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Reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite: a combined DFT/experimental study

机译：二甲醚羰基化与丝光沸石上乙酸甲酯的反应机理：联合DFT /实验研究

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The reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite was studied theoretically with periodic density functional theory calculations including dispersion forces and experimentally in a fixed bed flow reactor at pressures between 10 and 100 bar, dimethyl ether concentrations in CO between 0.2 and 2.0%, and at a temperature of 438 K. The theoretical study showed that the reaction of CO with surface methyl groups, the rate-limiting step, is faster in the eight-membered side pockets than in the twelve-membered main channel of the zeolite; the subsequent reaction of dimethyl ether with surface acetyl to form methyl acetate was demonstrated to occur with low energy barriers in both the side pockets and in the main channel. The present analysis has thus identified a path, where the entire reaction occurs favourably on a single site within the side pocket, in good agreement with previous experimental studies. The experimental study of the reaction kinetics was consistent with the theoretically derived mechanism and in addition revealed that the methyl acetate product inhibits the reaction - possibly by sterically hindering the attack of CO on the methyl groups in the side pockets.
机译：通过周期性密度泛函理论计算，包括分散力，并在固定床流动反应器中于10至100 bar的压力下，在CO中的二甲醚浓度为0.2至2.0％的条件下，从理论上研究了丝光沸石上二甲醚羰基化为乙酸甲酯的反应机理。理论研究表明，CO与表面甲基的反应（限速步骤）在八元侧袋中比在十二元主通道中快。随后证明了二甲醚与表面乙酰基反应生成乙酸甲酯的反应在侧袋和主通道中均具有低能垒。因此，本分析确定了一条路径，在该路径中，整个反应均有利地发生在侧袋内的单个位置，与先前的实验研究高度吻合。反应动力学的实验研究与理论推导的机理相符，此外还表明乙酸甲酯产物抑制了反应-可能是由于空间上阻碍了CO对侧袋中甲基的进攻。

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