Solvothermal Synthesis of Unsupported NiMo Catalyst with High Activity in Hydrodesulfurization of 4,6-Dimethyldibenzothiophene

Environmental legislation has focused its attention on improving air quality. In this context, the presence of sulfur compounds in fuels, such as diesel and gasoline, is undesirable. When sulfur is combusted, compounds are emitted as SOx (SO2 and SO3) into the atmosphere, causing acid rain and respiratory diseases. For this reason, environmental norms have been established to reduce the sulfur content of fuels. Sulfur (mainly as alkylbenzothiophenes, dibenzothiophenes and alkyldibenzothiophenes) is removed in refineries through a process called hydrodesulfurization (HDS). HDS is performed at an industrial level with the use of NiMo, CoMo or NiW catalysts supported on alumina. Unsupported MoS2 (bulk) catalysts have recently attracted attention due to their high activity and selectivity in HDS. In this study, bulk NiMo catalyst precursors were synthesized using solvothermal methods with varying pH and solvothermal synthesis time. The precursors and catalysts were characterized using scanning electron microscopy with energy dispersive X-ray spectroscopy (EDS) microanalysis, X-ray diffraction (XRD), textural properties using liquid nitrogen physisorption at 77 K, Raman spectroscopy and high-resolution transmission electron microscopy (HTREM). The results indicate that the morphology of the NiMoO4 precursors synthesized in an ethanol/water mixture varies, forming “grains,” “flakes” or “rods,” depending on the dwell time and synthesis conditions. The catalytic activity results show that the bulk NiMo catalyst synthesized at 2 h presented higher selectivity and catalytic activity in the HDS of 4,6-DMDBT when compared to a supported reference catalyst (NiMo/γ-Al2O3).