PdCl_2-CuCl_2/AC催化乙醇氧化羰化合成碳酸二乙酯工艺条件的研究  

Synthesis of Diethyl Carbonate by Gas-phase Oxidative Carbonylation of Ethanol Over a Heterogeneous Catalytic Flow Reactor

作　　者：陈兴权[1] 高飞[2] 徐崇福[1] 

机构地区：[1]江苏工业学院化工系,江苏常州213016 [2]宁夏大学能源化工重点实验室,宁夏银川750021

出　　处：《精细化工》2006年第8期817-821,共5页Fine Chemicals

基　　金：2004年宁夏区教育厅基金;"973"前期预演项目(基金号2003CCA03200);教育部重点科技项目(基金号01137)~~

摘　　要：碳酸二乙酯（DEC）是一种主要的碳酸酯，可以作为有机合成的中间体、溶剂以及油品添加剂使用。该文以三苯基膦PdCl2-CuCl2负载活性炭作催化剂，通过连续流动气固相反应床，对乙醇直接气相氧化羰化合成DEC的反应进行了研究。结果表明：在消除内外扩散的条件下，开始随着反应温度的升高，乙醇的转化率逐渐升高到25％，当温度超过443K时，DEC的选择性下降到91％；反应压力越高，乙醇的转化率越大，但DEC的选择性保持在93％；CO和O2的摩尔比控制在4—8有利于DEC的合成；空速控制在1260—2500h^-1时对乙醇的转化率和DEC的选择性影响不大，分别稳定在30％和95％左右，但DEC的时空产率变化明显，从27g DEC／（L cat·h）增加到203g DEC／（L cat·h）。Diethyl carbonate （ DEC ）, an important intermediate of organic synthesis, solvent and fuel additive, was synthesized by oxidative carbonylation of ethanol in gaseous phase over a heterogeneous catalyst triphenylphosphine -PdCl2-CuCl2 supported on activated carbon using a laboratory-scale continuous flow reactor. The conversion of ethanol increases with reaction temperature when the effects of internal diffusion and external diffusion are excluded, but the selectivity for DEC decreases to 91% when temperature rises, so the optimum temperature is 403 - 443 K. The conversion of ethanol increases with pressure but the selectivity for DEC retains 93%. The optimum volume ratio of CO/O2 is 4 - 8. When the space velocity is controlled in the range 1 260 -2 500 h^-1, the conversion of ethanol and DEC selectivity keep unchanged（ about 30% and 95% respectively） because the influence of external diffusion was eliminated ,but the STY of DEC kept increasing due to increasing material quantity.

关 键 词：碳酸二乙酯 氧化羰化 乙醇 

分 类 号：TQ426.92[化学工程]