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Reactivity of acid gas pollutants with Ca(OH)2 at low temperature in the presence of water vapour
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[eng] The reactivity of Ca-based sorbents with acid gases (specifically SO2, HCl and NO2) at low temperature has been a subject of interest in the last decades, since it constitutes the fundamental reactive system in a number of technologies aimed at the reduction of acid gas emission from industrial combustors or incinerator plants. However, a complete understanding of the chemistry involved still presents unsolved challenges. This thesis has been devoted to provide new insight on the kinetic modeling and reaction mechanism of the system Ca(OH)2-SO2 (+NO2) and direct evidence of the role of water on them. The mechanistic pathways of the Ca(OH)2-NO2 (+SO2) and Ca(OH)2-HCl systems are also discussed. The experimental breakthrough curves of SO2 obtained from a Ca(OH)2 bed reactor are successfully simulated by a semi-empirical kinetic model (DM-ISCM). This model takes into account (1) the deactivation of the reagent surface as the reaction product deposits on the surface and (2) an outward solid-state diffusion of hydrated Ca2+ and HO- ions from the inner Ca(OH)2/CaSO3·(1/2)H2O interface to the outer CaSO3(1/2)·H2O/gas one. The examination of Ca(OH)2 single crystals reacted with SO2 by atomic force microscopy (AFM) reveals that the reaction product crystallizes forming "needle-like" features irrespective of the RH at which reaction takes place. Furthermore, the AFM explorations provide evidence of product crystal (CaSO3·(1/2)H2O) mobility on the surface of the reactant crystal and further product crystal aggregation, as long as the crystal is in contact with water vapor. This finding suggests that once a product crystal is formed during the reaction, it is removed from its position, and consequently, new surface of Ca(OH)2 is opened up for further reaction. A reaction mechanism that might be consistent with the DM-ISCM and AFM results would consist of the following steps: (1) formation of an adsorbed water layer on the reagent surface; (2) hydration of SO2 with adsorbed water molecules to form SO2·zH2O complexes; (3) reaction of the complexes with Ca(OH)2 to form the reaction product CaSO3·(1/2)H2O by a solid-state mechanism; (4) diffusion of product crystallites and rearrangement of the reacted surface to form needle-like features; (5) ionic solid-state diffusion or reaction with residual active surface. Although in all the steps the adsorbed water could play a role, the most relevant one that might account for the outstanding effect of the RH on the reactivity of the system could be step (4). It could be proposed that product crystallites diffusion is promoted by the formation of H-bonds. On the other hand, the mechanistic pathway proposed for the system Ca(OH)2-NO2 is based on redefining the reactions that take place in aqueous solution, but considering their solid state character. It consists of two consecutive reactions: (1) NO2 reacts with Ca(OH)2 to give Ca(NO3)2 and Ca(NO2)2; (2) the product Ca(NO2)2 further reacts with adsorbed water to form NO and Ca(NO3)2. Furthermore, when SO2 is also present in the gas phase, a redox reaction between CaSO3 and NO2 could also occur. These reactions are consistent with the results from solid analyses and they seem to be promoted by adsorbed water. Moreover, the formation of Ca(NO3)2 and Ca(NO2)2 hygroscopic salts might account for the strong enhancement of the ability of Ca(OH)2 to capture SO2 under the presence of NO2. The SO2 experimental breakthrough curves obtained in these conditions are also reasonably well described by the DM-ISCM. Regarding the Ca(OH)2-HCl system, a possible mechanistic pathway consistent with our experimental results and the those seemingly diverse from literature concerns two consecutive reactions: (1) formation of Ca(OH)Cl, and (2) final formation of CaCl2 from the reaction between Ca(OH)Cl and HCl. A kinetic control of these reactions might be suggested, that is, depending on the experimental conditions, the second reaction does not take place. This second reaction is only expected to be promoted at high HCl concentrations and temperatures and/or at high reaction times.
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BAUSACH MERCADER, Marta. Reactivity of acid gas pollutants with Ca(OH)2 at low temperature in the presence of water vapour. [consulta: 13 de desembre de 2025]. [Disponible a: https://hdl.handle.net/2445/35400]