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Mechanism of glycerol dehydration and dehydrogenation: an experimental and computational correlation
Mecanismo para la deshidratación y deshidrogenación del glicerol: correlación experimental y computacional
DOI:
https://doi.org/10.15446/dyna.v86n208.69941Palabras clave:
hydroxyacetone formation mechanism, glycerol dehydration, glycerol dehydrogenation, glycerol conversion, biomass valorization. (en)mecanismo de formación de hidroxiacetona, deshidratación de glicerol, deshidrogenación de glicerol, conversión de glicerol, valorización de biomasa. (es)
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Experimental formation of hydroxyacetone (HA) from glycerol over La2CuO4 catalyst under mild experimental conditions (533 K, N2 atmosphere) was correlated with molecular modeling results with the aim to propose reaction pathways. Based on these results, a novel mechanism in terms of elementary reactions is proposed for gaseous phase process. The results suggest that there are two main routes that contribute to HA formation. The main and more feasible reaction pathway corresponds to the direct 1,2-dehydration of glycerol. The second pathway involves the dehydrogenation of glycerol to produce glyceraldehyde, which is then dehydrated toward HA through the formation of a six-membered cyclic transition state during the hydrogenation step. Finally, the pyruvaldehyde formation pathway was found to be a parallel reaction to the HA formation which could be displaced by tuning the reaction conditions. HA formation as a result of pyruvaldehyde hydrogenation was also proposed, but it was found to be a less important route.
La formación de hidroxiacetona (HA) a partir de glicerol sobre el catalizador La2CuO4 fue evaluada desde una perspectiva experimental (533 K en atmósfera de N2) y computacional con el objetivo de proponer rutas de reacción. Un mecanismo novedoso, en términos de reacciones elementales se propone para la reacción en fase gaseosa. Este mecanismo sugiere dos rutas principales que contribuyen a la formación de HA. La ruta principal corresponde a la 1,2-deshidratación del glicerol, mientras la segunda ruta involucra la deshidrogenación de glicerol para producir gliceraldehído, el cual es posteriormente deshidratado hacia HA a través de la formación de un estado de transición cíclico de seis miembros. La formación de piruvaldehído se presenta como una reacción paralela a la formación de HA, la cual puede ser desplazada modulando las condiciones de reacción. La formación de HA a partir del piruvaldehído es una ruta menos importante.
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