Catalytic performance of silicalite-1 modified HY zeolite in the hydrolysis of cellulose
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摘要: 采用silicalite-1对HY型分子筛进行修饰，得到具有核壳结构的复合分子筛HY/silicalite-1。通过X射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）、N2的吸附-脱附及吡啶吸附红外（Py-FTIR）等手段对不同晶化时间合成的HY/silicalite-1复合分子筛进行了表征，研究了复合分子筛对纤维素水解的催化性能。结果表明，晶化时间直接影响复合分子筛的晶体生长规律和两组分的相对含量，最佳晶化时间为16-24 h，所得到的复合分子筛外貌呈核壳结构，silicalite-1附晶生长在HY型分子筛的表面；随着晶化时间的延长，复合分子筛的表面由胶浊状变为光滑，最终变为鳞片状；其B酸量先减少后增加，而L酸量则先增加后减少。其中，晶化时间为24 h的HY/silicalite-1复合分子筛B酸量最大，L酸量最小，对纤维素水解反应具有良好的催化性能，葡萄糖收率由HY型分子筛催化获得的28.0%大幅提高至45.8%。Abstract: A core-shell composite zeolite (HY/silicalite-1) was prepared by modifying HY zeolite with silicalite-1 and characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM), Transmission electron microscope (TEM), N2 sorption and IR spectra of pyridine adsorption (Py-FTIR); the catalytic performance of HY/silicalite-1 composite zeolite in the hydrolysis of cellulose was then investigated in comparison with that of HY. The results show that the crystallization time has a significant influence on the crystal growth of the HY/silicalite-1 composite zeolite and the relative content of two components. With the optimum crystallization time of 16-24 h, a core-shell structure for the HY/silicalite-1 composite zeolite is achieved, where the silicalite-1 crystal grows over the surface of HY zeolite; with the prolongation of the crystallization time, the morphology of the composite zeolite changes from rough turbid to smooth and eventually to scale-like surface. The amount of Br nsted acid sites decreases first and then increases with the increase of the crystallization time, whereas the amount of Lewis acid sites changes in the opposite direction. In particular, the HY/silicalite-1 composite zeolite obtained with a crystallization time of 24 h exhibits excellent catalytic performance in the hydrolysis of cellulose to glucose; over it, the yield of glucose reaches 45.8% at 130℃, much higher than the value of 28.0% over the HY zeolite.
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Key words:
- composite zeolite /
- silicalite-1 /
- HY /
- cellulose /
- hydrolysis /
- crystallization time
1) 本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813). -
图 1 不同晶化时间合成HY/silicalite-1复合分子筛的XRD谱图
Figure 1 XRD patterns of HY/silicalite-1 composite zeolites with different crystallization time
图 2 不同晶化时间HY/silicalite-1的扫描电镜和透射电镜照片
Figure 2 SEM ((a1), (b1), (c1), (d1)) and TEM ((a2), (b2), (c2), (d2)) images of the HY/silicalite-1 composite zeolites prepared with different crystallization times: ((a1), (a2)) 6 h; ((b1), (b2)) 10 h; ((c1), (c2)) 16 h; ((d1), (d2)) 24 h
图 3 不同晶化时间合成的HY/silicalite-1氮气吸附-脱附曲线和孔径变化曲线
Figure 3 N2 adsorption and desorption isotherms (a) and the corresponding BJH pore size distribution (b) of the HY/silicalite-1 composite zeolites prepared with different crystallization times
图 4 不同反应时间对纤维素水解反应的影响
Figure 4 Reaction results for the hydrolysis of cellulose over HY (a) and HY/silicalite-1 (b) reaction conditions: 0.5 g MCC, 10.0 g [Emim]Cl, mCat.:mMCC = 0.5, 130 ℃
表 1 样品的红外酸度分析
Table 1 Amounts of Brnsted and Lewis acid sites in the HY/silicalite-1 composites
Sample Acid amount /(mmol·g-1) B/L total Brönsted Lewis HY 1.272 0.799 0.473 1.7 HY/silicalite-1-6 h 0.813 0.459 0.354 1.3 HY/silicalite-1-10 h 0.703 0.238 0.465 0.5 HY/silicalite-1-16 h 0.782 0.267 0.515 0.5 HY/silicalite-1-24 h 0.769 0.546 0.223 2.4 
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表 2 不同催化剂的最佳反应效果
Table 2 Best results for the hydrolysis of cellulose over HY and HY/silicalite-1
Catalyst Time t/h Product yield wmol/% Glucose
selectivity s/%TRS oligosaccharide glucose 5-HMF HY 2 97.0 1.2 28.0 13.3 29 HY/silicalite-1 3.5 97.5 16.0 45.8 5.6 46
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