Kinetic Modelling of Anisole Hydrodeoxygenation Using Aromatic-Selective Ru/TiO₂ Catalyst
DOI:
https://doi.org/10.29356/jmcs.v69i1.2290Keywords:
Kinetic modeling, hydrodeoxygenation, anisole, demethoxylation, demethylation, Ru, TiO₂Abstract
A Langmuir-Hinshelwood kinetic model is proposed to describe the anisole hydrodeoxygenation over a Ru/TiO2 catalyst in a continuous fixed-bed reactor. Key operating parameters, such as pressure, temperature, and weight hourly space velocity, were studied to ensure operation within the kinetic regime. The proposed kinetic model was successfully validated, and two adjacent catalytic sites were considered: one dedicated to the dissociative adsorption of hydrogen and the other to the adsorption and reaction of anisole and its reaction products. The model demonstrated a good fit with the experimental data, revealing a preference for the demethoxylation pathway leading to benzene formation over the demethylation pathway, which favors phenol formation. Characterization of the Ru/TiO2 catalyst using XRD, TPR-H2, TPD-NH3, and XPS revealed the presence of highly dispersed Ru particles and oxophilic sites, including both acidic sites and oxygen vacancies, validating the two-site model. The kinetic parameters indicated that the conversion of cyclohexanol to cyclohexane was the fastest reaction step, and the demethoxylation pathway was favored over the demethylation on the Ru/TiO2 catalyst.
Resumen. Se propone un modelo cinético Langmuir-Hinshelwood para describir la reacción de hidrodesoxigenación de anisol utilizando un catalizador Ru/TiO2 en un reactor de flujo continuo de lecho fijo. Se evaluaron inicialmente las condiciones de operación, como la presión, temperatura y velocidad espacial, con el fin de asegurar que el sistema opere dentro del régimen cinético. El modelo considera la presencia de dos sitios catalíticos adyacentes: uno destinado a la adsorción disociativa del hidrógeno y otro para la adsorción y reacción tanto de anisol como de sus productos de reacción. El modelo mostró un buen ajuste con los datos experimentales, indicando una ruta preferencial hacia la desmetoxilación, que produce benceno, frente a la desmetilación, que favorece la formación de fenol. La caracterización del catalizador Ru/TiO2 mediante técnicas de XRD, TPR-H2, TPD-NH3 y XPS reveló la presencia de partículas de Ru0 altamente dispersas y sitios oxofílicos superficiales, incluidos sitios ácidos y vacantes de oxígeno, lo que valida el uso del modelo de dos sitios propuesto. Los parámetros cinéticos indicaron que la conversión de ciclohexanol a ciclohexano es el paso de reacción más rápido, y se favoreció la ruta de desmetoxilación sobre la desmetilación en presencia del catalizador Ru/TiO2.
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Copyright (c) 2024 Victor Martinez-Jimenez, Reyna Ríos-Escobedo, J. Gabriel Flores Aguilar, Cindy García-Mendoza, Julia Aguilar-Pliego, José Antonio de los Reyes, Victor Alejandro Suárez-Toriello
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