多重孔洞MFI沸石材料的合成, 形貌調控及其於異相催化反應的研究

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研究生：	蕭旭明 Hsiao, Hsu-Ming
論文名稱：	多重孔洞MFI沸石材料的合成, 形貌調控及其於異相催化反應的研究 Synthesis and Morphological Control of Hierarchical MFI Zeolite Materials and Their Applications in Heterogeneous Catalysis
指導教授：	楊家銘 Yang, Chia-Ming
口試委員:	林弘萍洪嘉呈楊家銘
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2013
畢業學年度：	101
語文別：	中文
論文頁數：	104
中文關鍵詞：	中孔洞沸石、異相催化
外文關鍵詞：	silicalite-1, TS-1, Friedel-Crafts alkylation, MFI
相關次數：	點閱：1 下載：0
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本論文旨在利用自行合成之兩端親水、中間疏水的結構導向試劑，應用於MFI沸石的合成。首先，藉由親核性取代反應，合成出兩端具四級銨官能基，中間為丙氧基分子的結構導向試劑 (命名為 N3(PO)n-N3，n = 2、32、67 )。接著進一步研究改變疏水端長度及結構導向試劑含量對於silicalite-1沸石形貌、孔洞的影響，及多重孔洞ZSM-5沸石對於異相催化的研究。在水熱法合成silicalite-1部分，添加N3-(PO)67-N3、N3-(PO)32-N3 可以合成具有層狀結構的silicalite-1，其中N3-(PO)32-N3可合成出具花朵型的形貌，而添加N3-(PO)2-N3為結構導向試劑時，可以合成出具有自我支撐結構能力並垂直交錯而成的silicalite-1，從氮氣吸脫附鑑定則可以找到微孔洞及狹長型的中孔洞分布。在合成TS-1、ZSM-5的部分，添加N3-(PO)2-N3同樣可以合成具有自我支撐結構能力並垂直交錯而成的TS-1，而添加N3-(PO)32-N3可以合成出花朵型層狀結構的ZSM-5，與傳統ZSM-5相比，具有較高的表面積及多重孔洞的產生。因此，本研究以Friedel-Crafts烷化反應進行催化測試，發現多重孔洞ZSM-5具有較高的轉化率，提升了催化活性。

In this study, a new-type of triblock structure directing agent (SDA) with hydrophobic middle part and hydrophilic ends was prepared and used in MFI zeolite synthesis. The SDA with propoxy middle part and quaternary ammonium ends (N3(PO)n-N3，n = 2、32、67) was synthesized by nucleophilic substitution reaction. The effects of the length of SDA on the morphology and catalytic activity of MFI zeolite was investigated by tuning the concentration of SDA with various length of hydrophobic part. In the synthesis of silicalite-1, lamellar structure was obtained by using N3-(PO)67-N3、N3-(PO)32-N3 as SDA, flower-like morphology was formed with N3-(PO)32-N3, and furthermore, self-pillared, intersectional and compressed octahedron was obtained by using N3-(PO)2-N3 as SDA. N2 physisorption isotherm showed that these prepared materials contain slit-type mesopores and zeolitic micropores. In the synthesis of TS-1 & ZSM-5, the self-pillared and intersectional structure of TS-1 was successfully obtained by using N3-(PO)2-N3 as SDA, and lamellar structure of ZSM-5 was also obtained by using N3-(PO)32-N3 as SDA. The hierarchical ZSM-5 has high BET surface area, large pore volume and exhibited much better catalytic activity in Friedel-Craft alkylations as compared to conventional ZSM-5.

謝誌    I
摘要    II
Abstract    III
目錄    IV
圖目錄    VII
表目錄    XIII
第 1 章 緒論    1
1-1 沸石    1
1-1-1 沸石簡介    1
1-1-2 沸石結構及分類    3
1-1-3 沸石酸性及觸媒上的應用    6
1-1-4 MFI沸石    9
1-1-5  MFI沸石的合成    11
1-2 具多重孔洞的沸石材料    14
1-2-1 後合成法    16
1-2-1-1 脫鋁法    16
1-2-1-2 脫矽法    18
1-2-2 硬模板法    19
1-2-3 軟模板法    21
1-3 研究動機    27
第 2 章 實驗部分    28
2-1 實驗藥品    28
2-2 結構導向試劑的合成與分析    29
2-2-1 具四級銨分子合成    32
2-2-2 兩性高分子的合成    32
2-3 水熱法合成silicalite-1    33
2-4 水熱法合成 TS-1    34
2-5 水熱法合成 ZSM-5    34
2-6  Friedel-Crafts 烷化反應    35
2-7 樣品命名    36
2-8 實驗鑑定儀器    37
2-8-1  X光粉末繞射儀 (Powdr X-Ray Diffractometer, PXRD)    37
2-8-2 熱重分析儀 (Thermo Gravimetric Analyzer, TGA)    39
2-8-3 氮氣物理吸脫附 (N2 physisorption)    39
2-6-4 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM)    44
2-6-5 核磁共振光譜儀 (Nuclear Magnetic Resonance Spectroscopy, NMR)    45
2-6-6 固態核磁共振光譜 (Solid state NMR)    46
2-6-7 傅立葉紅外線轉換光譜儀 (FT-IR spectrometer)    48
2-6-8紫外光-可見光光譜儀 (UV-Vis spectrophotometer)    48
2-6-9 氣相層析 (Gas chromatography, GC)    49
第 3 章 結果與討論    51
3-1 結構導向試劑的合成與鑑定    51
3-2 水熱法合成silicalite-1    55
3-2-1 以N3-(PO)67-N3合成之silicalite-1的探討    55
3-2-2 以N3-(PO)32-N3合成之silicalite-1的探討    62
3-2-3 以N3-(PO)2-N3合成之silicalite-1的探討    69
3-2-4 傅立葉紅外線光譜(FT-IR)對沸石結構的分析    75
3-3  合成時間對silicalite-1的影響之研究    78
3-3-1 縮短合成時間對於沸石成長的影響    78
3-3-2 水熱時間對N3-(PO)2-N3合成silicalite-1的影響    83
3-4 水熱法合成TS-1、ZSM-5沸石材料的研究    86
3-4-1  N3-(PO)2-N3對TS-1合成的探討    86
3-4-2  N3-(PO)n-N3對ZSM-5合成的探討    90
3-4-3  Friedel-Crafts烷化反應    95
第 4 章 結論    98
第 5 章 參考文獻    99

                                

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