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Search / Korean Journal of Chemical Engineering
Korean Chemical Engineering Research,
Vol.50, No.2, 217-222, 2012
염기 촉매를 이용한 디메틸카보네이트 합성에서 ZnCl2 조촉매의 영향
Effect of ZnCl2 Co-catalyst in the Synthesis of Dimethyl Carbonate from Ethylene Carbonate and Methanol by Using Base Catalysts
김동우, 박문석, 김문일, 박대원
이산화탄소를 이용하여 디메틸카보네이트(DMC)를 제조하는 반응은 지구온난화 현상의 주요 원인으로 지적되는 이산화탄소의 효율적 전환 방법의 하나로 주목 받고 있다. DMC는 유독한 포스겐과 디메틸슬페이트를 대체하는 반응 매개체, 가솔린 연료 첨가제, 폴리카보네이트 수지의 전구체 등으로 다양하게 활용되고 있다. 본 연구에서는 에틸렌카보 네이트(EC)와 메탄올의 에스테르 교환반응에 의한 DMC의 제조 반응에 대하여 이온성 액체와 금속 촉매의 특성을 조사하였다. 촉매 스크리닝 실험 결과 [Choline][OH]와 [BMIm][OH]가 금속염인 MgO, ZnO, CaO보다 더 좋은 촉매 활성을 나타내었다. [Choline][OH] 촉매에 대해서 반응변수인 반응온도, MeOH/EC 몰비, 이산화탄소 압력이 반응에 미 치는 영향을 고찰하였다. 반응온도가 높고 MeOH/EC 몰비가 클수록 EC의 전화율이 증가하였다. 그러나 이산화탄소 압력의 영향에서는 1.34 MPa에서 최고의 DMC 수율을 나타내었고 그 이상의 압력에서는 DMC 수율이 오히려 감소하였다. ZnCl2를 조촉매로 사용한 경우 각각 촉매의 활성보다 더 높은 활성을 나타내어 시너지 효과가 관찰되었으며, 이것은 혼합촉매의 산-염기적 특성에 기인하는 것으로 판단된다.
The synthesis of dimethyl carbonate(DMC) is a promising reaction for the use of naturally abundant carbon dioxide. DMC has gained considerable interest owing to its versatile chemical reactivity and unique properties such as high oxygen content, low toxicity, and excellent biodegradability. In this study, the synthesis of DMC through the transesterification of ethylene carbonate(EC) with methanol was investigated by using ionic liquid and metal oxide catalysts. The screening test of different catalysts revealed that choline hydroxide ([Choline][OH]) and 1-n-butyl-3-methyl imidazolium hydroxide([BMIm][OH]) had better catalytic performance than metal salts catalysts such as MgO, ZnO and CaO. The effects of reaction parameters such as reaction temperature, MeOH/EC mole ratio, and carbon dioxide pressure on the reactivity of [Choline][OH] catalyst were discussed. High temperature and high MeOH/EC mole ratio were favorable for high conversion of EC. However, the yield of DMC showed a maximum when carbon dioxide pressure was 1.34 MPa, and then it decreased for higher carbon dioxide pressure. Zinc chloride(ZnCl2) was used as co-catalyst with the ionic liquid catalyst. The mixed catalyst showed a synergy effect on the EC conversion and DMC yield probably due to the acid-base properties of the catalysts.
Keywords: Ethylene Carbonate; Methanol; Dimethyl Carbonate; Ionic Liquid Catalyst
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