负载型磷钼钒杂多酸催化果糖一锅法制备2,5-二甲酰基呋喃  

One-pot synthesis of 2,5-diformylfuran from fructose by PMo V-HPAs catalyst supported on silica

作　　者：赵树伟[1] 杨真真[1] 齐崴[1,2,3] 苏荣欣[1,2,3] 何志敏[1,2] 

机构地区：[1]天津大学化工学院化学工程研究所 [2]化学工程联合国家重点实验室(天津大学) [3]天津市膜科学与海水淡化技术重点实验室,天津300072

出　　处：《化工进展》2017年第1期189-195,共7页Chemical Industry and Engineering Progress

基　　金：天津市自然科学基金(16JCYBJC19600);北洋青年学者计划(2012)项目

摘　　要：首先制备了兼具酸性和催化醇氧化活性的Keggin型杂多酸H_4PMo_11VO_40,为使其可以重复利用,又制备了孔道均匀、比表面积大的介孔二氧化硅作为载体,并将H_4PMo_11VO_40固载在二氧化硅上作为催化剂,实现了在外加氧气条件下,一锅法催化果糖经脱水和氧化制备2,5-二甲酰基呋喃(2,5-DFF)。对杂多酸及载体进行了一系列表征,通过优化反应过程得到了最佳反应条件:在120℃下,DMSO作为溶剂,催化剂、果糖与DMSO质量比为1∶10∶100,反应时间4h,前1h通入N_2,体系生成5-HMF并防止了果糖的直接氧化,后3h通入O_2,催化氧化5-HMF生成2,5-DFF,所得2,5-DFF的最高收率为48.4%。催化剂的重复利用实验表明:使用5次后再次负载仍可保持较高的催化活性。A Kegin structure molybdovanadophosphoric heteropolyacids（PMoV-HPAs）was developed and used as the catalyst for one-pot synthesis of 2,5-diformyfuran（2,5-DFF）from fructose with oxygen as the oxidant under environmentally benign conditions. Mesoporous silica was prepared to be the carrier. The TEM mapping and other characterizations showed that the PMoV-HPAs was successfully supported on mesoporous silica. With DMSO as the solvent,the optimal reaction temperature was 120℃ and the best mass ratio of catalyst/fructose/DMSO was 1∶10∶100. In order to prevent the oxidation of fructose in the initial stage,the first one hour of the reaction was protected by nitrogen under atmospheric pressure,and the acidic site（H）offered by the PMoV-HPAs promoted the dehydration of fructose to 5-hydroxymethylfurfural（5-HMF）. During the next three hours,the metallic site（V）catalyzed the aerobic oxidation of 5-HMF to 2,5-DFF under atmospheric pressure of oxygen and finally a maximum yield of 48.4% for 2,5-DFF was achieved. In addition,H4PMo11VO/SiO2 could be reusable after 5 cycles without significant loss of activity,and it can achieve the best activity after impregnated again.

关 键 词：磷钼钒杂多酸 生物质 催化 果糖 2 5-二甲酰基呋喃 

分 类 号：TQ032.4[化学工程]