OXIDATIVE AMMONOLYSIS OF 4-METHYLPYRIDINE ON OXIDE VANADIUM-TITANIUM-ZIRCONIUM CATALYST MODIFIED BY TIN AND TUNGSTEN OXIDES

Abstract

Catalysts based on vanadium pentoxide modified by Ti, Sn, Zr and W oxides were tested in the oxidative ammonolysis of 4-methylpyridine. The role of the main process parameters such as temperature, the ratio of the initial components in the conversion of the methyl group to the nitrile one, and the optimal conditions for the oxidative ammonolysis of 4-methylpyridine were determined. It is determined that the V-Ti-Zr-O-catalyst and the sample containing 9% of tungsten oxide are superior in catalytic activity to the V-Ti-Zr-Sn-O contact. Conditions that ensure a high selectivity for the formation of 4-cyanopyridine were found. The highest yield of the target product (85-86%) was obtained on V-Ti-Zr-W-O at 270 °C, and the yield of 4-cyanopyridine was 87.5% at 310° C on the V-Ti-Zr-Sn-O catalyst. The phase composition and structural changes occurring in modified vanadium oxide catalysts have been studied. It is determined that mixed V-Ti-Zr-Sn-O and V-Ti-Zr-W-O catalysts contain ZrV2O7, the monoclinic modification of ZrO2 (baddeleyite), TiO2 (anatase), SnO2, WO3, and V2O5. In catalysts, it can exist in small amounts as a separate VO2 phase. The V-Ti-Zr-W-O catalyst showed the best catalytic properties. It has highactivity and selectivity towards 4-cyanopyridine.

References

[1] Suvorov B.V. Oxidative ammonolysis of organic compounds. Alma-Ata: “Science” of the Kazakh SSR, 1971. 210 p.

[2] Yakhontov L.N., KarpmanYa.S. Coke-chemical β-picolinic fraction as a complex raw ma-terial in the production of heterocyclic drugs // Chem. Heterocycl. Compd. 1981. No. 4. P. 435-447.

[3] Vorobyev P.B., Gabdrakipov V.Z., Mikhailovskaya T.P., Sembaev D.Kh. Reactivity of isomeric picolines under conditions of oxidative ammonolysis on a vanadium oxide catalyst // Russian Journal of General Chemistry. 2001. Vol. 71, No. 4. Р. 605-607. Doi 10.1023/A:1012395504813

[4] Suvorov B.V., Mikhailovskaya T.P. Synthesis of 4-cyanopyridine by oxidative ammo-nolysis of 4-picoline on vanadium-titanium-tin catalyst // Russian Journal of Applied Chemistry. 1995. Vol. 68, No. 2. P. 275-277.

[5] Kulkarni S.J., Ramachandra R.R., Subrahmayam M., Farsinavis S., Kanta R.P., Rama R.A.V. Oxidation and ammoxidation of 4-picoline over vanadium-silico-aluminophosphate catalysts // Indian J. of Chem. Sect. A. 1996. Vol. 35, No. 9. P. 740-745.

[6] Jacques C. Vedrine. Metal Oxides in Heterogeneous Catalysis. 2018. 618 p. https://doi.org/10.1016/C2016-0-01790-4

[7] Martin A., Lücke B. Ammoxidation and Oxidation of Substituted Methyl Aromatics on Vanadium-containing Catalysts // Catalysis Today. 2000. Vol. 57, No. (1-2). Р. 61-70. DOI: 10.1016/S0920-5861(99)00309-0

[8] Mikhailovskaya T.P., Yugay O.K., Chukhno N.I., Sembaev D.Kh. Oxidative Ammonolysis of 3- and 4-Pyridines on Vanadium Oxide Catalysts Modified with Titanium and Tin Oxides // Russian Journal of Applied Chemistry. 2012. Vol. 85, No. 2. P. 191-195.

[9] Glubokovskikh L.K., Mikhailovskaya T.P., Suvorov B.V. Nitriles of picolinic and isonicotinic acids, their synthesis and some aspects of practical use // Russian Journal of Applied Chemistry. 1999. Vol. 72. No. 7. P. 1139-1142.

[10] Yoshinori Goto, Ken-ichi Shimizu, Toru Murayama, Wataru Ueda. Hydrothermal synthesis of microporous W-V-O as an efficient catalyst for ammoxidation of 3-picoline // Appl. Catal. A General. 2015. 509. DOI: 10.1016/j.apcata.2015.10.011

[11] Burch R. Zirconium in Catalysis – Its Uses and Potential // England: University of Liverpool, 1987. 26 p.

[12] Chary K.V.R., Kishan G., Narayana K.V., Bhaskar T. Ammoxidation of 3-Picoline to Nico-tinonitrile over Highly Dispersed V2O5/ZrO2 Catalysts // J. Chem. Research (S). 1998. P. 314-315.

[13] Sembaev D.Kh., Ivanovskaya F.A., Pochtennaya V.M.. Catalysts for Alkylbenzene and Alkylpyridine Ammoxidation // Eurasian Chem.Tech. Journal. 2000. No. 2. P. 113-116.

[14] Sembaev D.Kh., Mikhailovskaya T.P., Serebryanskaya A.P.. Oxidative ammonolysis of 4-methylpyridine on oxide vanadium-titanium-zirconium catalyst // Izvestiya MES RK, NAS RK. Ser. chem. 2003. No. 6. P. 89-94.