Research on Chemical Intermediates

, Volume 23, Issue 1, pp 25–40 | Cite as

Surface species in the direct amination of methanol over Brønsted acidic mordenite catalysts

  • CH. Gründling
  • G. Eder-Mirth
  • J. A. Lercher


Quantitative in situ infrared spectroscopy in combination with kinetic analysis is utilized to derive mechanistic aspects for the reaction of methanol with ammonia on Brønsted acidic mordenite. Under non-reactive conditions, a coadsorption complex between methanol and ammonia is found, in which only ammonia is in direct interaction with the Brønsted acid sites of the zeolite. This complex is proposed to be the precursor for the formation of protonated methylamines in the zeolite pores which are formed in sequential order up to tetramethylammonium ions. These methylamines are unable to desorb under reaction conditions in the absence of ammonia. They leave the surface either by ammonia adsorption assisted desorption or by scavenging of methyl groups from protonated methylamines by ammonia. Both steps are concluded to be potentially rate determining.


Zeolite Methylamine Mordenite Surface Species Bronsted Acid 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    L.D. Pesce and W.R. Jenks, in J.A. Kent (Ed.), Riegel's Handbook of Industrial Chemistry, 9th ed., Van Nostrand Reinold, New York, 1992, p. 1109.Google Scholar
  2. 2.
    M.G. Turcotte and T.A. Johnson, in J.I. Kroschwitz (Ed.), Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed., John Wiley & Sons, New York, 1992, Vol. 2, p. 369.Google Scholar
  3. 3.
    L.A. Hamilton, US Patent 3.384.667, 1968.Google Scholar
  4. 4.
    D.G. Parker and A.J. Tompsett, GB Patent 20119394B, 1982.Google Scholar
  5. 5.
    F.J. Weigert, US Patent 4.313.003, 1982.Google Scholar
  6. 6.
    M. Deeba and R.N. Chochran, Eur. Patent Appl. 85.408, 1983Google Scholar
  7. 7.
    A.J. Tompsett, US Patent 4.436.938, 1984.Google Scholar
  8. 8.
    Y. Ashina, M. Fujita, K. Niwa, and Y. Yagi, Eur. Patent Appl., 125.616, 1984.Google Scholar
  9. 9.
    R.D. Shannon, M. Keane, Jr., L. Abrams, R.H. Staley, T.E. Gier, D.R. Corbin, and G.C. Sonnichsen, J. Catal., 113, 367 (1988).CrossRefGoogle Scholar
  10. 10.
    R.D. Shannon, M. Keane, Jr., L. Abrams, R.H. Staley, T.E. Gier, D.R. Corbin, and G.C. Sonnichsen, J. Catal., 114, 8 (1988).CrossRefGoogle Scholar
  11. 11.
    R.D. Shannon, M. Keane, Jr., R.H. Staley, T.E. Gier, and G.C. Sonnichsen, J. Catal., 115, 79 (1989).CrossRefGoogle Scholar
  12. 12.
    Y. Ashina, T. Fujita, M. Fukatsu, K. Niwa and Y. Yagi, Stud. Surf. Sci. Catal. 28, 779 (1986).CrossRefGoogle Scholar
  13. 13.
    K. Segawa and H. Tachibana, J. Catal, 131, 482 (1991).CrossRefGoogle Scholar
  14. 14.
    U. Dingerdissen, E. Nagy and F. Fetting, Chem.-Ing. Tech., 63, 625 (1991).CrossRefGoogle Scholar
  15. 15.
    A. Kogelbauer, Ch. Gründling, and J.A. Lercher, Stud. Surf. Sci. Catal., 84, 1475 (1994).CrossRefGoogle Scholar
  16. 16.
    I. Mochida, A. Yasutake, H. Fujitsu and K. Takeshita, J. Catal., 82, 313 (1983).CrossRefGoogle Scholar
  17. 17.
    M. Keane, Jr., G.C. Sonnichsen, L. Abrams, D.R. Corbin, T.E. Gier, and R.D. Shannon, Appl. Catal., 32, 361 (1987).CrossRefGoogle Scholar
  18. 18.
    L. Abrams, D.R. Corbin, and M. Keane, Jr., J. Catal., 126, 610 (1990).CrossRefGoogle Scholar
  19. 19.
    F. Fetting and U. Dingerdissen, Chem. Eng. Technol., 15, 202 (1992).CrossRefGoogle Scholar
  20. 20.
    F.J. Weigert, J. Catal., 103, 20 (1987).CrossRefGoogle Scholar
  21. 21.
    D.T. Chen, L. Zhang, J.M. Kobe, Chen Yi, and J.A. Dumesic, J. Molec. Catal., 93, 337 (1994).CrossRefGoogle Scholar
  22. 22.
    M. Sawa, M. Niwa, and Y. Murakami, Zeolites, 10, 532 (1990).CrossRefGoogle Scholar
  23. 23.
    G. Mirth, F. Eder and J.A. Lercher, J. Appl. Spectrosc., 48, 194 (1994).CrossRefGoogle Scholar
  24. 24.
    A. Kogelbauer, Ph.D. Thesis, TU Vienna, Austria, 1991.Google Scholar
  25. 25.
    M.T. Aronson, R.J. Gorte, and W.E. Farneth, J. Catal., 105, 455 (1987).CrossRefGoogle Scholar
  26. 26.
    G. Mirth, J.A. Lercher, M.W. Anderson and J. Klinowski, J. Chem. Soc. Faraday Trans., 4, 702 (1988).Google Scholar
  27. 27.
    L. Kubelkova, J. Novakova, and K. Nedomova, J. Catal., 124, 441 (1990).CrossRefGoogle Scholar
  28. 28.
    G. Mirth, A. Kogelbauer, and J.A. Lercher, in R. van Ballmoos et al. (Eds.), Proc. 9th IZC, Butterworth-Heinemann, Montreal, 1992, p. 251.Google Scholar
  29. 29.
    L.H. Little, Infrared Spectra of Adsorbed Species, Academic Press, London, 1966, p. 180.Google Scholar
  30. 30.
    A. Kogelbauer, J.A. Lercher, K.H. Steinberg, F. Roessner, A. Soellner, R.V. Dmitriev, J. Chem. Soc. Faraday Trans., 88, 2283 (1992).CrossRefGoogle Scholar
  31. 31.
    M.M. Mortland, J.J. Fripiat, J. Chaussidon, and J. Uytterhoeven, J. Phys. Chem., 67, 248 (1963).CrossRefGoogle Scholar
  32. 32.
    E.H. Teunissen, R.A. van Santen, A.P.J. Jansen, and F.B. Duijneveldt, J. Phys. Chem., 97, 203 (1993).CrossRefGoogle Scholar
  33. 33.
    B. Chenon and C. Sandorfy, Can. J. Chem., 36, 1181 (1958).CrossRefGoogle Scholar
  34. 34.
    A.K. Ghosh and G. Curthoys, J. Chem. Soc. Faraday Trans. I, 80, 99 (1984).CrossRefGoogle Scholar
  35. 35.
    C. Brisette and C. Sandorfy, Can. J. Chem., 38, 34 (1960)CrossRefGoogle Scholar
  36. 36.
    E. Jobson, A. Baiker, and A. Wokaun, J. Chem. Soc. Faraday Trans., 86, 1131 (1990).CrossRefGoogle Scholar
  37. 37.
    A. Kogelbauer and J.A. Lercher, J. Chem. Soc. Faraday Trans., 88, 2283 (1992).CrossRefGoogle Scholar
  38. 38.
    A. Kogelbauer, Ch. Gründling, and J.A. Lercher, J. Phys. Chem., submitted for publication (1995).Google Scholar
  39. 39.
    D.T. Chen, L. Zhang, Chen Yi and J.A. Dumesic, J. Catal., 146, 257 (1994).CrossRefGoogle Scholar
  40. 40.
    D.J. Parrillo, R.J. Gorte, and W.E. Farneth, J. Am. Chem. Soc., 115, 12441 (1993).CrossRefGoogle Scholar
  41. 41.
    Ch. Gründling, Ph. D. Thesis, University of Twente, the Netherlands, 1995.Google Scholar

Copyright information

© Springer 1997

Authors and Affiliations

  • CH. Gründling
    • 1
  • G. Eder-Mirth
    • 1
  • J. A. Lercher
    • 1
  1. 1.Department of Chemical TechnologyUniversity of TwenteEnschedeThe Netherlands

Personalised recommendations