An ab initio study of hydrotreating of thiirene and thiirane on MoS3H3+ catalytic site

Thiirene and thiirane have been chosen as model molecules representative of products present in crude oil to study the key steps in hydrotreating. The hydrotreating which can be desulfurization, deoxygenation or denitrogenation is the treatment of oil crude products under hydrogen pressure in presence of catalysts. This process leads to hydrogenolysis of carbon-heteroatom bond accompanied by heteroatom elimination. The catalytic site used is based on molybdenum disulfide (MoS2), which is considered as active phase in the commercial catalysts containing molybdenum atoms. Two steps characterise the desulfurization process: the adsorption and the carbon-sulfur bond cleavage. The thiirene geometry has been destroyed through the cleavage of one of the carbon-sulfur bonds. The calculation results showed that the desulfurization of the thiirene and thiirane do follow a heterolytic process. At the end of process, the reaction pathways are the same with an activation energy which was higher for thiirane than for thiirene. These results confirmed the same catalytic site and molecules obtained in previous works in the EHT method.