This chapter describes some aspects of the reactivity of POMs as catalysts for the selective oxidation of isobutane to methacrylic acid. If developed at the industrial level, this reaction could represent an alternative to the current production method via the ACH route. P/Mo Keggin-type POMs are active and selective catalysts for this reaction.

The following considerations are relevant:

1. The catalytic performance depends a great deal on the reaction conditions, and specifically on the isobutane-to-oxygen ratio in the feed. Usually isobutane-rich conditions are claimed to be more selective, and the reason for this is that under these conditions the operative POM is a partially reduced one, and a more reduced POM is intrinsically more selective than a fully oxidized one. High isobutane partial pressures help to improve the selectivity, avoiding further oxidation of methacrylic acid.

2. The presence of transition metal ions as cations for the Keggin polyanion is necessary in order to develop an active and selective catalyst.

Future perspectives in this field, and opportunities for the commercialization of the process of isobutane oxidation, depend on the development of more active and stable POMs-based catalysts.


2. Abe, T. in Science and Technology in Catalysis 1998, Kodansha, Tokyo, 1999, p. 461.

3. Krieger, H.; Kirch, L. S. U.S. Patent 4,260,822 (1981), assigned to Rohm and Haas Company.

4. Yamamatsu, S.; Yamaguchi, T. European Patent 425,666 (1989), assigned to Asahi Chemical, Company; Japanese Patent 02,042,032 (1990).

5. Ernst, B.; Haeberle, T.; Siegert, H.J.; Gruber, W. DE Patent 42 40 085 A1 (1994), assigned to Rohm GmbH Chemische Fabrik; U.S. Patent 5,380,932 (1995).

6. Matsuura, I.; Aoki, Y. Japanese Patent 05,331,085 (1996), assigned to Nippon Catalytic Chemical Industry, CA 121:107989 (1996).

7. Nagai, K.; Nagaoka, Y.; Sato, H.; Ohsu, M. European Patent 418,657 (1990), assigned to Sumitomo Chemical Company.

8. Nagai, K.; Nagaoka, Y.; Ishii, N. European Patent 495,504 A2 (1992), assigned to Sumitomo Chemical Company.

9. Kuroda, T.; Okita, M. Japanese. Patent 04-128,247 (1991), assigned to Mitsubishi Rayon Company.

10. Ushikubo, T. Japanese Patent 06,172,250 (1992), assigned to Mitsubishi Chemical Industry.

11. Yamamatsu, S.; Yamaguchi, T. U.S. Patent 5,191,116 (1993), assigned to Asahi Kasei Kogyo Kabushiki Kaisha.

12. Kawakami, K.; Yamamastu, S.; Yamaguchi, T. Japanese Patent 03,176,438 (1991), assigned to Asahi Chemical Industry Company.

13. Imai, H.; Nakatsuka, M.; Aoshima, A. Japanese Patent 62,132,832 (1987), assigned to Asahi Chemical Industry Company.

14. Mizuno, N.; Tateishi, M.; Iwamoto, M. Appl. Catal., A: General, 1994, 118, L1.

15. Mizuno, N.; Tateishi, M.; Iwamoto, M. J. Catal., 1996, 163, 87.

16. Mizuno, N.; Suh, D.-J.; Han, W.; Kudo, T. J. Mol. Catal. A, 1996, 114, 309.

17. Mizuno, N.; Han, W.; Kudo, T. J. Catal., 1998, 178, 391.

18. Inumaru, K.; Ono, A.; Kubo, H.; Misono, M. J. Chem. Soc., Faraday Trans., 1998, 94, 1765.

19. Min, J. S.; Mizuno, N. Catal. Today, 2001, 66, 47.

20. Ueda, W.; Suzuki, Y.; Lee, W.; Imaoka, S. Stud. Surf. Sci. Catal., 1996, 101, 1065.

22. Li, W.; Oshihara, K.; Ueda, W. Appl. Catal., A: General, 1999, 182, 357.

23. Paul, S.; Le Courtois, V.; Vanhove, D. Ind. Eng. Chem., Res., 1997, 36, 3391.

24. Sultan, M.; Paul, S.; Vanhove, D. Stud. Surf. Sci. Catal., 1999, 122, 283.

25. Sultan, M.; Paul, S.; Fournier, M.; Vanhove, D. Appl. Catal. A, 2004, 259, 141.

26. Langpape, M.; Millet, J. M. M.; Ozkan, U. S.; Boudeulle, M. J. Catal., 1999, 181, 80.

27. Langpape, M.; Millet, J. M. M.; Ozkan, U. S.; Delichere, P. J. Catal., 1999, 182, 148.

28. Langpape, M.; Millet, J. M. M. Appl. Catal. A, 2000, 200, 89.

29. Cavani, F.; Etienne, E.; Favaro, M.; et al. Catal. Lett., 1995, 32, 215.

30. Busca, G.; Cavani, F.; Etienne, E.; et al. J. Molec. Catal., 1996, 114, 343.

31. Cavani, F.; Etienne, E.; Hecquet, G.; et al. in Catalysis of Organic Reactions, Malz, R. E. (Ed.) Marcel Dekker, New York, 1996, p. 107.

32. Cavani, F.; Mezzogori, R.; Pigamo, A.; Trifiro, F. C.R. Acad. Sci. Paris, Seerie IIc, Chimie, 2000, 3, 523.

33. Cavani, F.; Mezzogori, R.; Pigamo, A.; Trifiro, F. Chem. Eng. J., 2001, 82, 33.

34. Cavani, F.; Mezzogori, R.; Pigamo, A.; Trifiro, F. Stud. Surf. Sci. Catal., 2001, 140, 141.

35. Cavani, F.; Mezzogori, R.; Pigamo, A.; Trifiro, F. Topics Catal., 2003, 23, 119.

36. Etienne, E.; Cavani, F.; Mezzogori, R. et al. Appl. Catal. A, 2003, 256, 275.

37. Knapp, C.; Ui, T.; Nagai, K.; Mizuno, N. Catal. Today, 2001, 71, 111.

38. Schindler, G.-P.; Knapp, C.; Ui, T.; Nagai, K. Top. Catal., 2003, 22, 117.

39. Schindler, G.-P.; Ui, T.; Nagai, K.; Appl. Catal. A, 2001, 206, 183.

40. Deng, Q.; Jiang, S.; Cai, T.; et al. J. Mol. Catal. A, 2005, 229, 165.

41. Khoobiar, S.; U.S. Patent 4,535,188 (1985), assigned to Halcon SD.

42. Brockwell, J. L.; Warren, B. K.; Young, M. A.; et al. WO Patent 97-36489 (1997), assigned to Union Carbide Chemicals and Plastics.

43. Hefner, W.; Machhammer, O.; Neumann, H. P.; et al. U.S. Patent 5,705,684 (1998), assigned to BASF.

44. Cavani, F.; Tanguy, A.; Trifiro, F.; Koutyrev, M. J. Catal., 1998, 174, 231.

45. Jalowiecki-Duhamel, L.; Monnier, A.; Barbaux, Y.; Hecquet, G. Catal. Today, 1996, 32, 237.

46. Albonetti, S.; Cavani, F.; Trifiro, F.; et al. J. Catal., 1994, 146, 491.

47. Marosi, L.; Cox, G.; Tenten, A.; Hibst, H. J. Catal., 2000, 194, 140.

48. Mestl, G.; Ilkehans, T.; Spielbauer, D.; et al. Appl. Catal A, 2001, 210, 13.

49. Jentoft, F. C.; Klokishner, S.; Krohnert, J.; et al. Appl. Catal. A, 2003, 256, 291.

50. Marchal-Roch, C.; Bayer, R.; Moisan, J. F.; et al. Topics Catal., 1996, 3, 407.

51. Ilkehans, Th.; Herzog, B.; Braun, Th.; Schlögl, R. J. Catal., 1995, 153, 275.

Was this article helpful?

0 0
Growing Soilless

Growing Soilless

This is an easy-to-follow, step-by-step guide to growing organic, healthy vegetable, herbs and house plants without soil. Clearly illustrated with black and white line drawings, the book covers every aspect of home hydroponic gardening.

Get My Free Ebook

Post a comment