臺灣博碩士論文加值系統

本研究探討磷化鎳之粒徑效應於4-甲基愈創木酚的加氫脫氧反應。利用低比表面積二氧化矽(SiO2-L)、高比表面積二氧化矽(SiO2-H)及中孔結構之二氧化矽(SBA-15)作為觸媒載體合成具有不同粒徑之磷化鎳。觸媒的物化性鑑定包括:氮氣物理吸附(BET)、X-ray繞射圖譜(XRD)、X射線光電子能譜(XPS)、感應耦合電漿原子發射光譜分析(ICP-AES)、穿透式電子顯微鏡(TEM)、氫氣程溫還原反應(H2-TPR)、氫氣程溫脫附反應(H2-TPD) 、一氧化碳的化學吸附(CO chemisorption)、一氧化碳程溫脫附(CO-TPD)以及氨氣的程溫脫附反應 (NH3-TPD)。
本實驗以程溫還原法合成三種二氧化矽擔載磷化鎳觸媒，載體比表面積較高者擁有較小粒徑之磷化鎳。此粒徑差異影響磷化鎳之加氫脫氧活性：較小粒徑之磷化鎳擁有較高氫氣吸附量及較高的鎳離子價態(Niδ+)；較大的磷化鎳活性點則具有相反的趨勢。利用批次式反應器於250℃及40 bar氫氣壓力下進行4-甲基愈創木酚加氫脫氧，發現觸媒物化性質的差異也反應在活性測試上；Ni2P/SiO2-L擁有最大轉化率但加氫活性與脫氧程度較弱，相對而言，Ni2P/SBA-15雖轉化率略低於其他兩種觸媒，但具有最佳加氫活性及脫氧程度。推測氫氣吸附量及鎳離子的氧化態對於4-甲基愈創木酚加氫脫氧扮演著重要的關鍵。

The aim of this study is to understand the particle size effect of nickel phosphide in hydrodeoxygenation (HDO) of 4-mathylguaiacol. Different surface areas of silica were used as the supports to synthesize nickel phosphide with varying particle sizes. Commercial SiO2 supports of low surface area (SiO2-L, 96 m2/g), high surface area (SiO2-H, 205 m2/g) and mesoporous SBA-15 (687 m2/g) were selected as the supports. Catalyst characterizations, including N2 physisorption, XRD, XPS, ICP-AES, TEM, H2-TPR, H2-TPD, CO chemisorption, CO-TPD, and NH3-TPD were performed.
Silica-supported nickel phosphide catalysts were prepared by temperature-programmed reduction. High surface area support had small particle size of nickel phosphide, while the low surface area counterpart has large nickel phosphide size. The particle size affects HDO activity of 4-methylguaiacol. The HDO of 4-methylguaiacol at 250℃ and 40 bar H2 in a batch reactor is used as a model reaction to explore the particle size effect of nickel phosphide. The small particle size of nickel phosphide had higher H2 uptake amount and higher partial positive charged Ni cations (Niδ+) than large counterpart. The activity test showed that the small particle size of nickel phosphide had lower conversion but higher hydrogenation and deoxygenation ability than large counterparts. H2 uptake was proposed to play a key role in 4-methylguaiacol hydrodeoxygenation reaction.

摘要 I
英文延伸摘要 II
誌謝 VIII
目錄 IX
表目錄 XII
圖目錄 XIII
第1章 前言 1
1.1 引言 1
1.2 研究動機 3
第2章 文獻回顧 5
2.1 木質纖維素簡介 5
2.2 加氫脫氧反應發展歷程 7
2.3 磷化鎳觸媒 8
2.3.1 磷化鎳觸媒結構 8
2.3.2 磷化鎳觸媒應用於加氫脫氧 9
第3章 實驗 11
3.1 比表面積分析儀 11
3.2 X光繞射儀(XRD) 12
3.3 X射線光電子能譜儀(XPS) 13
3.4 感應耦合電漿原子發射光譜分析儀(ICP-AES) 15
3.5 高解析度穿透式電子顯微鏡(HR-TEM) 16
3.6 自動式化學吸脫附儀 16
3.6.1 氫氣程溫還原反應(H2-TPR) 18
3.6.2 氫氣程溫脫附(H2-TPD) 18
3.6.3 一氧化碳化學吸附 (CO uptake) 19
3.6.4 一氧化碳程溫脫附(CO-TPD) 20
3.6.5 氨氣程溫脫附(NH3-TPD) 21
3.7 觸媒製備 22
3.7.1 SBA-15載體製備 22
3.7.2 磷化鎳觸媒製備 22
3.8 磷化鎳觸媒活性測試 23
3.9 產物定性與定量分析 24
3.9.1 液體產物分析 24
3.9.2 氣體產物分析 25
3.10 實驗設備與藥品 26
第4章 結果與討論 28
4.1 觸媒物理性質鑑定 28
4.1.1 觸媒比表面積及組成分析 28
4.1.2 觸媒X-ray繞射結果 30
4.1.3 觸媒穿透式電子顯微鏡成像 31
4.2 觸媒化學性質鑑定 33
4.2.1 觸媒氫氣程溫還原 33
4.2.2 一氧化碳化學吸附與程溫脫附 34
4.2.3 X光光電子圖譜（XPS） 37
4.2.4 觸媒氨氣及氫氣程溫脫附 38
4.3 觸媒活性測試 41
4.3.1 4-甲基愈創木酚加氫脫氧反應 41
4.3.2 甲酚加氫脫氧反應 45
4.3.3 4-甲基愈創木酚反應機制 47
第5章 結論 48
第6章 未來方向 49
6.1 鎳與磷配位效應 49
6.2 布朗士特酸(PO-H)反應性 49
6.3 觸媒設計 50
參考文獻 51
附錄 57
1.1 質傳阻力影響 57
1.2 觸媒與載體孔徑分布 59
發表文獻 60

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