镁铁复合金属氧化物催化环己酮氧化制备己内酯  

Synthesis of Caprolactone by the Oxidation of Cyclohexanone over Composite Mg-Fe Oxide Catalysts

作　　者：周志伟[1,2] 秦娟 林加明[1] 武文良[1] 顾志强[2] 刘晓勤[1] 

机构地区：[1]南京工业大学化学化工学院,江苏南京210009 [2]江苏扬农化工集团有限公司,江苏扬州225009 [3]江苏省科技金融服务中心,江苏南京210042

出　　处：《石油化工》2015年第7期828-832,共5页Petrochemical Technology

基　　金："江苏省博士后科研资助计划"资助项目(1302121C);北京石油化工学院恩泽生物质精细化工北京市重点实验室开放课题资助项目;江苏高校优势学科建设工程资助项目

摘　　要：以Mg(NO3)2和Fe(NO3)3为前体,采用共沉淀法制备了一系列镁铁复合金属氧化物;采用XRD、N2吸附-脱附和CO2-TPD等手段对所制备的镁铁复合金属氧化物的物化性质进行了表征,以分子氧为氧化剂,考察了镁铁复合金属氧化物对环己酮氧化制备己内酯反应的催化性能。表征结果显示,镁铁复合金属氧化物中出现了新相铁酸镁,增大了其比表面积和孔体积。当Mg O与Fe2O3的摩尔比为4时,所得镁铁复合金属氧化物试样(Mg-Fe-4)具有适宜的比表面积、孔体积和碱量,催化性能较高。以Mg-Fe-4为催化剂,在m(Mg-Fe-4)∶m(环己酮)=0.26、m(苯甲醛)∶m(环己酮)=2.6、m(乙腈)∶m(环己酮)=25、O2初始压力为1.0 MPa、反应温度80℃、反应时间6 h的条件下,环己酮的转化率达92.8%,己内酯的选择性达91.4%。Composite Mg-Fe oxides were prepared from magnesium nitrate and ferric nitrate via coprecipitation and were characterized by means of XRD,N2 adsorption-desorption and CO2-TPD. Their catalytic performances in the oxidation of cyclohexanone to caprolactone with molecular oxygen were investigated. The XRD results indicated that magnesium ferrite formed in the composite oxides,which led to the bigger specific surface area and porous volume. When the mole ratio of Mg O to Fe2O3 was 4,the prepared Mg-Fe-4 catalyst showed the highest catalytic performance among the prepared catalysts due to its appropriate specific surface area,porous volume and basicity. The influences of various reaction conditions on the catalytic performances of the Mg-Fe-4 catalyst were discussed. Under the conditions of mass ratio of Mg-Fe-4 to cyclohexanone 0.26,mass ratio of pro-oxygenic agent benzaldehyde to cyclohexanone 2.6,mass ratio of acetonitrile to cyclohexanone 25,initial O2 pressure 1.0 MPa,reaction temperature 80 ℃ and reaction time 6 h,the conversion of cyclohexanone and the selectivity to caprolactone reached 92.8% and 91.4%,respectively.

关 键 词：镁铁复合金属氧化物催化剂 环己酮 己内酯 分子氧 氧化 

分 类 号：TQ426.82[化学工程]