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Isomerization of 1-butene on supported and unsupported metal-oxygen cluster compounds (heteropoly oxometalates)

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Abstract

On 12-tungstophosphoric acid (HPW) supported on silica, 1-butene is isomerized to cis- and trans-2-butene at 100°C and higher while a temperature of 150°C is required to form isobutene. While the conversion remains at 80–90% regardless of the loading of HPW on the support and the reaction temperature, the selectivity to isobutene reaches a maximum of 33% at a loading of 23% HPW/SiO2 and 300–350°C. Small quantities of C n (n = 3,..., 8) species are also formed. These results together with those from ammonia poisoning, temperature-programmed desorption of ammonia,1H MAS NMR and infrared spectroscopy show that HPW/SiO2 possesses sites of strength as high as or higher than those on HZSM-5, that such sites are required for the skeletal isomerization process and that both mono- and bimolecular processes are occurring on the catalyst. The absence of dependence of conversion of 1-butene and selectivities to cis- and trans-2-butene on loading and reaction temperature can best be rationalized on the basis of a rapid attainment of an equilibrium between the aforementioned three species and sec-butyl carbenium ions from which pool the energy barrier to the primary butyl carbenium and hence to isobutene is surmounted, given appropriate conditions.

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References

  1. S. Meijers, L.H. Gielgens and V. Ponec, J. Catal. 156 (1995) 147.

    Google Scholar 

  2. R. Robert, P.R. Rajamohanan, S.G. Hedge, A.J. Chandwadkar and P. Ratnasamy, J. Catal. 155 (1995) 345.

    Google Scholar 

  3. L.H. Gielgens, M.G.H. van Kampen, M.M. Broek, R. van Hardeveld and V. Ponec, J. Catal. 154 (1995) 201.

    Google Scholar 

  4. L.H. Gielgens, I.H.E. Veenstra, V. Ponec, M.J. Haanepen and J.H.C. van Hoof, Catal. Lett. 32 (1995) 195.

    Google Scholar 

  5. F. Garciaochoa and A. Santos, AICHE Journal 41 (1995) 286.

    Google Scholar 

  6. W.Q. Xu, Y.G. Yin, S.L. Suib, J.C. Edwards and C.L. Oyoung, J. Phys. Chem. 99 (1995) 9443.

    Google Scholar 

  7. C.L. Oyoung, R.J. Pellet, D.G. Casey, J.R. Ugolini and R.A. Sawicki, J. Catal. 151 (1995) 467.

    Google Scholar 

  8. S.M. Yang, D.H. Guo, J.S. Lin and G.T. Wang, Stud. Surf. Sci. Catal. 84 (1994) 1677.

    Google Scholar 

  9. Z.X. Cheng and V. Ponec, J. Catal. 148 (1994) 607.

    Google Scholar 

  10. Z.X. Cheng and V. Ponec, Catal. Lett. 27 (1994) 113;

    Google Scholar 

  11. Z.X. Cheng and V. Ponec, Catal. Lett. 25 (1994) 337.

    Google Scholar 

  12. G. Shahid and N. Sheppard, J. Chem. Soc. Faraday Trans. 90 (1994) 513.

    Google Scholar 

  13. G. Shahid and N. Sheppard, J. Chem. Soc. Faraday Trans. 90 (1994) 507.

    Google Scholar 

  14. P. Patrono, A. La Ginestra, G. Ramis and G. Busca, Appl. Catal. A 107 (1994) 249.

    Google Scholar 

  15. P. Beltrame, L. Forni, A. Talamini and G. Zuretti, Appl. Catal. A 110 (1994) 39.

    Google Scholar 

  16. A.C. Butler and C.P. Nicolaides, Catal. Today 18 (1993) 443.

    Google Scholar 

  17. J. Szabo, G. Szabo, J. Vangestel and D. Cornet, Appl. Catal. A 96 (1993) 319.

    Google Scholar 

  18. Y. Hong, F.R. Cheng and J.J. Fripiat, Catal. Lett. 17 (1993) 187.

    Google Scholar 

  19. J. Szabo, J. Perrotey, G. Szabo, J.C. Duchet and D. Cornet, J. Mol. Catal. 67 (1991) 79.

    Google Scholar 

  20. G. Shahid and N. Sheppard, Can. J. Chem. 69 (1991) 1812.

    Google Scholar 

  21. A.T. Aguayo, J.M. Arandes, M. Olazar and J. Bilbao, Ind. Eng. Chem. Res. 29 (1990) 1172.

    Google Scholar 

  22. J. Engelhardt, J. Goldwasser and W.K. Hall, J. Catal. 76 (1982) 48.

    Google Scholar 

  23. I.C. Hisatsune, J. Catal. 75 (1982) 425.

    Google Scholar 

  24. H. Itoh, A. Tada and H. Hattori, J. Catal. 76 (1982) 235.

    Google Scholar 

  25. V. Mintsa-Eya, L. Hilaire, R. Toroude, F.G. Gault, B. Moraweck and B. Renouprez, J. Catal. 76 (1982) 169.

    Google Scholar 

  26. A.J. van Roosmalen and J.C. Mol, J. Catal. 78 (1982) 17.

    Google Scholar 

  27. J. Goldwasser and W.K. Hall, J. Catal. 71 (1981) 53.

    Google Scholar 

  28. J. Goldwasser, J. Engelhardt and W.K. Hall, J. Catal. 71 (1981) 381.

    Google Scholar 

  29. E. Rodevas, T. Yamaguchi, H. Hattori and K. Tanabe, J. Catal. 69 (1981) 434.

    Google Scholar 

  30. M.P. Rosynek, J.S. Fox and J.L. Jensen, J. Catal. 71 (1981) 64.

    Google Scholar 

  31. I. Suzuki, J. Catal. 68 (1981) 220.

    Google Scholar 

  32. T. Yamaguchi, Y. Tanaka and K. Tanabe, J. Catal. 65 (1980) 442.

    Google Scholar 

  33. J. Goldwasser and W.K. Hall, J. Catal. 63 (1980) 520.

    Google Scholar 

  34. B.E. Langner, J. Catal. 65 (1980) 416.

    Google Scholar 

  35. M.R.S. Manton and J.C. Davitz, J. Catal. 69 (1979) 156.

    Google Scholar 

  36. Y. Nakano, T. Iizuka, H. Hattori and K. Tanabe, J. Catal. 57 (1979) 1.

    Google Scholar 

  37. M.P. Rosynek and J.S. Fox, J. Catal. 49 (1977) 285.

    Google Scholar 

  38. Y. Sakai and H. Hattori, J. Catal. 42 (1976) 37.

    Google Scholar 

  39. G.E. Martin and L.W. Hill, J. Catal. 42 (1976) 344.

    Google Scholar 

  40. T. Vematsu, K. Inamura, K. Hirai and H. Hashimoto, J. Catal. 45 (1976) 68.

    Google Scholar 

  41. H. Hoser and S. Krzyanowski, J. Catal. 38 (1975) 366.

    Google Scholar 

  42. V.R. Choudhary, Chem. Ind. Dev. 8 (1974) 32.

    Google Scholar 

  43. A. Ghorbel, C. Hoang-Van and S.J. Teichner, J. Catal. 33 (1974) 123.

    Google Scholar 

  44. V. Ragaini, J. Catal. 34 (1974) 1.

    Google Scholar 

  45. T. Vematsu, K. Tsukada and H. Hashimoto, J. Catal. 32 (1974) 369.

    Google Scholar 

  46. J.B. Nagy, M. Guelton and E.G. Derouane, J. Catal. 55 (1970) 43.

    Google Scholar 

  47. K. Tanabe,Solid Acids and Bases (Academic Press, New York, 1970).

    Google Scholar 

  48. J.W. Hightower and W.K. Hall, J. Phys. Chem. 71 (1967) 1014.

    Google Scholar 

  49. J.W. Hightower, H.R. Gerberich and W.K. Hall, J. Catal. 7 (1967) 57.

    Google Scholar 

  50. D.M. Golden, K.W. Egger and S.W. Benson, J. Am. Chem. Soc. 86 (1964) 5416.

    Google Scholar 

  51. J.B. Peri,Proc. 3rd Int. Congr. on Catalysis (North-Holland, Amsterdam, 1964) p. 1100.

    Google Scholar 

  52. H.P. Leftin and M.C. Hobson, Adv. Catal. 14 (1964) 115.

    Google Scholar 

  53. J. Wei and C.D. Prater, Adv. Catal. 13 (1962) 203.

    Google Scholar 

  54. L.H. Little, H.E. Klauser and C.H. Amberg, Can. J. Chem. 39 (1961) 42.

    Google Scholar 

  55. J.B. Peri,Proc. 2nd Int. Congr. on Catalysis (Technip, Paris, 1961).

    Google Scholar 

  56. W.O. Haag and H. Pines, J. Am. Chem. Soc. 82 (1960) 387.

    Google Scholar 

  57. L.H. Little,Infrared Spectra of Adsorbed Species (Academic Press, New York, 1966).

    Google Scholar 

  58. P. Patrono, A. La Ginestra, G. Ramis and G. Busca, Appl. Catal. A 107 (1994) 249.

    Google Scholar 

  59. P.J. Lucchesi, P.L. Carter and D.J.C. Yates, J. Phys. Chem. 66 (1962) 1451.

    Google Scholar 

  60. L.H. Little, H.E. Klauser and C.H. Amberg, Can. J. Chem. 39 (1961) 42.

    Google Scholar 

  61. S. Kasztelan and J.B. Moffat, J. Catal. 109 (1988) 206.

    Google Scholar 

  62. S.S. Hong and J.B. Moffat, Appl. Catal. 109 (1994) 117.

    Google Scholar 

  63. S. Kasztelan, E. Payen and J.B. Moffat, J. Catal. 125 (1990) 45.

    Google Scholar 

  64. D.M. Brouwer and J.M. Oelderik, Rec. Trav. Chim. Pays Bas 87 (1968) 721.

    Google Scholar 

  65. D.M. Brouwer, Rec. Trav. Chim. Pays Bas 87 (1968) 1435.

    Google Scholar 

  66. T.J. Weeks Jr. and A.P. Bolton, J. Chem. Soc. Faraday I 70 (1974) 1676.

    Google Scholar 

  67. P. Beltrame, L. Forni, A. Talamani and G. Zuretti, Appl. Catal. A 110 (1994) 39.

    Google Scholar 

  68. H.H. Mooiweer, K.P. De Jong, B. Kraushaar-Czarnetzki and W.H.J. Stork, in:Studies in Surface Science and Catalysis, Vol. 84, eds. J. Weitkamp, H.G. Karge, H. Pfeifer and W. Hölderich (Elsevier, Amsterdam, 1994) p. 2327.

    Google Scholar 

  69. J.G. Highfield and J.B. Moffat, J. Catal. 88 (1984) 177.

    Google Scholar 

  70. H. Pfeifer, in:Acidity and Basicity of Solids, eds. J. Fraissard and L. Petrakis (Kluwer, Dordrecht, 1994) p. 255.

    Google Scholar 

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  1. Department of Chemistry and the Guelph-Waterloo Centre for Graduate Work in Chemistry, University of Waterloo, N2L3G1, Waterloo, Ontario, Canada

    S. Gao & J. B. Moffat

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  1. S. Gao
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Gao, S., Moffat, J.B. Isomerization of 1-butene on supported and unsupported metal-oxygen cluster compounds (heteropoly oxometalates). Catal Lett 42, 105–111 (1996). https://doi.org/10.1007/BF00814474

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