Research on Chemical Intermediates

, Volume 29, Issue 6, pp 575–587 | Cite as

Metal oxide-modified ZnO/SiO 2 catalysts for cyclo-dehydrogenation of ethylenediamine with propyleneglycol to 2-methylpyrazine

  • Ilnam Park
  • Youngwoo Rhee
  • Jeongho Lee
  • Yohan Han
  • Jongyeol Jeon
  • Hyungrok Kim
Article

Abstract

Metal oxide-modified ZnO /SiO2 catalysts were studied for the cyclo-dehydrogenation of ethylenediamine with propyleneglycol to 2-methylpyrazine at 633 K. The ZnO/SiO2 catalyst showed fairly good ethylenediamine conversion and quantitative propyleneglycol conversion with about 60 mol% of 2-methylpyrazine selectivity, which is due to the existence of large amount of unconverted intermediate, 2-methylpiperazine. Metal oxide (CuO, NiO, Co3O4)-modified ZnO/SiO2 catalysts were prepared to facilitate the dehydrogenation of 2-methylpiperazine to 2-methylpyrazine. About 82 mol% of 2-methylpyrazine selectivity was achieved on CuO and Co3O4 modified ZnO/SiO2 catalysts, with significant increases of pyrazine selectivity. The catalytic properties of the metal oxidemodified ZnO/SiO2 catalysts, pretreated with hydrogen gas as in the cyclo-dehydrogenation, were compared using the well-known probe reaction, the dehydrogenation/ dehydration of cyclohexanol to cyclohexanone or phenol/cyclohexene. The selectivities of pyrazine in the cyclo-dehydrogenation on the metal oxide-modified ZnO/SiO2 catalysts were correlated with the phenol selectivities of the probe reaction. It is proposed that the metallic site of catalyst is responsible for the formation of pyrazine from ethylenediamine dimerization. The improved 2-methylpyrazine yield on CuO/ZnO/SiO2 catalyst was explained by the proper adjustment of catalytic properties, which could be differentiated by the phenol selectivity in the cyclohexanol probe reaction. Thus, the large enhancement of 2-methylpiperazine dehydrogenation to 2-methylpyrazine and the suppression of excess pyrazine formation are supposed to occur on the metallic Cu formed in situ during the reaction during the cyclo-dehydrogenation of ethylenediamine with propyleneglycol.

2-METHYLPYRAZINE ETHYLENEDIAMINE PROPYLENEGLYCOL CYCLOHEXANOL DEHYDROGENATION CATALYST. 

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REFERENCES

  1. 1.
    K. Sato, Japan Patent No. 56, 479 (1976).Google Scholar
  2. 2.
    S. Yasuda, T. Niwa and Y. Shoji, Japan Patent No. 258,168 (1985).Google Scholar
  3. 3.
    G. V. Lsagulyants and K. M. Gitis (Eds), in: Catalysis of Organic Reactions, p. 443. Marcel Dekker, New York, NY (1998).Google Scholar
  4. 4.
    L. Forni, G. Stern and M. Gatti, Appl. Catal. A 29, 161 (1987).Google Scholar
  5. 5.
    L. Forni and R. Miglio (Eds), in: Heterogenous Catalysis and Fine Chemicals III, p. 329. Elsevier, Amsterdam (1993).Google Scholar
  6. 6.
    S. Yasuda, T. Niva and N. Asegava, Japan Patent No. 117,480 (1974).Google Scholar
  7. 7.
    R. Anand and B. S. Rao, Catal. Commun. 3, 29 (2002).Google Scholar
  8. 8.
    L. Forni and P. Pollesel, J. Catal. 130, 403 (1991).Google Scholar
  9. 9.
    T. Shoji, T. Nakaishi and M. Mikata, Japan Patent No. 225,543 (1996).Google Scholar
  10. 10.
    J. Lee, H. Baek, H. Shin, H. Kim and S. Hong, Korea Patent No. 9,882 (1997).Google Scholar
  11. 11.
    S. C. Roy, H. L. Prasad, P. Dutta, A. Bhattacharya, B. Singh, S. Kumar, S. Maharaj, V. K. Kaushik, S. M. Pillai and M. Ravindranathan, Appl. Catal. A 220, 153 (2001).Google Scholar
  12. 12.
    W. P. Dow, Y. P. Wang and T. J. Huang, J. Catal. 160, 155 (1996).Google Scholar
  13. 13.
    J. Xi, Z. Wang and G. Lu, Appl. Catal. A 225, 77 (2002).Google Scholar
  14. 14.
    W. J. Wang and Y. W. Chen, Appl. Catal. A 77, 223 (1991).Google Scholar
  15. 15.
    G. Jacobs, P. M. Patterson, Y. Zhang, T. Das, J. Li and B. H. Davis, Appl. Catal. A 233, 215 (2002).Google Scholar
  16. 16.
    H. E. Swift and J. E. Bozik, J. Catal. 12, 5 (1968).Google Scholar
  17. 17.
    J. T. Richardson and W. C. Lu, J. Catal. 42, 275 (1976).Google Scholar
  18. 18.
    Z. Paál, A. Péter and P. Tétényl, React. Kinet. Catal. Lett. 1, 121 (1974).Google Scholar
  19. 19.
    G. Cut and R. Jaeger, Chem. Eng. Sci. 37, 319 (1982).Google Scholar
  20. 20.
    L. Forni and R. Miglio (Eds), in: HeterogenousCatalysis and Fine Chemicals II, p. 367. Elsevier, Amsterdam (1991).Google Scholar

Copyright information

© VSP 2003 2003

Authors and Affiliations

  • Ilnam Park
  • Youngwoo Rhee
  • Jeongho Lee
  • Yohan Han
  • Jongyeol Jeon
  • Hyungrok Kim

There are no affiliations available

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