Deuterium Tracer Experiments Prove the Thiophenic Hydrogen Involvement During the Initial Step of Thiophene Hydrodesulfurization
- 88 Downloads
We reassess literature data and demonstrate that the intermolecular hydrogen transfer occur likely during the primary catalytic interaction between thiophene molecules, rendering it the credible thiophene hydrodesulfurization (HDS) pathway. Deuterium tracer experiments prove that thiophenic hydrogen plays a part in direct C–S cleavage, in the initial step of thiophene HDS. Hypothetical surface intermediates for thiophene exchange do not precede, i.e. do not form prior to the surface intermediates for thiophene HDS. Therefore the established thiophene exchange/HDS scheme and the sequence of events are not the viable concepts. Since the deuterium data also indicate that C4H5S(a)—radicals are not formed this means there are no common surface or reaction intermediates for the thiophene exchange and HDS and both reactions proceed parallel.
KeywordsThiophene hydrodesulfurization mechanism Deuterium tracer experiments Intermolecular hydrogen transfer HD exchange
During the preparation of this manuscript, A.B. had financial support by the European Union (Real-SOFC contract # SES6-CT-2003-502612, and Marie Curie contract MIRG-CT-2006-042095), and by the Swiss Competence Center for Energy and Mobility CCEM (project “Computational Engineering of Multi-Scale Transport in Small-Scale Surface Based Energy Conversion”, CEMTEC).
- 6.Topsøe H, Clausen BS, Massoth FE (1996) Hydrotreating catalysis. Science and technology. In: Anderson JR, Boudart M (eds) Catalysis—science and technology, vol 11. Springer-Verlag, BerlinGoogle Scholar
- 12.Satterfield CN, Roberts GW (1968) J Am Inst Chem Eng 14:159Google Scholar
- 20.Cowley SW (1975) Ph.D. Dissertation. Southern Illinois University, Carbondate, IllinoisGoogle Scholar
- 23.Katsapov GYa, Khalikov RKh, Talipov GSh, Gudkov BS, Nekrasov NV (1978) Neftekhimiya 18:426Google Scholar