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研究生： 張亦甫
Yi-Fu Chang
論文名稱： 過渡金屬催化劑對乙醇蒸氣重組與氧化蒸氣重組反應之研究
The study of ethanol steam reforming and oxidative steam reforming on transition-metal catalysts
指導教授： 王禎翰
Wang, Jeng-Han
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2010
畢業學年度： 98
語文別： 中文
論文頁數： 140
中文關鍵詞： 乙醇重組 、過渡金屬催化劑 、蒸氣重組 、氧化蒸氣重組 、氫能
英文關鍵詞： ethanol reforming, transition-metal catalysts, steam reforming, oxidative steam reforming, hydrogen fuel
論文種類： 學術論文
相關次數： 點閱：174  下載：10 
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    • 本研究以 Polyvinylpyrrolidone (PVP)法，來製備以Al2O3為支撐物的Co、Ni、Cu、Ru、Rh、Pd、Ag、Ir、Pt、Au金屬觸媒並利用X-ray 繞射儀(XRD)、能量散射光譜儀(EDS)來分析觸媒特性，應用在乙醇的蒸氣重組反應(Steam reforming)與氧化蒸氣重組(Oxidative steam reforming)的催化，而催化反應在常壓及設定溫度(400℃-600℃)的實驗條件中於石英固定反應床進行。反應產物利用in situ之方式，有系統的以氣相層析儀(Gas Chromatography)進行分析。
    實驗結果發現氧化蒸氣重組反應的乙醇轉換效率與氫氣產率在所有實驗設定的溫度範圍中都比蒸氣重組反應來得高，而改變Gas hourly space velocity (GHSV)對反應的影響很小。在催化觸媒中Ru、Rh、Ir有最好的乙醇轉氫能力及最高的氫氣產率，而Cu、Ag、Au 則是有最佳的乙醇氧化能力。
    　　另外可以發現Co、Ni、Pd、Pt 在乙醇催化過程中擁有最高的乙烯選擇率可推斷是走乙醇脫水的催化路徑。將實驗配合之前所做的電腦理論計算的結果可以歸納出Ru、Rh、Ir之所以有最高的氫氣產率是因為它們擁有最好的碳-碳鍵結斷裂能力讓乙醇能完全分解；Cu、Ag、Au 有最佳的乙醇氧化能力是歸因於它們的氧化過程中鍵形成的能障最低，Co、Ni、Pd、Pt則是在其表面上有相對較低的碳氧鍵解離能障。

    In the current research,catalysts of Co、Ni、Cu、Ru、Rh、Pd、Ag、Ir、Pt、Au supported on Al2O3 have been prepared by the Polyvinylpyrrolidone (PVP) method and characterized by XRD,EDS. The experiments of ethanol steam reforming (SRE) and oxidative steam reforming (OSRE) of the catalysts have been carried out in the quartz fixed-bed reactor at the temperature range of 400℃- 600℃ in the ambient pressure. The products have been systematically analyzed by in situ Gas Chromatography (GC) to elucidate the mechanism.
    　　The result shows that OSRE has a better conversion efficiency and hydrogen yield than SR in all the temperature range, while Gas hourly space velocity (GHSV) had limited effect on the reaction. Comparing the activity of the catalysts, Ru, Rh and Ir show the best performance with the highest H2 yield; on the other hand, Cu, Ag and Au are good for ethanol oxidation.
    　　Furthermore, the other metal catalysts of Co, Ni, Pd and Pt show higher selectivity of C2H4 and might follow the dehydration process. Comparison with previous computational work,the higher H2 yield of Ru, Rh and Ir can 4 be attributed to their lower C-C bond breaking step and results fully decomposition of ethanol. The excellent oxidative ability of Cu, Ag and Au corresponds to the lower bond formation barrier in the oxidation process. Finally, the dehydration process on Co, Ni, Pd and Pt are related to the lower C-O dissociation barriers on these surfaces.

    第一章: 緒論 15 1-1 前言。 15 1-2 氫能的介紹與運用。 15 1-3 乙醇重組來製造氫氣。 18 1-4 實驗動機與方向。 20 第二章: 實驗 23 2-1 實驗用藥品與器材儀器。 23 2-1-1: 活性金屬及其前趨物。 23 2-1-2: 其它。 24 2-1-3: 實驗器材與儀器。 26 2-2 金屬催化劑的製備。 27 2-2-1 : 製備金屬氧化物支撐物 – (Al2O3)。 27 2-2-2 : 用含浸法(Impregnation method)製備金屬催化劑。 29 2-2-3 : 用添加檸檬酸鈉的含浸法製備金屬催化劑。 31 2-2-4 : 用添加PVP 的含浸法(簡稱PVP法)制備金屬催化劑。 33 2-3 樣品的命名。 34 2-4 催化劑的特性鑑定。 35 2-4-1 : X光粉末繞射儀(XRD)。 35 2-4-2 : 能量散射光譜儀(EDS)。 35 2-5 催化劑的乙醇重組反應活性測試。 37 2-5-1: 實驗裝置設置。 37 2-5-2: Steam reforming(SRE)條件設置。 41 2-5-3: Oxidative steam reforming(OSRE)條件設置。 41 2-5-4: 分析儀器條件以及檢量線製作。 43 2-5-5: 轉換效率計算法與產物的selectivity與yield公式。 50 第三章: 結果與討論 51 3-1 各金屬觸媒的特性鑑定。 51 3-1-1: X光繞射圖譜 – 證明金屬有吸附在支撐物上。 51 3-1-2: EDS圖譜 – 測量金屬(Metal)/氧化物(Oxide)的比例。 54 3-2 觸媒製備方法與不同裝置對催化活性之影響。 55 3-2-1: 不同的催化劑製備方法對乙醇重組催化的反應性影響。 55 3-2-2: 不同實驗裝置對催化劑的催化效果影響。 56 3-3 觸媒催化效率結果比較。 59 3-3-1: 反應溫度對催化劑的結果影響 - 比較YH2與XETOH。 70 3-3-2: 各個sample OSRE催化效果的比較- 比較YH2與XETOH。 72 3-3-3: 各個sample SRE催化效果的比較- 比較YH2與XETOH。 77 3-3-4: OSRE與SRE催化效率比較。 82 3-3-5: GHSV的大小對於sample催化效果的影響- 比較YH2與XETOH。 84 3-3-6: 各金屬催化劑的產物分佈比較-比較選擇率(Si)與產率(Yi) 。 87 3-4 由產物分佈與理論計算結果探討催化劑的乙醇重組反應機制。 100 3-4-1: 理論計算的反應路徑趨勢。 100 3-4-2: 解離路徑的探討 – 銠(Rh)、銣(Ru)、銥(Ir)三金屬。 108 3-4-3: 氧化路徑的探討 – 銅(Cu)、銀(Ag)、金(Au)三金屬。 110 3-4-4: 脫水路徑的探討 – 鈷(Co)、鎳(Ni)、鈀(Pd)、鉑(Pt)四金屬。 112 3-5 結論與未來研究方向。 114 3-5-1: 結論。 114 3-5-2: 未來研究方向。 116 附錄: 硫化氫與水在鍺(100)表面上的反應機制理論計算。 117 緒論 117 S-1 前言。 117 S-2 鍺與矽半導體材料的介紹與運用。 119 S-3 實驗動機與方向。 121 S-4 DFT理論計算介紹。 121 S-5 計算模型與條件設置。 125 S-6 計算結果。 127 S-7 結論。 133 參考文獻 134 附錄參考文獻 138 圖錄 10 表錄 12 補充數據: 比表面積測定 138 補充數據: 檸檬酸合成法還原順序對實驗的影響 139

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