臺灣博碩士論文加值系統

含釩的MCM-41可以由直接水熱法（V-MCM-41）和含浸（V/MCM-41）兩種方式合成而得。觸媒的鑒定包括ICP-AES、X射線繞射、氮氣吸附、高溫氧氣化學吸附、固態核磁共振儀、氫氣程溫還原、氨氣溫度程控脫附以及霍式轉換紅外線光譜。XRD圖譜顯示所有鍛燒後的觸媒皆呈現良好的MCM-41結構。而鍛燒後的V-MCM-41系列觸媒具有相似的29Si NMR圖譜。由51V NMR結果顯示，觸媒經鍛燒並在空氣中吸水後，使V5+由四配位轉為六配位形式鍵結。對所有的觸媒而言，增加釩的含量會使表面積變小，但是氧氣化學吸附量、酸量以及TPR實驗中氫氣的消耗量和還原溫度皆隨著釩含量增加而增加。由觸媒吸附啶的IR圖譜，我們可以推測觸媒結構中四配位釩所提供的弱Lewis酸性點為觸媒具有弱酸性質的主要因素。
利用批式反應器，把觸媒應用在具代表性的烷基芳香族化合物的氧化反應上：二苯甲烷與TBHP在一大氣壓、60℃氧化生成苯甲酮。結果顯示，除了釩含量最高的觸媒（9.1%V/MCM-41）可能因為表面積較小的緣故，其餘觸媒隨著釩含量增加，二苯甲烷轉化率皆成比例增加。而觸媒酸量亦是影響催化活性因素之一；由NH3-TPD及啶-FTIR的結果顯示，觸媒中釩所提供的路易士酸性點才是影響催化活性的主要因素。除此之外，觸媒對二并甲苯、二氫及4-硝基乙苯等苯甲基位置的氧化具有良好的催化活性。另外，以水熱合成法合成之V-MCM-41的催化活性比用含浸方式合成之V/MCM-41來得好。然而在液相催化反應中，MCM-41矽酸鹽結構中的釩活性金屬會有明顯的脫去現象，導致再生觸媒的催化活性些微降低。

Two types of vanadium-containing MCM-41 were synthesized via direct hydrothermal (V-MCM-41) and impregnation (V/MCM-41) methods. The catalysts were characterized by ICP-AES, XRD, N2-sorption, high temperature oxygen chemisorption (HTOC) measurements, 29Si and 51V NMR, TPR of H2, TPD of NH3 and FTIR techniques. The powder XRD patterns of all calcined samples exhibit characteristic MCM-41 structure. The 29Si NMR spectra of the calcined V-MCM-41 samples reveal similar patterns. Based on 51V NMR results, calcination followed by hydration in the air results in the transformation of tetrahedral V5+ into octahedral V5+ coordination due to addition of water molecules. For all samples, an increase of V content causes the decrease of surface area but enhances the amount of O2-chemisorption, the amount of weak acid sites in the NH3-TPD experiments and both the amount and the reduction temperature of H2 gas in the TPR experiments. The pyridine-FTIR investigations suggest the weak acid sites as Lewis acid sites which are associated with tetrahedrally coordinated vanadium.
The catalysts were applied to a typical alkyl aromatic oxidation reaction of diphenylmethane (DPM) with tert-butyl hydroperoxide to produce benzophenone at 1 atm and 60℃ in a stirred batch reactor. The DPM conversion is proportional to the catalyst V content except at the highest V loading (9.1% V/MCM-41), probably due to its remarkably lower surface area. The acid amounts of these catalysts also affect the catalytic activity. Base on th results from NH3-TPD and pyridine-FTIR, the Lewis acid sites associated with vanadium are the major factor catalyzing the oxidation of diphenylmethane. Moreover, the catalysts were also utilized for the oxidation of fluorene, 9,10-dihydroanthracene and 4-nitroethylbenzene at benzylic position with excellent yields. In addition, the V-MCM-41 prepared with hydrothermal method was more active than V/MCM-41 prepared with impregnation. Leaching of active vanadium species from the silicate matrix during liquid phase reaction was found and the regenerate catalysts exhibited a slightly lose in its activity.

第一章 緒論 1
1.1. 觸媒簡介 1
1.2. 沸石結構及分類 3
1.3. MCM-41觸媒 7
1.4. 含活性金屬的MCM-41 14
1.5. 論文動機與目的 15
第二章 實驗 18
2.1. 觸媒簡寫代號 18
2.2. 實驗試劑 18
2.2.1. 觸媒原料、製備及處理 18
2.2.2. 催化反應試劑 20
2.2.3. 鑑定產物的試劑 21
2.2.4. 其他實驗試劑 22
2.3. 實驗儀器 22
2.4. 觸媒性質的鑑定 24
2.4.1. 沸石晶體測定 24
2.4.2. 觸媒表面積的測定 24
2.4.3. 觸媒酸性質的測定 25
2.4.4. 觸媒還原性質的測定 27
2.4.5. 化學吸附 28
2.4.6. 固體表面酸之測量 30
2.5. 催化反應 33
2.5.1. 批式反應器（Batch reactor） 33
2.5.2. 產物的鑒定 35
2.5.3. 流出效應 39
第三章 結果與討論 40
3.1. 觸媒的物理性質 40
3.1.1. 觸媒晶體的測定 40
3.1.2. 29Si及51V的NMR光譜圖 45
3.1.3. 觸媒金屬含量、表面積及金屬分散度 49
3.1.4. 觸媒的還原性質 53
3.1.5. 觸媒酸性質 56
3.1.6. FTIR與啶(pyridine)-FTIR圖譜 59
3.2. 二苯甲烷在批式反應器的催化反應 63
3.2.1. 攪拌轉速對催化反應的影響 63
3.2.2. 觸媒重量對催化反應的影響 64
3.2.3. 溶劑對催化反應的影響 64
3.2.4. 反應溫度對催化反應的影響 68
3.2.5. 觸媒對催化反應的影響 68
3.3. 再生觸媒的鑒定與催化反應 75
3.3.1. 再生觸媒之XRD圖譜 75
3.3.2. 再生觸媒之H2-TPR圖譜 76
3.3.3. 再生觸媒之NH3-TPD圖譜 77
3.3.4. 再生觸媒之表面積與氧氣吸附 78
3.3.5. 再生觸媒之催化反應 79
3.3.6. 二苯甲烷氧化生成苯甲酮之反應機構 82
3.4. 其他芳香族反應物的探討 83
3.4.1. 二并甲苯的氧化反應 83
3.4.2. 二氫的氧化反應 85
3.4.3. 乙苯的氧化反應 88
3.4.4. 4-硝基乙苯的氧化反應 90
第四章 結論 92

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