臺灣博碩士論文加值系統

本研究著眼於設計HZSM-5(矽/鋁比為11.5)觸媒於甲醇芳香化。第一部份的研究主題為除矽與含浸鎵於HZSM-5觸媒的協同效應探討。結果顯示，除矽法不僅能夠提高中孔隙度，降低芳香族產物的擴散阻力，還能提升布朗斯特酸的強度。此外，除矽法所製造出的中孔有利於鎵的前驅物(Ga(NO3)3 6H2O)更容易擴散進入HZSM-5孔洞內，並與布朗斯特酸形成環化脫氫(cyclodehydrogenation)的活性點。具有除矽及含浸鎵金屬的HZSM-5(Ga/AT-0.01)於500oC下產出最高的芳香族選擇率。
第二部分則透過改變不同鹼處理條件以及含浸少量的鎵(1 wt%)，製備一系列HZSM-5觸媒。結果顯示，隨著鹼處理濃度提高，鎵與布朗斯特酸接觸的量就越多，但過高的鹼處理濃度(AT-0.2)則大幅破壞了HZSM-5的結構。因此，適中鹼處理後的觸媒(Ga/AT-0.05)於500oC下具有最佳的甲醇芳香化能力。另一項重要的發現是是透過適當的鹼處理能均一化HZSM-5的微孔孔徑分佈(0.55nm)，並能在反應中促進p- 與 m-xylenes的選擇率。

In this study we focus on designing HZSM-5 (Si/Al ratio = 11.5) in methanol aromatization. The first part is to explore the synergistic effect of disilication and Ga doping in HZSM-5. Desilication not only increases mesoporisity and reduces mass transfer resistance, but also enhances Brønsted acidity. In addition, gallium precursor, (Ga(NO3)3 6H2O), is easier to diffuse into HZSM-5 cavities and contacts with Brønsted acid to form cyclodehydrogenation center compared to its pristine counterpart. Ga-doped, desilicated HZSM-5 (Ga-AT0.01) has maximum aromatics selectivity at 500℃.
The second part of this work is to synthesize Ga-doped, desilicated HZSM-5 with systematically increased alkalinity. Enhancing alkalinity in desilicatoin can improve the amounts of (GaO)+-Brønsted acid site. However, severe alkalinity can destroyed HZSM-5 structure (AT-0.2). This leads Ga/AT-0.05 to be an optimal MTA catalyst.

目錄
摘要 I
英文延伸摘要 II
誌謝 VI
目錄 VII
圖目錄 IX
表目錄 XI
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 沸石觸媒的特性[4] 3
2.2 甲醇轉化為芳香族的可能反應機制 9
2.3 沸石觸媒改質之研究 14
第三章 實驗 19
3.1 X光繞射儀 19
3.2 比表面積分析儀 20
3.3穿透式電子顯微鏡 22
3.4 掃描式電子顯微鏡 22
3.5 固態魔角旋轉核磁共振儀[48] 23
3.6 感應耦合電漿原子發射光譜分析儀[49] 26
3.7 氨氣程溫脫附 28
3.8 氫氣程溫還原 29
3.9 甲醇程溫脫附 29
3.10 積碳程溫氧化反應 30
3.11 熱重分析儀 30
3.12 氣相層析儀 31
3.13 產物定性與定量分析 35
3.14 實驗設備及藥品 37
3.15 觸媒製備及命名 39
3.16 觸媒MTA反應性及壽期測試 40
第四章 結果與討論 42
4.1 觸媒物性鑑定 42
4.1.1 觸媒XRD鑑定 42
4.1.2 觸媒氮氣等溫吸脫附曲線 43
4.1.3 觸媒表面形貌(SEM) 45
4.1.4 觸媒29Si MAS NMR鑑定結果 46
4.1.5 觸媒27Al MAS NMR鑑定結果 48
4.1.6 觸媒71Ga MAS NMR鑑定結果 49
4.2 觸媒化性鑑定 51
4.2.1 觸媒氨氣程溫脫附圖譜 51
4.2.2 觸媒氫氣程溫還原圖譜 53
4.2.3 觸媒甲醇程溫脫附圖譜 54
4.3 除矽與含浸鎵之HZSM-5觸媒於甲醇轉化為芳香族中的協同效應 57
4.4 Ga/R與Ga/AT-x觸媒反應活性測試 62
4.5 Ga/AT-x之芳香族產物分佈分析 69
4.6 觸媒壽期測試及積碳 71
第五章 結論 73
第六章 未來方向 74
參考資料 75
發表文獻 81

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