SO_4^(2-)/ZrO_2-SiO_2的制备及其催化合成丁酸丁酯  

Preparation of SO_4^(2-)/ZrO_2-SiO_2 Catalyst for Synthesis of Butyl Butyrate

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》2006年第9期810-814,共5页Petrochemical Technology

基　　金：上海市重点学科建设基金资助项目(P1501)

摘　　要：采用分别沉淀/混合沉淀法、改性共沉淀法和以硅溶胶为硅源的共沉淀法制备了SO42-/ZrO2-S iO2固体超强酸催化剂;考察了沉淀剂及沉淀终点的pH等制备条件对分别沉淀/混合沉淀法制备的SO42-/ZrO2-S iO2催化剂催化合成丁酸丁酯活性的影响;探索了ZrO2-S iO2的制备方法、反应时间对SO42-/ZrO2-S iO2催化剂活性的影响。实验结果表明,以硝酸铵为沉淀剂,当沉淀终点的pH为7~8时,采用分别沉淀/混合沉淀法制备的SO42-/ZrO2-S iO2催化剂的活性较高(酯化率88.7%),但分别沉淀/混合沉淀法制备的ZrO2-S iO2组成不均匀;以硅溶胶为硅源采用共沉淀法制备的SO42-/ZrO2-S iO2催化剂催化合成丁酸丁酯,在正丁醇0.48m ol、正丁酸0.40m ol、反应时间3h、不添加任何带水剂的条件下,酯化率高达96.4%,该方法制备的催化剂稳定性和再生性能好,制备成本低。SO4^2-/ZrO2-SiO2 solid super-acid as catalysts for synthesis of butyl butyrate were prepared by mixing precipitates, modified co-precipitation and co-precipitation with silica sol as silicon source. Effects of precipitant and precipitation end pH value on activity of SO2-/ZrO2-SiO2 catalyst prepared by mixing precipitates were investigated. Effects of different preparation methods of ZrO2-SiO2 and esterification time on activity of SO4^2-/ZrO2-SiO2 catalyst were studied. SO4^2-/ZrO2-SiO2 catalyst prepared by mixing precipitates with ammonium nitrate as precipitant and end pH at 7 - 8 exhibits high activity（ 88. 7% ）, but composition of ZrO2-SiO2 is not homogeneous. Yield of esterification over SO4^2-/ZrO2-SiO2 catalyst prepared by alternative co-precipitation with silica sol as silicon source can reach 96.4% when n-butyric acid 0.48 tool, n-butyl alcohol 0.40 mol, reaction time 3 h and without any entrainer. The latter catalyst has high activity, high stability, good regeneration property and low preparation cost.

关 键 词：氧化锆 氧化硅 硫酸 固体超强酸 正丁醇 正丁酸 丁酸丁酯 酯化 

分 类 号：TQ426[化学工程]