Spain
Tetrahydroborates: Development and Potential as Hydrogen Storage Medium
Oct 2017
Publication
The use of fossil fuels as an energy supply becomes increasingly problematic from the point of view of both environmental emissions and energy sustainability. As an alternative hydrogen is widely regarded as a key element for a potential energy solution. However differently from fossil fuels such as oil gas and coal the production of hydrogen requires energy. Alternative and intermittent renewable energy sources such as solar power wind power etc. present multiple advantages for the production of hydrogen. On the one hand the renewable sources contribute to a remarkable reduction of pollutants released to the air and on the other hand they significantly enhance the sustainability of energy supply. In addition the storage of energy in form of hydrogen has a huge potential to balance an effective and synergetic utilization of renewable energy sources. In this regard hydrogen storage technology is a key technology towards the practical application of hydrogen as “energy carrier”. Among the methods available to store hydrogen solid-state storage is the most attractive alternative from both the safety and the volumetric energy density points of view. Because of their appealing hydrogen content complex hydrides and complex hydride-based systems have attracted considerable attention as potential energy vectors for mobile and stationary applications. In this review the progresses made over the last century on the synthesis and development of tetrahydroborates and tetrahydroborate-based systems for hydrogen storage purposes are summarized.
Solid State Hydrogen Storage in Alanates and Alanate-Based Compounds: A Review
Jul 2018
Publication
The safest way to store hydrogen is in solid form physically entrapped in molecular form in highly porous materials or chemically bound in atomic form in hydrides. Among the different families of these compounds alkaline and alkaline earth metals alumino-hydrides (alanates) have been regarded as promising storing media and have been extensively studied since 1997 when Bogdanovic and Schwickardi reported that Ti-doped sodium alanate could be reversibly dehydrogenated under moderate conditions. In this review the preparative methods; the crystal structure; the physico-chemical and hydrogen absorption-desorption properties of the alanates of Li Na K Ca Mg Y Eu and Sr; and of some of the most interesting multi-cation alanates will be summarized and discussed. The most promising alanate-based reactive hydride composite (RHC) systems developed in the last few years will also be described and commented on concerning their hydrogen absorption and desorption performance.
Thermodynamic, Economic and Environmental Assessment of Renewable Natural Gas Production Systems
May 2020
Publication
One of the options to reduce the dependence on fossil fuels is to produce gas with the quality of natural gas but based on renewable energy sources. It can encompass among other biogas generation from various types of biomass and its subsequent upgrading. The main aim of this study is to analyze under a combined technical economic and environmental perspective three of the most representative technologies for the production of biomethane (bio-based natural gas): (i) manure fermentation and its subsequent upgrading by CO2 removal (ii) manure fermentation and biogas methanation using renewable hydrogen from electrolysis and (iii) biomass gasification in the atmosphere of oxygen and methanation of the resulted gas. Thermodynamic economic and environmental analyses are conducted to thoroughly compare the three cases. For these purposes detailed models in Aspen Plus software were built while environmental analysis was performed using the Life Cycle Assessment methodology. The results show that the highest efficiency (66.80%) and the lowest break-even price of biomethane (19.2 €/GJ) are reached for the technology involving fermentation and CO2 capture. Concerning environmental assessment the system with the best environmental performance varies depending on the impact category analyzed being the system with biomass gasification and methanation a suitable trade-off solution for biomethane production.
Hydrogen Effects on Progressively Cold-Drawn Pearlitic Steels: Between Donatello and Michelangelo
Sep 2017
Publication
This paper reviews previous research by the author in the field of hydrogen effects on progressively cold-drawn pearlitic steels in terms of hydrogen degradation (HD) hydrogen embrittlement (HE) or at the micro-level hydrogen-assisted micro-damage (HAMD) thus affecting their microstructural integrity and compromising the (macro-)structural integrity of civil engineering structures such as prestressed concrete bridges. It is seen that hydrogen effects in pearlitic microstructure (either oriented or not) are produced at the finest micro-level by plastic tearing in the form in general of hydrogen damage topography (HDT) with different appearances depending of the cold drawing degree evolving from the so-called tearing topography surface (TTS) in hot-rolled (not cold-drawn at all) or slightly cold-drawn pearlitic steels to a sort of enlarged and oriented TTS (EOTTS) in heavily drawn steels (the pronounced enlargement and marked orientation being along the wire axis or cold drawing direction). Whereas the pure TTS mode (null or low degree of cold drawing) resembles the Michelangello stone sculpture texture (MSST) the EOTTS mode does the same in relation to the Donatello wooden sculpture texture (DWST).
Hydrogen-assisted Cracking Paths in Oriented Pearlitic Microstructures: Resembling Donatello Wooden Sculpture Texture (DWST) & Mantegna’s Dead Christ Perspective (MDCP)
Jun 2020
Publication
Progressive cold drawing in eutectoid steel produces a preferential orientation of pearlitic colonies and ferrite/cementite lamellae thus inducing strength anisotropy in the steel and mixed mode propagation. While in the hot rolled steel (not cold drawn) the pearlitic microstructure is randomly oriented and the crack progresses in hydrogen by breaking the ferrite/cementite lamellae in heavily drawn steels the pearlitic microstructure is fully oriented and the predominant mechanism of hydrogen assisted cracking is the delamination (or decohesion) at the ferrite/cementite interface.
Industrial Robots Fuel Cell Based Hybrid Power-Trains: A Comparison between Different Configurations
Jun 2021
Publication
Electric vehicles are becoming more and more popular. One of the most promising possible solutions is one where a hybrid powertrain made up of a FC (Fuel Cell) and a battery is used. This type of vehicle offers great autonomy and high recharging speed which makes them ideal for many industrial applications. In this work three ways to build a hybrid power-train are presented and compared. To illustrate this the case of an industrial robot designed to move loads within a fully automated factory is used. The analysis and comparison are carried out through different objective criteria that indicate the power-train performance in different battery charge levels. The hybrid configurations are tested using real power profiles of the industrial robot. Finally simulation results show the performance of each hybrid configuration in terms of hydrogen consumption battery and FC degradation and dc bus voltage and current regulation.
Techno-economic Modelling of Water Electrolysers in the Range of Several MW to Provide Grid Services While Generating Hydrogen for Different Applications: A Case Study in Spain Applied to Mobility with FCEVs
Jun 2019
Publication
The use of hydrogen as energy carrier is a promising option to decarbonize both energy and transport sectors. This paper presents an advanced techno-economic model for calculation of optimal dispatch of large-scale multi MW electrolysis plants in order to obtain a more accurate evaluation of the feasibility of business cases related to the supply of this fuel for different end uses combined with grid services' provision. The model is applied to the Spanish case using different scenarios to determine the minimum demand required from the FCEV market so that electrolysis facilities featuring several MW result in profitable business cases. The results show that grid services contribute to the profitability of hydrogen production for mobility given a minimum but considerable demand from FCEV fleets.
Experimental Study of Biogas-Hydrogen Mixtures Combustion in Conventional Natural Gas Systems
Jul 2021
Publication
Biogas is a renewable gas with low heat energy which makes it extremely difficult to use as fuel in conventional natural gas equipment. Nonetheless the use of hydrogen as a biogas additive has proven to have a beneficial effect on flame stability and combustion behavior. This study evaluates the biogas–hydrogen combustion in a conventional natural gas burner able to work up to 100 kW. Tests were performed for three different compositions of biogas: BG70 (30% CO2) BG60 (40% CO2) and BG50 (50% CO2). To achieve better flame stability each biogas was enriched with hydrogen from 5% to 25%. The difficulty of burning biogas in conventional systems was proven as the burner does not ignite when the biogas composition contains more than 40% of CO2. The best improvements were obtained at 5% hydrogen composition since the exhaust gas temperature and thus the enthalpy rises by 80% for BG70 and 65% for BG60. The stability map reveals that pure biogas combustion is unstable in BG70 and BG60; when the CO2 content is 50% ignition is inhibited. The properties change slightly when the hydrogen concentrations are more than 20% in the fuel gas and do not necessarily improve.
Photocatalytic Production of Hydrogen from Binary Mixtures of C-3 Alcohols on Pt/TiO2: Influence of Alcohol Structure
Oct 2018
Publication
The effect of alcohol structure on photocatalytic production of H2 from C-3 alcohols was studied on 0.5% Pt/TiO2. A C-2 alcohol (ethanol) was also included for comparative purposes. For individual reactions from 10% v/v aqueous solutions of alcohols hydrogen production followed the order ethanol ≈ propan-2-ol > propan-1- ol > propane-123-triol > propane-12-diol > propane-13-diol. The process was found to be quite sensitive to the presence of additional alcohols in the reaction medium as evidenced by competitive reactions. Therefore propan-2-ol conversion was retarded in the presence of traces of the other alcohols this effect being particularly significant for vicinal diols. Additional experiments showed that adsorption of alcohols on Pt/TiO2 followed the order propane-123-triol > propane-12-diol > propane-13-diol > propan-1-ol > ethanol > propan-2-ol. Adsorption studies (DRIFT) and monitoring of reaction products showed that the main photocatalyzed process for propan-2-ol and propan-1-ol transformation is dehydrogenation to the corresponding carbonyl compound (especially for propan-2-ol both in the liquid and the gas phase). In the case of liquid-phase transformation of propan-1-ol ethane was also detected which is indicative of the dissociative mechanism to lead to the corresponding C-1 alkane. All in all competitive reactions proved to be very useful for mechanistic studies.
Optimal Strategies of Deployment of Far Offshore Co-located Wind-wave Energy Farms
Nov 2021
Publication
The most profitable offshore energy resources are usually found away from the coast. Nevertheless the accessibility and grid integration in those areas are more complicated. To avoid this problematic large scale hydrogen production is being promoted for far offshore applications. The main objective of this paper is to analyze the ability of wave energy converters to maximize hydrogen production in hybrid wind and wave far offshore farms. To that end wind and wave resource data are obtained from ERA5 for different locations in the Atlantic ocean and a Maximum Covariance Analysis is proposed for the selection of the most representative locations. Furthermore the suitability of different sized wave energy converters for auxiliary hydrogen production in the far offshore wind farms is also analysed. On that account the hydrodynamic parameters of the oscillating bodies are obtained via simulations with a Boundary Element Method based code and their operation is modelled using the software tool Matlab. The combination of both methodologies enables to perform a realistic assessment of the contribution of the wave energy converters to the hydrogen generation of an hybrid energy farm especially during those periods when the wind turbines would be stopped due to the variability of the wind. The obtained results show a considerable hydrogen generation capacity of the wave energy converters up to 6.28% of the wind based generation which could remarkably improve the efficiency of the far offshore farm and bring important economical profit. Wave energy converters are observed to be most profitable in those farms with low covariance between wind and waves where the disconnection times of the wind turbines are prone to be more prolonged but the wave energy is still usable. In such cases a maximum of 101.12 h of equivalent rated production of the wind turbine has been calculated to be recovered by the wave energy converters.
Prospective Techno-economic and Environmental Assessment of a National Hydrogen Production Mix for Road Transport
Nov 2019
Publication
Fuel cell electric vehicles arise as an alternative to conventional vehicles in the road transport sector. They could contribute to decarbonising the transport system because they have no direct CO2 emissions during the use phase. In fact the life-cycle environmental performance of hydrogen as a transportation fuel focuses on its production. In this sense through the case study of Spain this article prospectively assesses the techno-economic and environmental performance of a national hydrogen production mix by following a methodological framework based on energy systems modelling enriched with endogenous carbon footprint indicators. Taking into account the need for a hydrogen economy based on clean options alternative scenarios characterised by carbon footprint restrictions with respect to a fossil-based scenario dominated by steam methane reforming are evaluated. In these scenarios the steam reforming of natural gas still arises as the key hydrogen production technology in the short term whereas water electrolysis is the main technology in the medium and long term. Furthermore in scenarios with very restrictive carbon footprint limits biomass gasification also appears as a key hydrogen production technology in the long term. In the alternative scenarios assessed the functional substitution of hydrogen for conventional fossil fuels in the road transport sector could lead to high greenhouse gas emission savings ranging from 36 to 58 Mt CO2 eq in 2050. Overall these findings and the model structure and characterisation developed for the assessment of hydrogen energy scenarios are expected to be relevant not only to the specific case study of Spain but also to analysts and decision-makers in a large number of countries facing similar concerns.
Hydrogen Recovery from Waste Gas Streams to Feed (High-Temperature PEM) Fuel Cells: Environmental Performance under a Life-Cycle Thinking Approach
Oct 2020
Publication
Fossil fuels are being progressively substituted by a cleaner and more environmentally friendly form of energy where hydrogen fuel cells stand out. However the implementation of a competitive hydrogen economy still presents several challenges related to economic costs required infrastructures and environmental performance. In this context the objective of this work is to determine the environmental performance of the recovery of hydrogen from industrial waste gas streams to feed high-temperature proton exchange membrane fuel cells for stationary applications. The life-cycle assessment (LCA) analyzed alternative scenarios with different process configurations considering as functional unit 1 kg of hydrogen produced 1 kWh of energy obtained and 1 kg of inlet flow. The results make the recovery of hydrogen from waste streams environmentally preferable over alternative processes like methane reforming or coal gasification. The production of the fuel cell device resulted in high contributions in the abiotic depletion potential and acidification potential mainly due to the presence of platinum metal in the anode and cathode. The design and operation conditions that defined a more favorable scenario are the availability of a pressurized waste gas stream the use of photovoltaic electricity and the implementation of an energy recovery system for the residual methane stream.
The Membrane-assisted Chemical Looping Reforming Concept for Efficient H2 Production with Inherent CO2 Capture: Experimental Demonstration and Model Validation
Feb 2018
Publication
In this work a novel reactor concept referred to as Membrane-Assisted Chemical Looping Reforming (MA-CLR) has been demonstrated at lab scale under different operating conditions for a total working time of about 100 h. This reactor combines the advantages of Chemical Looping such as CO2 capture and good thermal integration with membrane technology for a better process integration and direct product separation in a single unit which in its turn leads to increased efficiencies and important benefits compared to conventional technologies for H2 production. The effect of different operating conditions (i.e. temperature steam-to-carbon ratio or oxygen feed in the reactor) has been evaluated in a continuous chemical looping reactor and methane conversions above 90% have been measured with (ultra-pure) hydrogen recovery from the membranes. For all the cases a maximum recovery factor of around 30% has been measured which could be increased by operating the concept at higher pressures and with more membranes. The optimum conditions have been found at temperatures around 600°C for a steam-to-carbon ratio of 3 and diluted air in the air reactor (5% O2). The complete demonstration has been carried out feeding up to 1 L/min of CH4 (corresponding to 0.6 kW of thermal input) while up to 1.15 L/min of H2 was recovered. Simultaneously a phenomenological model has been developed and validated with the experimental results. In general good agreement is observed with overall deviations below 10% in terms of methane conversion H2 recovery and separation factor. The model allows better understanding of the behavior of the MA-CLR concept and the optimization and design of scaled-up versions of the concept.
Comparative Analysis of Energy and Exergy Performance of Hydrogen Production Methods
Nov 2020
Publication
The study of the viability of hydrogen production as a sustainable energy source is a current challenge to satisfy the great world energy demand. There are several techniques to produce hydrogen either mature or under development. The election of the hydrogen production method will have a high impact on practical sustainability of the hydrogen economy. An important profile for the viability of a process is the calculation of energy and exergy efficiencies as well as their overall integration into the circular economy. To carry out theoretical energy and exergy analyses we have estimated proposed hydrogen production using different software (DWSIM and MATLAB) and reference conditions. The analysis consolidates methane reforming or auto-thermal reforming as the viable technologies at the present state of the art with reasonable energy and exergy efficiencies but pending on the impact of environmental constraints as CO2 emission countermeasures. However natural gas or electrolysis show very promising results and should be advanced in their technological and maturity scaling. Electrolysis shows a very good exergy efficiency due to the fact that electricity itself is a high exergy source. Pyrolysis exergy loses are mostly in the form of solid carbon material which has a very high integration potential into the hydrogen economy.
Hydrogen as an Energy Vector to Optimize the Energy Exploitation of a Self-consumption Solar Photovoltaic Facility in a Dwelling House
Nov 2019
Publication
Solar photovoltaic (PV) plants coupled with storage for domestic self-consumption purposes seem to be a promising technology in the next years as PV costs have decreased significantly and national regulations in many countries promote their installation in order to relax the energy requirements of power distribution grids. However electrochemical storage systems are still unaffordable for many domestic users and thus the advantages of self-consumption PV systems are reduced. Thus in this work the adoption of hydrogen systems as energy vectors between a PV plant and the energy user is proposed. As a preliminary study in this work the design of a PV and hydrogen-production self-consumption plant for a single dwelling is described. Then a technical and economic feasibility study conducted by modeling the facility within the Homer Energy Pro energy systems analysis tool is reported. The proposed system will be able to provide back not only electrical energy but also thermal energy through a fuel cell or refined water covering the fundamental needs of the householders (electricity heat or cooling and water). Results show that although the proposed system effectively increases the energy local use of the PV production and reduces significantly the energy injections or demands into/from the power grid avoiding power grid congestions and increasing the nano-grid resilience operation and maintenance costs may reduce its economic attractiveness for a single dwelling.
Water Electrolysis for the Production of Hydrogen to Be Employed in the Ironmaking and Steelmaking Industry
Nov 2021
Publication
The way to decarbonization will be characterized by the huge production of hydrogen through sustainable routes. Thus the basic production way is water electrolysis sustained by renewable energy sources allowing for obtaining “green hydrogen”. The present paper reviews the main available technologies for the water electrolysis finalized to the hydrogen production. We describe the fundamental of water electrolysis and the problems related to purification and/or desalinization of water before electrolysis. As a matter of fact we describe the energy efficiency issues with particular attention to the potential application in the steel industry. The fundamental aspects related to the choice of high-temperature or low-temperature technologies are analyzed.
Preliminary Design of a Self-Sufficient Electrical Storage System Based on Electrolytic Hydrogen for Power Supply in a Residential Application
Oct 2021
Publication
The use of renewable energy and hydrogen technology is a sustainable solution for the intermittent feature of renewable energies. Hence the aim of the present work is to design a self-sufficient system for a one-family house by coupling a solar photovoltaic array and an anion exchange membrane water electrolyzer (AEMWE). The first step is the selection of the photovoltaic panel by using PV-SYST 7.0 software. Then the hydrogen production system is calculated by coupling the electrolyzer and photovoltaic panel current–potential curves. A fuel cell is selected to use the hydrogen produced when solar energy is not available. Finally the hydrogen storage tank is also estimated to store hydrogen for a design basis of four consecutive cloudy days according to the hydrogen consumption of the fuel cell. The whole system is designed by a simple procedure for a specific location in Ciudad Real (Spain) for January which is known as the coldest month of the year. The simple procedure described in this work could be used elsewhere and demonstrated that the hydrogen production at low scale is a suitable technology to use renewable energy for self-energy supporting in a residential application without any connection to the grid.
Comprehensive Analysis of the Combustion of Low Carbon Fuels (Hydrogen, Methane and Coke Oven Gas) in a Spark Ignition Engine through CFD Modeling
Nov 2021
Publication
The use of low carbon fuels (LCFs) in internal combustion engines is a promising alternative to reduce pollution while achieving high performance through the conversion of the high energy content of the fuels into mechanical energy. However optimizing the engine design requires deep knowledge of the complex phenomena involved in combustion that depend on the operating conditions and the fuel employed. In this work computational fluid dynamics (CFD) simulation tools have been used to get insight into the performance of a Volkswagen Polo 1.4L port-fuel injection spark ignition engine that has been fueled with three different LCFs coke oven gas (COG) a gaseous by-product of coke manufacture H2 and CH4. The comparison is made in terms of power pressure temperature heat release flame growth speed emissions and volumetric efficiency. Simulations in Ansys® Forte® were validated with experiments at the same operating conditions with optimal spark advance wide open throttle a wide range of engine speed (2000–5000 rpm) and air-fuel ratio (λ) between 1 and 2. A sensitivity analysis of spark timing has been added to assess its impact on combustion variables. COG with intermediate flame growth speed produced the greatest power values but with lower pressure and temperature values at λ = 1.5 reducing the emissions of NO and the wall heat transfer. The useful energy released with COG was up to 16.5% and 5.1% higher than CH4 and H2 respectively. At richer and leaner mixtures (λ = 1 and λ = 2) similar performances were obtained compared to CH4 and H2 combining advantages of both pure fuels and widening the λ operation range without abnormal combustion. Therefore suitable management of the operating conditions maximizes the conversion of the waste stream fuel energy into useful energy while limiting emissions.
Challenges and Prospects of Renewable Hydrogen-based Strategies for Full Decarbonization of Stationary Power Applications
Oct 2021
Publication
The exponentially growing contribution of renewable energy sources in the electricity mix requires large systems for energy storage to tackle resources intermittency. In this context the technologies for hydrogen production offer a clean and versatile alternative to boost renewables penetration and energy security. Hydrogen production as a strategy for the decarbonization of the energy sources mix has been investigated since the beginning of the 1990s. The stationary sector i.e. all parts of the economy excluding the transportation sector accounts for almost three-quarters of greenhouse gases (GHG) emissions (mass of CO2-eq) in the world associated with power generation. While several publications focus on the hybridization of renewables with traditional energy storage systems or in different pathways of hydrogen use (mainly power-to-gas) this study provides an insightful analysis of the state of art and evolution of renewable hydrogen-based systems (RHS) to power the stationary sector. The analysis started with a thorough review of RHS deployments for power-to-power stationary applications such as in power generation industry residence commercial building and critical infrastructure. Then a detailed evaluation of relevant techno-economic parameters such as levelized cost of energy (LCOE) hydrogen roundtrip efficiency (HRE) loss of power supply probability (LPSP) self-sufficiency ratio (SSR) or renewable fraction (fRES) is provided. Subsequently lab-scale plants and pilot projects together with current market trends and commercial uptake of RHS and fuel cell systems are examined. Finally the future techno-economic barriers and challenges for short and medium-term deployment of RHS are identified and discussed.
A Hybrid Intelligent Model to Predict the Hydrogen Concentration in the Producer Gas from a Downdraft Gasifier
Apr 2022
Publication
This research work presents an artificial intelligence approach to predicting the hydrogen concentration in the producer gas from biomass gasification. An experimental gasification plant consisting of an air-blown downdraft fixed-bed gasifier fueled with exhausted olive pomace pellets and a producer gas conditioning unit was used to collect the whole dataset. During an extensive experimental campaign the producer gas volumetric composition was measured and recorded with a portable syngas analyzer at a constant time step of 10 seconds. The resulting dataset comprises nearly 75 hours of plant operation in total. A hybrid intelligent model was developed with the aim of performing fault detection in measuring the hydrogen concentration in the producer gas and still provide reliable values in the event of malfunction. The best performing hybrid model comprises six local internal submodels that combine artificial neural networks and support vector machines for regression. The results are remarkably satisfactory with a mean absolute prediction error of only 0.134% by volume. Accordingly the developed model could be used as a virtual sensor to support or even avoid the need for a real sensor that is specific for measuring the hydrogen concentration in the producer gas.
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