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The influence of Al 2 O 3 –ZrO 2  and TiO 2 –ZrO 2  supports on NiMo-supported catalysts at a different sulfur concentration in a model hydrodeoxygenation (HDO)-hydrodesulfurization (HDS) co-processing reaction has been studied in this work. A competition effect between phenol and dibenzothiophene (DBT) for active sites was evidenced. The competence for the active sites between phenol and DBT was measured by comparison of the initial reaction rate and selectivity at two sulfur concentrations (200 and 500 ppm S). NiMo/TiO 2 –ZrO 2  was almost four-fold more active in phenol HDO co-processed with DBT than NiMo/Al 2 O 3 –ZrO 2  catalyst. Consequently, more labile active sites are present on NiMo/TiO 2 –ZrO 2  than in NiMo/Al 2 O 3 –ZrO 2  confirmed by the decrease in co-processing competition for the active sites between phenol and DBT. DBT molecules react at hydrogenolysis sites (edge and rim) preferentially so that phenol reacts at hydrogenation sites (edge and edge). However, the hydrogenated capacity would be lost when the sulfur content was increased. In general, both catalysts showed similar functionalities but different degrees of competition according to the highly active NiMoS phase availability. TiO 2 –ZrO 2  as the support provided weaker metal-support interaction than Al 2 O 3 –ZrO 2 , generating a larger fraction of easily reducible octahedrally coordinated Mo- and Ni-oxide species, causing that NiMo/TiO 2 –ZrO 2  generated precursors of MoS 2  crystallites with a longer length and stacking but with a higher degree of Ni-promotion than NiMo/Al 2 O 3 –ZrO 2  catalyst.

international journal of chemical reactor engineering

Co-processing of hydrodeoxygenation and hydrodesulfurization of phenol and dibenzothiophene with NiMo/Al 2 O 3 –ZrO 2  and NiMo/TiO 2 –ZrO 2  catalysts