Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
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Synthesis of Dimethyl Carbonate from Methanol and Supercritical Carbon Dioxide over K2CO3/ZrO2 Catalysts

메탄올과 초임계 이산화탄소로부터 K2CO3/ZrO2 촉매를 이용한 디메틸카보네이트 (Dimethyl Carbonate) 합성

  • Hong, Seung Tae (Department of Chemical & Biomolecular Engineering, Sogang University) ;
  • Park, Hyung Sang (Department of Chemical & Biomolecular Engineering, Sogang University) ;
  • Lim, Jong Sung (Department of Chemical & Biomolecular Engineering, Sogang University) ;
  • Yoo, Ki-Pung (Department of Chemical & Biomolecular Engineering, Sogang University)
  • 홍승태 (서강대학교 화공생명공학과) ;
  • 박형상 (서강대학교 화공생명공학과) ;
  • 임종성 (서강대학교 화공생명공학과) ;
  • 유기풍 (서강대학교 화공생명공학과)
  • Received : 2008.01.02
  • Accepted : 2008.04.14
  • Published : 2008.06.30
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Abstract

The synthesis of dimethyl carbonate (DMC) from methanol and supercritical carbon dioxide over $K_2CO_3/ZrO_2$ catalysts have been studied. The catalysts were prepared by impregnating $ZrO_2$ with an aqueous $K_2CO_3$ solution. The optimum calcination temperature to disperse K species on the $ZrO_2$ surface was found to be 673 K. Monoclinic $ZrO_2$ was not active, as itself, for the DMC production. However, when the $K_2CO_3$ was impregnated on the $ZrO_2$, the catalytic performance was improved. Besides the catalyst, $CH_3I$ was used as a promoter. The $CH_3I$ promoter as well as the $K_2CO_3/ZrO_2$ catalyst was found to take an important role to improve the production of DMC. The optimum quantities for the catalyst and the promoter were estimated. The effect of the catalyst and the promoter for the DMC synthesis from methanol and supercritical carbon dioxide was investigated and the reaction mechanism was proposed.

메탄올과 초임계 이산화탄소를 이용하여 $K_2CO_3/ZrO_2$ 촉매상에서 디메틸 카보네이트(dimethyl carbonate, DMC)를 합성하였다. $K_2CO_3$를 함침법으로 지르코니아에 담지시켜 촉매를 제조하였다. 673 K에서 소성했을 때, 칼륨 성분이 지르코니아 표면에 최대한 고르게 분산되었다. 단사정계(monoclinic)의 결정 구조를 갖는 지르코니아 자체는 DMC 생성에 대한 활성이 없었지만 $K_2CO_3$를 담지시켰을 경우 촉매 성능이 향상되었다. 촉매 외에 촉진제로 $CH_3I$를 사용하였다. 촉매와 촉진제의 사용은 DMC 생성을 향상시키는데 중요한 역할을 하였다. 촉매와 촉진제를 적정량 사용하였을 경우 DMC 생성량을 향상시킬 수 있었지만 과량으로 사용했을 경우 DMC 생성 외에 다른 부반응에도 영향을 미쳤다. 메탄올과 초임계 이산화탄소로부터 DMC 생성에 대한 촉매와 촉진제의 영향 및 그 반응 메카니즘을 제시하였다.

Keywords

Acknowledgement

Supported by : 서강대학교

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