臺灣博碩士論文加值系統

氫氣是最清淨的燃料，也是燃料電池的直接或間接燃料。然而地表上並不存在天然氫氣，氫氣主要來自於碳氫化合物（主要為甲烷）的轉化。由此所得之氫氣多含有少量不易去除之一氧化碳，會造成燃料電池因鉑電極的毒化而失去作用。因此有效且經濟的去除富氫中的一氧化碳乃為一重要課題，而利用適當觸媒促進富氫中一氧化碳的選擇性氧化已被證實為一有效方法。然而迄今，有效的觸媒多以貴重金屬（如鉑或金）為基礎，經濟性上仍待改善。
本研究以微乳化法製備以銅金屬為基礎的奈米級CuO/CeO2觸媒，並探討製備變因對觸媒性能的影響，包括：以不同配比製備載體、以不同溶劑（甲醇或去離子水）洗淨載體與以不同含浸時間擔載銅。所製備觸媒則以XRD、BET及TEM鑑定包括晶相、比表面積及粒徑分布等相關特性，並置入連續式填充床反應器進行富氫中一氧化碳選擇性氧化以測試其性能。
鑑定結果證實以微乳化法可以製備奈米級CuO/CeO2觸媒，其平均粒徑約為5 nm，有助於銅觸媒的分散性，增加其活性。選擇性氧化實驗顯示一氧化碳轉化率隨溫度的上升而增加，以甲醇（相對於去離子水）洗淨載體與較長的含浸時間的觸媒也具有較高轉化率；而一氧化碳的選擇率則隨轉化率的上升而下降；要同時達成100%轉化率與選擇率顯然仍尚待努力。所製最佳CuO/CeO2觸媒於140℃可以得到100%轉化率與50%選擇率，相較於以貴重金屬為基礎的觸媒，這樣的性能並不遜色，卻具有經濟上的優勢。

Hydrogen gas is the cleanest fuel, and the direct or indirect fuel for all types of fuel cell. However, hydrogen gas does not exist in nature, and mainly comes from the transformation of methane. Nevertheless, the product gas always carries trace amount of carbon monoxide, which in turn will result in the poisoning of the catalyst in the fuel cell and render the fuel cell inactive. Therefore, the elimination of carbon monoxide from the hydrogen rich gas effectively and economically is an important issue. So far, such catalysts are mainly based on novel metals, like Pt or Au. They are effective but expensive.
The current study employed Cu-based CuO/CeO2 catalyst, which is prepared through microemulsion and is of nanoscale. The effects of several catalyst preparation parameters on the performance of the catalyst for selective oxidation of CO in the hydrogen rich gas are investigated, including: varying emulsion mixture composition in preparing the CeO2 support, two different solvents (methanol or D. I. water) for cleaning the CeO2 support, and varying Cu impregnation time. The resulting catalysts are characterized with XRD, BET and TEM for their crystallinity, specific surface area and particle size distribution, and placed in a continuous packed-bed reactor to test their performance in catalyzing the selective oxidation of CO.
The characterization has revealed that nanoscale CuO/CeO2 catalysts can be prepared via microemulsion with an average particle size of about 5 nm. The selective oxidation experiments have shown that CO conversion increases with increasing temperature and is higher with methanol-cleaning or with longer impregnation time, and that the CO selectivity decreases with increasing CO conversion. To achieve 100% conversion and 100% selectivity simultaneously is yet to be accomplished. The CuO/CeO2 catalyst obtained from the best combination of preparation parameters is capable of achieving 100% CO conversion at a temperature as low as 140°C with a CO selectivity of 50%. Its performance is comparable to that of novel metal based catalysts, but its cost is much lower.

目 錄
中文摘要 Ⅰ
英文摘要 Ⅲ
誌謝 Ⅴ
目錄 Ⅵ
圖目錄 IX
表目錄 XI
第一章 研究動機 1
第二章 文獻回顧 5
2-1 燃料電池發展與燃料氣中CO的去除 5
2-1-1 CO選擇性甲烷化 7
2-1-2 CO替換轉化 7
2-1-3 膜處理 7
2-1-4 CO選擇性氧化 8
2-2 CeO2 10
2-2-1 CeO2的性質 10
2-2-2 CeO2的擔體 12
2-2-3 CeO2的應用 13
2-3 界面活性劑 14
2-3-1 界面活性劑的作用 15
2-3-2 界面活性劑的分類 18
2-4 觸媒的製備原理與方法 22
2-4-1 共沉澱法 22
2-4-2 溶膠-凝膠法 23
2-4-3 含浸法 24
2-4-4 微乳化法 26
2-5 選擇性氧化觸媒 35
2-5-1 Pt觸媒 35
2-5-2 Au觸媒 35
2-5-3 CuO觸媒 36
第三章 研究方法與裝置 37
3-1 研究方法 37
3-1-1 何謂選擇性氧化 37
3-1-2 選擇性氧化的探討 37
3-1-3 CuO/CeO2觸媒 37
3-2 研究藥品與氣體 39
3-3 儀器設備 40
3-4 擔體製備 41
3-5 觸媒製備 43
3-6 觸媒鑑定 45
3-6-1 XRD樣品製備與測試 45
3-6-2 TEM樣品製備與測試 45
3-6-3 BET樣品製備與測試 46
3-7 活性測試 47
3-7-1 活性反應裝置圖 48
3-7-2 CuO/CeO2觸媒之活性測試研究 49
3-7-3 選擇率與轉化率之計算 50
第四章 研究結果與討論 51
4-1 CeO2載體與CuO/CeO2觸媒的鑑定 51
4-1-1 XRD結構分析 51
4-1-2 BET結構分析 53
4-1-3 TEM結構分析 55
4-2 富氫環境下CO選擇性氧化的反應特性 65
4-2-1 不同含浸時間對於選擇性氧化反應的影響 65
4-2-2 不同洗淨方法對於選擇性氧化反應的影響 69
4-2-3 不同莫耳比例對於選擇性氧化反應的影響 73
第五章 結論 77
參考文獻 79

圖 目 錄
圖2-1 CeO2晶體結構圖 11
圖2-2 界面活性劑結構圖 14
圖2-3 界面活性劑之增溶作用 17
圖2-4 乳化劑分子於乳膠粒表面上狀態 18
圖2-5 (Ⅰ) AOT、(Ⅱ) SDS、(Ⅲ) TX-100界面活性劑分子結構圖21
圖2-6 含浸製備觸媒的解析圖 25
圖2-7 乾燥時間對物質沉積於孔洞中分佈情況 26
圖2-8 微胞結構圖 29
圖2-9 不同界面活性劑濃度對微胞形狀和液晶相排列的影響 30
圖2-10 乳化液型態圖 30
圖2-11 界面活性劑於極性與非極性溶液中分子形成微胞排列方法 31
圖2-12 逆微胞間相互作用 32
圖2-13 逆微胞系統中製造超微粒子的方法 33
圖3-1 CuO/CeO2觸媒進行CO氧化作用示意圖 38
圖3-2 活性反應裝置圖 48
圖4-1 CeO2載體與CuO/CeO2觸媒之X-ray繞射光譜圖 52
圖4-2 CuO/CeO2觸媒(去離子水洗)之X-ray繞射光譜圖 52
圖4-3 CeO2載體(去離子水洗)TEM圖 56
圖4-4 CeO2載體(甲醇洗)TEM圖 57
圖4-5 CuO/CeO2觸媒(去離子水洗)TEM圖 58
圖4-6 CuO/CeO2觸媒(甲醇洗)TEM圖 59
圖4-7 CeO2載體(去離子水洗)粒徑分佈圖 61
圖4-8 CeO2載體(甲醇洗)粒徑分佈圖 62
圖4-9 CuO/CeO2觸媒(去離子水洗)粒徑分佈圖 63
圖4-10 CuO/CeO2觸媒(甲醇洗)粒徑分佈圖 64
圖4-11 CuO/CeO2觸媒於不同含浸時間的選擇性氧化反應之CO轉
化率(實線)；CO選擇率(虛線) 66
圖4-12 CuO/CeO2觸媒於不同含浸時間的選擇性氧化反應之O2轉
化率 67
圖4-13 CuO/CeO2觸媒於不同含浸時間的選擇性氧化反應之CO2轉
化莫耳百分率 68
圖4-14 CuO/CeO2觸媒於不同洗淨方法的選擇性氧化反應之CO轉
化率轉化率(實線)；CO選擇率(虛線) 70
圖4-15 CuO/CeO2觸媒於使用不同洗淨方法的選擇性氧化反應之
O2選擇率 71
圖4-16 CuO/CeO2觸媒於使用不同洗淨方法的選擇性氧化反應之
CO2轉化莫耳百分率 72
圖4-17 CuO/CeO2觸媒於CO選擇性氧化反應之CO轉化率(實線)
；CO選擇率(虛線) 74
圖4-18 CuO/CeO2觸媒於CO選擇性氧化反應之O2選擇率 75
圖4-19 CuO/CeO2觸媒於CO選擇性氧化反應之CO2轉化莫耳百
分率 76

表 目 錄
表2-1 CeO2物理性質 12
表2-2 常見各類型的界面活性劑 20
表3-1 使用的藥品 39
表3-2 使用的氣體 39
表3-3 使用之儀器與設備 40
表4-1 CeO2載體與CuO/CeO2觸媒的比表面積 54
表4-2 CeO2載體與CuO/CeO2觸媒的以TEM測得之平均粒徑 60

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