固体超强酸SO_4^(2-)/TiO_2-Al_2O_3的制备及其催化合成冰片  

Preparation of SO_4^(2-)/TiO_2-Al_2O_3 Soild Superacid Catalyst and Its Catalytic Activity for Borneol Synthesis

作　　者：王鹤林[1] 蒋丽红[1] 王亚明[1] 焦星星 潘登[1] 

机构地区：[1]昆明理工大学化学工程学院,昆明650500

出　　处：《材料导报》2017年第22期43-49,共7页Materials Reports

基　　金：国家自然科学基金(U1202265)

摘　　要：采用溶胶-凝胶法和浸渍法制备了系列SO_4^(2-)/TiO_2-Al_2O_3固体超强酸催化剂,运用XRD、NH_3-TPD、FT-IR、PyFTIR、XPS、SEM等技术手段,研究了复合催化剂材料的结构与性质,初步探讨了固体超强酸SO_4^(2-)/TiO_2-Al_2O_3催化剂的构效关系,得到适宜的催化剂制备条件为:n(TiO_2)/n(Al_2O_3)=1∶2、硫酸浸渍浓度1mol/L、催化剂焙烧温度500℃。考察了物料物质的量比、催化剂用量、反应时间等对催化合成冰片的影响。结果表明,在物料物质的量比为1∶0.4,催化剂用量为α-蒎烯质量的7%,采用程序升温方式(65℃-1h,75℃-4h,90℃-1h)加热的条件下,固体超强酸SO_4^(2-)/TiO_2-Al_2O_3催化剂的催化活性最高,α-蒎烯的转化率高达100%,龙脑的收率高达59.74%,SO_4^(2-)/TiO_2-Al_2O_3固体超强酸催化剂在重复使用6次的条件下,α-蒎烯的转化率均不变,龙脑的收率下降2.99%,催化剂的重复使用性良好。A series of sulphated Al_2O_3-TiO_（2 ）mixed oxides were prepared by sol-gel and dipping process and used as catalysts in synthesis of borneol.The structure and properties of SO_4^（2-）/TiO_2-Al_2O_3solid superacid catalysts were characterized by XRD,NH_3-TPD,FT-IR,Py-FTIR,XPS,SEM techniques,and relationship between the catalytic performance and the structure was explored.The optimal condition for the preparation of the catalyst was obtained as follows：n（TiO_2）/n（Al_2O_3）=1∶2,concentration of impregnation 1mol/L,calcination temperature of the catalysts 500℃.Meanwhile,the effects of the dosage of level of catalyst,molar ratio ofα-pinene to oxalic acid,reaction time on borneol synthesis reaction was investigated.The results showed that when the dosage of level of catalyst was 6%and molar ratio ofα-pinene to oxalic acid was 1∶0.4,by using the program temperature heating method（65℃-1h,75℃-4h,90℃-1h）,i.e.the optimized condition,the resultant solid superacid SO_4^（2-）/TiO_2-Al_2O_3catalyst performed the best catalytic effect to borneol synthesis reaction,asα-pinene was completely converted and high selectivity of borneol（58.63%yield）was achieved.After 6times reuse,the catalyst still maintained good performance—α-pinene conversion rate unchanged,yield of borneol decreased by 2.99%.

关 键 词：SO42-/TiO2-Al2O3固体超强酸 酯化 龙脑 催化 稳定性 

分 类 号：O624[理学—有机化学]