Hydrodesulfurization for cleaner air: HDS of dibenzothiophene and its hydrogenated intermediates over sulfided Mo/g-Al2O3

FUEL 29

Roel Prins, roel.prins@chem.ethz.ch, Institute for Chemical and Bioengineering, Swiss Federal Institute of Technology (ETH), Wolfgang-Pauli Strasse 10, Zurich, 8093, Switzerland and Huamin Wang, huamin.wang@chem.ethz.ch, Institute of Chemical and Bioengineering, Institute of Chemical and Bioengineering, ETH Zurich, 8093 Zurich, Switzerland, Wolfgang-Pauli Str. 10, 8093 Zurich, Switzerland.
To obtain insight into the HDS mechanism of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene, two hydrogenated intermediates of DBT, tetrahydro- and hexahydro-DBT, were synthesized, and their HDS was investigated over sulfided Mo/g-Al2O3 at 300 °C and 5.0 MPa. The interconversion of tetrahydro- and hexahydro-DBT was fast and the two compounds quickly came to equilibrium. H2S strongly inhibited the desulfurization of DBT and its two hydrogenated intermediates. 2-Methylpiperidine strongly inhibited the interconversion of the tetrahydro- and hexahydro-DBT and their desulfurization. With the inhibition of 2-methylpiperidine, 1-cyclohexen-1-yl-benzene was observed. Tetrahydro-DBT mainly undergoes hydrogenation to hexahydro-DBT and desulfurization to 1-cyclohexen-1-yl-benzene, which is then hydrogenated to cyclohexylbenzene. The breaking of two C-S bonds occurs by hydrogenolysis. Hexahydro-DBT mainly undergoes dehydrogenation to tetrahydro-DBT and then desulfurization of tetrahydro-DBT occurs to produce 1-cyclohexen-1-yl-benzene and cyclohexylbenzene. At the same time, hexahydro-DBT also undergoes desulfurization and its C-S bonds breaking occurs by hydrogenolysis. The desulfurization of tetrahydro-DBT is faster than that of hexahydro-DBT.