Suppression of inactive sites in NiMo@amorphous alumina catalysts for hydrodesulfurization reaction: Effect of Ga doping

Abstract

Hydrodesulfurization (HDS) reaction activity depends on the formation of active NiMoS (completely sulfided multilayer type 2 sites) and inactive NiAl2O4/NixSy phases on the catalyst surface. These inactive phases not only itself inactive for the reaction but also hinder the formation of active NiMoS phases. In addition, the formation of strong Mo-O-Al bonds also lowers the reducibility of the catalyst, suggesting lesser catalytic activity (type 1 sites, partially sulfided single-layer sites). To this end, we report the formation of NiMo/Ga doped amorphous alumina (A-Al2O3) catalysts prepared by the colloidal synthesis method. A-Al2O3 was chosen as a support because it has lower surface energy, better physicochemical properties, and enhanced acidic sites than the crystalline alumina phase, which favours the formation of type 2 sites or weak metal-support interaction (completely sulfided multilayer NiMoS sites). Further, the Ga doping in A-Al2O3 support substitute the tetrahedral Al sites and form GaAl2O4 phases by reducing NiAl2O4 inactive sites, and the free Ni decorate the edges of MoS2 to form HDS active NiMoS sites. Therefore, NiMo/Ga doped A-Al2O3 catalyst (at 1 wt% Ga loading) reported enhanced HDS catalytic activity (25%), HDS reaction rate constant (kHDS-2.15 times) and turn over frequency (TOF-1.3 times) than the conventional NiMo/γ-Al2O3 catalysts.