Selective hydrogenation of C4-alkynes over a copper on silica catalyst

R. A. Koeppel, J. T. Wehrli, M. S. Wainwright, D. L. Trimma, N. W. Cant

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Abstract

The selective gas phase hydrogenation of 1-butyne, 1-butene-3-yne, 1,3-butadiene and of an industrial C4-feed stream has been examined in a flow system employing a Cu/SiO2 catalyst. The variations in product distributions with temperature, hydrogen partial pressure and C4-reactant partial pressure have been determined together with the kinetics and activation energies. No butane formation was observed for all experiments, proving the Cu/SiO2 catalyst to be highly selective for the formation of alkenes. Butene isomerisation was found to be negligible for all reactions. Catalyst deactivation, as a result of the build-up of oligomeric material on the catalyst surface was particularly pronounced for the C4-alkynes but could be minimised by applying elevated temperatures and increased hydrogen partial pressures. Orders of reaction with respect to hydrogen (1.1-1.5), 2-butene (zero) and the C4-reactants (zero) indicate that the strengths of adsorption decrease in the sequence: alkyne > dialkene > alkene ≥ hydrogen. Apparent activation energies for the formation of 1-butene were measured as 69 kJ mol (1-butyne), 62 kJ mol (1-butene-3-yne) and 63 kJ mol (1,3-butadiene). In competitive hydrogenation reactions the alkynes were selectively hydrogenated while 1,3-butadiene was found to be inert. Thus the catalyst can be used for the selective removal of alkynes from industrial C4-streams.

Original languageEnglish
Pages (from-to)163-177
Number of pages15
JournalApplied Catalysis A, General
Volume120
Issue number1
DOIs
Publication statusPublished - 8 Dec 1994

Keywords

  • Alkyne hydrogenation
  • butadiene
  • butyne
  • Copper/silica
  • Deposition-precipitation
  • Hydrogenation

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    Koeppel, R. A., Wehrli, J. T., Wainwright, M. S., Trimma, D. L., & Cant, N. W. (1994). Selective hydrogenation of C4-alkynes over a copper on silica catalyst. Applied Catalysis A, General, 120(1), 163-177. https://doi.org/10.1016/0926-860X(94)80340-4