固体超强酸SO_4^(2-)/ZrO_2-SiO_2的制备及其催化性能的研究  

Preparation and Catalytic Performance of SO_4^(2-)/ZrO_2-SiO_2 Solid Superacid

作　　者：卢冠忠[1] 苏勇[2] 张顺海[2] 毛东森[1] 

机构地区：[1]上海应用技术学院化学工程系应用催化研究所,上海200235 [2]华东理工大学石油化工学院,上海201512

出　　处：《石油化工高等学校学报》2007年第1期5-8,共4页Journal of Petrochemical Universities

基　　金：上海市重点学科建设项目(P1501)。

摘　　要：分别以氧氯化锆、硅溶胶和氨水为锆源、硅源和沉淀剂,采用共沉淀法制备Zr(OH)4-Si(OH)4,110℃干燥后经硫酸浸渍、干燥和焙烧制得SO42-/ZrO2-SiO2固体超强酸。XRD和比表面积测定结果表明,SiO2的引入对SO42-/ZrO2催化剂的结构产生了重要影响,从而使其比表面积明显增大。以所制备的SO42-/ZrO2-SiO2固体超强酸为催化剂,代替浓硫酸用于丁酸和丁醇的酯化反应,考察了硫酸浸渍液浓度、焙烧温度等制备条件对其催化性能的影响。结果表明,采用硫酸浸渍液浓度为1.0 mol/L,焙烧温度为550℃所制备的SO42-/ZrO2-SiO2催化剂,在丁醇和丁酸的物质的量比为1.2及不添加任何带水剂的条件下,丁酸丁酯的收率高达90%以上,优于SO42-/TiO2-WO3和TiSi W12O40/TiO2催化剂。A solid superacid catalyst, SO4^2-/ZrO2-SiO2, was prepared by impregnating the Zr（OH）4 -Si（OH）4 coprecipitate with a sulfuric acid solution, then drying and calcinating, in which the Zr（OH）4 -Si（OH）4 coprecipitate was prepared with zirconium oxychloride as zirconia sources, silica solution as silica sources and aqueous ammonia as precipitant, respectively, then drying at 110℃. The results from XRD and surface area measurements indicate that the addition of SiO2 strongly changes the structure of SO4^2-/ZrO2hence greatly increases its surface area. The effect of preparation conditions such as concentration of sulfuric acid and calcination temperature on the catalytic performance of SO4^2-/ZrO2-SiO2 substituted for sulfuric acid for the esterification of n--butanoic acid with n--butyl alcohol was studied. The results show that the yield of butyric butyl using the SO4^2-/ZrO2-SiO2 catalyst prepared with the concentration of H2SO4 by 1.0 mol/L and the calcination temperature of 550 ℃ is higher than 90 % when the molar ratio of butyl alcohol to butanoic acid is 1.2 ： 1 and without addition of entrainer, which is superior to the reported results obtained using SO4^2-/ZrO2-WO3 and TiSiW12 O40/TiO2 catalysts under comparable experiments.

关 键 词：固体超强酸 SO4^2-/ZrO2-SiO2 丁酸丁酯 

分 类 号：O643.3[理学—物理化学]