Italy

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.

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.

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.

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.

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.

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)

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.

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.

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.

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.

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.

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.

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.

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.

"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. "

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.

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.

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.

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.

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.

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.

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.

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.

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%.

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.

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.

Industrial and public interest in hydrogen technologies has risen strongly recently as hydrogen is the ideal means for medium to long term energy storage transport and usage in combination with renewable and green energy supply. In a future energy system the production storage and usage of green hydrogen is a key technology. Hydrogen is and will in future be even more used for industrial production processes as a reduction agent or for the production of synthetic hydrocarbons especially in the chemical industry and in refineries. Under certain conditions material based systems for hydrogen storage and compression offer advantages over the classical systems based on gaseous or liquid hydrogen. This includes in particular lower maintenance costs higher reliability and safety. Hydrogen storage is possible at pressures and temperatures much closer to ambient conditions. Hydrogen compression is possible without any moving parts and only by using waste heat. In this paper we summarize the newest developments of hydrogen carriers for storage and compression and in addition give an overview of the different research activities in this field.

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.

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.

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.

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.

Hydrogen is a highly efficient and clean renewable energy source and water splitting through electrocatalytic hydrogen evolution is a most promising approach for hydrogen generation. Layered transition metal dichalcogenides-based nano-structures have recently attracted significant interest as robust and durable catalysts for hydrogen evolution. We systematically investigated the platinum (Pt) based dichalcogenides (PtS₂ PtSe₂ and PtTe₂) as highly energetic and robust hydrogen evolution electrocatalysts. PtTe₂ catalyst unveiled the rapid hydrogen evolution process with the low overpotentials of 75 and 92 mV (vs. RHE) at a current density of 10 mA cm⁻² and the small Tafel slopes of 64 and 59 mV/dec in acidic and alkaline medium respectively. The fabricated PtTe₂ electrocatalyst explored a better catalytic activity than PtS₂ and PtSe₂. The density functional theory estimations explored that the observed small Gibbs free energy for H-adsorption of PtTe₂ was given the prominent role to achieve the superior electrocatalytic and excellent stability activity towards hydrogen evolution due to a smaller bandgap and the metallic nature. We believe that this work will offer a key path to use Pt based dichalcogenides for hydrogen evolution electrocatalysts.

Magnesium alloys have been widely studied as materials for temporary implants but their use has been limited by their corrosion rate. Recently coatings have been proven to provide an effective barrier. Though only little explored in the field Atomic Layer Deposition (ALD) stands out as a coating technology due to the outstanding film conformality and density achievable. Here we provide first insights into the corrosion behavior and the induced biological response of 100 nm thick ALD TiO₂ HfO₂ and ZrO₂ coatings on AZ31 alloy by means of potentiodynamic polarization curves electrochemical impedance spectroscopy (EIS) hydrogen evolution and MTS colorimetric assay with L929 cells. All three coatings improve the corrosion behavior and cytotoxicity of the alloy. Particularly HfO₂ coatings were characterized by the highest corrosion resistance and cell viability slightly higher than those of ZrO₂ coatings. TiO2 was characterized by the lowest corrosion improvements and though generally considered a biocompatible coating was found to not meet the demands for cellular applications (it was characterized by grade 3 cytotoxicity after 5 days of culture). These results reveal a strong link between biocompatibility and corrosion resistance and entail the need of taking the latter into consideration in the choice of a biocompatible coating to protect degradable Mg-based alloys.

This paper presents two different scenarios for the energy system of the Netherlands that achieve the Dutch government’s national target of near net-zero greenhouse gas emissions in 2050. Using the system optimisation model OPERA the authors have analysed the technology sector and cost implications of the assumptions underlying these scenarios. While the roles of a number of key energy technology and emission mitigation options are strongly dependent on the scenario and cost assumptions the analysis yields several common elements that appear in both scenarios and that consistently appear under differing cost assumptions. For example one of the main options for the decarbonisation of the Dutch energy system is electrification of energy use in end-use sectors and for the production of renewable hydrogen with electrolysers. As a result the level of electricity generation in 2050 will be three to four times higher than present generation levels. Ultimately renewable energy – particularly from wind turbines and solar panels – is projected to account for the vast majority of electricity generation around 99% in 2050. Imbalances between supply and demand resulting from this variable renewable electricity production can be managed via flexibility options including demand response and energy storage. Hydrogen also becomes an important energy carrier notably for transportation and in industry. If import prices are lower than costs of domestic production from natural gas with CCS or through electrolysis from renewable electricity (2.4–2.7 €/kgH2) the use of hydrogen increases especially in the built environment.

In the present work an Ir/CeO₂ catalyst was prepared by the deposition–precipitation method and tested in the decomposition of hydrazine hydrate to hydrogen which is very important in the development of hydrogen storage materials for fuel cells. The catalyst was characterised using different techniques i.e. X-ray photoelectron spectroscopy (XPS) transmission electron microscopy (TEM) scanning electron microscopy (SEM) equipped with X-ray detector (EDX) and inductively coupled plasma—mass spectroscopy (ICP-MS). The effect of reaction conditions on the activity and selectivity of the material was evaluated in this study modifying parameters such as temperature the mass of the catalyst stirring speed and concentration of base in order to find the optimal conditions of reaction which allow performing the test in a kinetically limited regime.

A research is under development at the Department of Agro-Environmental Sciences of the University of Bari “Aldo Moro” in order to investigate the suitable solutions of a power system based on solar energy (photovoltaic) and hydrogen integrated with a geothermal heat pump for powering a self sustained heated greenhouse. The electrical energy for heat pump operation is provided by a purpose-built array of solar photovoltaic modules which supplies also a water electrolyser system controlled by embedded pc; the generated dry hydrogen gas is conserved in suitable pressured storage tank. The hydrogen is used to produce electricity in a fuel cell in order to meet the above mentioned heat pump power demand when the photovoltaic system is inactive during winter night-time or the solar radiation level is insufficient to meet the electrical demand. The present work reports some theoretical and observed data about the electrolyzer operation. Indeed the electrolyzer has required particular attention because during the experimental tests it did not show a stable operation and it was registered a performance not properly consistent with the predicted performance by means of the theoretical study.

H₂ production from solar electricity in the region of the Atacama Desert – Chile – has been identified as strategical for global hydrogen exportation. In this study the full supply chain of solar hydrogen has been investigated for 2018 and projected to scenarios for 2025-2030. Multi-year hourly electrical profiles data have been used from real operating PV plants and simulated Concentrated Solar Power “CSP” plants with Thermal Energy Storage “TES” as well as commercial electricity Power Purchase Agreement “PPA” prices reported in the Chilean electricity market were considered. The Levelized Cost of Hydrogen “LCOH” of each production pathway is calculated by a case-sensitive techno-economic MATLAB/Simulink model for utility scale (multi-MW) alkaline and PEM electrolyser technologies. Successively different distribution storage and transportation configurations are evaluated based on the 2025 Japanese case study according to the declared H2 demand. Transport in the form of liquefied hydrogen (LH2) and via ammonia (NH3) carrier is compared from the port of Antofagasta CL to the port of Osaka JP.

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.

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.

Integrated water electrolysis is a core principle of new process configurations for decarbonized heavy industries. Water electrolysis generates H2 and O2 and involves an exchange of thermal energy. In this manuscript we investigate specific traditional heavy industrial processes that have previously been performed in nitrogen-rich air environments. We show that the individual process streams may be holistically integrated to establish new decarbonized industrial processes. In new process configurations CO2 capture is facilitated by avoiding inert gases in reactant streams. The primary energy required to drive electrolysis may be obtained from emerging renewable power sources (wind solar etc.) which have enjoyed substantial industrial development and cost reductions over the last decade. The new industrial designs uniquely harmonize the intermittency of renewable energy allowing chemical energy storage. We show that fully integrated electrolysis promotes the viability of decarbonized industrial processes. Specifically new process designs uniquely exploit intermittent renewable energy for CO2 conversion enabling thermal integration H2 and O2 utilization and sub-process harmonization for economic feasibility. The new designs are increasingly viable for decarbonizing ferric iron reduction municipal waste incineration biomass gasification fermentation pulp production biogas upgrading and calcination and are an essential step forward in reducing anthropogenic CO2 emissions.

The upcoming stricter limitations on both pollutant and greenhouse gases emissions represent a challenge for the shipping sector. The entire ship design process requires an approach to innovation with a particular focus on both the fuel choice and the power generation system. Among the possible alternatives natural gas and hydrogen based propulsion systems seem to be promising in the medium and long term. Nonetheless natural gas and hydrogen storage still represents a problem in terms of cargo volume reduction. This paper focuses on the storage issue considering compressed gases and presents an innovative solution which has been developed in the European project GASVESSEL® that allows to store gaseous fuels with an energy density higher than conventional intermediate pressure containment systems. After a general overview of natural gas and hydrogen as fuels for shipping a case study of a small Roll-on/Rolloff passenger ferry retrofit is proposed. The study analyses the technical feasibility of the installation of a hybrid power system with batteries and polymer electrolyte membrane fuel cells fuelled by hydrogen. In particular a process simulation model has been implemented to assess the quantity of hydrogen that can be stored on board taking into account boundary conditions such as filling time on shore storage capacity and cylinder wall temperature. The simulation results show that if the fuel cells system is run continuously at steady state to cover the energy need for one day of operation 140 kg of hydrogen are required. Using the innovative pressure cylinder at a storage pressure of 300 bar the volume required by the storage system assessed on the basis of the containment system outer dimensions is resulted to be 15.2 m3 with a weight of 2.5 ton. Even if the innovative type of pressure cylinder allows to reach an energy density higher than conventional intermediate pressure cylinders the volume necessary to store a quantity of energy typical for the shipping sector is many times higher than that required by conventional fuels today used. The analysis points out as expected that the filling process is critical to maximize the stored hydrogen mass and that it is critical to measure the temperature of the cylinder walls in order not to exceed the material limits. Nevertheless for specific application such as the one considered in the paper the introduction of gaseous hydrogen as fuel can be considered for implementing zero local emission propulsion system in the medium term.

Hydrogen as an energy carrier is very versatile in energy storage applications. Developments in novel sustainable technologies towards a CO2-free society are needed and the exploration of all-solid-state batteries (ASSBs) as well as solid-state hydrogen storage applications based on metal hydrides can provide solutions for such technologies. However there are still many technical challenges for both hydrogen storage material and ASSBs related to designing low-cost materials with low-environmental impact. The current materials considered for all-solid-state batteries should have high conductivities for Na+ Mg2+ and Ca2+ while Al3+-based compounds are often marginalised due to the lack of suitable electrode and electrolyte materials. In hydrogen storage materials the sluggish kinetic behaviour of solid-state hydride materials is one of the key constraints that limit their practical uses. Therefore it is necessary to overcome the kinetic issues of hydride materials before discussing and considering them on the system level. This review summarizes the achievements of the Marie Skłodowska-Curie Actions (MSCA) innovative training network (ITN) ECOSTORE the aim of which was the investigation of different aspects of (complex) metal hydride materials. Advances in battery and hydrogen storage materials for the efficient and compact storage of renewable energy production are discussed.

Optimal design and operation of multi-energy systems involving seasonal energy storage are often hindered by the complexity of the optimization problem. Indeed the description of seasonal cycles requires a year-long time horizon while the system operation calls for hourly resolution; this turns into a large number of decision variables including binary variables when large systems are analyzed. This work presents novel mixed integer linear program methodologies that allow considering a year time horizon with hour resolution while significantly reducing the complexity of the optimization problem. First the validity of the proposed techniques is tested by considering a simple system that can be solved in a reasonable computational time without resorting to design days. Findings show that the results of the proposed approaches are in good agreement with the full-scale optimization thus allowing to correctly size the energy storage and to operate the system with a long-term policy while significantly simplifying the optimization problem. Furthermore the developed methodology is adopted to design a multi-energy system based on a neighborhood in Zurich Switzerland which is optimized in terms of total annual costs and carbon dioxide emissions. Finally the system behavior is revealed by performing a sensitivity analysis on different features of the energy system and by looking at the topology of the energy hub along the Pareto sets.

The safest way to store hydrogen is in solid form physically entrapped in molecular form in highly porous materials or chemically bound in atomic form in hydrides. Among the different families of these compounds alkaline and alkaline earth metals alumino-hydrides (alanates) have been regarded as promising storing media and have been extensively studied since 1997 when Bogdanovic and Schwickardi reported that Ti-doped sodium alanate could be reversibly dehydrogenated under moderate conditions. In this review the preparative methods; the crystal structure; the physico-chemical and hydrogen absorption-desorption properties of the alanates of Li Na K Ca Mg Y Eu and Sr; and of some of the most interesting multi-cation alanates will be summarized and discussed. The most promising alanate-based reactive hydride composite (RHC) systems developed in the last few years will also be described and commented on concerning their hydrogen absorption and desorption performance.

This study evaluates the environmental profile of a real biomass-based hydrogen production small-scale (1 MWth) system composed of catalytic candle indirectly heated steam gasifier coupled with zinc oxide (ZnO) guard bed water gas shift (WGS) and pressure swing absorber (PSA) reactors. Environmental performance from cradle-to-gate was investigated by life cycle assessment (LCA) methodology. Biomass production shows high influence over all impact categories. In the syngas production process the main impacts observed are global warming potential (GWP) and acidification potential (AP). Flue gas emission from gasifier burner has the largest proportion of total GWP. The residual off gas use in internal combustion engine (ICE) leads to important environmental savings for all categories. Hydrogen renewability score is computed as 90% due to over 100% decline in non-renewable energy demand. Sensitivity analysis shows that increase in hydrogen production efficiency does not necessarily result in decrease in environmental impacts. In addition economic allocation of environmental charges increases all impact categories especially AP and photochemical oxidation (POFP).

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.

A pilot power system formed by photovoltaic panels alkaline electrolyser and fuel cell stacks was designed and set up to supply the heating system of an experimental greenhouse. The aim of this paper is to analyse the main safety aspects of this power system connected to the management of the pressured hydrogen such as the explosion limits of the mixture hydrogen-oxygen the extension of the danger zone the protection pressure vessels and the system to make unreactive the plant. The electrolyser unit is the core of this plant and from the safety point of view has been equipped with devices able to highlight the mal-functions before they cause damages. Alarm situations are highlighted and the production process is cut off in safe conditions in the event that the operational parameters have an abnormal deviation from the design values. Also the entire power system has been designed so that any failure to its components does not compromise the workers’ safety even if the risk analysis is in progress because technical operation are being carried out for enhancing the plant functionality making it more suitable to the designed task of supplying electrically the green-house heating system during cold periods. Some experimental data pertinent to the solar radiation and the corresponding hydrogen pro-duction rate are also reported. At present it does not exist a well-established safety reference protocol to design the reliability of these types of power plants and then the assumed safety measures even if related to the achieved pilot installation can represent an original base of reference to set up guidelines for designing the safety of power plants in the future available for agricultural purposes.

Nowadays the combustion of fossil fuels for transportation has a major negative impact on the environment. All nations are concerned with environmental safety and the regulation of pollution motivating researchers across the world to find an alternate transportation fuel. The transition of the transportation sector towards sustainability for environmental safety can be achieved by the manifestation and commercialization of clean hydrogen fuel. Hydrogen fuel for sustainable mobility has its own effectiveness in terms of its generation and refueling processes. As the fuel requirement of vehicles cannot be anticipated because it depends on its utilization choosing hydrogen refueling and onboard generation can be a point of major concern. This review article describes the present status of hydrogen fuel utilization with a particular focus on the transportation industry. The advantages of onboard hydrogen generation and refueling hydrogen for internal combustion are discussed. In terms of performance affordability and lifetime onboard hydrogen-generating subsystems must compete with what automobile manufacturers and consumers have seen in modern vehicles to date. In internal combustion engines hydrogen has various benefits in terms of combustive properties but it needs a careful engine design to avoid anomalous combustion which is a major difficulty with hydrogen engines. Automobile makers and buyers will not invest in fuel cell technology until the technologies that make up the various components of a fuel cell automobile have advanced to acceptable levels of cost performance reliability durability and safety. Above all a substantial advancement in the fuel cell stack is required.

The present work aims to assess the influence of the composition of blends of hydrogen (H2 ) and Natural Gas (NG) on Dual Fuel (DF) combustion characteristics including gaseous emissions. The 3D-CFD study is carried out by means of a customized version of the KIVA-3V code. An automotive 2.8 L 4-cylinder turbocharged diesel engine was previously modified in order to operate in DF NG–diesel mode and tested at the dynamometer bench. After validation against experimental results the numerical model is applied to perform a set of combustion simulations at 3000 rpm–BMEP = 8 bar in DF H2/NG-diesel mode. Different H2–NG blends are considered: as the H2 mole fraction varies from 0 vol% to 50 vol% the fuel energy within the premixed charge is kept constant. The influence of the diesel Start Of Injection (SOI) is also investigated. Simulation results demonstrate that H2 enrichment accelerates the combustion process and promotes its completion strongly decreasing UHC and CO emissions. Evidently CO2 specific emissions are also reduced (up to about 20% at 50 vol% of H2 ). The main drawbacks of the faster combustion include an increase of in-cylinder peak pressure and pressure rate rise and of NOx emissions. However the study demonstrates that the optimization of diesel SOI can eliminate all aforementioned shortcomings.

Hydrogen produced by renewable sources represents an interesting way to reduce the energetic dependence on fossil fuels in the transportation sector. This paper shows a feasibility study for the production storage and distribution of hydrogen in the western Sicilian context using three different renewable sources: wind biomass and sea wave. The objective of this study is the evaluation of the hydrogen demand needed to replace all diesel supplied buses with electrical buses equipped with fuel cells. An economic analysis is presented with the evaluation of the avoidable greenhouse gas emissions. Four different scenarios correlate the hydrogen demand for urban transport to the renewable energy resources present in the territories and to the modern technologies available for the production of hydrogen. The study focuses on the possibility of tapping into the potential of renewable energies (wind biomass and sea wave) for the production of hydrogen by electrolysis. The use of hydrogen would reduce significantly the emissions of particulate and greenhouse gases in the urban districts under analysis.