Zhang Luxin, Xing Xu, Sun Ruijun, Hu Meng
College of Environmental and Municipal Engineering, Shaanxi Key Laboratory of Environmental Engineering, Key Lab of Northwest Water Resource, Environment and Ecology, MOE, Xi'an University of Architecture and Technology Xi'an 710055 P. R. China
RSC Adv. 2022 Aug 16;12(36):23118-23128. doi: 10.1039/d2ra01866g.
Selective catalytic conversion of carbohydrates to 5-ethoxymethylfurfural (EMF) is a critical approach to the biorefinery. In this work, solid acid catalysts of γ-AlOOH and CeO@BO were used to convert carbohydrates to EMF in a one-pot process, performed in an ethanol/DMSO solvent system. The synergistic effect of γ-AlOOH and CeO@BO was studied. Furthermore, the morpho-structural properties of the catalysts were characterized, and the effects of reaction time, reaction temperature, catalyst load, and the amount of cosolvent on the conversion of glucose to EMF were examined and optimized. Under the reaction conditions of 170 °C for 20 h, glucose, sucrose, cellobiose, inulin and starch were used as raw materials, and the EMF yield range was 9.2-27.7%. The results showed that the synergistic effect of γ-AlOOH and CeO@BO further causes the combination of multiple acid sites with different types and strength distributions. Particularly, the collaboration between weak, medium-strong, and strong acid, as well as between Lewis and Brønsted acidity, is of great significance for EMF generation. The reusability experiments showed that the combined catalytic system was easily separated and maintained catalytic activity for five successive reactions without further intermediate regeneration steps. This work provides a promising route for the catalytic conversion of biomass-derived carbohydrates into EMF.
将碳水化合物选择性催化转化为5-乙氧基甲基糠醛(EMF)是生物炼制的关键途径。在本工作中,使用γ-AlOOH和CeO@BO固体酸催化剂在乙醇/二甲基亚砜溶剂体系中一锅法将碳水化合物转化为EMF。研究了γ-AlOOH和CeO@BO的协同效应。此外,对催化剂的形态结构性质进行了表征,并考察和优化了反应时间、反应温度、催化剂负载量和共溶剂用量对葡萄糖转化为EMF的影响。在170℃反应20 h的条件下,以葡萄糖、蔗糖、纤维二糖、菊粉和淀粉为原料,EMF产率范围为9.2-27.7%。结果表明,γ-AlOOH和CeO@BO的协同效应进一步导致了多种不同类型和强度分布的酸位点的组合。特别是,弱酸、中强酸和强酸之间以及路易斯酸度和布朗斯特酸度之间的协同作用对EMF的生成具有重要意义。可重复使用性实验表明,该组合催化体系易于分离,无需进一步的中间再生步骤即可在连续五次反应中保持催化活性。这项工作为将生物质衍生的碳水化合物催化转化为EMF提供了一条有前景的途径。