有机膦配位催化剂的结构与活性关系　Ⅶ．碱性添加剂作用的原位红外光谱研究  

Relationship between Structure and Activity of Organo-Phosphine Coordinated Catalysts(Ⅶ)Effect of Alkli-Additive

作　　者：孙衍文[1] 刘铁元 包鹏[1] 姚彩兰[1] 李达刚[1] 

机构地区：[1]中国科学院兰州化学物理研究所

出　　处：《分子催化》1994年第4期299-304,共6页Journal of Molecular Catalysis(China)

摘　　要：本文报导了应用加压原位红外光谱技术考察ＫＯＨ添加剂对钴－膦催化剂平衡系统的组成及催化活性物种的影响．结果表明，羧酸钴─三烷基膦组成的二元体系催化剂在烯烃氢甲酰化条件下生成了游离的羧酸使烯烃异构化副反应增加．添加适量的ＫＯＨ，组成钴－膦－钾三元体系催化剂，中和了部分游离羧酸，使烯烃异构化副反应显著减少．但是ＫＯＨ过量时，在催化剂平衡体系中生成较多的非活性的［Ｃｏ（ＣＯ）_４］－离子，使催化活性物种ＨＣｏ（ＣＯ）_３Ｌ的浓度明显减少．从而降低了高碳醇的生成速度．The effects of alkali additives on Co-P catalysts under hydroform ylation conditions were studied by in situ-IR spectroscopy.It was found that the hydroxides of lithium,sodium,calcium,magnesium and barium can not be used because of their poor solubility in alcohols.Using potassium acetate as additive,the conversion of olefines and yield of alcohols are higher,but more alkanes and isoolefines are produced.Potassium hydroxide was found to be more suitable.In the Co-P binary catalytic system free acid was produced which increased the by-reactlon of olefine isomerization.In the ternary system of Co-P-KOH by adding appropriate amount of KOH the isomerization could be decreased appreciably because the free acid was partly neutralized.When an excessive amount of KOH was added the production rate of detergent alcohols was decreased because a non-active anion[Co(CO)_4]was formed which reduces the concetration of the active species.

关 键 词：原位红外光谱 氢甲酰化 钴膦管化剂 催化剂 配位 

分 类 号：TQ426.92[化学工程]