Hierarchization of Mordenite as NiW Sulfide Catalysts Support: Towards Efficient Hydrodesulfurization

NiW‐based catalysts were supported on Al2O3, commercial mordenite (HM), and hierarchical mordenite prepared by acid–base–acid treatment (HM–M). Their catalytic performance was evaluated in the hydrodesulfurization (HDS) of dibenzothiophene (DBT) and 4,6‐dimethyldibenzothiophene (4,6‐DMDBT) at 613 K under 4 MPa as total pressure. In the HDS of DBT, NiW/Al2O3 exhibited better catalytic activity than NiW/HM and NiW/HM–M. On the contrary, NiW/HM–M exhibited the highest catalytic performance in the HDS of 4,6‐DMDBT, attributed to different factors: an improved dispersion of the active phase, a better accessibility to the active sites owing to the creation of mesoporosity, and an additional reaction route (isomerization) owing to the acidic properties of the zeolitic support. These results show the potential interest of hierarchical mordenite as support for HDS catalysts, with the presence of mesoporosity beneficial to the HDS of large and refractory molecules. Hierarchy rules: In the hydrodesulfurization of dibenzothiophene (DBT) and 4,6‐dimethyldibenzothiophene (4,6‐DMDBT), NiW on mesoporous mordenite shows higher activity than mordenite‐based catalysts, and, in the latter case, also higher activity than on alumina, attributed to an improved dispersion of the active phase, a better accessibility to the active sites, and the additional isomerization route owing to the acidic properties of the zeolitic support.