新型HPWs/MIL-101催化剂的制备及其对环戊烯选择氧化反应的催化性能  

Preparation of HPWs/MIL-101 Catalyst and Its Performance for the Selective Oxidation of Cyclopentene

作　　者：杨新丽[1] 刘洋[1] 戴维林[2] 苗永霞[1] 毛璞[1] 

机构地区：[1]河南工业大学化学化工学院,河南郑州450001 [2]复旦大学化学系,上海200433

出　　处：《石油化工》2014年第7期759-766,共8页Petrochemical Technology

基　　金：国家自然科学基金项目(20903035;21373054);河南工业大学研究生教育创新计划(2012YJCX36)联合资助项目

摘　　要：采用浸渍法在介孔金属-有机骨架材料MIL-101上负载磷钨酸(HPWs),制得一种新型HPWs/MIL-101非均相催化剂。利用XRD、N2吸附、TG和FTIR等手段对该催化剂进行了表征,研究了该催化剂在环戊烯(CPE)选择氧化制备戊二醛(GA)反应中的催化性能。实验结果表明,MIL-101对HPWs具有很高的负载阈值,且将HPWs固载到MIL-101上后MIL-101仍能很好地保持其晶体骨架结构。HPWs高度分散在MIL-101的介孔笼中,与MIL-101有较强的相互作用,提高了该催化剂的热稳定性且可有效防止HPWs的流失。在HPWs负载量为30%(w)、n(CPE)∶n(H2O2)∶n(HPWs)=1 000∶2 100∶3、V(叔丁醇)∶V(CPE)=10、35℃、24 h时,CPE转化率达到100.0%,GA收率达到70.1%。该催化剂具有较好的重复使用性能。HPWs/MIL-101 catalysts were prepared by impregnation to immobilize phosphotungstic acids（HPWs） on MIL-101 with chromium（Ⅲ） terephthalate metal-organic framework, and characterized by XRD, N2 adsorption, TG and FTIR. The catalytic performances of HPWs/MIL-101 in the preparation of glutaraldehyde（GA） through the selective oxidation of cyclopentene（CPE） were investigated. It was found that the metal-organic framework MIL-101 exhibited high loading threshold for HPWs and its crystal structure was kept well after HPWs loading. The active HPWs were dispersed into the cavities of MIL-101 and there was strong interaction between HPWs and MIL-101, which increased the thermal stability of HPWs/MIL-101 catalysts and effectively prevented HPWs from being washed away. The conversion of CPE and selectivity to GA could reach 100.0% and 70.1% respectively under the conditions of HPWs loading 30%（w）, n（CPE） ： n（H2O2） ： n（HPWs） 1 000 ： 2 100 ： 3, V（tert-butyl alcohol） ： V（CPE） 10, 35℃, 24 h. The catalyst had good reusability.

关 键 词：磷钨酸 金属-有机骨架MIL-101 环戊烯 选择氧化 戊二醛 

分 类 号：TQ426.91[化学工程]