Effect of Silica, Activated Carbon, and Alumina Supports on NiMo Catalysts for Residue Upgrading

The effect of different supports such as silica (SBA-15), activated carbon (AC), and mesoporous alumina (Al2O3) on catalytic activities of hydrotreating nickel molybdenum (NiMo) catalysts was demonstrated for upgrading vacuum residue. Nitrogen adsorption-desorption analysis showed that SBA-15 and the AC-supported NiMo catalyst possessed a very high surface area compared to the alumina-supported catalyst. However, NiMo/Al2O3 catalyst possesses a higher pore diameter and pore volume with an appropriate surface area. X-ray diffraction (XRD) analysis showed that active metals were dispersed in the catalytic supports. Transmission electron microscopy (TEM) analysis revealed the presence of type II active MoS2 sites in the NiMo/Al2O3 catalyst, which showed weak metal-support interactions having a high intrinsic activity. Catalyst activities such as hydrodesulfurization (HDS), hydrodemetallization (HDM) and asphaltene conversion (HDAs), and hydrocracking conversions of a vacuum residue were evaluated. The highest hydrotreating and hydrocracking conversions were observed with the NiMo catalyst supported on mesoporous alumina. The results also supported that the catalyst that has a large pore diameter, high pore volume, and better active metals dispersion is highly desirable for the upgrading of a vacuum residue.

Complete Hydrodesulfurization of Dibenzothiophene via Direct Desulfurization Pathway over Mesoporous TiO2-Supported NiMo Catalyst Incorporated with Potassium

Mesoporous TiO2 containing different potassium content was prepared from potassium titanate by mediating the pH value of the ion exchange, which was used as catalytic support to load NiMo for hydrodesulfurization of dibenzothiophene. The as-prepared samples were characterized by X-ray diffraction, N2 physical adsorption/desorption, temperature-programmed reduction, scanning electron microscope/energy dispersive X-ray mapping analysis, high resolution transmission electron microscopy, and pyridine-adsorbed Fourier transform infrared spectroscopy. The characterization results showed that NiO and MoO3 were well dispersed on mesoporous TiO2 with varying potassium content. A crystal NiMoO4 phase was formed on the TiO2 with relatively high potassium content, which could decrease the reduction temperature of oxidized active species. The evaluation results from the hydrodesulfurization displayed that as the potassium content of the catalyst increased, the dibenzothiophene conversion firstly increased and then slightly decreased when potassium content exceeded 6.41 wt %. By contrast, the direct desulfurization selectivity could continuously increase along with the potassium content of catalyst. Furthermore, the change in direct desulfurization selectivity of a TiO2-supported NiMo catalyst was independent of the reaction condition. The mesoporous TiO2-supported NiMo catalyst incorporated with potassium could have near both 100% of dibenzothiophene and 100% of direct desulfurization selectivity. According to the structure–performance relationship discussion, the incorporation of potassium species could benefit the formation of more sulfided active species on mesoporous TiO2. Moreover, excessive free potassium species may poison the active sites of the hydrogenation pathway. Both factors determined the characteristics of complete hydrodesulfurization of dibenzothiophene via a direct desulfurization pathway for potassium-incorporated mesoporous TiO2 supported NiMo catalysts.