금속인산화물에서의 3-피콜린의 가암모니아 산화반응

신채호; 장태선; 조득희; 이동구; 이영길

HWAHAK KONGHAK, Vol.35, No.2, 270-275, April, 1997

Export Citation

금속인산화물에서의 3-피콜린의 가암모니아 산화반응

Ammoxidation of 3-Picoline over Metal Phosphate Catalysts

신채호, 장태선, 조득희, 이동구, 이영길

초록

몰리브덴, 바나듐, 철, 티탄, 지르코늄을 각각 포함하는 금속인산화물을 수용액상에서 금속염과 인산의 반응으로 제조하였다. 제조된 금속인산화물은 X-선회절분석 및 열중량분석을 통해 상변이과정을 관찰하였다. 제조된 금속인산화물 촉매 중 몰리브덴인산화물이 3-피콜린의 가암모니아 산화반응에서 가장 높은 촉매활성을 나타냈다. 가암모니아 산화반응 후 몰리브덴인산화물 촉매는 인/몰리브덴(P/Mo)=0.5 촉매의 경우 X-선회절분석결과 (NH₄)₃PO₄·12MoO₃·xH₂O상이 검출되었고, P/Mo=1.0인 경우에는 MoOPO₄상이 관찰되었다. 반응에 있어서 3-피콜린의 전환율 증가에 따라 3-시아노피리딘의 선택도가 증가하였으며 동시에 아미드와 산의 선택도는 감소하였다.

Metal Phosphates containing respectively molybdenum, vanadium, iron, titanium and zirconium were prepared by the reaction with metal salt and phosphoric acid in the medium of water. Phase transformation of the metal phosphate was detected by X-ray diffraction and thermogravimetric analysis. Molybdenum, phosphate catalyst had the best catalytic activity in ammoxidation of 3-picoline. The solid phase (NH₄)₃PO₄·12MoO₃·xH₂O was detected by XRD analysis in the catalyst with P/Mo=0.5 atomic ratio and MoOPO₄ was observed in P/Mo=1.0 catalyst after ammoxidation for 24 hrs. The correlation between conversion of 3-picoline and selectivity of 3-cyanopyridine has the proportional relation. The increase of 3-cyanopyridine selectivity depends on the decrease of amide plus acid selectivity.

Keywords:Metal Phosphate Catalyst;3-Picoline;Ammoxidation;XRD;TGA

[References]

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[Referenced By]

[1] Suvorov BV, Int. Chem. Eng., 8, 588 (1968)

[2] Sant BR, Rao SB, Rao JR, Thakur RS, Praida KM, J. Sci. Ind. Res., 43, 543 (1984)

[3] Otamiral JC, Anderson A, Catal. Today, 3, 211 (1988)

[4] Ray S, Singh B, Choudhury A, Roy SK, Mukherjee PM, Ind. J. Technol., 21, 4619 (1983)

[5] Anderson A, J. Catal., 69, 465 (1981)

[6] Anderson A, Lundin ST, J. Catal., 65, 9 (1980)

[7] Covani F, Parrinello F, Trifiro F, J. Mol. Catal., 43, 716 (1987)

[8] Ito M, Tanaka H, Matsumoto A, Bull. Chem. Soc. Jpn., 41, 716 (1968)

[9] Abdelouakab FB, Olier R, Guilhaume N, Lefebre F, Volta JC, J. Catal., 134, 151 (1992)

[10] Bordes E, Courtine P, J. Catal., 57, 236 (1979)

[11] Hutchings GJ, Appl. Catal., 72, 1 (1991)

[12] Hodnett BK, Catal. Rev.-Sci. Eng., 27(3), 373 (1985)

[13] Barbaux Y, Dekiouk M, LeMaguer D, GerMember L, Huchette D, Grimblot J, Appl. Catal., 90, 51 (1990)

[14] Dekiouk M, Boisdron N, Pietrzyk S, Barbaux Y, Grimblot J, Appl. Catal., 90, 61 (1990)

[15] Vedrine JC, Millet JMM, Volta JC, Faraday Discuss. Chem. Soc., 87, 207 (1989)

[16] Clearfield A, Kalnins JM, J. Inorg. Nucl. Chem., 38, 849 (1976)

[17] Clearfield A, "Inorganic Ion Exchange Materials," CRC Press, Boca Raton, FL (1982)

[18] Othmer K, "Encyclopedia of Chemical Technology," 3rd Ed., John Wiley and Sons, New York, NY, 15, 684 (1981)