高分子铑配合物（PYBRh）催化甲醇羰基化为乙酸和乙酸酐的动力学研究  

Kinetic Study of Cabonylation of Methanol to Acetic Acid and Acetic Anhydride over Polymer-Rhodium Complex(PYBRh)

作　　者：潘平来[1] 柳忠阳[1] 黄茂开[1] 王允富[1] 袁国卿[1] 

机构地区：[1]中国科学院化学研究所

出　　处：《分子催化》1995年第2期97-104,共8页Journal of Molecular Catalysis(China)

基　　金：国家自然科学基金

摘　　要：采用２－乙烯吡啶－丁烯酮共聚物为配体，与四羰基二氯二铑形成顺二羰基铑（Ⅰ）配合物（ＰＹＢＲｈ），用于催化甲醇羰基化制备乙酸和乙酸酐的反应动力学研究．结果表明，其对反应物甲醇和一氧化碳均为零级反应，在一定范围内，对高分子铑催化剂及助催化剂碘甲烷均为一级反应，极性溶剂的加入可以提高甲醇羰基化速度。通过实验结果计算了其反应活化能，活化熵和热焓。研究证明其反应机理与小分子能催化剂相似。The kinetic study of carbonylation of methanol to acetic acid and acetic anhydride over a cisdicarbonyl-rhodium complex(PYBRh)with the copolymer of 2-vinyl pyridine and methyl vinyl ketone shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order with respect to the concentrations of promoter methyl iodide and rhodium in the complex. Polar solvents can accelerate the reaction.Activation parameters were calculated from the experimental results, being comparable to that of a reference system.A mechanism similar to that of low molecular weight rhodium catalyst was proposed.

关 键 词：铑 配合物 动力学 甲醇 羰基化 乙酸 催化 

分 类 号：O643.32[理学—物理化学] O643.36[理学—化学]