Synthesis of Hierarchical TS-1 and Its Recycling Catalytic Property for Oxidative Desulfurization

Because of its unique pore structure, good hydrothermal stability and high specific surface area, hierarchical TS-1 zeolite (HTS-1) has become an important catalyst for the deep oxidative desulfurization of fuel oils. In this work, HTS-1 has been successfully synthesized by a hydrothermal crystallization method using the C-SiO2 composite as both silicon source and mesoporous template, tetrapropylammonium hydroxide as microporous template, and tetrabutylorthotitanate as titanium source. The C-SiO2 composite is obtained by mild carbonization of the SiO2/T-40 (Tween 40) xerogel, which is prepared by the two step sol-gel method. The reaction conditions for the oxidative desulfurization (ODS) of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) over HTS-1 are optimized systematically, and the recycling performances of HTS-1 are investigated in detail. After the 15th run, HTS-1 still maintains high DBT conversion (90.6%) and 4,6-DMDBT conversion (86.0%) without deactivation. The samples before and after recycle tests are characterized by XRD, FT-IR, CHN analysis, UV-Vis and SEM techniques. The results indicate that the crystal structure and morphology of regenerated HTS-1 samples are well kept, which accounts for the good structural stability and reusability of HTS-1. In addition, active intermediates for the ODS of bulky organic sulfides over HTS-1, i.e., Ti-peroxo (Ti-OOtBu) species, are captured by the UV-Vis technique. Finally, a possible reaction mechanism for the ODS process over HTS-1 is proposed.

Automated summary

In this study, hierarchical TS-1 zeolite (HTS-1) was successfully synthesized by hydrothermal crystallization method and its application in the deep oxidative desulfurization of fuel oils was investigated. The reaction conditions were optimized and the recycling performance of the catalyst was studied in detail. The results showed that HTS-1 exhibited good structural stability and reusability.