Self-Assembly of Hierarchically Porous ZSM-5/SBA-16 with Different Morphologies and Its High Isomerization Performance for Hydrodesulfurization of Dibenzothiophene and 4,6-Dimethyldibenzothiophene

ZSM-5/SBA-16 (ZS) composite materials with different morphologies were synthesized successfully. The series supports were utilized to prepare NiMo/ZS for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) hydrodesulfurization (HDS) reactions. Series ZS supports and NiMo/ZS were well characterized to investigate their structure–property relationship. The NiMo/ZS catalyst (NiMo/ZS-3) with uniform morphology and well-ordered pore channels showed the maximum <i>k</i>_HDS and TOF values of DBT and 4,6-DMDBT HDS. The <i>k</i>_HDS value (13.9 × 10^–4 mol g^–1 h^–1) of DBT over NiMo/ZS-3 was more than 2 times greater than that over the reference NiMo/ZS-M catalyst (5.5 × 10^–4 mol g^–1 h^–1), 3 times greater than that over the NiMo/SBA-16 catalyst (4.4 × 10^–4 mol g^–1 h^–1), and almost 4 times greater than that over the NiMo/ZSM-5 catalyst (3.5 × 10^–4 mol g^–1 h^–1). Furthermore, the <i>k</i>_HDS value (8.4 × 10^–4 mol g^–1 h^–1) of 4,6-DMDBT over NiMo/ZS-3 was more than 3 times greater than that over the reference NiMo/ZS-M catalyst (2.8 × 10^–4 mol g^–1 h^–1), more than 4 times greater than that over the NiMo/SBA-16 catalyst (1.7 × 10^–4 mol g^–1 h^–1), and almost 5 times greater than that over the NiMo/ZSM-5 catalyst (1.6 × 10^–4 mol g^–1 h^–1). The superior DBT and 4,6-DMDBT HDS performances were assigned to the uniform morphology, well-ordered pore channels, and high B/L ratio of the NiMo/ZS-3 catalyst and the suitable dispersion of the MoS₂ active phases. HYD was the preferential route for DBT HDS, while ISO was the preferential route for 4,6-DMDBT HDS because of the high B/L ratio of NiMo/ZS-3. Moreover, the DBT and 4,6-DMDBT HDS reaction networks of the series NiMo/ZS are presented