Maya crude hydrodemetallization and hydrodesulfurization catalysts: An effect of TiO 2 incorporation in Al 2O 3

Abstract

Hydrotreating of Maya heavy crude oil over high specific surface area CoMo/TiO 2–Al 2O 3 oxide supported catalysts was studied in an integral reactor close to industrial practice. Activity studies were carried out with Maya crude hydrodesulfurization (HDS), hydrodemetallization (HDM), hydrodenitrogenation (HDN), and hydrodeasphaltenization (HDAs) reactions. The effect of support composition, the method of TiO 2 incorporation, and the catalyst deactivation are examined. Supported catalysts are characterized by BET specific surface area (SSA), pore volume (PV), pore size distribution (PSD), and atomic absorption. It has been found that sulfided catalysts showed a wide range of activity variation with TiO 2 incorporation into the alumina, which confirmed that molybdenum sulfided active phases strongly depend on the nature of support. The pore diameter and nature of the active site for HDS, HDM, HDN, and HDAs account for the influence of the large reactant molecules restricted diffusion into the pore, and/or the decrease in the number of active sites due to the MoS 2 phases buried with time-on-stream. The textural properties and hysteresis loop area of supported and spent catalysts indicated that catalysts were deactivated at the pore mouth due to the metal and carbon depositions. The atomic absorption results agreed well regarding the textural properties of spent catalysts. Thus, incorporation of TiO 2 with γ-Al 2O 3 alters the nature of active metal interaction with support, which may facilitate the dispersion of active phases on the support surface. Therefore, the TiO 2 counterpart plays a promoting role to HDS activity due to the favorable morphology of MoS 2 phases and metal support interaction.