High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides

Metal oxides are potential materials for thermochemical heat storage via reversible endothermal/exothermal redox reactions, and among them, cobalt oxide and manganese oxide are attracting attention. The synthesis of mixed oxides is considered as a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering issues, and the materials potential for thermochemical heat storage application needs to be assessed. This work proposes a study combining thermodynamic calculations and experimental measurements by simultaneous thermogravimetric analysis and calorimetry, in order to identify the impact of iron oxide addition to Co and Mn-based oxides. Fe addition decreased the redox activity and energy storage capacity of Co3O4/CoO, whereas the reaction rate, reversibility and cycling stability of Mn2O3/Mn3O4 was significantly enhanced with added Fe amounts above ~15 mol%, and the energy storage capacity was slightly improved. The formation of a reactive cubic spinel explained the improved re-oxidation yield of Mn-based oxides that could be cycled between bixbyite and cubic spinel phases, whereas a low reactive tetragonal spinel phase showing poor re-oxidation was formed below 15 mol% Fe. Thermodynamic equilibrium calculations predict accurately the behavior of both systems. The possibility to identify other suitable mixed oxides becomes conceivable, by enabling the selection of transition metal additives for tuning the redox properties of mixed metal oxides destined for thermochemical energy storage applications

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International audienc

Experimental and thermodynamic study of Co-Fe and Mn-Fe based mixed metal oxides for thermochemical energy storage application

Metal oxides are potential materials for thermochemical heat storage, and among them, cobalt oxide and manganese oxide are attracting attention. Furthermore, studies on mixed oxides are ongoing, as the synthesis of mixed oxides could be a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering, selected for thermochemical heat storage application. The addition of iron oxide is under investigation and the obtained results are presented. This work proposes a comparison of thermodynamic modelling with experimental data in order to identify the impact of iron oxide addition to cobalt oxide and manganese oxide. Fe addition decreased the redox activity and energy storage capacity of Co3O4, whereas the cycling stability of Mn2O3 was significantly improved with added Fe amounts above 20 mol% while the energy storage capacity was unchanged. The thermodynamic modelling method to predict the behavior of the Mn-Fe-O and Co-Fe-O systems was validated, and the possibility to identify other mixed oxides becomes conceivable, by enabling the selection of transition metals additives for metal oxides destined for thermochemical energy storage applications

Natural gas-fueled multigeneration for reducing environmental effects of brine and increasing product diversity: thermodynamic and economic analyses

Water scarcity threatens human life and it is likely to be a main concern in the next century. In this work, a novel multigeneration system (MGS) is introduced and assessed with energy, exergy, and economic analyses. This MGS includes a gas cycle, multieffect distillation, an absorption refrigeration cycle, a heat recovery steam generator, and electrodialysis. Electrodialysis is integrated into this configuration to produce sodium hydroxide and hydrogen chloride from brine to prevent its release to the environment with harmful impacts. The other products are electricity, cooling, and demineralized water. For the evaluation of the proposed system, one computer code is provided in engineering equation solver software. For physical properties calculation, the library of this software is used. The MGS produces 614.7 GWh of electrical energy, 87.44 GWh of cooling, 12.47 million m3 of demineralized water, and 0.092 and 0.084 billion kg of sodium hydroxide and hydrogen chloride over a year. Energy and exergy evaluations demonstrate that the MGS energy and exergy efficiencies are 31.3% and 18.7%, respectively. The highest and lowest value of exergy destruction rate is associated with the combustion chamber and pump, respectively. The economic evaluation indicates that the net present value of this proposed system is 3.8 billion US$, while the internal rate of return and payback period, respectively, are 0.49 and 2.1 years.Peer ReviewedPostprint (published version

A review of solar thermochemical CO2 splitting using ceria-based ceramics with designed morphologies and microstructures

ABSTRACT: This review explores the advances in the synthesis of ceria materials with specific morphologies or porous macro- and microstructures for the solar-driven production of carbon monoxide (CO) from carbon dioxide (CO2). As the demand for renewable energy and fuels continues to grow, there is a great deal of interest in solar thermochemical fuel production (STFP), with the use of concentrated solar light to power the splitting of carbon dioxide. This can be achieved in a two-step cycle, involving the reduction of CeO2 at high temperatures, followed by oxidation at lower temperatures with CO2, splitting it to produce CO, driven by concentrated solar radiation obtained with concentrating solar technologies (CST) to provide the high reaction temperatures of typically up to 1,500 degrees C. Since cerium oxide was first explored as a solar-driven redox material in 2006, and to specifically split CO2 in 2010, there has been an increasing interest in this material. The solar-to-fuel conversion efficiency is influenced by the material composition itself, but also by the material morphology that mostly determines the available surface area for solid/gas reactions (the material oxidation mechanism is mainly governed by surface reaction). The diffusion length and specific surface area affect, respectively, the reduction and oxidation steps. They both depend on the reactive material morphology that also substantially affects the reaction kinetics and heat and mass transport in the material. Accordingly, the main relevant options for materials shaping are summarized. We explore the effects of microstructure and porosity, and the exploitation of designed structures such as fibers, 3-DOM (three-dimensionally ordered macroporous) materials, reticulated and replicated foams, and the new area of biomimetic/biomorphous porous ceria redox materials produced from natural and sustainable templates such as wood or cork, also known as ecoceramics.info:eu-repo/semantics/publishedVersio

3DOM ceria ecoceramics from sustainable cork templates for solar thermochemical CO2 splitting

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Vaporisation et/ou stabilisation de métaux lourds au cours du traitement thermique de déchet : cas des déchets ménagers solides et des boues de dragage

International audienceThe fate of heavy metals is one of the main problems that operators of solid waste incineration plants have to deal with to reduce the overall environmental impact of the plant and of the ultimate residue. The question is : should the process conditions avoid toxic metal vaporisation, thus increasing their concentration in bottom ash ? Or, on the contrary, should they favour metal release in combustion gases, thus requiring the highest performance air pollution control (APC) systems and stabilising materials? In order to examine the industrial impact of these two possibilities, we are currently developing two complementary approaches.The first one is concerned with the fate of heavy metals in incineration of municipal wastes and sludge, and coal combustion. We characterised physico-chemically the ultimate residues, and we developed a complete thermodynamic and experimental study of the behaviour of heavy metals in waste incinerators and coal combustors. We developed a general method (inverse method) to identify the kinetics of vaporisation of heavy metals from the on-line analysis of the exhaust gas of solid waste incineration. The second approach deals with the transformation of heavy metals contained in fly ash and dredged materials into phosphate components, using orthophosphate as stabilising agent.The technique involves a chemical treatment followed by a thermal treatment (sintering), that reduce the leachability of heavy metals. Better knowledge of thermal treatment of polluted wastes should lead to safer processes and residue reuse opportunities.La maîtrise des émissions de métaux lourds (ML) est un des problèmes majeurs qui se posent aux opérateurs des UIOM pour réduire l'impact environnemental des incinérateurs puis des déchets ultimes. Nos équipes développent deux approches complémentaires autour de la vaporisation des métaux et de leur stabilisation. Dans la première approche, après avoir caractérisé les résidus ultimes, nous avons développé une étude thermodynamique et expérimentale du comportement des ML dans les procédés de combustion et incinération. Nous avons développé une méthode générale (méthode inverse) permettant d'identifier la cinétique de vaporisation des métaux à partir de l'analyse en ligne des fumées d'incinérateur. La deuxième approche s'intéresse à la stabilisation par les orthophosphates des ML contenus dans les cendres volantes et dans les matériaux de dragage. La technique consiste en un traitement chimique suivi d'un frittage, qui limitent la vaporisation et réduisent la lixiviabilité des ML. Ces connaissances scientifiques doivent aider à une meilleure maîtrise des traitements thermiques de déchets pollués et une meilleure valorisation matière des résidus

Redox Cycles, Active Materials, and Reactors Applied to Water and Carbon Dioxide Splitting for Solar Thermochemical Fuel Production: A Review

The solar thermochemical two-step splitting of H2O and CO2 based on metal oxide compounds is a promising path for clean and efficient generation of hydrogen and renewable synthetic fuels. The two-step process is based on the endothermic solar thermal reduction of a metal oxide releasing O2 using a high-temperature concentrated solar heat source, followed by the exothermic oxidation of the reduced oxide with H2O and/or CO2 to generate pure H2 and/or CO. This pathway relates to one of the emerging and most promising processes for solar thermochemical fuel production encompassing green H2 and the recycling/valorization of anthropogenic greenhouse gas emissions. It represents an efficient route for solar energy conversion and storage into renewable and dispatchable fuels, by directly converting the whole solar spectrum using heat delivered by concentrating systems. This eliminates the need for photocatalysts or intermediate electricity production, thus bypassing the main limitations of the low-efficient photochemical and electrochemical routes currently seen as the main green methods for solar fuel production. In this context, among the relevant potential redox materials, thermochemical cycles based on volatile and non-volatile metal oxides are particularly attractive. Most redox pairs in two-step cycles proceed with a phase change (solid-to-gas or solid-to-liquid) during the reduction step, which can be avoided by using non-stoichiometric oxides (chiefly, spinel, fluorite, or perovskite-structured materials) through the creation of oxygen vacancies in the lattice. The oxygen sub-stoichiometry determines the oxygen exchange capacity, thus determining the fuel production output per mass of redox-active material. This paper provides an overview of the most advanced cycles involving ZnO/Zn, SnO2/SnO, Fe3O4/FeO, ferrites, ceria, and perovskites redox systems by focusing on their ability to perform H2O and CO2 splitting during two-step thermochemical cycles with high fuel production yields, rapid reaction rates, and performance stability. Furthermore, the possible routes for redox-active material integration and processing in various solar reactor technologies are also described