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Zeolite-promoted hydrolysis of cellulose in ionic liquid, insight into the mutual behavior of zeolite, cellulose and ionic liquid

机译:沸石促进离子液体中纤维素的水解,洞察沸石,纤维素和离子液体的相互作用

摘要

In this paper, a variety of H-type zeolites were demonstrated as efficient catalysts for hydrolysis of cellulose in ionic liquid (IL) to afford high yield of glucose under mild condition without a pretreatment process. By supplying water gradually as the reaction progresses. HY with the acid amount of 11.1 mol% promoted the highest glucose yield of 50.0% at 130 degrees C, and the yield of the three main products (glucose, cellobiose and 5-hydroxymethylfurfural) was up to 97.2%. It was found that the pore size, the acid amount, the water amount and the timing of water addition are critical factors for high hydrolysis efficiency. XRD characterization suggested that the framework structure of zeolite was particularly stable in 1-butyl-3-methylimidazolium chloride ([BMIm]Cl), while the cell parameter were enlarged due to the dilatation effect of [BMIm]Cl. Elemental analysis of the IL-treated HY demonstrated that IL entered the channel of HY. As such, part of the intra-channel space of HY was occupied, making the average pore diameter, pore volume and the BET surface area of IL-treated HY all decreased, which were demonstrated by physisorption characterization. FT-IR through pyridine adsorption showed that H+ cations generated in-situ from the Bronsted acid sites of zeolite were the key active species for the good hydrolysis performance, while the Lewis acid sites did not exhibit high activity. By simple calcination, the recovered HY showed excellent reusability. Finally, the proposed reaction pathway and recycle of the catalyst were presented. (C) 2012 Elsevier B.V. All rights reserved.
机译:在本文中,已证明各种H型沸石可作为在离子液体(IL)中水解纤维素的有效催化剂,从而在温和条件下无需预处理即可提供高产率的葡萄糖。随着反应的进行逐渐供水。酸含量为11.1 mol%的HY在130℃时促进了50.0%的最高葡萄糖收率,并且三种主要产物(葡萄糖,纤维二糖和5-羟甲基糠醛)的收率高达97.2%。已发现,孔径,酸量,水量和加水时间是提高水解效率的关键因素。 XRD表征表明,沸石的骨架结构在1-丁基-3-甲基咪唑鎓氯化物([BMIm] Cl)中特别稳定,而由于[BMIm] Cl的扩张作用,使得细胞参数增大。经IL处理的HY的元素分析表明,IL进入HY通道。这样,HY的通道内空间的一部分被占据,使得经IL处理的HY的平均孔径,孔体积和BET表面积均减小,这通过物理吸附表征证明。通过吡啶吸附的FT-IR表明,从沸石的布朗斯台德酸位点原位产生的H +阳离子是良好的水解性能的关键活性物种,而路易斯酸位点没有表现出高活性。通过简单的煅烧,回收的HY显示出优异的可重复使用性。最后,提出了拟议的反应途径和催化剂的循环利用。 (C)2012 Elsevier B.V.保留所有权利。

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