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

doi:10.16085/j.issn.1000-6613.2017.01.024

化工进展 ›› 2017, Vol. 36 ›› Issue (01): 189-195.DOI: 10.16085/j.issn.1000-6613.2017.01.024

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

赵树伟¹, 杨真真¹, 齐崴^1,2,3, 苏荣欣^1,2,3, 何志敏^1,2

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

收稿日期:2016-04-08 修回日期:2016-05-27 出版日期:2017-01-05 发布日期:2017-01-05
通讯作者: 齐崴,教授,从事生物基化学品领域的研究。E-mail:qiwei@tju.edu.cn。
作者简介:赵树伟(1989-)男,硕士研究生。E-mail:2013207116@tju.edu.cn。
基金资助:
天津市自然科学基金（16JCYBJC19600）及北洋青年学者计划（2012）项目。

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

ZHAO Shuwei¹, YANG Zhenzhen¹, QI Wei^1,2,3, SU Rongxin^1,2,3, HE Zhimin^1,2

1 Chemical Engineering Research Center, School of Chemical Engineering and Technology, Tianijn University;
2 State Key Laboratory of Chemical Engineering, Tianjin University;
3 Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin 300072, China

Received:2016-04-08 Revised:2016-05-27 Online:2017-01-05 Published:2017-01-05

摘要/Abstract

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H₄PMo₁₁VO₄₀，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H₄PMo₁₁VO₄₀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N₂，体系生成5-HMF并防止了果糖的直接氧化，后3h通入O₂，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。

关键词: 磷钼钒杂多酸, 生物质, 催化, 果糖, 2,5-二甲酰基呋喃

Abstract: 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.

Key words: molybdovanadophosphoric heteropolyacids, biomass, catalysis, fructose, 2,5-diformyfuran

中图分类号:

TQ032.4

赵树伟, 杨真真, 齐崴, 苏荣欣, 何志敏. 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[J]. 化工进展, 2017, 36(01): 189-195.

ZHAO Shuwei, YANG Zhenzhen, QI Wei, SU Rongxin, HE Zhimin. One-pot synthesis of 2,5-diformylfuran from fructose by PMoV-HPAs catalyst supported on silica[J]. Chemical Industry and Engineering Progree, 2017, 36(01): 189-195.

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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 PMoV-HPAs catalyst supported on silica

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