Mechanisms of Thiophene Hydrodesulfurization on Model Molybdenum Catalysts

Abstract

Hydrodesulfurization (HDS) activities and selectivities were measured for thiophene, tetrahydrothiophene (THT), and 1-buta-nethiol on silica-supported molybdenum catalysts at a pressure of 1 atm and temperatures ranging from 530 to 795 K. The model catalysts, which were previously characterized, feature isolated molybdenum atoms in the +2, +4, and +6 oxidation states and molybdenum dimers with each molybdenum atom in the +4 oxidation state. Silica-supported MoS2was used for reference. Activities for thiophene and THT HDS correlate with oxidation state. Mo(II) is most active among dispersed catalysts. 1-Butanethiol activities were much larger than thiophene or THT activities and were roughly equal on all dispersed catalysts. Apparent activation energies of 43.4 and 48.5 kJ/mol were determined for thiophene HDS on Mo(II) and MoS2/SiO2, respectively. Apparent activation energies of 132 and 174 kJ/mol were determined for THT HDS on Mo(II) and MoS2/SiO2, respectively. Dihydrothiophene, THT and 1-butanethiol were formed in thiophene HDS over Mo(II) and MoS2/SiO2. The major products of thiophene and THT HDS were 1-butene, 2-butene, andn-butene. Butadiene,i-butane,i-butene, methane, ethane, ethene, propane, and propene were formed in small amounts. Butadiene is thought to be the initial product of thiophene and THT desulfurization and undergoes subsequent hydrogenation and isomerization to yield the observed products. A common mechanism for HDS of thiophene and THT with 2,5-DHT as an intermediate is discussed.