有机化学 ›› 2018, Vol. 38 ›› Issue (4): 940-948.DOI: 10.6023/cjoc201709007 上一篇    下一篇

研究简报

磷钨酸盐催化蔗糖制备5-羟甲基糠醛

邱果a, 王新承b, 黄崇品a, 张璞a, 李英霞a, 陈标华a   

  1. a 北京化工大学 化工资源有效利用国家重点实验室 北京 100029;
    b 北京石油化工学院 燃料清洁化及高效催化减排技术北京市重点实验室 北京 102617
  • 收稿日期:2017-09-05 修回日期:2017-11-08 发布日期:2017-11-21
  • 通讯作者: 黄崇品 E-mail:huangcp@mail.buct.edu.cn
  • 基金资助:

    国家自然科学基金(No.21476021)资助项目.

Synthesis of 5-Hydroxymethylfurfural from Sucrose Catalyzed by Phosphotungstate

Qiu Guoa, Wang Xinchengb, Huang Chongpina, Zhang Pua, Li Yingxiaa, Chen Biaohuaa   

  1. a State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029;
    b Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology, Beijing Institute of Petrochemical Technology, Beijing 102617
  • Received:2017-09-05 Revised:2017-11-08 Published:2017-11-21
  • Contact: 10.6023/cjoc201709007 E-mail:huangcp@mail.buct.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21476021)

5-羟甲基糠醛(5-HMF)是一种重要的平台化物,在塑料、聚合物和燃料等领域有着重要应用,因而由碳水化合物脱水制备5-HMF的研究引起了广泛关注.通过合成Nb0.6PW12O40、Sn0.75PW12O40、CrPW12O40、CePW12O40等磷钨酸盐催化剂,并采用傅里叶变换红外光谱、X射线衍射、紫外光谱分析、热重、NH3-程序升温脱附法等手段进行表征,进而系统研究了蔗糖脱水制备5-HMF的反应,对催化剂种类、溶剂类型、反应温度、反应时间、催化剂及反应物用量等条件进行了优化.实验结果表明,以二甲基亚砜为溶剂,Nb0.6PW12O40为催化剂,在80℃下反应90 min,蔗糖接近完全转化(99.3%),5-HMF收率达到62.54%,且该催化剂循环使用5次后,5-HMF的收率仍有59%.最后,推导了该体系催化蔗糖脱水制备5-HMF的反应机理,该研究对进一步探究碳水化合物脱水制备5-HMF有着重要的借鉴意义.

关键词: 5-羟甲基糠醛, 蔗糖, 磷钨酸盐

5-Hydroxymethylfurfural (5-HMF) is one of the most important biomass-derived platform compounds and can be used to produce various chemicals. The synthesis of 5-hydroxymethylfurfural (5-HMF) from sucrose catalyzed by a variety of phosphotungstate (Nb0.6PW12O40, Sn0.75PW12O40, CrPW12O40, CePW12O40) has been studied, and the catalysts are characterized by FTIR, XRD, UV-Vis, TGA, NH3-TPD and NMR. The optimum yield of 5-HMF reached 62.54% with 99.3% conversion of sucrose, using Nb0.6PW12O40 in dimethyl sulfoxide (DMSO) at 80℃ under 0.1 MPa of N2 with reaction time of 90 min. Moreover, Nb0.6PW12O40 could be reused five times without loss of activity, and the reaction mechanism was proposed. This study has reference significance for carbohydrate conversion to 5-HMF.

Key words: 5-hydroxymethylfurfural, sucrose, phosphotungstate