Oxidation of 3- and 4-Methylpyridines on Vanadium-Anatase and Vanadium-Rutile Catalysts

Authors

  • O. K. Yugay “A.B. Bekturov Institute of Chemical Sciences” JSC, 106, Sh. Ualikhanov str., Almaty, Kazakhstan
  • T. P. Mikhailovskaya “A.B. Bekturov Institute of Chemical Sciences” JSC, 106, Sh. Ualikhanov str., Almaty, Kazakhstan
  • D. Kh. Sembaev “A.B. Bekturov Institute of Chemical Sciences” JSC, 106, Sh. Ualikhanov str., Almaty, Kazakhstan
  • P. B. Vorobyev “A.B. Bekturov Institute of Chemical Sciences” JSC, 106, Sh. Ualikhanov str., Almaty, Kazakhstan

DOI:

https://doi.org/10.18321/ectj132

Abstract

Heterogeneous catalytic vapor-phase oxidation of methylpyridines is "green", the most simple and perspective method for obtaining pyridinecarboxylic acids. Vanadium-titanium catalysts have a wide application in some important industrial processes of oxidation. Oxidation of 3-and 4-methylpyridine on vanadium-titanium catalysts has been investigated and for its preparation various titanium crystal modifications were used. Characterization of the catalysts was carried out by using the X-ray diffraction, N2-adsorbtion and thermal dissociation of V2O5. It was found that the use of anatase type of TiO2 with a higher BET surface area enhances the activity of the vanadium-titanium catalyst extremely. XRD-characterization of catalysts demonstrated that the only V2O5 and anatase or V2O5 and rutile phase was detected. It was established that the use of titanium dioxide of crystal modifications of anatase increases on the order of the dissociation rate V2O5. It was shown that vanadium-titanium catalysts' activity and selectivity in investigated processes depends on TiO2 crystal modifications.V2O5-anatase is more active and selective in formation of pyridine carboxylic acids. V2O5-rutile in the process of oxidation of 4-methylpyridine on the catalyst forms the mixture of isonicotinic acid and its aldehyde. Connection between the dissociation rate of V2O5 in catalysts of V2O5-anatase and V2O5-rutile and their activity in isomeric methylpyridines oxidation was established. High surface area, anatase structure of titanium are the key parameters determining the activity and selectivity of vanadium-titanium oxidation catalysts.

References

1. Lebedev N.N. Chemistry and technology of the basic organic and petrochemical synthesis. Chemistry, Moscow, USSR, 1988, p. 592.

2. Suvorov B.V. Ammoxidation of organic compounds. Nauka, Alma-Ata, 1971, p. 209.

3. G.C. Bond. Preparation and properties of vanadium/titanium monolayer catalysts, Appl. Catal. A-Gen., 157, 91-103 (1997).

4. Lawrie L. Handbook of Industrial Catalysts. Springer, 2011, p. 490.

5. D. Srinivasa, W.F. Hölderich, S. Kujathb, M.H. Valkenbergb, T. Rajaa, L. Saikiaa, R. Hinzeb, V. Ramaswamya. Active sites in vanadium/titanium catalysts for selective aerial oxidation of ȕ-picoline to nicotinic acid // J. Catal., 259 (2), 165-173 (2008).

6. S.K. Maurya, P. Patil, S.B. Umbarkar, M.K. Gurjar, M. Dongare, S. Rudiger, E. Kemnitz, Vapor phase oxidation of 4-fluorotoluene over vanadium-titanium catalyst // J. Mol. Cat. AChem., 234(1-2), 51-57 (2005).

7. A. Gervasini, P. Carniti, J. Keränen, L. Niinistö, A. Auroux, Surface characteristics and activity in selective oxidation of o-xylene of supported V2O5 catalysts prepared by standard impregnation and atomic layer deposition, Catal. Today, 96, 187-194 (2004).

8. D.A.H. Hanaor, C.C. Sorrell. Review of the anatase to rutile phase transformation // J. Mater. Sci., 46, 855-874 (2011).

9. G.I. Golodets, I.T. Chashechnikova, L.G. Svintsova, V.M. Vorotyntsev, V.V. Borovik, Influence of crystal modification of TiO2 on catalytic properties of Ni-TiO2 contacts for Fisher-Tropsch synthesis, RKCL, 34, 267-272 (1987).

10. G.I. Golodets, L.N. Raevskaia, L.G. Svintsova, Oxidation of toluene on rutile and anatase, Theoret. and experim. Chemistry, 3, 384, (1987).

11. D.Kh. Sembaev, L.I. Saurambaeva, B.V. Suvorov, Kh.T. Suleimanov. The connection between the phase composition and the catalytic action of vanadium-titanium oxide contacts reactions of vapor-phase oxidation of o-xylene. Kinetics and Catalysis, 20, 750-755 (1979).

12. O.K. Yugay, D.Kh. Sembaev. Oxidation of 2- methyl-5-ethylpyridine on different crystal modifications of TiO2, Izv. Ministerstva nauki - Akademii nauk RK, ser. khim., 4, p. 9-11 (1998).

13. B.V. Suvorov, A.D. Kagarlitsky, Kh. Sembaev, I.S. Kolodina, A.I. Loiko. US Patent 3799888 (1974). Method of preparing a catalyst of vanadium-titanium oxides for vapor phase oxidation and oxidizing ammonolysis of aromatic and heterocyclic compounds.

14. Margolis L.Ya. Heterogeneous catalytic oxidation of hydrocarbons. Chemistry, Moscow, USSR, 1977, p. 326.

15. K. Mori, A. Miyamoto, Y. Murakami, Promoting effect of TiO2 (anatase) support on the activity of V2O5 for the oxidation of ethylene, Z. Phys. Chem., 131, 251–254 (1982).

16. M. Gasior, I. Gasior, B. Grzybowska, o-Xylene oxidation on the V2O5- TiO2 oxide system. I.Dependence of catalytic properties on the modification of TiO2, Appl. Catal., 10, 87-100 (1984).

Downloads

Published

2012-11-15

How to Cite

Yugay, O. K., Mikhailovskaya, T. P., Sembaev, D. K., & Vorobyev, P. B. (2012). Oxidation of 3- and 4-Methylpyridines on Vanadium-Anatase and Vanadium-Rutile Catalysts. Eurasian Chemico-Technological Journal, 14(4), 337–342. https://doi.org/10.18321/ectj132

Issue

Vol. 14 No. 4 (2012)

Section

Articles

License

You are free to: Share — copy and redistribute the material in any medium or format. Adapt — remix, transform, and build upon the material for any purpose, even commercially.

Eurasian Chemico-Technological Journal applies a Creative Commons Attribution 4.0 International License to articles and other works we publish.

Subject to the acceptance of the Article for publication in the Eurasian Chemico-Technological Journal, the Author(s) agrees to grant Eurasian Chemico-Technological Journal permission to publish the unpublished and original Article and all associated supplemental material under the Creative Commons Attribution 4.0 International license (CC BY 4.0).

Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI.