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摘要: 采用水热晶化法制备了HUSY@MFI核壳结构复合分子筛。通过XRD、SEM、N2吸附-脱附、NH3-TPD及吡啶吸附红外等手段表征催化剂的结构和性质。结果表明,HUSY@MFI晶粒在形貌上呈椭球状,表面是鳞片状结构的MFI型分子筛,里面是光滑的HUSY型分子筛,焙烧模板剂前几乎没有或只有很少量的N2能进入其孔道结构,致密的壳层MFI覆盖在HUSY型分子筛表面,形成了新的弱酸位,而中强酸强度和酸类型并没有受到影响,复合分子筛的表面酸量及总酸量减少。将所制备的HUSY@MFI复合分子筛催化剂应用于以离子液体1-乙基-3-甲基咪唑氯盐([Emim]Cl)为溶剂的纤维素水解反应中,与HUSY催化的纤维素水解相比,HUSY@MFI复合分子筛催化纤维素水解反应的速率较慢,葡萄糖收率由30.9%提高到41.3%。Abstract: In this paper, core-shell composite zeolites (HUSY@MFI) were prepared by hydrothermal method. The composite zeolites were characterized by XRD, SEM, N2-adsorption, NH3-TPD and Py-FTIR. The results indicated that HUSY@MFI has both HUSY and MFI structure. Scanning Electron Microscope (SEM) reflects a core-shell morphology of HUSY@MFI. The particles displayed an elliptical sphere structure with scale-like surface. The growth of MFI shell results in a decrease of external acid density and the total acid sites. When the HUSY@MFI was used as catalyst instead of HUSY in hydrolysis of cellulose to glucose in 1-ethyl-3-methylimidazolium chloride ([Emim]Cl), the glucose yield could be significantly improved from 30.9% to 41.3%.
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Key words:
- HUSY@MFI /
- HUSY /
- cellulose /
- hydrolysis /
- glucose
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表 1 样品的孔参数
Table 1 Pore parameters of the samples
Sample Surface area ABET /(m2·g-1) Pore volume v/(cm3·g-1) micropore mesopore total micropore mesopore total HUSY 679 134 813 0.27 0.23 0.50 MFI 239 134 373 0.10 0.11 0.21 HUSY@MFI(calcined) 334 150 484 0.14 0.12 0.26 HUSY@MFI(non-calcined) 29 24 53 0.01 0.03 0.04 表 2 样品的红外酸度分析
Table 2 Brønsted acid sites and Lewis acid sites of the catalysts
Sample Total acid/
(mmol·g-1)Acid amount/
(mmol·g-1)B/L brønsted lewis HUSY 0.843 0.543 0.300 1.8 HUSY@MFI 0.486 0.286 0.200 1.4 表 3 不同催化剂的最佳反应效果
Table 3 Best results of the reactions with different catalysts
Catalyst Time t/h Yield w/% TRS oligosaccharide glucose 5-HMF HUSY@MFI 3.5 88 5.5 41.29 3.97 HUSY 2 65 3.12 30.91 7.82 -
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