Reaction Kinetics and Catalysis Letters

, Volume 68, Issue 1, pp 153–163 | Cite as

Features of deposit formation from 1,3-butadiene over Pd catalysts

  • A. Sárkány
Article

Abstract

Formation of carbonaceous deposits from 1,3-butadiene has been investigated over a group of Pd catalysts. Hydrogen generated in decomposition of diene at 473–523 K participates in diene hydrogenation, resulting in the formation ofn-butenes. XRD measurements have confirmed formation of dissolved carbon (PdCx) phase. DRIFT measurements over 0.06 wt.%Pd/γ-Al2O3 have revealed bands at 1575 and 1464 cm−1, suggesting formation of carboxylate structures. Selectivity of the competitive hydrogenation in 1,3-butadiene and propene mixture R(BD)/R(Pr) has been measured on “fresh” and poisoned samples. Accumulation of deposits has decreased the R(BD)/R(Pr) ratio. The results have been interpreted by transport hindrance and a greater prevalence of non-selective low coordination sites on the poisoned surface. Measurements over Pd, Cu, Pt and Rh catalysts have shown that the highn-butane selectivity over Pt and Rh is also accompanied with low R(BD)/R(Pr) values, suggesting that thermodynamic and mechanistic factors are not entirely separable.

Keywords

Carbonaceous deposit dissolved carbon transport hindrance competitive hydrogenation 

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References

  1. 1.
    G. C. Bond, J. S. Rank:Proc. 3rd Int. Congr. Catal. Amsterdam, Vol. 2, 1225 (1965).Google Scholar
  2. 2.
    G. Webb:Comprehensive Chemical Kinetics, Vol. 20, p. 1. Ed. C.H. Bamford and C.E.H. Tipper, Elsevier 1978.Google Scholar
  3. 3.
    M.L. Derrien:Stud. Surf. Sci. Catal.,27, 613 (1986).CrossRefGoogle Scholar
  4. 4.
    A. Sárkány:Appl. Catal. A,165, 87 (1997).CrossRefGoogle Scholar
  5. 5.
    A. Sárkány:Stud. Surf. Sci. Catal.,101, 111 (1997).CrossRefGoogle Scholar
  6. 6.
    A.S. Al-Ammar, G. Webb:J. Chem. Soc. Faraday Trans. I,74, 657 (1978).CrossRefGoogle Scholar
  7. 7.
    S.D. Jackson, N.J. Casey:J. Chem. Soc. Faraday Trans. I,91, 3269 (1995).CrossRefGoogle Scholar
  8. 8.
    S.J. Thomson, G. Webb.J. Chem. Soc. Chem. Commun., 139 (1976).Google Scholar
  9. 9.
    A. Sárkány:J. Catal.,180, 149 (1998).CrossRefGoogle Scholar
  10. 10.
    S.B. Ziemecki, G.A. Jones,J. Catal.,95, 621 (1985).CrossRefGoogle Scholar
  11. 11.
    M. Maciejewski, A. Baiker:J. Phys. Chem.,98, 285 (1994).CrossRefGoogle Scholar
  12. 12.
    H.C. Brown, J. Chandrasekharan, K.K. Wang:Pure Appl. Chem.,55, 1387 (1983).Google Scholar
  13. 13.
    D. Eisenbach, E. Gallei:J. Catal.,56, 377 (1979).CrossRefGoogle Scholar
  14. 14.
    A. Sárkány, H. Lieske, T. Szilágyi, L. Tóth:Proc. 8th Int Congr. Catal. Berlin, Vol. 2, p. 613 (1984).Google Scholar
  15. 15.
    A. Corado, A. Kiss, H. Knözinger, H.-D. Müller:J. Catal.,37, 68 (1975).CrossRefGoogle Scholar
  16. 16.
    J. Najbar, R.P. Eischens:Proc. 19th Int. Congr. Catal. Calgary, Vol. 3, p. 1434 (1988).Google Scholar
  17. 17.
    W. Herti, A.M. Cuenca:J. Phys. Chem.,77, 1120 (1973).CrossRefGoogle Scholar
  18. 18.
    S. Hub, L. Hilaire, R. Touroude:Appl. Catal.,36, 307 (1988).CrossRefGoogle Scholar
  19. 19.
    J.P. Boitiaux, J. Cosyns, E. Robert:Appl. Catal.,49, 235 (1989).CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó 1999

Authors and Affiliations

  • A. Sárkány
    • 1
  1. 1.Institute of Isotope and Surface Chemistry, Chemical Research CenterHungarian Academy of SciencesBudapestHungary

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