超重力法制备Ce-Mn氧化物载体氧化羰基合成碳酸二苯酯  

Preparation of Ce-Mn oxides supports by high gravity method and its application in synthesis of diphenyl carbonate through oxidative carbonylation process

作　　者：张林锋[1] 贺玉成[2] 杨小俊[2] 陈卫[2] 吴元欣[1,2] 

机构地区：[1]天津大学化工学院,天津300072 [2]武汉工程大学化工与制药学院绿色化工过程省部共建教育部重点实验室,湖北武汉430074

出　　处：《化学工程》2014年第9期53-58,共6页Chemical Engineering(China)

基　　金：湖北省自然科学基金资助项目(2013CFB322);湖北省教育厅青年项目(Q20131503)

摘　　要：分别采用溶胶-凝胶法、共沉淀法和超重力反应共沉淀法制备铈锰复合氧化物前驱体,再经过高温焙烧得到氧化羰基化合成碳酸二苯酯的催化剂载体。通过XRD,H2-TPR,BET,TEM等手段对不同方法制备所得载体进行表征,结果表明:采用超重力反应共沉淀法所制备的Ce-Mn复合氧化物载体Mn较多进入CeO2中形成Ce-Mn-O共熔体,由于Mn的掺杂而产生的晶格畸变和由此产生的氧缺陷更多,晶体颗粒较小且分布均匀,比表面积大;当负载质量分数为0.5%Pd后用于苯酚氧化羰基化合成碳酸二苯酯,在反应总压为5 MPa,CO与O2分压比为93∶7、反应时间6 h、反应温度100℃时,碳酸二苯酯单程收率可达21.79%,选择性在99.1%以上。且运用旋转填充床设备实现物料在超重力条件下共沉淀制备Ce-Mn复合氧化物载体的制备过程简单,操作方便可控,载体质量稳定,非常适合批量生产。Cerium-manganese composite oxide precursor was prepared by the methods of sol-gel,co-precipitation,high gravity reactive co-precipitation,respectively,and the catalysis support used in the synthesis of diphenyl carbonate by oxidative carbonylation method was obtained after high-temperature calcination. The supports were investigated by XRD,H2-TPR and BET. The results show that much Mn in the as-prepared support obtained from the HGPR method is doped into the CeO2 to form the Ce-Mn-O solid solution. The particles size and distribution of the support obtained are smaller and uniform,the specific surface area is larger,and the crystal lattice distortion in it that is caused by the effect of Mn doping produces more oxygen defect. After loading of mass fraction 0. 5% Pd,the single pass yield of the catalyst obtained is 21. 79% with the selectivity up to 99. 1% when the total reaction pressure is 5 MPa,CO and O2 partial pressure ratio is 93∶ 7,reaction time is 6 h and the reaction temperature is100 ℃. As the raw materials are reacted at high gravity environment in the rotating packed bed equipment,the process is simple and controllable,the quality of the prepared Ce-Mn composite oxide support is stable,and it is very suitable for mass production.

关 键 词：超重力反应 共沉淀法 铈锰复合氧化物 氧化羰基化法 碳酸二苯酯 

分 类 号：TQ225.52[化学工程—有机化工]