Spain

Renewable methanol obtained from CO₂ and hydrogen provided from renewable energy was proposed to close the CO₂ loop. In industry methanol synthesis using the catalyst CuO/ZnO/Al₂O₃ occurs at a high pressure. We intend to make certain modification on the traditional catalyst to work at lower pressure maintaining high selectivity. Therefore three heterogeneous catalysts were synthesized by coprecipitation to improve the activity and the selectivity to methanol under mild conditions of temperature and pressure. Certain modifications on the traditional catalyst Cu/Zn/Al₂O₃ were employed such as the modification of the synthesis time and the addition of Pd as a dopant agent. The most efficient catalyst among those tested was a palladium-doped catalyst 5% Pd/Cu/Zn/Al₂O₃. This had a selectivity of 64% at 210 °C and 5 bar.

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.

In the present work methane carbon monoxide hydrogen and the binary mixtures 20 % CH4–80 % H2 80 % CH4–20 % H2 25 % CO–75 % H2 (by volume) were considered as fuels of a naturally aspirated port-fuel injection four-cylinder Volkswagen 1.4 L spark-ignition (SI) engine. The interest in these fuels lies in the fact that they can be obtained from renewable resources such as the fermentation or gasification of residual biomasses as well as the electrolysis of water with electricity of renewable origin in the case of hydrogen. In addition they can be used upon relatively easy modifications of the engines including the retrofitting of existing internal combustion engines. It has been found that the engine gives similar performance regardless the gaseous fuel nature if the air–fuel equivalence ratio (λ) is the same. Maximum brake torque and mean effective pressure values within 45–89 N⋅m and 4.0–8.0 bar respectively have been obtained at values of λ between 1 and 2 at full load engine speed of 2000 rpm and optimum spark-advance. In contrast the nature of the gaseous fuel had great influence upon the range of λ values at which a fuel (either pure or blend) could be used. Methane and methane-rich mixtures with hydrogen or carbon monoxide allowed operating the engine at close to stoichiometric conditions (i.e. 1 < λ < 1.5) yielding the highest brake torque and mean effective pressure values. On the contrary hydrogen and hydrogen-rich mixtures with methane or carbon monoxide could be employed only in the very fuel-lean region (i.e. 1.5 < λ < 2). The behavior of carbon monoxide was intermediate between that of methane and hydrogen. The present study extends and complements previous works in which the aforementioned fuels were compared only under stoichiometric conditions in air (λ = 1). In addition a simple zero-dimensional thermodynamic combustion model has been developed that allows describing qualitatively the trends set by the several fuels. Although the model is useful to understand the influence of the fuels properties on the engine performance its predictive capability is limited by the simplifications made.

Residues and by-products from vegetables and fruit wholesale markets are suitable for recovery in the form of energy through anaerobic digestion allowing waste recovery and introducing them into the circular economy. This suitability is due to their composition structural characteristics and to the biogas generation process which is stable and without inhibition. However it has been observed that the proportion of methane and the level of degradation of the substrate is low. It is decided to study whether the effect of pretreatments on the substrate is beneficial. Freezing ultrafreezing and lyophilization pretreatments are studied. A characterization of the substrates has been performed the route of action of pretreatment determined and the digestion process studied to calculate the generation of biogas methane hydrogen and the proportions among these. Also a complete analysis of the process has been performed by processing the data with mathematical and statistical methods to obtain disintegration constants and levels of degradation. It has been observed that the three pretreatments have positive effects when increasing the solubility of the substrate increasing porosity and improving the accessibility of microorganisms to the substrate. Generation of gases are greatly increased reaching a methane enrichment of 59.751%. Freezing seems to be the best pretreatment as it increases the biodegradation level the speed of the process and the disintegration constant by 306%.

Despite their high thermal efficiency (>50%) large two-stroke (2 T) diesel engines burning very cheap heavy fuel oil (HFO) produce a high level of carbon dioxide (CO₂). To achieve the low emission levels of greenhouse gases (GHG) that will be imposed by future legislation the use of hydrogen (H₂) as fuel in 2 T diesel engines is a viable option for reducing or almost eliminate CO₂ emissions. In this work from experimental data and system modelling an analysis of dual combustion is carried out considering different strategies to supply H₂ to the engine and for different H2 fractions in energy basis. Previously a complete thermodynamic model of a 2 T diesel engine with an innovative scavenging model is developed and validated. The most important drawbacks of this type of engines are controlled in this work using dual combustion and water injection reducing nitrogen oxides emissions (NOx) self-ignition and combustion knocking. The results show that the developed model matches engine performance data in diesel mode achieving a higher efficiency and mean effective pressure (MEP) in hydrogen mode of 53% and 14.62 bar respectively.

Palladium-based membranes for hydrogen separation have been studied by several research groups during the last 40 years. Much effort has been dedicated to improving the hydrogen flux of these membranes employing different alloys supports deposition/production techniques etc. High flux and cheap membranes yet stable at different operating conditions are required for their exploitation at industrial scale. The integration of membranes in multifunctional reactors (membrane reactors) poses additional demands on the membranes as interactions at different levels between the catalyst and the membrane surface can occur. Particularly when employing the membranes in fluidized bed reactors the selective layer should be resistant to or protected against erosion. In this review we will also describe a novel kind of membranes the pore-filled type membranes prepared by Pacheco Tanaka and coworkers that represent a possible solution to integrate thin selective membranes into membrane reactors while protecting the selective layer. This work is focused on recent advances on metallic supports materials used as an intermetallic diffusion layer when metallic supports are used and the most recent advances on Pd-based composite membranes. Particular attention is paid to improvements on sulfur resistance of Pd based membranes resistance to hydrogen embrittlement and stability at high temperature.

A 100% renewable economy would give a lasting solution to the challenges raised by climate change energy security sustainability and pollution. The conversion of the present transport system appears to be one of the most difficult aspects of such renewable transition. This study reviews the technologies and systems that are being proposed or proven as alternative to fossil-fuel based transportation and their prospects for their entry into the post-carbon era from both technological and energetic viewpoints. The energetic cost of the transition from the current transportation system into global 100% renewable transportation is estimated as well as the electrical energy required for the operation of the new renewable transportation sector. A 100% renewable transport providing the same service as global transport in 2014 would demand about 18% less energy. The main reduction is expected in road transport (69%) but the shipping and air sectors would notably increase their consumptions: 163% and 149% respectively. The analysis concludes that a 100% renewable transportation is feasible but not necessarily compatible with indefinite increase of resources consumption. The major material and energy limitations and obstacles of each transport sector for this transition are shown.

Considering a simple regenerative Brayton cycle the impact of using different fuel blends containing a variable volumetric percentage of hydrogen in methane was analysed. Due to the potential of hydrogen combustion in gas turbines to reduce the overall CO2 emissions and the dependency on natural gas further research is needed to understand the impact on the overall thermodynamic cycle. For that purpose a qualitative thermodynamic analysis was carried out to assess the exergetic and energetic efficiencies of the cycle as well as the irreversibilities associated to a subsystem. A single step reaction was considered in the hypothesis of complete combustion of a generic H2/CH4 mixture where the volumetric H2 percentage was represented by fH2 which was varied from 0 to 1 defining the amount of hydrogen in the fuel mixture. Energy and entropy balances were solved through the Engineering Equation Solver (EES) code. Results showed that global exergetic and energetic efficiencies increased by 5% and 2% respectively varying fH2 from 0 to 1. Higher hydrogen percentages resulted in lower exergy destruction in the chamber despite the higher air-excess levels. It was also observed that higher values of fH2 led to lower fuel mass flow rates in the chamber showing that hydrogen can still be competitive even though its cost per unit mass is twice that of natural gas.

The growth of the world’s energy demand over recent decades in relation to energy intensity and demography is clear. At the same time the use of renewable energy sources is pursued to address decarbonization targets but the stochasticity of renewable energy systems produces an increasing need for management systems to supply such energy volume while guaranteeing at the same time the security and reliability of the microgrids. Locally distributed energy storage systems (ESS) may provide the capacity to temporarily decouple production and demand. In this sense the most implemented ESS in local energy districts are small–medium-scale electrochemical batteries. However hydrogen systems are viable for storing larger energy quantities thanks to its intrinsic high mass-energy density. To match generation demand and storage energy management systems (EMSs) become crucial. This paper compares two strategies for an energy management system based on hydrogen-priority vs. battery-priority for the operation of a hybrid renewable microgrid. The overall performance of the two mentioned strategies is compared in the long-term operation via a set of evaluation parameters defined by the unmet load storage efficiency operating hours and cumulative energy. The results show that the hydrogen-priority strategy allows the microgrid to be led towards island operation because it saves a higher amount of energy while the battery-priority strategy reduces the energy efficiency in the storage round trip. The main contribution of this work lies in the demonstration that conventional EMS for microgrids’ operation based on battery-priority strategy should turn into hydrogen-priority to keep the reliability and independence of the microgrid in the long-term operation.

Hydrogen storage in the solid state represents one of the most attractive and challenging ways to supply hydrogen to a proton exchange membrane (PEM) fuel cell. Although in the last 15 years a large variety of material systems have been identified as possible candidates for storing hydrogen further efforts have to be made in the development of systems which meet the strict targets of the Fuel Cells and Hydrogen Joint Undertaking (FCH JU) and U.S. Department of Energy (DOE). Recent projections indicate that a system possessing: (i) an ideal enthalpy in the range of 20–50 kJ/mol H2 to use the heat produced by PEM fuel cell for providing the energy necessary for desorption; (ii) a gravimetric hydrogen density of 5 wt. % H2 and (iii) fast sorption kinetics below 110 ◦C is strongly recommended. Among the known hydrogen storage materials amide and imide-based mixtures represent the most promising class of compounds for on-board applications; however some barriers still have to be overcome before considering this class of material mature for real applications. In this review the most relevant progresses made in the recent years as well as the kinetic and thermodynamic properties experimentally measured for the most promising systems are reported and properly discussed.