Second row transition metal sulfides for the hydrotreatment of coal-derived naphtha II. Removal of individual sulfur compounds

Abstract

The disappearance of individual sulfur compounds has been investigated during the hydrotreatment (simultaneous removal of sulfur, nitrogen and oxygen) of coal-derived naphtha over each of the bulk second row transition metal sulfides. The sulfur compounds in the naphtha mainly consist of thiols/sulfides, thiophene and substituted thiophenes. Thiols/sulfides are, in general, more easily converted than thiophenic compounds are. Lighter thiols/sulfides are intermediates in the conversion of higher boiling thiols/sulfides or thiophenes. Side chain alkyl CC bond breaking is predominant during the disappearance of thiophenes over the Zr and Nb catalysts while CS bond breaking is predominant over the other catalysts. Thiophenic compounds are hydrogenated prior to desulfurization over the Mo, Ru, Rh and Pd sulfides. Highly substituted thiophenes are the compounds most difficult to convert over the Mo, Ru, Rh and Pd sulfides. The substituted thiophenes exhibit different reactivity trends over molybdenum sulfide, on one hand, and the Group VIII sulfides, on the other, indicating different adsorption modes and surface mechanisms for their conversion over these catalysts. Individual sulfur compounds do not follow first order kinetics and the disappearance rate is limited by product inhibition. The overall removal of sulfur does not follow simple first or second order kinetics since the individual compounds do not react in parallel, independent or first order reactions.