Alumina-supported cobalt–molybdenum sulfide modified by tin via surface organometallic chemistry: application to the simultaneous hydrodesulfurization of thiophenic compounds and the hydrogenation of olefins

Abstract

Surface organometallic chemistry has been used to deposit tin atoms on an alumina-supported cobalt–molybdenum sulfide. The EXAFS spectra at the Mo and Co K-edges were not changed significantly by tin doping, which means that the initial morphology of sulfide phases was preserved during the synthesis. 119Sn Mössbauer spectroscopy indicated that the main neighbors of the deposited tin atoms were sulfur and oxygen atoms with no significant formation of metallic tin particles. Tin seems thus to have been deposited either on the sulfide slabs through sulfur bridges or on the support via oxygen bonding. According to the infrared spectroscopy, tin doping led to the blocking of different surface sites with slight electronic structure modification. Those surface sites are sulfur vacancies on sulfide slabs, Al3+ or hydroxyl groups on the support, or “interfacial” sites: support hydroxyl groups H-bonded with sulfide phases.The impact of tin doping on the activity and selectivity of the sulfide phases was studied by catalytic tests carried out using a synthetic FCC gasoline feed. Three main reactions were found to be involved: hydrodesulfurization of sulfur-containing molecules, double-bond isomerization and hydrogenation of olefins. Olefin hydrogenation was preceded by double-bond isomerization reaction, which gave quickly thermodynamically equilibrated composition. No clear correlation could be made between tin doping and isomerization performance and catalyst support was proposed as the main actor for this reaction. Small amounts of tin had little effect on the hydrogenation activity, but higher loadings resulted in an important decrease in activity. Contrary to the case of olefin hydrogenation, thiophene hydrodesulfurization activity decreased drastically at a low tin loading, and continued to decrease but more slightly at higher loadings. By comparison of the activity variations and the characterization results, the sulfur vacancies were found to play a major role in the hydrodesulfurization process. Interfacial sites were assumed to be involved in one of the key steps in the olefin hydrogenation pathway.