Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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Dimethyl Carbonate Synthesis by Methanol Oxidative Carbonylation

메탄올 산화 카르보닐화에 의한 디메틸카보네이트 합성

  • Nam, Jeong-Kwang (Environment & Research Center, Korea Research Institute of Chemical, Technology(KRICT)) ;
  • Cho, Deug-Hee (Environment & Research Center, Korea Research Institute of Chemical, Technology(KRICT)) ;
  • Suh, Jeong-Kwon (Environment & Research Center, Korea Research Institute of Chemical, Technology(KRICT)) ;
  • Kim, Seong-Bo (Environment & Research Center, Korea Research Institute of Chemical, Technology(KRICT))
  • 남정광 (한국화학연구원 환경자원연구센터) ;
  • 조득희 (한국화학연구원 환경자원연구센터) ;
  • 서정권 (한국화학연구원 환경자원연구센터) ;
  • 김성보 (한국화학연구원 환경자원연구센터)
  • Published : 2011.10.01
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Abstract

The synthesis of dimethyl carbonate by liquid phase oxidative carbonylation of methanol was studied under batch reaction system. Reaction factors such as effect on various metals, anion containing in copper catalyst, temperature, carbon monoxide and oxygen molar ratio and copper content were investigated. In particular $CuCl_2{\cdot}2H_2O$ showed the excellent of the methanol conversion 65.2%, DMC selectivity 96.6% reaction condition under 1.0 g, $150^{\circ}C$, MeOH/CO/$O_2$=0.2/0.215/0.05 (molar ratio). $CuCl_2$ led to corrosion of the reactor. Thus, a new catalyst system using supports was investigated to resolve these corrosion problem. Influence on various supports were examined and copper catalyst supported on zeolite Y showed the most excellent activity on the formation of dimethyl carbonate. The amount of Fe dissolved during the reaction using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometer) was compared with catalysts, calcined Cu/zeolite Y showed the lower value below 5% than $CuCl_2-2H_2O$.

회분식 고압반응기에서 메탄올 산화 카르보닐화 방법에 의한 디메틸 카보네이트 제조에 대하여 연구하였다. 다양한 금속의 영향과 구리촉매에 결합된 음이온 및 반응온도, 일산화탄소, 산소의 반응물 몰비, 구리촉매 함유량 등 여러 반응조건들을 검토하였다. 특히 $CuCl_2{\cdot}2H_2O$ 촉매가 1.0 g, $150^{\circ}C$, MeOH/CO/$O_2$=0.2/0.215/0.05(molar ratio) 반응조건에서 메탄올 전환율 65.2%, 선택도 96.6%로 좋은 활성을 보였다. $CuCl_2$는 반응기의 부식을 일으킨다. 이러한 문제점을 개선하기 위하여 DMC 제조에서 담체를 이용한 새로운 촉매시스템을 검토하였다. 여러 종류의 담체중 산성이 큰 제오라이트 Y를 담체로 사용한 경우 가장 활성이 우수하였다. ICP-AES(Inductively Coupled Plasma-Atomic Emission Spectrometer)를 이용해 반응기에 용출된 Fe 양을 비교하였을 때, 제오라이트를 담체로 사용하여 제조된 구리촉매는 $CuCl_2-2H_2O$ 촉매를 직접 사용한 경우에 비해 반응기로 용출되는 철의 양은 5% 이하이었다.

Keywords

References

  1. Richter, M., Fait, M. J. G., Eckelt, R., Schneider, M., Radnik, J. and Heidemann, D., "Gas-phase Carbonylation of Methanol to Dimethyl Carbonate on Chloride-free Cu-precipitated Zeolite Y at Normal Pressure," J. Catal., 245, 11-24(2007). https://doi.org/10.1016/j.jcat.2006.09.009
  2. Keller, N., Rebmann, G. and Keller, V., "Catalysts, Mechanisms and Industrial Processes for the Dimethylcarbonate Synthesis," J. Mol. Catal. A-Chem., 35, 1-18(2002).
  3. Ono, Y., "Catalysis in the Production and Reactions of Dimethyl Carbonate, an Environmentally Benign Building Block," Appl. Catal. A: Gen., 155, 133-166(1997). https://doi.org/10.1016/S0926-860X(96)00402-4
  4. Delledonne, D., Rivetti, F. and Romano, U., "Developments in the Production and Application of Dimethylcarbonate," Appl. Catal. A: Gen., 221, 241-251(2001). https://doi.org/10.1016/S0926-860X(01)00796-7
  5. Romano, U., Tesel, R., Cipriani, G. and Micucci, L., "Method for the Preparation of Esters of Carbonic Acid," U.S Patent No. 4,218,391(1980).
  6. Miyazaki, H., Shiomi, Y., Fujitsu, S. and Masunaga, K., "Process for the Preparation of Oxalic Acid Diesters," U.S Patent No. 4,384,133(1983).
  7. Curnutt, G. L., "Dihydrocarbyl Carbonates Using a Nitrogen-containing Coordination Compound Supported on Activated Carbon," U.S Patent No. 4,625,044(1986).
  8. Zhang, Y. and Bell, A. T., "The Mechanism of Dimethyl Carbonate Synthesis on Cu-exchanged Zeolite Y," J. Catal., 255, 153-161 (2008). https://doi.org/10.1016/j.jcat.2008.01.033
  9. Anderson, S. A., Manthata, S. and Root, T. W., "The Decomposition of Dimethyl Carbonate Over Copper Zeolite Catalysts," Appl. Catal. A: Gen., 280, 117-124(2005). https://doi.org/10.1016/j.apcata.2004.10.003
  10. Zheng, X. and Bell, A. T., "A Theoretical Investigation of Dimethyl Carbonate Synthesis on Cu-Y Zeolite," J. Phys. Chem. C, 112, 5043-5047(2008). https://doi.org/10.1021/jp711415g
  11. Anderson, S. A. and Root, T. W., "Investigation of the Effect of Carbon Monoxide on the Oxidative Carbonylation of Methanol to Dimethyl Carbonate over Cu+X and Cu+ZSM-5 Zeolites," J. Mol. Catal. A-Chem., 220, 247-255(2004). https://doi.org/10.1016/j.molcata.2004.06.006
  12. Zhong, L., Ruiyu, W., Huayan, Z. and Kechang, X., "Preparation of CuY Catalyst Using $CuCl_2$ as Precursor for Vapor Phase Oxidative Carbonylation of Methanol to Dimethylcarbonate," Fuel, 89, 1339-1343(2010). https://doi.org/10.1016/j.fuel.2009.10.021

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