PdCl_2/Cu-HMS催化乙醇氧化羰基化合成碳酸二乙酯  

Synthesis of Diethyl Carbonate by Oxidative Carbonylation of Ethanol over PdCl_2/Cu-HMS Catalyst

作　　者：张萍波[1] 张震[1] 王曦[1] 王胜平[1] 马新宾[1] 

机构地区：[1]天津大学化工学院绿色合成与转化教育部重点实验室,天津300072

出　　处：《石油化工》2006年第7期685-688,共4页Petrochemical Technology

基　　金：国家自然科学基金资助项目(20576093);教育部"新世纪优秀人才支持计划"项目(NCET-04-0242);天津科学委员会资助项目(05YFJMJC09800)

摘　　要：制备了含Cu的介孔杂原子分子筛Cu-HM S和PdC l2/Cu-HM S催化剂,考察了其催化乙醇氧化羰基化合成碳酸二乙酯(DEC)的反应性能。通过X射线衍射、X射线光电子能谱、电感耦合等离子体原子发射光谱、红外光谱的表征表明,Cu离子以高度分散的状态进入HM S分子筛骨架,并保持了良好的介孔结构的有序性,同时PdC l2的负载在一定程度上提高了Cu-HM S分子筛的介孔规整度。通过催化剂活性的考察发现,载体表面的Pd与骨架中Cu之间的协同作用有利于该反应体系活性中心的形成,PdC l2/Cu-HM S催化剂表现出较佳的活性,DEC选择性达100.0%、乙醇转化率为5.1%、DEC时空收率达到110.50g/(L.h)。助剂的加入在不同程度上提高了PdC l2/Cu-HM S催化剂的活性,其中四乙基溴化胺(TEAB)的效果最佳,TEAB的最佳负载量为n(TEAB)∶n(Pd)=12∶1,产物DEC的时空收率达到187.93g/(L.h)。Synthesis of diethyl carbonate（DEC） by gas phase oxidative carbonylation of ethanol over PdCl2/Cu-HMS catalyst was investigated. The modified support Cu-HMS, synthesized through neutral templating route, could keep mesoporous structure even after it was calcined repeatedly to remove template. HMS, Cu-HMS and PdCl2/Cu-HMS were characterized by means of XRD, XPS, ICP and IR. Results indicated that copper fully and highly dispersed into HMS framework. Degree of order of molecular sieves was improved after PdCl2 was loaded on Cu-HMS. Interaction between Pd2^＋ loaded on Cu-HMS surface and Cu^2＋ in Cu-HMS framework showed synergistic effect and facilitated the producing of active centers in PdCl2/Cu-HMS catalyst. The catalyst exhibited excellent selectivity （100.0%）to DEC, ethanol conversion （5.1% ） and space time yield （STY） of DEC （ 110.50 g/（ L·h） ）. Performance of PdCl2/Cu-HMS catalyst was greatly enhanced by addition of tetraethyl ammonium bromide（TEAB） as promoter. Under n（TEAB） ： n（Pd）12 ： 1 ,STY of DEC was 187.93 g/（L·h）.

关 键 词：碳酸二乙酯 HMS分子筛 氧化羰基化 乙醇 铜 钯 催化剂 

分 类 号：TQ426.8[化学工程]