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메탄올 카르보닐화에 의한 메틸포메이트 합성의 반응속도론과 촉매비활성화

Kinetics and Catalyst Deactivation for Methyl Formate Synthesis by Methanol Carbonylation

HWAHAK KONGHAK, June 1994, 32(3), 317-324(8), NONE
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Abstract

메탄올 카르보닐화반응에 의한 메틸포메이트 합성에서의 반응속도론과 촉매의 비활성화에 대하여 연구하였다. 알칼리 메톡사이드를 촉매로한 액상반응에서 반응은 빠르게 평형에 도달하며, 메틸포메이트에 대한 선택성은 100%에 근접하였다. 반응속도는 반응물인 메탄올 및 일산화탄소에 각각 1차의 반응치수를 보였으며, 각각의 알칼리 금속에 따른 반응속도는 K+>Na+>Li+순이었다. 반응중 중간활성체는 alcoholate이온으로 생각하였으며, 이를 기초로 전재한 속도론은 실험결과와 일치함을 알 수 있었다. 수분과 이산화탄소가 반응에 미치는 영향은 심각하였으며, 이러한 촉매독이 촉매량보터 당량비 이상으로 투입될 경우 촉매는 거의 모든 활성을 상실하였다.
Kinetics and catalyst deactivation have been studied for methyl formate synthesis by methanol carbonylation. In a liquid phase reaction, alkali catalysts drove the methanol carbonylation rapidly to equilibrium and showed almost 100% selectivity to methyl formate. A kinetic study showed that the reaction was of first order both in methanol and CO concentrations. The rate depended on alkali metal of the catalyst in the order, K>Na>Li. A rate equation was derived from a mechanism which assumed that alcoholate ion was the active catalytic intermediate. The equation fitted the experimental data satisfactorily. The catalyst was indeed sensitive to the small amount of H2O or CO2 added to the reaction mixture. It was almost completely deactivated when more than a stoichiometric amount of H2O or CO2 relative to the amount of the catalyst was added.

Keywords

References

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