磷钨酸盐催化蔗糖制备5-羟甲基糠醛

Synthesis of 5-Hydroxymethylfurfural from Sucrose Catalyzed by Phosphotungstate

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Nb_(0.6)PW_(12)O_(40)、Sn_(0.75)PW_(12)O_(40)、Cr PW_(12)O_(40)、Ce PW_(12)O_(40)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、NH_3-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,Nb_(0.6)PW_(12)O_(40)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.

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 （Nb0.6PWl2040, Sn0.ysPW12040, CrPWt2040, CePW1204o） has been studied, and the catalysts are character- ized by FTIR, XRD, UV-vis, TGA, NH3-TPD and NMR. The optimum yield of 5-HMF reached 62.54% with 99.3% conver- sion of sucrose, using Nb0.6PWI2040 in dimethyl sulfoxide （DMSO） at 80 ℃ under 0.1 MPa of N2 with reaction time of 90 min. Moreover, Nb0,6PW12040 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.