Mass-transfer-enhanced hydrodesulfurization of dibenzothiophenes over yolk–shell micro-mesoporous catalysts

Abstract

Hierarchical yolk–shell structured TS-1-SiO₂ micro-mesoporous composites (TY_xS_y) with different mass transfer properties were fabricated as supports for the fabrication of high-efficiency NiMo/TY_xS_y. The shell thickness and yolk size of such yolk–shell composites were precisely controlled by introducing the nonpolar additive 1,3,5-trimethylbenzene and modulating its incorporation dosage. An appropriate yolk–shell thickness facilitated the hydrodesulfurization (HDS) of macromolecular sulfur-containing compounds, and the yolk–shell structured NiMo/TY_xS_y micro-mesoporous catalysts exhibited superior HDS catalytic performance. Among all as-prepared catalysts, NiMo/TY₁₀S₁₃ achieved the highest turnover frequency (7.5 × 10^–4 s^–1 for dibenzothiophene (DBT) and 6.1 × 10^–4 s^–1 for 4,6-dimethyldibenzothiophene (4,6-DMDBT)), apparent HDS rate constants (2.6 × 10^–7 mol·g^–1·s^–1 for DBT and 2.1 × 10^–7 mol·g^–1·s^–1 for 4,6-DMDBT), and optimal desulfurization efficiencies of DBT (98%) and 4,6-DMDBT (93.3%). Additionally, this catalyst favored the direct desulfurization pathway for DBT HDS and the isomerization pathway for 4,6-DMDBT HDS.

Graphical abstract

Keywords

yolk–shell TS-1-SiO₂ / mass transfer / yolk–shell thickness / hydrodesulfurization / dibenzothiophenes

References

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