Spain

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).

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.

Methanol can be obtained through CO₂ hydrogenation in a membrane reactor with higher yield or lower pressure than in a conventional packed bed reactor. In this study we explore a new kind of membrane with the potential suitability for such membrane reactors. Silicone–ceramic composite membranes are synthetized and characterized for their capability to selectively remove water from a mixture containing hydrogen CO₂ and water at temperatures typical for methanol synthesis. We show that this membrane can achieve selective permeation of water under such harsh conditions and thus is an alternative candidate for use in membrane reactors for processes where water is one of the products and the yield is limited by thermodynamic equilibrium.

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%.

A study was carried out on the valorization of different waste plastics (HDPE PP PS and PE) their mixtures and biomass/HDPE mixtures by means of pyrolysis and in line oxidative steam reforming. A thermodynamic equilibrium simulation was used for determining steam reforming data whereas previous experimental results were considered for setting the pyrolysis volatile stream composition. The adequacy of this simulation tool was validated using experimental results obtained in the pyrolysis and in line steam reforming of different plastics. The effect the most relevant process conditions i.e. temperature steam/plastic ratio and equivalence ratio have on H2 production and reaction enthalpy was evaluated. Moreover the most suitable conditions for the oxidative steam reforming of plastics of different nature and their mixtures were determined. The results obtained are evidence of the potential interest of this novel valorization route as H2 productions of up to 25 wt% were obtained operating under autothermal conditions.

The decarbonization of the industrial sector is imperative to achieve a sustainable future. Carbon capture and storage technologies are the leading options but lately the use of CO2 is also being considered as a very attractive alternative that approaches a circular economy. In this regard power to gas is a promising option to take advantage of renewable H2 by converting it together with the captured CO2 into renewable gases in particular renewable methane. As renewable energy production or the mismatch between renewable production and consumption is not constant it is essential to store renewable H2 or CO2 to properly run a methanation installation and produce renewable gas. This work analyses and optimizes the system layout and storage pressure and presents an annual cost (including CAPEX and OPEX) minimization. Results show the proper compression stages need to achieve the storage pressure that minimizes the system cost. This pressure is just below the supercritical pressure for CO2 and at lower pressures for H2 around 67 bar. This last quantity is in agreement with the usual pressures to store and distribute natural gas. Moreover the H2 storage costs are higher than that of CO2 even with lower mass quantities; this is due to the lower H2 density compared with CO2 . Finally it is concluded that the compressor costs are the most relevant costs for CO2 compression but the storage tank costs are the most relevant in the case of H2.

Various Pt-based materials (unsupported Pt PtRu PtCo) were investigated as catalysts for recombining hydrogen and oxygen back into water. The recombination performance correlated well with the surface Pt metallic state. Alloying cobalt to platinum was observed to produce an electron transfer favouring the occurrence of a large fraction of the Pt metallic state on the catalyst surface. Unsupported PtCo showed both excellent recombination performance and dynamic behaviour. In a packed bed catalytic reactor when hydrogen was fed at 4% vol. in the oxygen stream (flammability limit) 99.5% of the total H2 content was immediately converted to water in the presence of PtCo thus avoiding safety issues. The PtCo catalyst was thus integrated in the anode of the membrane-electrode assembly of a polymer electrolyte membrane electrolysis cell. This catalyst showed good capability to reduce the concentration of hydrogen in the oxygen stream under differential pressure operation (1–20 bar) in the presence of a thin (90 μm) Aquivion® membrane. The modified system showed lower hydrogen concentration in the oxygen flow than electrolysis cells based on state-of-the-art thick polymer electrolyte membranes and allowed to expand the minimum current density load down to 0.15 A cm−2 . This was mainly due to the electrochemical oxidation of permeated H2 to protons that were transported back to the cathode. The electrolysis cell equipped with a dual layer PtCo/IrRuOx oxidation catalyst achieved a high operating current density (3 A cm−2 ) as requested to decrease the system capital costs under high efficiency conditions (about 77% efficiency at 55 °C and 20 bar). Moreover the electrolysis system showed reduced probability to reach the flammability limit under both high differential pressure (20 bar) and partial load operation (5%) as needed to properly address grid-balancing service

Prestressing steel wires are manufactured by cold drawing during which a preferential orientation is achieved in the matter of pearlitic colonies and lamellae. In addition to this general trend special (unconventional) pearlitic pseudocolonies evolve during the heavy-drawing manufacture process affecting the posterior macro- micro- and nano-structural integrity of the material. This paper discusses the important role of such a special microstructural unit (the pearlitic pseudocolony) in the fracture process in air (inert) environment in the presence of crack-like defects as well as in the case of environmentally assisted cracking (stress corrosion cracking by localized anodic dissolution) or hydrogen embrittlement. Results clearly demonstrate the key role of pearlitic pseudocolonies in promoting crack deflection (and thus mixed-mode propagation) after a global mode I cracking especially in the case of fracture in air and stress corrosion cracking.

After nearly 25 years of service some of the wires of the tendons of “La Arena” bridge (Spain) started to exhibit the effects of environmental degradation processes. “La Arena” is cable-stayed bridge with 6 towers and a reference span between towers of about 100 meters. After a maintenance inspection of the bridge evidences of corrosion were detected in some of the galvanized wires of the cables. A more in-deep analysis of these wires revealed that many of them exhibited loss of section due to the corrosion process. In order to clarify the causes of this degradation event and to suggest some remedial actions an experimental program was designed. This program consisted of tensile and fatigue tests on some strand samples of the bridge together with a fractographic analysis of the fracture surfaces of the wires its galvanized layer thickness and some hydrogen measurements (hydrogen embrittlement could be another effect of the environmental degradation process).Once the type and extension of the flaws in the wires was characterized a structural integrity assessment of the strands was performed with the aim of quantifying the margins until failure and establishing some maintenance recommendations.

Covalent organic frameworks (COFs) are crystalline porous organic polymers built from covalent organic blocks that can be photochemically active when incorporating organic semiconducting units such as triazine rings or diacetylene bridges. The bandgap charge separation capacity porosity wettability and chemical stability of COFs can be tuned by properly choosing their constitutive building blocks by extension of conjugation by adjustment of the size and crystallinity of the pores and by synthetic post-functionalization. This review focuses on the recent uses of COFs as photoactive platforms for the hydrogen evolution reaction (HER) in which usually metal nanoparticles (NPs) or metallic compounds (generally Pt-based) act as co-catalysts. The most promising COF-based photocatalytic HER systems will be discussed and special emphasis will be placed on rationalizing their structure and light-harvesting properties in relation to their catalytic activity and stability under turnover conditions. Finally the aspects that need to be improved in the coming years will be discussed such as the degree of dispersibility in water the global photocatalytic efficiency and the robustness and stability of the hybrid systems putting emphasis on both the COF and the metal co-catalyst.