添加氧化鋯促進劑的稻殼灰分擔體銅觸媒應用於甲醇部份氧化產氫之研究

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姓名

林惠聰(Hui-tsung Lin) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

添加氧化鋯促進劑的稻殼灰分擔體銅觸媒應用於甲醇部份氧化產氫之研究
(Effects of ZrO2-promoter on catalytic performance of Cu RHA catalysts for production of hydrogen by partial oxidation of methanol)

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摘要(中)

本研究以沉澱固著法製備含ZrO2促進劑的銅金屬觸媒，分別探討ZrO2含量、煅燒溫度、進料比例(O2/CH3OH)及反應溫度等變因對觸媒活性的影響，目標為評估所製備觸媒的效能並找出最佳操作條件。研究中利用感應耦合電漿原子放射光譜儀(ICP-AES)、熱重分析儀(TGA)、X-ray繞射分析儀(XRD)、N2O解離吸附(N2O titration)、程式升溫還原(TPR)和穿透式電子顯微鏡(TEM)等儀器，分別對各觸媒進行物性分析鑑定。以甲醇部份氧化反應(POM)探討各項操作變因對於甲醇轉化率、氫氣選擇率及一氧化碳選擇率之影響。
由XRD圖譜得知，含有ZrO2的觸媒，其Cu的繞射峰會有減弱趨勢，而且在高溫煅燒下，抗燒結能力也會大幅提升。N2O及TEM結果顯示，ZrO2的存在可提高Cu在擔體上的分散度，使Cu顆粒的粒徑維持在5 nm以下。TGA的結果提供了煅燒溫度的參考範圍，對照POM活性測試可知最佳煅燒溫度為673 K，而最佳的反應物進料比為O2/CH3OH=0.3，反應溫度為523 K時觸媒有最好的活性表現。

摘要(英)

Using rice husk ash (RHA) as support, we prepared the Cu catalysts by deposition-precipitation method. ZrO2 was added as promoter to Cu/Zr/RHA catalysts and these nano-catalysts were tested for hydrogen production by partial oxidation of methanol to identify the activity. A detail study for physical property of Cu/Zr/RHA catalysts was analyzed by ICP-AES, TGA, XRD, N2O titration, TEM, and TPR.
XRD results indicated that the copper diffraction peak of Cu/Zr/RHA was weaker than Cu/RHA, and the Cu diffraction peak would not increase with higher calcination temperature. It means ZrO2 phase stabilized the copper, preventing crystallite growth. N2O results and TEM images exhibited that ZrO2 enhanced Cu dispersion and Cu particle size was almost under 5 nm. TGA result suggests that the suitable calcination temperature is above 650 K. In TPR patterns, CuO reduction temperature was decreased by ZrO2, and this phenomenon was correlated to XRD. We tested the catalysts activity for various parameters such as promoter loading, calcination temperature, feed ratio and reaction temperature. Zirconium oxide was believed to enhance the activity of catalyst and the best operation parameters to optimize catalyst’s performance are calcination temperature 673 K; O2/CH3OH feed ratio 0.3 and reaction temperature 523 K.

關鍵字(中)

★ 銅觸媒
★ 氧化鋯
★ 稻殼灰分
★ 甲醇部份氧化產氫

關鍵字(英)

★ Cu catalyst
★ Zirconia
★ partial oxidation of methanol

論文目次

第一章緒論 1
1-1 前言 1
1-2 燃料電池 1
1-3 甲醇產氫反應 3
1-4 研究內容與論文架構 4
第二章文獻回顧 6
2-1 銅觸媒的性質 6
2-2 ZrO2對觸媒的影響 6
2-3 Cu-ZrO2觸媒的製備 8
2-4 銅觸媒的活性點 9
2-5 擔體作用 9
第三章實驗方法與裝置 11
3-1 稻殼灰分擔體的製備 11
3-1-1 水洗程序 11
3-1-2 酸洗程序 11
3-1-3 熱解程序 14
3-1-4 碳燒程序 14
3-2 銅觸媒擔載於稻殼灰分擔體的製備 17
3-3 銅觸媒的鑑定分析 18
3-3-1 感應耦合電漿原子放射光譜儀 (ICP-AES) 18
3-3-2 熱重分析 (TGA) 18
3-3-3 X-ray繞射分析(XRD) 20
3-3-4 程式升溫還原 (TPR) 24
3-3-5 N2O分解吸附 (N2O-Titration) 26
3-3-6 穿透式電子顯微鏡 (TEM) 29
3-4 活性測試--甲醇部份氧化產氫反應 32
3-5 實驗流程與操作變因 34
3-6 數據計算與處理 36
3-6-1 銅觸媒理論載量的定義與計算 36
3-6-2 甲醇轉化率的計算 37
3-6-3 氫氣選擇率及一氧化碳選擇率的計算 41
3-7 藥品、氣體及儀器設備 42
3-7-1 藥品 42
3-7-2 氣體 42
3-7-3 儀器設備 42
第四章結果與討論 45
4-1 物性分析 45
4-1-1 觸媒上各成份含量分析 (ICP-AES) 45
4-1-2 熱重分析 (TGA) 47
4-1-3 X-ray繞射分析 (XRD) 47
4-1-4 程式升溫還原分析 (TPR) 50
4-1-5 N2O分解吸附反應分析 (N2O-titration) 50
4-1-6 穿透式電子顯微鏡測量 (TEM) 56
4-2 化性分析 60
4-2-1 促進劑添加對觸媒活性的影響 60
4-2-2 煅燒溫度對觸媒活性的影響 60
4-2-3 反應物進料比對觸媒活性的影響 68
4-2-4 反應溫度對觸媒活性的影響 72
4-2-5 Cu/Zr/RHA和Cu/Zr/SiO2之間的比較 76
第五章結論 84
參考文獻 86

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指導教授

張奉文(Feg-Wen Chang)

審核日期

2010-7-6

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