磁性Mn-Fe载体制备及其在合成碳酸二苯酯中应用  

Preparation of magnetic Mn-Fe supporters and its application in synthesis of diphenyl carbonate

作　　者：张林锋[1] 周洁[2] 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》2015年第4期60-63,共4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：采用溶胶-凝胶法制备Mn-Fe复合氧化物前驱体,经过高温焙烧得到具有软磁特性的氧化羰基合成碳酸二苯酯的催化剂载体,并通过XRD,H2-TPR,BET,VSM等手段对载体和催化剂进行表征。XRD测试结果表明:低于500℃焙烧温度下Mn-Fe复合氧化物载体具有完整的尖晶石型结构,高于500℃时出现杂相且随温度升高杂相峰强不断增加;H2-TPR测试结果表明:Mn-Fe复合氧化物载体具有较好的低温氧化性能,但随着焙烧温度升高还原峰温度不断向高温偏移;BET法比表面积测试结果显示:500℃下焙烧得到的载体比表面积达到29.53m2/g,VSM测试结果显示经负载后催化剂比饱和磁化强度达到43.16Am2/kg。当负载质量分数为0.5%Pd后用于苯酚氧化羰基合成碳酸二苯酯,在反应总压为5MPa、CO与O2分压比为93∶7、反应时间4h、反应温度100℃时,碳酸二苯酯单程收率可达28.33%,选择性在99.1%以上。Manganese-iron composite oxide precursor was prepared by sol-gel method, then after high-temperature calcination the soft magnetic catalyst support used in synthesis of diphenyl carbonate through oxidative earbonylation method was deserved. The supports were investigated by XRD, H2-TPR, BET and VSM. XRD characterization results show that the Mn-Fe composite oxide support obtained at the calcination temperature below 500℃ has the complete spinel structure, whereas when the calcination temperature above 500 ℃ the peaks belonging to the impurity phase begins to appear, with its intensity increasing as the calcination temperature rising; H2-rI＇PR resuhs reveal that the Mn-Fe composite oxide supporters demonstrate well low-temperature oxidative performance, but as the calcination temperature rising the reduction peak temperature shifts to the high temperature continuously; the BET test results show that the SBET of the Mn-Fe composite oxides support obtained at the calcination temperature of 500℃ is 29.53 m^2/g; the VSM results show that after loading the saturation magnetization of the catalyst reaches 43.16 Am^2/kg. After loading of 0.5% Pd （mass fraction）, the single pass yield of the obtained catalyst is 28.33%, with the selective up to 99.1% when the total reaction pressure is 5 MPa, CO and O2 partial pressure ratio is 93 ： 7, reaction time is 4 h and the reaction temperature is 100℃.

关 键 词：溶胶-凝胶法 锰铁复合氧化物 磁性催化剂 氧化羰基化法 碳酸二苯酯 

分 类 号：TQ245.24[化学工程—有机化工]