Magnetically recyclable Ni(Co)-promoted MoS2 catalysts with greigite (G) core were synthesized and their activity and selectivity in hydrodeoxygenation of stearic acid were investigated. The activity of the catalysts tested at… Click to show full abstract
Magnetically recyclable Ni(Co)-promoted MoS2 catalysts with greigite (G) core were synthesized and their activity and selectivity in hydrodeoxygenation of stearic acid were investigated. The activity of the catalysts tested at 320 °C and H2 initial pressure of 3.5 MPa could be ranked as NiMo/G > CoMo/G > Mo/G. Two main products were detected, C18 (through HDO pathway) and C17 hydrocarbons (through DCO pathway). HDO was the dominant pathway for all of the catalysts. As for the C18/C17 ratio, the catalysts were found to be in the order: Mo/G > CoMo/G ≈ NiMo/G. The Paraffin/Olefin ratio was over 1 for all of the catalysts with NiMo/G showing the highest ratio. Stearic acid was found to have an inhibiting effect on the adsorption of intermediates over the active sites. Moreover, the concentrations of intermediates decreased at high conversions of stearic acid. The formation of the intermediate aldehyde is through C–O hydrogenolysis of the fatty acid following the protonation, dehydrogenation, and hydride addition steps. The same steps were suggested to be involved in the transformation of the aldehyde to the alcohol. Formation of Cn-1 hydrocarbons was found to be via decarbonylation route. The enhancement of the DCO pathway over the promoted catalysts was related to the electron transfer from the promoting atom to an adjacent sulphur atom and reduction in sulphur-metal bond strength.
               
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