Alloying cobalt to platinum was observed to produce an electron transfer favouring the occurrence of a large fraction of the Pt metallic state on the catalyst surface. Unsupported PtCo showed both excellent recombination performance and dynamic behaviour. In a packed bed catalytic reactor when hydrogen was fed at 4% vol. in the oxygen stream (flammability limit) 99.5% of the total H2 content was immediately converted to water in the presence of PtCo thus avoiding safety issues. The PtCo catalyst was thus integrated in the anode of the membrane-electrode assembly of a polymer electrolyte membrane electrolysis cell. This catalyst showed good capability to reduce the concentration of hydrogen in the oxygen stream under differential pressure operation (1–20 bar) in the presence of a thin (90 μm) Aquivion® membrane. The modified system showed lower hydrogen concentration in the oxygen flow than electrolysis cells based on state-of-the-art thick polymer electrolyte membranes and allowed to expand the minimum current density load down to 0.15 A cm−2 . This was mainly due to the electrochemical oxidation of permeated H2 to protons that were transported back to the cathode. The electrolysis cell equipped with a dual layer PtCo/IrRuOx oxidation catalyst achieved a high operating current density (3 A cm−2 ) as requested to decrease the system capital costs under high efficiency conditions (about 77% efficiency at 55 °C and 20 bar). Moreover the electrolysis system showed reduced probability to reach the flammability limit under both high differential pressure (20 bar) and partial load operation (5%) as needed to properly address grid-balancing service
Toward a Non-destructive Diagnostic Analysis Tool of Exercises Pipelines: Models and Experiences
Dec 2018
Publication
Strategic networks of hydrocarbon pipelines in long time service are adversely affected by the action of aggressive chemicals transported with the fluids and dissolved in the environment. Material degradation phenomena are amplified in the presence of hydrogen and water elements that increase the material brittleness and reduce the safety margins. The risk of failure during operation of these infrastructures can be reduced if not prevented by the continuous monitoring of the integrity of the pipe surfaces and by the tracking of the relevant bulk properties. A fast and potentially non-destructive diagnostic tool of material degradation which may be exploited in this context is based on the instrumented indentation tests that can be performed on metals at different scales. Preliminary validation studies of the significance of this methodology for the assessment of pipeline integrity have been carried out with the aid of interpretation models of the experiments. The main results of this ongoing activity are illustrated in this contribution.
A Preliminary Energy Analysis of a Commercial CHP Fueled with H2NG Blends Chemically Supercharged by Renewable Hydrogen and Oxygen
Dec 2016
Publication
Currently Power-to-Gas technologies are considered viable solutions to face the onset problems associated with renewable capacity firming. Indeed carbon-free hydrogen production converting renewable electricity excess and its injection into natural gas pipelines is considered a short- to medium-term solution. In this way the so-called H2NG blends can be fired within internal combustion engines and micro gas turbines operating in CHP mode offering better environmental-energy performances in machines. As regards the distributed energy generation scenario the local H2 production by means of electrolysis for methane enrichment will be more cost-effective if the oxygen is fruitfully used instead of venting it out like a by-product as usually occurs. This study focuses on the usefulness of using that oxygen to enrich the air-fuel mixture of an internal combustion engine for micro-CHP applications once it has been fuelled with H2NG blends. Thus the main aim of this paper is to provide a set of values for benchmarking in which H2NG blends ranging in 0%-15% vol. burn within an ICE in partial oxy-fuel conditions. In particular a preliminary energy analysis was carried out based on experimental data reporting the engine operating parameters gains and losses in both electrical and heat recovery efficiency. The oxygen content in the air varies up to 22% vol. A Volkswagen Blue Tender CHP commercial version (19.8 kWel. of rated electrical power output) was considered as the reference machine and its energy characterization was reported when it operated under those unconventional conditions.
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.
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.
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