Two-Step, Oxygen-Free Route to Higher Hydrocarbons from Methane Over Ruthenium Catalysts

  • Manoj M. Koranne
  • D. Wayne Goodman

Abstract

The direct conversion of methane to higher hydrocarbons over a Ru/SiO2 catalyst as well as Cu-Ru/SiO2 catalysts has been investigated via a two-step, oxygen-free route. The reaction consists of decomposition of methane over supported Ru catalysts at temperatures (TCH4) between 400 to 800K to produce surface carbonaceous species followed by rehydrogenation of these species to higher hydrocarbons at TH2 of 368K. A 3% Ru/SiO2 catalyst exhibited high initial ethane yields, but accumulation of “inactive” carbon led to a complete deactivation of this catalyst in few reaction cycles. For a Cu-Ru/SiO2 catalyst (Cu/Ru=0.1), about 95% carbon deposited could be hydrogenated at 368K thus improving the net ethane yield. However, when tested for multiple reaction cycles, the Cu-Ru/SiO2 catalyst (Cu/Ru=0.1) exhibited a rather slow deactivation, which was mainly attributed to gradual accumulation of inactive carbon on the surface of the catalyst. These results are consistent with the known tendency for Cu to deposit on low coordination Ru sites and with previous suggestions that carbon is predominantly formed on such sites.

Keywords

Methane Furnace Dust Enthalpy Helium 

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References

  1. 1.
    G.E. Keller and M.M. Bhasin, J. Catal, 73:9 (1982).CrossRefGoogle Scholar
  2. 2.
    T. Ito and J.H. Lunsford, Nature, 314:721 (1985).CrossRefGoogle Scholar
  3. 3.
    Y. Amenomiya, V.I. Birss, M. Goledzinowski, J. Galuszka, and A.R. Sanger, Catal. Rev. Sci. Eng, 32:163 (1990).CrossRefGoogle Scholar
  4. 4.
    R. Pitchai and K. Klier, Catal. Rev. Sci. Eng., 28:13 (1986).CrossRefGoogle Scholar
  5. 5.
    N.D. Spencer and C.J. Pereira, J. Catal, 116:399 (1989).CrossRefGoogle Scholar
  6. 6.
    M.M. Koranne, J.G. Goodwin, Jr., and G. Marcelin, J. Phys. Chem., 97:673 (1993).CrossRefGoogle Scholar
  7. 7.
    J.M. Fox, Catal. Rev. Sci. Eng, 35:169 (1993).CrossRefGoogle Scholar
  8. 8.
    T. Koerts and R.A. van Santen, J. Chem. Soc. Chem. Commun., 1281 (1991).Google Scholar
  9. 9.
    T. Koerts, M.J. Deelen, and R.A. van Santen, J. Catal, 138:101 (1992).CrossRefGoogle Scholar
  10. 10.
    M. Belgued, P. Pareja, A. Amariglio, and H. Amariglio, Nature, 352:789 (1991).CrossRefGoogle Scholar
  11. 11.
    M. Belgued, H. Amariglio, P. Pareja, A. Amariglio, and J. Saint-Just, Catal Today, 13:437 (1992).CrossRefGoogle Scholar
  12. 12.
    M.-C. Wu. and D.W. Goodman, J. Am. Chem. Soc, 116:1364 (1994).CrossRefGoogle Scholar
  13. 13.
    P. Lenz-Solomun, M.-C. Wu., and D.W. Goodman, Catal. Lett., 25:75 (1994).CrossRefGoogle Scholar
  14. 14.
    M.-C. Wu, P. Lenz-Solomun, and D.W. Goodman, J. Vac. Sci. Tech., in press (1994).Google Scholar
  15. 15.
    M.M. Koranne and D.W. Goodman, Catal. Lett., in press (1994).Google Scholar
  16. 16.
    M.W. Smale and T.S. King, J. Catal, 119:441 (1989).CrossRefGoogle Scholar
  17. 17.
    T.S. King, X. Wu, and B.C. Gerstein, J. Am. Chem. Soc, 108:6056 (1986).CrossRefGoogle Scholar
  18. 28.
    X. Wu, B.C. Gerstein, and T.S. King, J. Catal, 121:271 (1990).CrossRefGoogle Scholar
  19. 19.
    C.H. Yang and J.G. Goodwin, Jr., J. Catal, 78:182 (1982).CrossRefGoogle Scholar
  20. 20.
    J.H. Sinfelt, J. Catal, 29:308 (1973).CrossRefGoogle Scholar
  21. 21.
    J.T. Yates, Jr., C.H.F. Peden. and D.W. Goodman, J. Catal, 94:576 (1985).CrossRefGoogle Scholar
  22. 22.
    D.W. Goodman and C.H.F. Peden, J. Catal, 95:321 (1985).CrossRefGoogle Scholar
  23. 23.
    J.E. Houston, C.H.F. Peden, D.S. Blair, and D.W. Goodman, Surf. Sci., 167:427 (1986).CrossRefGoogle Scholar
  24. 24.
    G.L. Haller, D.E. Reasasco, and J. Wang, J. Catal, 84:477 (1983).CrossRefGoogle Scholar
  25. 25.
    M.-C. Wu, Q. Xu, and D.W. Goodman, J. Phys. Chem., in press (1994).Google Scholar

Copyright information

© Springer Science+Business Media New York 1995

Authors and Affiliations

  • Manoj M. Koranne
    • 1
  • D. Wayne Goodman
    • 1
  1. 1.Department of ChemistryTexas A & M UniversityCollege StationUSA

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