Catalysis Letters

, Volume 61, Issue 1–2, pp 15–25 | Cite as

Kinetic model of an oxygen‐free methane conversion on a platinum catalyst

  • M. Wolf
  • O. Deutschmann
  • F. Behrendt
  • J. Warnatz


In many metal‐catalyzed conversion processes of hydrocarbons at atmospheric pressure a carbonaceous overlayer quickly builds up at the catalyst covering nearly the whole surface. However, the metal still remains catalytically active. Several models have been proposed over the years to explain the crucial role of the carbonaceous overlayer during the conversion of hydrocarbons. The model presented here contemplates adsorbate effects, which means that surface carbon modifies the dehydrogenation activity of Pt. A hydrocarbon reaction mechanism on platinum, including C1 and C2 species, is established. The mechanism is based on elementary reactions offering the opportunity of using the same mechanism for a wide range of applications. It is also applied to extended simulations of higher pressures and smaller flow velocities revealing increased C2H6 yields under these conditions.

oxygen‐free methane conversion platinum carbon layer catalysis hydrocarbon surface kinetics modeling 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. [1]
    D.A. Hickman and L.D Schmidt, AIChE J. 39 (1993) 1164.CrossRefGoogle Scholar
  2. [2]
    A.S. Bodke and L.D. Schmidt, J. Catal. 179 (1998) 138.CrossRefGoogle Scholar
  3. [3]
    K.L. Hohn, P.M. Witt, M.B. Davis and L.D. Schmidt, Catal. Lett. 54 (1998) 113.CrossRefGoogle Scholar
  4. [4]
    M. Baerns, K. van der Wiele and J.R.H. Ross, Catal. Today 4 (1989) 471.CrossRefGoogle Scholar
  5. [5]
    J.A. Labinger, Quimica 48 (1993).Google Scholar
  6. [6]
    M. Belgued, H. Amariglio, P. Pareja, A. Amariglio and J. Saint-Just, Catal. Today 13 (1992) 437.CrossRefGoogle Scholar
  7. [7]
    T. Koerts and R.A. van Santen, in: New Frontiers in Catalysis, Proc. 10th Int. Congress on Catalysis, eds. L. Guczi et al. (Elsevier, Amsterdam, 1993) p. 1065.Google Scholar
  8. [8]
    M. Belgued, A. Amariglio, P. Pareja and H. Amariglio, J. Catal. 159 (1996) 441.CrossRefGoogle Scholar
  9. [9]
    F. Solymosi, A. Erdöhelyi and J. Cserenyi, Catal. Lett. 16 (1992) 399.CrossRefGoogle Scholar
  10. [10]
    L. Guczi, R.A. van Santen and K.V. Sarma, Catal. Rev. Sci. Eng. 38 (1996) 249.Google Scholar
  11. [11]
    Y. Zi-Feng, X. Jin-Zhen, S. Shi-Kong and W. Hong-Li, J. Nat. Gas Chem. 5 (1996) 261.Google Scholar
  12. [12]
    O. Deutschmann, R. Schmidt, F. Behrendt and J. Warnatz, in: Twenty-Sixth Symposium (International) on Combustion (The Combustion Institute, Pitsburgh, 1996) p. 1747.Google Scholar
  13. [13]
    P.A. Bui, D.G. Vlachos and P.R. Westmoreland, Surf. Sci. 385 (1997) L1029.CrossRefGoogle Scholar
  14. [14]
    G. Veser, J. Frauhammer and L.D. Schmidt, in: AIChE Meeting, Los Angeles, 16–21 November 1997, paper 266d.Google Scholar
  15. [15]
    Communications between D.K. Zerkle (Los Alamos National Laboratories), L.D. Schmidt et al. (University of Minnesota), and O. Deutschmann et al. (IWR, University of Heidelberg).Google Scholar
  16. [16]
    J. Warnatz, M.D. Allendorf, R.J. Kee and M.E. Coltrin, Combust. Flame 96 (1994) 393.CrossRefGoogle Scholar
  17. [17]
    P. Deuflhard, E. Hairer and J. Zugck, Numer. Math. 51 (1987) 501.CrossRefGoogle Scholar
  18. [18]
    D.A. Hickman and L.D. Schmidt, J. Catal. 136 (1992) 300.CrossRefGoogle Scholar
  19. [19]
    M. Belgued, A. Amariglio, P. Pareja and H. Amariglio, J. Catal. 159 (1996) 449.CrossRefGoogle Scholar
  20. [20]
    K. Christmann, Introduction to Surface Physical Chemistry, Topics in Physical Chemistry (Springer, New York, 1991) p. 69.Google Scholar
  21. [21]
    A. Burcat, in: Combustion Chemistry, ed. W.C. Gardiner (Springer, New York, 1984).Google Scholar
  22. [22]
    R.J. Kee and J.A. Miller, in: Complex Chemical Reaction Systems: Mathematical Modelling and Simulation, eds. J. Warnatz and W. Jger (Springer, Heidelberg, 1987).Google Scholar
  23. [23]
    E. Shustorovich, Metal Surface Reaction Energetics (VCH, Weinheim, 1991) pp. 191-223.Google Scholar
  24. [24]
    E. Shustorovich and A.T. Bell, Surf. Sci. 205 (1988) 492.CrossRefGoogle Scholar
  25. [25]
    S.W. Benson, in: Thermochemical Kinetics, 2nd Ed. (Wiley-Interscience, New York, 1976) p. 22.Google Scholar
  26. [26]
    H.P. Bonzel and H.J. Krebs, Surf. Sci. 91 (1980) 499.CrossRefGoogle Scholar
  27. [27]
    G.A. Somorjai, Introduction to Surface Chemistry (Wiley-Interscience, New York, 1994) p. 505.Google Scholar
  28. [28]
    S.M. Davis, F. Zaera and G.A. Somorjai, J. Catal. 77 (1982) 439.CrossRefGoogle Scholar
  29. [29]
    S.J. Thomson and G. Webb, J. Chem. Soc. Chem. Commun. (1976) 526.Google Scholar
  30. [30]
    T.M. Duncan, P. Winslow and A.T. Bell, Chem. Phys. Lett. 102 (1983) 163.CrossRefGoogle Scholar
  31. [31]
    F. Zaera, Chem. Rev. 95 (1995) 2651.CrossRefGoogle Scholar
  32. [32]
    Y.Y. Tong, A.J. Renouprez, G.A. Martin and J.J. van der Klink, in: 11th Int. Congress on Catalysis — 40th Anniversary, Vol. 101 B, eds. J.W. Hightower, W.N. Delgass, E. Iglesia and A.T. Bell (Elsevier, Amsterdam, 1996) pp. 901-910.Google Scholar
  33. [33]
    A.Ya. Tontegode, Prog. Surf. Sci. 38 (1991) 201.CrossRefGoogle Scholar
  34. [34]
    X.Q.D. Li, T. Radojicic and R. Vanselow, Surf. Sci. Lett. 225 (1990) L29.CrossRefGoogle Scholar
  35. [35]
    R. Schlögl, in: Handbook of Heterogenous Catalysis, Vol. 1, eds. G. Ertl, H. Knözinger and J. Weitkamp (Wiley-VCH, Weinheim, 1997) pp. 152-153.Google Scholar
  36. [36]
    R. Hoffmann, in: Solids and Surfaces: A Chemist's View of Bonding in Extended Structures (Wiley-VCH, Weinheim, 1988) pp. 76 ff and 114 ff.Google Scholar
  37. [37]
    K. Burdett, in: Molecular Shapes (Wiley-Interscience, New York, 1980).Google Scholar
  38. [38]
    M. Wolf, O. Deutschmann, F. Behrendt and J. Warnatz, in: Natural Gas Conversion V, Stud. Surf. Sci. Catal., Vol. 119, eds. A. Parmaliana, D. Sanfilippo, F. Frusteri, A. Vaccari and F. Arena (Elsevier, Amsterdam, 1998) p. 271.Google Scholar
  39. [39]
    G.A. Somorjai, in: Chemistry in Two Dimensions: Surfaces (Cornell University Press, Ithaca, NY, 1981) p. 483.Google Scholar
  40. [40]
    X.L. Zhou and J.M. White, Chem. Phys. Lett. 142 (1987) 376.CrossRefGoogle Scholar
  41. [41]
    F. Solymosi, Catal. Today 28 (1996) 193.CrossRefGoogle Scholar

Copyright information

© Kluwer Academic Publishers 1999

Authors and Affiliations

  • M. Wolf
    • 1
  • O. Deutschmann
    • 1
  • F. Behrendt
    • 1
  • J. Warnatz
    • 1
  1. 1.Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR)Universität HeidelbergHeidelbergGermany E-mail:

Personalised recommendations