臺灣博碩士論文加值系統

本研究使用晶種誘導的結晶方式合成不同鋁與鎵比例之奈米尺徑H-[Ga, Al]ZSM-5，探討觸媒內布朗斯特酸與非骨架鎵對於甲醇轉化為芳香族(MTA)反應的協同效應。在物化性結果上，由於合成過程中鎵離子相對於鋁離子較難嵌入ZSM-5骨架內，因此鎵含量的提升會導致布朗斯特酸量下降，但非骨架鎵含量隨之上升。
在反應性測試上，發現含鎵觸媒比一般HZSM-5具有更高的芳香族產率，說明具有脫氫活性的非骨架鎵能夠促進MTA反應中芳香族的生成。為了證實非骨架鎵的效用，我們以酸處理的方式選擇性除去觸媒內的非骨架鎵，且與原先的觸媒進行比較，發現含鎵觸媒經酸處理後的芳香族產率有明顯下降，且脫氫訊號大幅降低，證實在非骨架鎵的協同下，觸媒能加速甲醇轉化為芳香族。而在所有觸媒中，非骨架鎵/布朗斯特酸比例為0.06的觸媒具有最高的芳香化能力(在500 oC的芳香族產率為79.5%)，此與布朗斯特酸和非骨架鎵之間的協同效應有關。在MTA反應中，相對多量的布朗斯特酸有助於甲醇與二甲醚進行脫水，以及後續低碳數烯烴類的聚合與環化反應，而非骨架鎵能將反應中間物的烯烷類脫氫，在布朗斯特酸的協同下加速芳香族的生成。

The aim of this study is to investigate the synergy of the extra-framework Ga species and the Brønsted acid of nanosized aluminogallosilicate MFI catalysts in methanol conversion to aromatics (MTA). A series of nanosized H-[Al]ZSM-5, H-[Ga, Al]ZSM-5, and H-[Ga]ZSM-5 catalysts with a fixed Si-to-M3+ ratio (M = Al and Ga) were synthesized by a seed-induced crystallization method. We found the concentration of the Brønsted acid decreased, while the concentration of extra-framework Ga species increased with the enhanced extent of Ga substitution in the catalysts. It is assumed that Ga is less prone to be incorporated into the ZSM-5 scaffold than Al is.
To reveal the catalytic nature of the extra-framework Ga species, an acid treatment was applied to selectively extract extra-framework Ga species of as-synthesized catalysts. A comparative evaluation of as-synthesized and acid-treated catalysts in MTA showed the dehydrogenative nature of the extra-framework Ga species, which is essential in the enhancement of aromatics. Among tested catalysts, H-[Ga, Al]ZSM-5 with a low extra-framework Ga-to-Brønsted acid ratio (0.06) was the most effective (The aromatics yield of 79.5% was achieved in MTA at 500 oC). The efficacy is due to the contact synergy of the extra-framework Ga species and the Brønsted acid. A high concentration of the Brønsted acid is needed to promote dehydration of methanol and dimethyl ether (DME) and then to facilitate subsequent oligomerization and cyclization. Extra-framework Ga species can dehydrogenate the intermediates including alkenes and alkanes, and with the assistance of neighboring Brønsted acid sites, cyclization can be accelerated.

目錄
摘要 I
英文延伸摘要 II
誌謝 VII
目錄 VIII
表目錄 XI
圖目錄 XII
第一章 前言 1
1.1 引言 1
1.2 研究動機 2
第二章 文獻回顧 3
2.1 沸石觸媒之特性 3
2.2 甲醇轉化為芳香族反應機制 9
2.3 沸石觸媒改質之研究 14
第三章 實驗 20
3.1 X光繞射儀(XRD) 20
3.2 比表面積分析儀 21
3.3 穿透式電子顯微鏡(TEM) 22
3.4 高解析度掃描式電子顯微鏡(SEM) 23
3.5 固態魔角旋轉核磁共振儀(MAS NMR) 24
3.6 感應耦合電漿原子發射光譜分析(ICP-AES) 26
3.7 自動式化學吸脫附儀 28
3.7.1 氨氣程溫脫附(NH3-TPD) 29
3.7.2 異丙胺程溫脫附(Isopropylamine-TPD) 30
3.7.3 甲醇程溫脫附(Methanol-TPD) 31
3.8 吡啶吸附紅外光譜(Pyridine-IR) 32
3.9 熱重分析儀 35
3.10 氣相層析儀 35
3.11 產物定性與定量分析 38
3.12 藥品與實驗設備 40
3.13 觸媒的製備與命名 43
3.13.1 晶種誘導結晶法之Seeding gel製備 43
3.13.2 奈米尺徑之HZSM-5製備 43
3.13.3 觸媒之酸處理方法 44
3.14 觸媒MTA反應性及壽期測試 45
第四章 結果與討論 46
4.1 觸媒物理性質鑑定 46
4.1.1 觸媒XRD鑑定 46
4.1.2 觸媒表面形貌(SEM＆TEM) 48
4.1.3 觸媒氮氣等溫吸脫附曲線 50
4.1.4 觸媒29Si MAS NMR與ICP-AES鑑定結果 54
4.1.5 觸媒27Al MAS NMR鑑定結果 56
4.1.6 觸媒71Ga MAS NMR鑑定結果 57
4.2 觸媒化學性質鑑定 58
4.2.1 觸媒氨氣與異丙胺程溫脫附圖譜 58
4.2.2 吸附吡啶觸媒之紅外光譜 63
4.3 奈米尺徑之H-[Ga, Al]ZSM-5於甲醇轉化為芳香族反應 67
4.4 非骨架鎵於MTA反應之探討 71
4.5 非骨架鎵與布朗斯特酸於MTA反應之協同效應 79
4.6 觸媒壽期測試及積碳 82
第五章 結論 86
第六章 未來方向 87
參考文獻 88

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