Dawson型磷钨钼杂多酸的制备及其对H_2O_2氧化环己酮制己二酸的催化  

Preparation of Tungstomolybdophosphate Acid with Dawson Structure and Its Catalytic Activity for the Synthesis of Adipic Acid via Hydrogen Peroxide Oxidaton of Cyclohexanone

作　　者：曹小华[1,2] 任杰[1] 柳闽生[3] 徐常龙[2] 严平[2] 

机构地区：[1]浙江工业大学化工与材料学院,杭州310014 [2]九江学院化学与环境工程学院,九江332005 [3]南京晓庄学院生物化工与环境工程学院,南京211171

出　　处：《应用化学》2012年第8期915-920,共6页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(21161009);江西省自然科学基金(20114BAB213002,2009GQH0053);江西省教育厅科技(GJJ10626,GJJ11613)资助项目

摘　　要：采用水热法制备了新型H6P2W9Mo9O62.24H2O催化剂,并用UV-Vis、FT-IR和TG-DTA等测试技术对催化剂进行了表征。以微波促进30%过氧化氢氧化环己酮制备己二酸合成反应为探针,考察了催化剂的催化性能。通过正交实验探讨了几种因素对反应的影响,确定了优化工艺条件为:n(环己酮)∶n(过氧化氢)∶n(草酸)∶n(催化剂)=100∶400∶1.25∶0.25,反应温度100℃,微波辐射功率400 W,反应时间3.5 h,己二酸产品的收率达87.33%,纯度可达99.7%。反应结束后,将反应后含催化剂的溶液浓缩至一定浓度,催化产率降低,重复使用5次收率降低为45.89%。Tungstomolybdophosphate acid with Dawson structure was prepared by hydrothermal synthesis and characterized by means of FT-IR, UV-Vis and TG-DTA. The synthesis of adipic acid from the reaction of cyclohexanone with 30% hydrogen peroxide under microwave irradiation was used as a probe to study the catalytic activity of tungstomolybdophosphate acid. The main effects of the reaction were optimized with orthogonal experiments. The results show that under the optimal conditions, i.e. the molar ratio of C6Hl0O： H2O2： H2C2O4： H6P2W9Mo9O62·24H2O= 100：400：1.25：0. 25, 100 °C for the reaction temperature, 400 W for the microwave power, and 3.5 h for the irradiation time, the isolated yield of adipic acid can reach 87.33% with a purity of 99. 7%. The filtration containing the catalyst can be concentrated by the rotary evaporation and be reused five times by facile separation of the product after reaction, with an isolated yield of above 45.89% for adipic acid.

关 键 词：H6P2W9Mo9O62·24H2O 水热合成 微波 己二酸 环己酮 

分 类 号：O614.6[理学—无机化学] TQ032.4[理学—化学]