Advertisement

Topics in Catalysis

, Volume 22, Issue 3–4, pp 191–203 | Cite as

Deactivation of Copper Metal Catalysts for Methanol Decomposition, Methanol Steam Reforming and Methanol Synthesis

  • Martyn V. Twigg
  • Michael S. SpencerEmail author
Article

Abstract

Laboratory and industrial results are reviewed to elucidate the general features of the deactivation of supported copper metal catalysts in various reactions involving methanol as reactant or product. Most catalyst types are based on Cu/ZnO formulations that contain stabilisers and promoters such as alumina, alkaline earth oxides and other oxides. These additional materials have several roles, including the inhibition of sintering and absorption of catalyst poisons. All copper catalysts are susceptible to thermal sintering via a surface migration process, and this is markedly accelerated by the presence of even traces of chloride. Care must be taken, therefore, to eliminate halides from copper catalysts during manufacture, and from reactants during use. Operating temperatures must be restricted, usually to below 300°C.

In methanol synthesis involving modern promoted Cu/ZnO/Al2 O3 catalysts neither poisoning nor coking is normally a significant source of deactivation; thermal sintering is the main cause of deactivation. In contrast, catalyst poisoning and coking have been observed in methanol decomposition and methanol steam reforming reactions.

copper catalyst deactivation zinc oxide methanol synthesis methanol steam reforming methanol decomposition sintering poisoning sulfur chloride 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. [1]
    G.W. Bridger and M.S. Spencer, in: Catalyst Handbook, 2nd edn, ed. M.V. Twigg (Manson Publishing, London, 1996) p. 441.Google Scholar
  2. [2]
    M.V. Twigg and M.S. Spencer, Appl. Catal. A 212 (2001) 161.Google Scholar
  3. [3]
    P.J. Denny and M.V. Twigg, in: Catalyst Deactivation, eds. B. Delmon and G.F. Froment (Elsevier, Amsterdam, 1980) p. 577.Google Scholar
  4. [4]
    R. Hughes, Deactivation of Catalysts (Academic Press, New York, 1994).Google Scholar
  5. [5]
    M.S. Spencer, Nature 323 (1985) 685.Google Scholar
  6. [6]
    P. Sabatier, Catalysis in Organic Chemistry, translated by E.E. Reid (The Library Press, London, 1923).Google Scholar
  7. [7]
    R. Conner and H. Adkins, J. Am. Chem. Soc. 53 (1931) 1091Google Scholar
  8. [7]
    H. Adkins, Reactions of Hydrogen with Organic Compounds over Copper-Chromium Oxide and Nickel Catalyst (University of Wisconsin Press, Madison, 1937).Google Scholar
  9. [8]
    J.S. Campbell, Ind. Eng. Chem. Process, Des. Dev. 9 (1970) 588.Google Scholar
  10. [9]
    Topics Catal. 3-4 (2003).Google Scholar
  11. [10]
    J. Ondar, C.R. Acad. Sci., Paris 249 (1959) 91.Google Scholar
  12. [11]
    B. Werlen and J. Ondar, J. Crystal Growth 9 (1971) 47.Google Scholar
  13. [12]
    P.J.H. Carnell, in: Catalyst Handbook, 2nd edn, ed. M.V. Twigg (Manson Publishing, London, 1996) ch. 4.Google Scholar
  14. [13]
    M.S. Spencer, Topics Catal. 8 (1999) 259.Google Scholar
  15. [14]
    L. Lloyd, D.E. Ridler and M.V. Twigg, in: Catalyst Handbook, 2nd edn, ed. M.V. Twigg (Manson Publishing, London, 1996) p. 283.Google Scholar
  16. [15]
    G.C. Chinchen, P.J. Denny, J.R. Jennings, M.S. Spencer and K.C. Waugh, Appl. Catal. 36 (1988) 1.Google Scholar
  17. [16]
    D.A. Whan and C.M. Hay, unpublished, quoted in [15].Google Scholar
  18. [17]
    A.F. Carley, P.R. Davies, R.V. Jones, K.R. Harikumar, G.V. Kulkarni and M.W. Roberts, Topics Catal. 11/12 (2000) 299.Google Scholar
  19. [18]
    A.F. Carley, P.R. Davies and M.W. Roberts, Topics Catal. 22 (2003).Google Scholar
  20. [19]
    D. Coulman, J. Winterlin, R.J. Behn and G. Ertl, Phys. Rev. Lett. 64 (1990) 1761.PubMedGoogle Scholar
  21. [20]
    A.F. Carley, P.R. Davies, G.V. Kulkarni and M.W. Roberts, Catal. Lett. 58 (1999) 93.Google Scholar
  22. [21]
    M. Muhler, E. Tornqvist, L. P. Nielsen, B.S. Clausen and H. Topsøe, Catal. Lett. 25 (1994) 1.Google Scholar
  23. [22]
    M.W. Roberts, Chem. Soc. Rev. (1996) 437.Google Scholar
  24. [23]
    L. Moroney, S. Rassias and M.W. Roberts, Surf. Sci. 105 (1981) L249.Google Scholar
  25. [24]
    A.F. Carley, P.R. Davies, R.V. Jones, K.R. Harikumar and M.W. Roberts, J. Chem. Soc. Chem. Commun. (2000) 185.Google Scholar
  26. [25]
    A.F. Carley, P.R. Davies, R.V. Jones, K.R. Harikumar and M.W. Roberts, Surf. Sci. 447 (2000) 39.Google Scholar
  27. [26]
    C.N. Satterfield, Heterogeneous Catalysis in Industrial Practice, 2nd edn. (Krieger, Florida, 1996).Google Scholar
  28. [27]
    P. Biloen, J.N. Helle, H. Verbeeke, F.M. Dautzenberg and W.M.H. Sachtler, J. Catal. 63 (1980) 112.Google Scholar
  29. [28]
    H.C. Dibben, P. Olesen, J.R. Rostrup-Nielsen, P.B. Tøttrup and N.R. Volengaard, Hydrocarbon Process. 65 (1986) 31.Google Scholar
  30. [29]
    J.R. Rostrup-Nielsen and I. Alstrup, in: Catalysis, ed. J.W. Ward (Elsevier, Amsterdam, 1988) p. 725.Google Scholar
  31. [30]
    G.D. Short, G.C. Chinchen and J.G. Williamson, US Patent 4788175 (1988).Google Scholar
  32. [31]
    G.C. Chinchen and J.R. Jennings, US Patent 4863894 (1989).Google Scholar
  33. [32]
    W.H. Cheng, Appl. Catal. B 7 (1995) 127.Google Scholar
  34. [33]
    M.V. Twigg and A.J.J. Wilkins, in: Structured Catalysts and Reactors, eds. A. Cybulski and J.A. Moulijn (Marcel Dekker, New York, 1998) p. 91.Google Scholar
  35. [34]
    M.V. Twigg and D.E. Webster, in: Structured Catalysts and Reactors, eds. A. Cybulski and J. A. Moulijn (Marcel Dekker, New York, 1998) p. 59.Google Scholar
  36. [35]
    M.V. Twigg and J.T. Richardson, Trans. IChemE. 80 A (2002) 183.Google Scholar
  37. [36]
    M.V. Twigg and J.T. Richardson, in: Preparation of Catalysts VI (Elsevier, Amsterdam, 1995) p. 345.Google Scholar
  38. [37]
    G.C. Chinchen, US Patent 4177252 (1979).Google Scholar
  39. [38]
    G.C. Chinchen, K. Mansfield and M.S. Spencer, Chemtech November (1990) 692.Google Scholar
  40. [39]
    S. Lee, V.R. Paramesharan and B.G. Lee, quoted in [50], p. 193.Google Scholar
  41. [40]
    S. Lee, A. Sawant and C.J. Kulik, quoted in [50], p. 193.Google Scholar
  42. [41]
    A. Sawant, Ph.D. Thesis, University of Akron, Akron, OH, 1987 (quoted in [50], p. 193).Google Scholar
  43. [42]
    H.H. Kung, Catal. Today 11 (1992) 443.Google Scholar
  44. [43]
    S.P.S. Andrew, Plenary Lecture, Post-Congress Symposium, 7th Int. Catalysis, Osaka, July 1980.Google Scholar
  45. [44]
    S.P.S. Andrew, in: Catalyst Handbook, 1st edn (Wolfe, London, 1970) p. 20.Google Scholar
  46. [45]
    S.P.S. Andrew, Chem. Eng. Sci. 36 (1981) 1431.Google Scholar
  47. [46]
    G.C. Chinchen, K.C. Waugh and D.A. Whan, Appl. Catal. 25 (1986) 101.Google Scholar
  48. [47]
    G.C. Chinchen and M.S. Spencer, Catal. Today 10 (1991) 293.Google Scholar
  49. [48]
    M.S. Spencer, ACS Symp. Ser. 298 (1986) 89.Google Scholar
  50. [49]
    M.R. Rahimpour, J. Fathikalajahi and A. Jahanmiri, Canad. J. Chem. Eng. 76 (1998) 753.Google Scholar
  51. [50]
    S. Lee, Methanol Synthesis Technology (CRC Press, Florida, 1990).Google Scholar
  52. [51]
    G.W. Roberts, D.M Brown, T.H. Hsiung and J.J. Lewnard, Chem. Eng. Sci. 45 (1990) 2713.Google Scholar
  53. [52]
    G.W. Roberts, D.M. Brown, T.H. Hsiung and J.J. Lewnard, in: Catalyst Deactivation, eds. C.H. Bartholomew and J.B. Butt (Elsevier, Amsterdam, 1991) p. 351.Google Scholar
  54. [53]
    S. Lee, Methanol Synthesis Technology (CRC Press, Florida, 1990) p. 169.Google Scholar
  55. [54]
    S. Lee, Methanol Synthesis Technology (CRC Press, Florida, 1990) p. 27.Google Scholar
  56. [55]
    S. Lee, Methanol Synthesis Technology (CRC Press, Florida, 1990) p. 175.Google Scholar
  57. [56]
    F.P. Daly, J. Catal. 89 (1984) 131.Google Scholar
  58. [57]
    R.M. Nix, T. Rayment, R.M. Lambert, J.R. Jennings and G. Owen, J. Catal. 106 (1987) 216.Google Scholar
  59. [58]
    R.M. Nix, R.W. Judd, R.M. Lambert, J.R. Jennings and G. Owen, J. Catal. 118 (1989) 175.Google Scholar
  60. [59]
    G. Owen, C.M. Hawkes, D. Lloyd, J.R. Jennings, R.M. Lambert, R.M. Nix, Appl. Catal. 33 (1987) 405.Google Scholar
  61. [60]
    Y. Choi and H.G. Stenger, Appl. Catal. B 38 (2002) 259.Google Scholar
  62. [61]
    R. Peters, H.G. Dusterwald and B. Hohlein, J. Power Sources 86 (2000) 507.Google Scholar
  63. [62]
    J.C. Amphlett, K.A.M. Creber, J.M. Davies, R.F. Mann, B.A. Peppley and D.M. Stokes, Int. J. Hydrogen Energy 19 (1994) 131.Google Scholar
  64. [63]
    T.R. Ralph and G.A. Hards, Chem. Ind. (1998) 337.Google Scholar
  65. [64]
    S. Golunski, Platinum Metals Rev. 42 (1998) 2.Google Scholar
  66. [65]
    C. Jiang, D.L. Trimm and M.S. Wainwright, Chem. Eng. Technol. 18 (1995) 1.Google Scholar
  67. [66]
    K. Takahashi, N. Takezawa and H. Kobayashi, Appl. Catal. 2 (1982) 383.Google Scholar
  68. [67]
    C.J. Jiang, D.L. Trimm, M.S. Wainwright and N.W. Cant, Appl. Catal. A 93 (1993) 245.Google Scholar
  69. [68]
    M.S. Spencer, Surf. Sci. 192 (1987) 323.Google Scholar
  70. [69]
    J.P. Breen, F.C. Meunier and J.R.H. Ross, Chem. Commun. (1999) 2247.Google Scholar
  71. [70]
    B.A. Peppley, J.C. Amphlett, L.M. Kearns and R.F. Mann, Appl. Catal. A. 179 (1999) 21.Google Scholar
  72. [71]
    M.M. Günter, T. Ressler, R.E. Jentoft and B. Bems, J. Catal. 203 (2001) 133.Google Scholar
  73. [72]
    B.A. Peppley, J.C. Amphlett, L.M. Kearns and R.F. Mann, Appl. Catal. A 179 (1999) 31.Google Scholar
  74. [73]
    C.P. Thurgood, J.C. Amphlett, R.F. Mann and B.A. Peppley, Topics Catal. 22 (2003).Google Scholar
  75. [74]
    W.H. Cheng, Appl. Catal. A 130 (1995) 13.Google Scholar
  76. [75]
    S.P. Tonner, D.L. Trimm, M.S. Wainwright and N.W. Cant, Ind. Eng. Chem. Prod. Res. Dev. 23 (1984) 384.Google Scholar
  77. [76]
    J.C. Amphlett, M.J. Evans, R.F. Mann and R.D. Weir, Can. J. Chem. Eng. 66 (1988) 950.Google Scholar
  78. [77]
    M.S. Spencer, Surf. Sci. 192 (1987) 329.Google Scholar
  79. [78]
    M.S. Spencer, Surf. Sci. 192 (1987) 336.Google Scholar
  80. [79]
    S.D. Jackson, D.S. Anderson, G.J. Kelly, T. Lear, D. Lennon and S.R. Watson, Topics Catal. 22 (2003).Google Scholar

Copyright information

© Plenum Publishing Corporation 2003

Authors and Affiliations

  1. 1.Johnson MattheyHertsUK
  2. 2.Chemistry DepartmentCardiff UniversityCardiff, WalesUK

Personalised recommendations