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Language: korean

Conflict of Interest: In relation to this article, we declare that there is no conflict of interest.

Publication history: Received April 24, 2017
Accepted August 18, 2017

This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/bync/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

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아닐린과 메탄올의 산화 카르보닐화에 의한 Methyl N-phenyl carbamate 제조 연구

Study on Preparation of Methyl N-Phenyl Carbamate by Oxidative Carbonylation of Aniline and Methanol

노종선^{1 2} 이관영¹ 김태순² 장태선² 윤병태² 김성보^2†

Jong-Seon Roh^{1 2} Kwan-Young Lee¹ Tae-Soon Kim² Tae-Seon Chang² Byung-Tae Yoon² Seong-Bo Kim^2†

¹고려대학교 화공생명공학과, 02841 서울특별시 성북구 안암로 145 ²한국화학연구원 온실가스자원화연구그룹, 34114 대전 유성구 가정로 141

¹Department of Chemical & Biological Engineering, Korea University Seoul Campus, 145, Anam-ro, Seongbuk-gu, Seoul, 02841, Korea ²Invironment & Resource Research Center, Korea Research Institute of Chemical Technology (KRICT), 141, Gajeong-ro, Yuseong-gu, Daejeon, 34114, Korea

sbkim@krict.re.kr

Korean Chemical Engineering Research, February 2018, 56(1), 119-124(6), 10.9713/kcer.2018.56.1.119 Epub 2 February 2018

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Abstract

아닐린과 메탄올의 산화 카르보닐화 방법에 의한 Methyl N-phenyl carbamate 제조는 기존의 포스겐을 사용하는 폴리머의 단량체 생산공정을 대체할 수 있는 환경 친화적인 공정으로 많은 관심을 가지고 있다. 본 연구에서는 담지체로 Y-zeolite, SiO2, Al2O3를 사용하여 불균일화 촉매를 제조하였고, 제조 된 불균일화 촉매를 이용하여 아닐린과 메탄올로부터 산화 카르보닐화 연속운전을 시도하였다. 회분식반응기를 이용하여 담지체를 결정하였으며, 담지된 palladium 촉매를 이용하여 조촉매의 영향과 반응온도, 반응압력 등 여러 반응최적조건을 확립하였다. 최적의 반응조건 MPC의 수율은 98.6%였으며, 반응속도론적 연구를 수행하였다. 각 반응온도의 반응속도상수로부터 얻어진 활성화 에너지는 각각 E=82.38kJ/mol, E=66.20 kJ/mol 이었다. 또한 확립된 반응조건에서 장시간 연속운전을 수행하여 카바메이트 공정 개발을 위한 기초자료를 구하였다.

The production of methyl N-phenyl carbamate by an oxidative carbonylation method of aniline and methanol is of great interest as an environmentally friendly process that can replace the monomer production process of a polymer produce using conventional phosgene. In this study, heterogeneous catalysts were prepared by using Y-zeolite, SiO2, Al2O3 as support, and oxidative carbonylation continuous operation from aniline and methanol was attempted using the prepared heterogeneous catalyst. Batch reactor was used to determine the support, and various reaction conditions such as reaction temperature, reaction pressure, and effect of promoter were established using palladium catalyst. A reaction kinetics study was conducted under optimum reaction conditions. The basic data for carbamate process development were obtained by performing continuous operation for a long time under established reaction condition.

Keywords

Methyl N-phenylcarbamate Oxidative carbonylation of aniline and methanol Pd/HY-zeolite Promoter NaI

References

Zhu GY, Li HQ, Cao Y, Liu HT, Li XT, Chen JQ, Tang Q, Ind. Eng. Chem. Res., 52(12), 4450 (2013)
Uriz P, Serra M, Salagre P, Castillon S, Claver C, Fernandez E, Tetrahedron Lett., 43, 1673 (2002)
Kim HS, Kim YJ, Lee H, Lee SD, Chin CS, J. Catal., 184(2), 526 (1999)
Wan BS, Liao SJ, Yu DR, Appl. Catal. A: Gen., 183(1), 81 (1999)
Chen B, Chuang SSC, J. Mol. Catal. A-Chem., 195(1-2), 37 (2003)
Toochinda P, Chuang SSC, Ind. Eng. Chem. Res., 43(5), 1192 (2004)
Ragaini F, Gasperini M, Cenini S, Arnera L, Caselli A, Macchi P, Casati N, Chem. Eur. J., 15, 8064 (2009)
Krogul A, Litwinienko G, J. Mol. Catal. A-Chem., 407, 204 (2015)
Leung TW, Dombek BDJ, Chem. Soc. Chem. Commun. 205-206(1996).
Alper H, Hartstock FW, J. Chem. Soc., Chem. Commun.1141-1142(1985).
Fukuoka S, Chono M, Kohno M, J. Org. Chem., 49, 1458 (1984)
Chen LJ, Ming FM, Li GX, Xiang, Kinet. Catal., 51, 672 (2010)
Gupte SP, Choudhari RV, J. Catal., 114, 246 (1988)