臺灣博碩士論文加值系統

本篇文章為，以磷化鎳觸媒行常壓加氫脫氧轉化木質素衍生物(鄰甲氧酚)為綠色芳香族之研究。選用氧化鋁、二氧化鋯、二氧化矽作為觸媒載體。其主要的物化性鑑定包括:氮氣的物理吸附(BET)、X-ray繞射圖譜(XRD)、一氧化碳的化學吸附(CO chemisorption)、氫氣程溫還原反應(H2-TPR)、氫氣程溫脫附反應(H2-TPD)以及氨氣的程溫脫附反應(NH3-TPD)。觸媒的反應性測試均以連續式固定化床作為反應系統。在三種觸媒中，Ni2P/Al2O3擁有最好的反應性但產生大量的積碳。相對而言，Ni2P/SiO2則為反應性最差與積碳量最少之觸媒。而在常壓下，對木質素衍生物進行加氫脫氧反應，其可能之反應途徑如下:脫甲氧基反應(DMO)、脫甲基反應(DME)、直接脫氧反應(DDO)、加氫反應(HYD)、轉甲基化反應、甲烷化反應。在低轉化率下的選擇率分析，Ni2P/SiO2此種觸媒促進DMO以及DDO之路徑。Ni2P/ZrO2則促進DME之路徑，Ni2P/Al2O3則進行轉甲基化反應和甲烷化反應。以上的差異性歸因於Ni2P在載體上之型態不同。二氧化矽載體上生成較小的Ni2P粒子且具有相當好的氫傳遞能力及活性，而二氧化鋯、氧化鋁載體上則生成較大顆粒。此外在time on stream的測試中，Ni2P/SiO2與其他兩種觸媒相比之下表現出高度的活性以及穩定性。假設Ni2P之型態為維持Ni2P/SiO2觸媒穩定性之關鍵步驟。過量的磷，可充分地補充形成Ni2P型態所需要的磷和維持觸媒表面皆為磷化的狀態。
關鍵字:磷化鎳、加氫脫氧、鄰甲氧酚

Atmospheric hydrodeoxygenation of guaiacol over Ni2P supported catalysts was investigated. Alumina, zirconia, and silica were selected as the supports. The physicochemical properties of these catalysts were surveyed by N2 physisorption, X-ray diffraction (XRD), inverse CO chemisorption, H2 temperature-programmed reduction (H2-TPR), H2 temperature-programmed desorption, and NH3 temperature-programmed desorption. Catalytic performances of these catalysts were tested in a continuous fixed-bed system.
Among tested catalysts, Ni2P/Al2O3 displayed the highest reactivity but produced considerable coke; Ni2P/SiO2, on the contrary, showed the lowest reactivity and the least amount of coke. A plausible mechanism of atmospheric guaiacol hydrodeoxygenation, containing demethoxylation (DMO), demethylation (DME), direct deoxygenation (DDO), hydrogenation (HYD), transalkylation, and methylation, was proposed.
The initial selectivity analysis showed that Ni2P/SiO2 promotes DMO and DDO routes while Ni2P/ZrO2 enhances DME; Ni2P/Al2O3 may play a role in transalkylation or methylation. The differences were attributed to Ni2P morphologies on these supports: SiO2 hosted small Ni2P particles, which were more active in H-transfer than large Ni2P clusters supported by ZrO2 or Al2O3. In addition, Ni2P/SiO2 possessed relatively high reactivity and stability compared to Ni2P/ZrO2 and Ni2P/Al2O3 within the first hour of time on-stream testing. Low coke accumulation and excess phosphorous, which may replenish Ni2P phase to maintain its fully phosphided state, were hypothesized to be responsible for the stability of Ni2P/SiO2.
Keyword: Nickel phosphided (Ni2P),
hydrodeoxygenation(HDO),guaiacol(GUA), supports.

目錄
摘要 I
Abstract II
目錄 III
表目錄 VI
圖目錄 VII
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 木質纖維素生質能組成部分 3
2.2 生質能源轉化的策略 5
2.3 磷化鎳觸媒(Ni2P) 7
2.4 加氫脫氧研究近程發展(HDO) 9
第三章 實驗 12
3.1 X光繞射儀 12
3.2 比表面積分析儀 13
3.3 X射線光電子能譜儀 14
3.4 熱重分析儀(TGA) 15
3.5 氫程溫還原反應(H2-TPR) 16
3.6 氫程溫脫附反應(H2-TPD) 17
3.7 一氧化碳化學吸附 18
3.8 氨氣化學吸附原理 21
3.9 實驗設備和藥品 23
3.10 觸媒製備 26
3.11 Ni2P觸媒活性測試 30
3.12 氣體產物定性與定量分析 32
3.13 積碳程溫氧化反應 36
第四章 結果與討論 37
4.1 Ni2P與NiO於不同載體之研究 37
4.1.1 觸媒物性鑑定XRD 37
4.1.2 不同載體觸媒氫氣程溫還原分析(H2-TPR) 39
4.1.3 不同載體觸媒氫氣程溫脫附分析(H2-TPD) 41
4.1.4 不同載體Ni2P觸媒氨氣程溫脫附圖譜 44
4.1.5 觸媒物化性鑑定結果統整 46
4.1.6 反應性測試Reactivity 48
4.1.7 反應機制(Mechanism) 51
4.1.8 初始反應下之選擇率(Initial selectivity) 53
4.1.9 Time on stream活性測試分析 58
4.1.10 載體的影響 62
4.2 不同Ni/P組成觸媒之研究 64
4.2.1 不同Ni/P組成之觸媒XRD鑑定 64
4.2.2 不同Ni/P組成觸媒氫氣程溫還原分析 66
4.2.3 不同Ni/P組成觸媒氫氣程溫脫附分析 68
4.2.4 不同Ni/P組成觸媒氨氣程溫脫附分析 73
4.2.5 不同Ni/P組成觸媒物化性鑑定結果統整 75
4.2.6 不同Ni/P組成觸媒反應性測試Reactivity 77
4.2.7 不同Ni/P反應機制 79
4.2.8 不同Ni/P組成初始反應下選擇率 81
4.2.9 Time on stream活性測試分析 86
第五章 結論 88
第六章 未來方向 90
參考文獻 91
發表文獻 101



表目錄
表2.1早期於常溫低壓下的木質素衍生物加氫脫氧研究 11
表3.1使用設備名稱 23
表3.2使用藥品名稱 24
表3.3使用的觸媒含量和其代表名稱 29
表4.1氫氣脫附量統整 43
表4.2物化性鑑定結果統整表 47
表4.3改變不同WHSV之產物碳產率統整表 50
表4.4不同Ni/P組成氫氣脫附量統整表 71
表4.5不同Ni/P組成物化性鑑定結果統整表 76
表4.6不同Ni/P組成反應性測試結果 78
表4.7不同Ni/P組成觸媒一階初始反應選擇率方程式統整 85


圖目錄
圖2.1木質纖維素之結構[22] 4
圖2.2木質纖維素合成燃料及化學品之路徑[22] 6
圖2.3磷化鎳(Ni2P)結構，藍點為金屬鎳、紅點為磷[43] 8
圖3.1AutoChem2920自動化化學吸附 19
圖3.2Ni/Al2O3 CO pusle result 19
圖3.3 Ni2P/Al2O3 CO Pulse result 20
圖3.4 Ni2P/SiO2 CO pulse result 20
圖3.5氨氣脈衝式吸附/程溫脫附系統 22
圖3.6 Ni2P/SiO2 NH3 pulse result 22
圖3.7連續式反應器示意圖 31
圖3.8 GC十向閥切換示意圖 33
圖3.9惠思通電橋示意圖 35
圖3.10甲烷化器和火焰離子化偵測器 35
圖4.1不同載體觸媒XRD繞射圖譜 38
圖4.2不同載體觸媒氫程溫還原圖譜 40
圖4.3不同載體觸媒氫程溫脫附圖譜 42
圖4.4氨氣程溫化學脫附圖譜 45
圖4.6反應機制 52
圖4.7為磷甲氧酚在(XGUA<20%)偽一階動力學的模型 55
圖4.8一階初始反應選擇率圖 56
圖4.9 Time on stream 60
圖4.10使用前後的觸媒XRD圖譜比較 61
圖4.11觸媒在載體上可能之結構 63
圖4.12不同Ni/P組成之XRD繞射圖譜 65
圖4.13不同Ni/P組成觸媒氫程溫還原圖譜 67
圖4.14不同Ni/P組成觸媒氫程溫脫附圖譜 70
圖4.16不同Ni/P組成氨氣程溫脫附圖譜 74
圖4.17不同Ni/P組成反應機制 80
圖4.18為不同Ni/P組成之觸媒其磷甲氧酚(XGUA<20%)假設的偽一階動力學模型 83
圖4.19不同Ni/P組成觸媒一階初始反應選擇率圖 84
表4.7不同Ni/P組成觸媒一階初始反應選擇率方程式統整 85
圖4.20不同Ni/P組成Time on stream 87

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