Sol-gel法制备S_2O_8^(2-)/ZrO_2-SiO_2及其微波辐射下催化合成乙酸正丁酯的研究  

Study on S_2O_8^(2-)/ZrO_2-SiO_2 prepared by sol-gel method and its catalytic synthesis of butyl acetate under microwave radiation

作　　者：徐骏[1] 王刚[1] 董成[1] 侯鑫[1] 张立庆[1] 

机构地区：[1]浙江科技学院生物与化学工程学院,浙江杭州310023

出　　处：《化学研究与应用》2015年第7期1058-1063,共6页Chemical Research and Application

基　　金：浙江省自然科学基金项目(编号Y404082)

摘　　要：以Zr O(NO3)2和正硅酸乙酯(TEOS)为原料,采用溶胶-凝胶法制备固体超强酸S2O82-/Zr O2-Si O2催化剂,以微波辐射下冰醋酸和正丁醇合成乙酸正丁酯为探针反应,探究了催化剂制备条件对催化活性的影响及反应条件对酯化反应的影响。运用Hammett指示剂法,BET法,XRD,TEM和FT-IR对催化剂进行了表征。结果表明,催化剂的最佳制备条件为nZr∶nSi=1∶10,焙烧时间3.0h,焙烧温度550℃,(NH4)2S2O8浸渍液浓度0.6 mol·L-1。微波辐射下酯化反应最优条件为:醇酸摩尔比2.2∶1,催化剂0.8g,反应时间35min,功率600W,此时产率为93.5%。该法制得的催化剂酸强度H0≤-13.16为超强酸,催化剂比表面较大,Si O2为无定形态,Zr O2为四方晶相,Zr O2在Si O2上分布相对均匀,且Si O2分布较为松散,基本呈多孔网状结构。Solid superacid S2O82-/ Zr O2-Si O2 was prepared with sol-gel method by using Zr O（ NO3）2and TEOS. The catalytic activity affected by preparation conditions and the factors of esterification between acetic acid and n-butanol under microwave irradiation were investigated. The characterizations of catalyst were tested by Hammett,BET method,XRD,TEM and FT-IR. The results show that,the optimal preparation conditions of catalyst were as follows： the molar ratio between Zr and Si was 1： 10,calcination time was3. 0h,calcination temperature was 550℃ and the concentration of（ NH4）2S2O8solution was 0. 6mol·L^-1. Under the optimal esterification conditions that the molar ratio of n-butanol to acetic acid was 2. 2： 1,the amount of catalyst was 0. 8g,the reaction time was35 min,and the power of microwave irradiation was 600 W,the yield of butyl acetate could reach 93. 5%. S2O82-/ Zr O2-Si O2 catalyst was superacid as its H0≤-13. 16,the Si O2 and Zr O2 containing in catalyst was noncrystalline and tetragonal. Zr O2 was equably distributed on Si O2 that had multiple cavities and showed honeycomb structure.

关 键 词：乙酸正丁酯 固体超强酸 溶胶-凝胶法 微波合成 

分 类 号：O643.32[理学—物理化学]