Italy
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.
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.
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.
Experimental and Theoretical Insights to Demonstrate the Hydrogen Evolution Activity of Layered Platinum Dichalcogenides Electrocatalysts
Mar 2021
Publication
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.
Moving Gas Turbine Package from Conventional Gas to Hydrogen Blend
Sep 2021
Publication
The current greatest challenge that all gas turbine manufactures and users have in front of them for the years to come is the energy transition while reducing CO2 footprint and to contrast climate change. To this aim the introduction of hydrogen as fuel gas (or its blend) is playing a very important role. The benefit from an environmental point of view is undisputed but the presence of hydrogen introduces a series of safety related aspects to be considered for the design of all systems of a gas turbine package. Most of the design standards developed and adopted in the past are based on conventional natural gas however physical properties of hydrogen require to analyze additional aspects or revise the current ones. In this context the design for safety is paramount as it is strongly impacted by the low energy ignition of hydrogen blend fuels. Baker Hughes has built its experience on several sites different Customers and applications currently installed. These gas turbines run with a variety of hydrogen blends with concentration as high as 100% hydrogen. Baker Hughes has achieved several milestones moving from design to experimental set up leveraging the internal infrastructures consolidating design assumptions. In this work the critical aspects such as material selection instrumentation electrical devices and components are discussed in the framework of package safety with the aim to evolve conventional design minimizing the impacts on package configurations.
On the Evaluation of ALD TiO 2 , ZrO 2 and HfO 2 Coatings on Corrosion and Cytotoxicity Performances
May 2021
Publication
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.
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.
Towards a Climate-neutral Energy System in the Netherlands
Jan 2022
Publication
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.
Green Hydrogen in Europe – A Regional Assessment: Substituting Existing Production with Electrolysis Powered by Renewables
Nov 2020
Publication
The increasing ambition of climate targets creates a major role for hydrogen especially in achieving carbon-neutrality in sectors presently difficult to decarbonise. This work examines to what extent the currently carbon-intensive hydrogen production in Europe could be replaced by water electrolysis using electricity from renewable energy resources (RES) such as solar photovoltaic onshore/offshore wind and hydropower (green hydrogen). The study assesses the technical potential of RES at regional and national levels considering environmental constraints land use limitations and various techno-economic parameters. It estimates localised clean hydrogen production and examines the capacity to replace carbon-intensive hydrogen hubs with ones that use RES-based water electrolysis. Findings reveal that -at national level- the available RES electricity potential exceeds the total electricity demand and the part for hydrogen production from electrolysis in all analysed countries. At regional level from the 109 regions associated with hydrogen production (EU27 and UK) 88 regions (81%) show an excess of potential RES generation after covering the annual electricity demand across all sectors and hydrogen production. Notably 84 regions have over 50% excess RES electricity potential after covering the total electricity demand and that for water electrolysis. The study provides evidence on the option to decarbonize hydrogen production at regional level. It shows that such transformation is possible and compatible with the ongoing transition towards carbon–neutral power systems in the EU. Overall this work aims to serve as a tool for designing hydrogen strategies in harmony with renewable energy policies.
Hydrous Hydrazine Decomposition for Hydrogen Production Using of Ir/CeO2: Effect of Reaction Parameters on the Activity
May 2021
Publication
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 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.
Hydrogen and Renewable Energy Sources Integrated System for Greenhouse Heating
Sep 2013
Publication
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.
Mechanical Spectroscopy Investigation of Point Defect-Driven Phenomena in a Cr Martensitic Steel
Oct 2018
Publication
The paper presents and discusses results of mechanical spectroscopy (MS) tests carried out on a Cr martensitic steel. The study regards the following topics: (i) embrittlement induced by Cr segregation; (ii) interaction of hydrogen with C–Cr associates; (iii) nucleation of Cr carbides. The MS technique permitted characterising of the specific role played by point defects in the investigated phenomena: (i) Cr segregation depends on C–Cr associates distribution in as-quenched material in particular a slow cooling rate (~150 K/min) from austenitic field involves an unstable distribution which leads to Cr concentration fluctuations after tempering at 973 K; (ii) hydrogen interacts with C–Cr associates and the phenomenon hinders hydrogen attack (HA) because hydrogen atoms bound by C–Cr associates are not able to diffuse towards grain boundaries and dislocation where CH4 bubbles may nucleate grow and merge to form the typical HA cracks; (iii) C–Cr associates take part in the nucleation mechanism of Cr7C3 carbides and specifically these carbides form by the aggregation of C–Cr associates with 1 Cr atom.
A Techno-Economic Analysis of Solar Hydrogen Production by Electrolysis in the North of Chile and the Case of Exportation from Atacama Desert to Japan
Aug 2020
Publication
H2 production from solar electricity in the region of the Atacama Desert – Chile – has been identified as strategical for global hydrogen exportation. In this study the full supply chain of solar hydrogen has been investigated for 2018 and projected to scenarios for 2025-2030. Multi-year hourly electrical profiles data have been used from real operating PV plants and simulated Concentrated Solar Power “CSP” plants with Thermal Energy Storage “TES” as well as commercial electricity Power Purchase Agreement “PPA” prices reported in the Chilean electricity market were considered. The Levelized Cost of Hydrogen “LCOH” of each production pathway is calculated by a case-sensitive techno-economic MATLAB/Simulink model for utility scale (multi-MW) alkaline and PEM electrolyser technologies. Successively different distribution storage and transportation configurations are evaluated based on the 2025 Japanese case study according to the declared H2 demand. Transport in the form of liquefied hydrogen (LH2) and via ammonia (NH3) carrier is compared from the port of Antofagasta CL to the port of Osaka JP.
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.
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.
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.
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.
Materials for Hydrogen-based Energy Storage - Past, Recent Progress and Future Outlook
Dec 2019
Publication
Michael Hirscher,
Volodymyr A. Yartys,
Marcello Baricco,
José Bellosta von Colbe,
Didier Blanchard,
Robert C. Bowman Jr.,
Darren P. Broom,
Craig Buckley,
Fei Chang,
Ping Chen,
Young Whan Cho,
Jean-Claude Crivello,
Fermin Cuevas,
William I. F. David,
Petra E. de Jongh,
Roman V. Denys,
Martin Dornheim,
Michael Felderhoff,
Yaroslav Filinchuk,
George E. Froudakis,
David M. Grant,
Evan MacA. Gray,
Bjørn Christian Hauback,
Teng He,
Terry D. Humphries,
Torben R. Jensen,
Sangryun Kim,
Yoshitsugu Kojima,
Michel Latroche,
Hai-wen Li,
Mykhaylo V. Lototskyy,
Joshua W. Makepeace,
Kasper T. Møller,
Lubna Naheed,
Peter Ngene,
Dag Noreus,
Magnus Moe Nygård,
Shin-ichi Orimo,
Mark Paskevicius,
Luca Pasquini,
Dorthe B. Ravnsbæk,
M. Veronica Sofianos,
Terrence J. Udovic,
Tejs Vegge,
Gavin Walker,
Colin Webb,
Claudia Weidenthaler and
Claudia Zlotea
Globally the accelerating use of renewable energy sources enabled by increased efficiencies and reduced costs and driven by the need to mitigate the effects of climate change has significantly increased research in the areas of renewable energy production storage distribution and end-use. Central to this discussion is the use of hydrogen as a clean efficient energy vector for energy storage. This review by experts of Task 32 “Hydrogen-based Energy Storage” of the International Energy Agency Hydrogen TCP reports on the development over the last 6 years of hydrogen storage materials methods and techniques including electrochemical and thermal storage systems. An overview is given on the background to the various methods the current state of development and the future prospects. The following areas are covered; porous materials liquid hydrogen carriers complex hydrides intermetallic hydrides electro-chemical storage of energy thermal energy storage hydrogen energy systems and an outlook is presented for future prospects and research on hydrogen-based energy storage
Process Integration of Green Hydrogen: Decarbonization of Chemical Industries
Sep 2020
Publication
Integrated water electrolysis is a core principle of new process configurations for decarbonized heavy industries. Water electrolysis generates H2 and O2 and involves an exchange of thermal energy. In this manuscript we investigate specific traditional heavy industrial processes that have previously been performed in nitrogen-rich air environments. We show that the individual process streams may be holistically integrated to establish new decarbonized industrial processes. In new process configurations CO2 capture is facilitated by avoiding inert gases in reactant streams. The primary energy required to drive electrolysis may be obtained from emerging renewable power sources (wind solar etc.) which have enjoyed substantial industrial development and cost reductions over the last decade. The new industrial designs uniquely harmonize the intermittency of renewable energy allowing chemical energy storage. We show that fully integrated electrolysis promotes the viability of decarbonized industrial processes. Specifically new process designs uniquely exploit intermittent renewable energy for CO2 conversion enabling thermal integration H2 and O2 utilization and sub-process harmonization for economic feasibility. The new designs are increasingly viable for decarbonizing ferric iron reduction municipal waste incineration biomass gasification fermentation pulp production biogas upgrading and calcination and are an essential step forward in reducing anthropogenic CO2 emissions.
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