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Energies 2020, 13, 5859 5 of 23 hydration/dehydration cycles, the temperature was uneven between the middle of the packed bed and the outside. During the first part of the heating, the outside of the packed bed remained at a higher temperature than the middle for at least one hour (70 min). Afterwards, the opposite was observed, with the outer part of the packed bed being at a lower temperature than the center. Under experimental conditions, the highest temperature reached was 475 ◦C. In fact, the study underlines the unevenness of the heat release rate and the poor thermal conductivity as main issues. To address the improvement of heat transfer through CaO/Ca(OH)2 in a packed bed reactor, a composite material using silicon carbide/silicon (SiC/Si) foam to support CaO/Ca(OH)2 in its pores (400 μm) was investigated [17]. Over ten cycles, the composite material retained a high reactivity and good stability of the bulk volume during dehydration/hydration reactions. A study was recently accomplished on CaO/Ca(OH)2 supported on ceramic honeycomb composed of silicon carbide and silicon (SiC-Si) [18]. The pellets of composite material were tested in a lab-scale packed bed reactor and were shown to enhance the heat transfer through the reaction bed. The inert honeycomb support did not form any side product during the tests; however, cracks and deformations appeared over the course of ten cycles. This approach is promising for the dispersion and shaping of packed beds using hydroxides for TCES. A CaO/Ca(OH)2/Na2CaSiO4 composite was synthesized using sodium silicate to bind CaO/Ca(OH)2 fine particles for fluidized or fixed beds [19]. This work noted the effect of the anisotropic expansion of Ca(OH)2 being the cause of the reduction in the crushing strength of the pellets. The adaptation/integration of powdered material systems to CSP irradiated reactors such as fluidized bed is necessary for an effective exploitation of the TCES system in a continuous flow over time. To this end, calcium hydroxide was modified with nanostructured flow agents such as nanostructured silicon and/or aluminum oxide [20]. The study focused on the modification of calcium hydroxide powder using nanostructured agents, in order to enhance the flowability of the material in dynamic energy storage systems. However, the mixtures all presented lower flowability than pure Ca(OH)2/CaO powder, as the agglomeration of the pure particles led to bigger particles with better flowability. In addition, the samples from the mixture generated side products such as calcium silicate and aluminate phases which contributed to the reduction in the total heat release measured for the material. With this conclusion, it is recommended to rather improve the stability of moderately bigger particles of pure material rather than mix them with additives as a means to enhance the flowability of the material. As the low thermal conductivity and cohesiveness of powder bulk material are ill-suited for moving bed reactors, studies usually aim for granular materials for such application. To answer this issue, a recent study investigated the effect of the encapsulation of CaO granules in ceramic and of Ca(OH)2 granules coated with Al2O3 nanostructured particles [21]. Both encapsulated materials could retain their shape after six hydration/dehydration cycles, but the ceramic shell of CaO was sometimes cracked or lost. On the one hand, the reaction performances of Ca(OH)2 encapsulated in Al2O3 proved to be similar to that of unmodified Ca(OH)2 granules, but the expansion of the material during the hydration step tended to clog the reactor tubes. On the other hand, CaO granules encapsulated in ceramic flowed freely through the reactor, but their reaction performances were reduced and they could not reach full conversion. As a maneuver to answer industrial requirements—e.g., for a moving bed reactor, with appropriate material size and stability, a composite based on calcium oxide was synthesized for TCES application, using the CaO/Ca(OH)2 system [22] mixed with carboxymethyl cellulose sodium (CMC) and vermiculite. When compared to the performances of pure Ca(OH)2 tablets, the composite tablets better retained their structural integrity over several hydration/dehydration cycles. Within the material, vermiculite provided enough space for the CaO/Ca(OH)2 reaction, with an average pore diameter between 11 and 16 nm depending on the synthesis conditions for the composite material. In addition, the backbone structure of the composite possessed abundant micropores and mesopores for the gas transport during the cycles. Furthermore, the decomposition temperature of Ca(OH)2 within the composite material was reduced, which is attributed to the generation of activated carbon during the carbonization of CMC. Finally, the gravimetric storage density of the granularPDF Image | Hi Temp Thermochemical Energy Storage via Solid Gas Reactions
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