Toward HYD/DEC selectivity control in hydrodeoxygenation over supported and unsupported Co(Ni)-MoS2 catalysts. A key to effective dual-bed catalyst reactor for co-hydroprocessing of diesel and vegetable oil

Abstract

Supported and unsupported (with or without Co and Ni promotors) MoS2-based catalysts were prepared using conventional incipient wetness impregnation method on pure and carbonized alumina with an appropriate aqueous solution of a 12-molybdophosphoric heteropolyacid and cobalt or nickel citrate. Unsupported MoS2 catalysts were synthesized by leaching away the supports from MoS2/Al2O3, MoS2/C/Al2O3 and using industrial CoMo/Al2O3 catalyst (named as Et-MoS2-Ind) with HF acid. Catalysts were investigated by low-temperature nitrogen adsorption and transmission electron microscopy techniques to characterize their structure and morphology. Catalysts were tested in hydrodeoxygenation (HDO) of oleic acid (OA) in an autoclave under hydrogen pressure. CoMoS2/Al2O3, NiMoS2/Al2O3, and Et-MoS2-Ind catalysts were also investigated as single and dual catalytic systems, using a bench-scale flow reactor in co-hydroprocessing of mixed feed, containing straight-run gas oil and 15 wt. % of waste sunflower oil. The results of the catalyst tests show that hydrogenation/decarbonylation (HYD/DEC) selectivity in oleic acid HDO strongly depends on catalyst type. The CoMoS2/C/Al2O3 and CoMoS2/Al2O3 catalysts show low HYD/(HYD + DEC) selectivity, equal to 0.55. Unpromoted MoS2/C/Al2O3, MoS2/Al2O3, Et-MoS2-Ind and Ref-MoS2 samples have quite similar HYD/(HYD + DEC) selectivity around 0.85. The highest HYD/(HYD + DEC) selectivity (0.95) was reached over Et-MoS2/C and Et-MoS2 samples, which indicated that HDO had gone through HYD route without any formation of CO and CO2. A double-bed catalyst reactor comprising of the upper-layer bulk Et-MoS2-Ind and the under-layer Co(Ni)–MoS2/Al2O3 catalysts are proposed for the effective co-hydroprocessing of diesel and vegetable oil.