Aniline Methylation Over Modified Micro- And Mesoporous Catalysts

  • O. A. Ponomoreva
  • E. E. Knyazeva
  • V. V. Yuschenko
  • I.I. Ivanova
Part of the NATO Science Series book series (NAII, volume 69)

Abstract

Methylation of aniline is an industrially important process, aimed at the synthesis of mono-N-methylaniline (NMA), di-N-methylaniline (NNDMA) and toluidines which are useful raw materials for organic syntheses as well as important intermediates in the dye-stuff production and in the pharmaceutical and agrochemical industries. Up till now, industrial processes leading to these products are based on the application of corrosive liquid acids as catalysts [1,2] and should be replaced by environmentally more benign processes using solid catalysts such as oxides, clays and zeolites. It is known that alkylation of aniline may take place on acidic [3, 4, 5, 6] and on basic zeolites [7,8]. Moreover, this reaction was performed even on zeolites with redox properties [3,9,10]. A detailed study of reaction mechanisms over zeolite catalysts pointed to existence of two mechanistic pathways: on acidic catalysts, the reaction proceeds via a methanol dehydration leading to surface methoxy groups as intermediates of N- alkylation, while on basic and redox catalysts, the reaction pathway includes methanol dehydrogenation leading to formaldehyde species, alkylation of aniline with formaldehyde to give N-methyleneaniline and hydrogenation of N- methyleneaniline to N-methylaniline [11, 12]. In this contribution, aniline methylation has been studied on various molecular sieve catalysts. The effects of both catalyst structure and nature of active sites were investigated. The catalyst structures selected covered a broad range of pore sizes from 5.5 Å to 30 Å. The nature of the active sites was altered to obtain acidic, basic and redox materials.

Keywords

Clay Porosity Microwave Carbide Zeolite 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Battacharya, A.K., and Nandi, S.K. (1975), Ind. Eng. Chem. Prod. Res. Dev. 14, 162.CrossRefGoogle Scholar
  2. 2.
    Doraiswamy, L.K., Venkata Kirshman, G.R., and Mukharjee, S.P.(1981), Chem. Eng.88, 78.Google Scholar
  3. 3.
    Narayanan, S., and Deshpande, K.(2000), Appl. Catal A: General 199,1.CrossRefGoogle Scholar
  4. 4.
    Chen, P.Y., Chen, M.C., Chen, H.Y., Chang, N.S., and Chuang, T.K. (1986), in Murakami, Y., Iijima, A., and Ward, J.W.(eds). “New Developments in Zeolite Science and Technology, Stud. Surf. Sci Catal”, Elsevier, Amsterdam, Vol. 28, p. 739.Google Scholar
  5. 5.
    Narayanan, S., Durga Kumari, V., and Sudhakar Rao A. (1994), Appl. Catal. A: General 111,133.CrossRefGoogle Scholar
  6. 6.
    Park, Y. K., Park, K. Y., and Woo, S. I. (1994), Catal. Lett.26, 169.CrossRefGoogle Scholar
  7. 7.
    Hari Prasad Rao, P.R., Massiani, P., and Barthomeuf, D. (1995), Catal. Lett.31, 115.CrossRefGoogle Scholar
  8. 8.
    Hari Prasad Rao, P.R., Massiani, P., and Barthomeuf, D. (1994), inWeitkamp, J., Karge, H.G., Pfeifer, H.,and Hölderich, W., (eds.) “Zeolites and Related Microporous Materials: State of the Art 1994, Stud. Surf. Sci Catal.”, Elsevier, Amsterdam, Vol. 84, p. 1449Google Scholar
  9. 9.
    Narayanan, S., Deshpande, K., and Prasad, B.P. (1994), J. Mol Catal.88, L271.CrossRefGoogle Scholar
  10. 10.
    Narayanan, S. and Prasad, B.P. (1995), J. Mol Catal.96, 57.CrossRefGoogle Scholar
  11. 11.
    Wei Wang, Seiler, M, Ivanova, I.I., Weitkamp, J., and Hunger, M. (2001) In situ stopped-flow (SF) MAS NMR spectroscopy: A novel NMR technique applied for the study of aniline methylation on a solid base catalyst, Chem.Comm., in press.Google Scholar
  12. 12.
    Ivanova, I.I,. Pomakhina E.B,. Rebrov A.I, Hunger, M., Kolyagin Y.G., Weitkamp, J. (2001), Surface species formed during aniline methylation on zeolite HY investigated by in situMAS NMR spectroscopy, J.Catal., in pressGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2002

Authors and Affiliations

  • O. A. Ponomoreva
    • 1
  • E. E. Knyazeva
    • 1
  • V. V. Yuschenko
    • 1
  • I.I. Ivanova
    • 1
  1. 1.Department of Chemistry, Leninskie GoryMoscow State UniversityMoscowRussia

Personalised recommendations