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研究生：	曾國銘 Tseng, Kuo-Ming
論文名稱：	探討金屬氧化物的支撐物對乙醇蒸氣重組反應的影響 Investigation of the effect of metal oxide supporters on ethanol steam reforming reaction
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：	2015
畢業學年度：	103
語文別：	中文
論文頁數：	90
中文關鍵詞：	乙醇蒸氣重組、氧化鈰、鈣鈦礦
英文關鍵詞：	Oxidative Steam Reforming of Ethanol, CeO2, BaZrO3
論文種類：	學術論文
相關次數：	點閱：174 下載：2
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本篇論文中，我們將 Rh、Ru兩種金屬分別附著在三種不同金屬氧化支撐上，來進行氧化乙醇蒸氣重組反應，而這三種氧化支撐物分別為，氧化鈰 (CeO2)、參雜了Dy的鈣鈦礦結構(Dy-doped BaZrO3) 和鈣鈦礦結構(BaZrO3)。透過XRD、EDX、TPR探討金屬與金屬氧化物是否符合。在乙醇蒸氣重組實驗中，使用不同氧氣量的條件下乙醇對氧氣比例為2~0.4、不同乙醇與水莫爾比例(1:1、1:3、1:5、1:7、1:10)及不同的溫度(300℃~600℃)來進行實驗。在催化劑中金屬的部分，我們發現Rh、Ru有助於C-C鍵斷裂，產生CO與CO2。在催化劑中支撐物的部分，我們選擇了螢石結構(CeO2)、鈣鈦礦結構(Dy-doped BaZrO3) 和鈣鈦礦結構(BaZrO3)有效的利用環境中氧氣與水，其中氧化鈰對氧具有高活性，在乙醇與莫爾比例為1:3，乙醇對氧氣比例在0.61，氫氣產率為72%，而鈣鈦礦結構(Dy-doped BaZrO3)與鈣鈦礦結構(BaZrO3)可以有效利用水，促使催化劑效能提升及氫氣產率提升，在乙醇與莫爾比例為1:10，乙醇對氧氣比例在0.58，氫氣產率為86%，所以可以看出BZDy及BZO比在氧的氧化鈰下具有更好的在乙醇氧化蒸氣重組反應中具有重要的影響。在乙醇蒸氣反應後，將催化劑進行XRD、EDX、TPO鑑定，在XRD鑑定與反應前並沒有差異，在EDX、TPO發現鈣鈦礦結構(Dy-doped BaZrO3)含碳量大於氧化鈰(CeO2) ，但在長時間反應中卻能維持高乙醇轉換及氫氣產率。

In this present work, we studied oxidative steam reforming of ethanol (OSRE) on the catalysts of Rh and Ru supported on CeO2, Dy-doped BaZrO3 (BZDy) and BaZrO3 (BZO). The samples were initially characterized by XRD,EDX and TPR and followed by the reforming experiments with various C/O Ratio: 2 to 0.4, Ethanol/ H2O molar ratios (1:1,1:3,1:5,1:7,1;10) and temperatures (300℃~600℃) to elucidate the effects from oxygen and steam on OSRE. Both Rh and Ru are well known for their superior capability of C-C bond cleavage and the main products from OSRE are CO and CO2 for all sample. Supports of CeO2, BZDy and BZO, on the other hand, have different specialties for oxygen and steam. CeO2 is highly active for oxygen and further improves OSRE performance at higher oxygen contents. Its best H2 yield 72% in ethanol/H2O=1:3, C/O Ratio: 0.61. BZDy and BZO have excellent activity for steam and enhance the hydrogen production in OSRE at higher steam contents. Its best good H2 yield 86% in ethanol/H2O=1:10, C/O Ratio: 0.58. Additionally, the enhancement from steam in BZDy and BZO-based catalysts are better than that from oxygen in CeO2-related catalysts, indicating that steam plays an more important role to improve OSRE performance. The post-experimental samples were also examined by XRD,EDX and TPO to identify the stability of those samples. The EDX and TPO results found that BZDy and BZO-based materials have more carbon deposition though their long-term stability were as good as CeO2-based catalysts.

第一章 : 緒論
1-1  介紹...............................................9
1-2  乙醇重組反應的基本理論與現階段研究介紹................10
1-3  金屬催化劑研究介紹..................................12
1-4  金屬氧化物支撐物現階段研究介紹.....................................................13
1-5  實驗動機與研究.....................................16
第二章 : 實驗部分
2-1  實驗用藥品.........................................18
2-2  實驗用氣體.........................................21
2-3  實驗器材與儀器.....................................22
2-4  催化劑的製備.......................................23
2-4-1  製備支撐物催化劑..................................23
2-4-2  金屬支撐物.......................................27
2-5  催化劑的特性鑑定....................................32
2-5-1  X光繞射分析(X-ray diffraction analysis,XRD)......32
2-5-2  能量散射光譜儀 (Energy dispersive X-ray .........33
2-5-3  H2/O2-TPR、TPO 程溫還原/氧化(Temperature-programmed reduction/Oxidation,TPR/TPO)...........................34
2-6  乙醇重組活性測試....................................36
2-7  活性測試及產物分析..................................38
2-8  乙醇重組實驗之操作條件..............................40
2-9  Gas Hour Space Velocity 、轉換效率與產率選擇率計算...41
第三章 : 結果與討論
3-1  XRD測試結果........................................43
3-2  元素組成 鑑定結果...................................46
3-3  H2-Temperature Programmed Reduction (H2-TPR) 分析結果 .......................................................47
3-4  催化劑活性測試.....................................51
3-4-1  催化劑，乙醇/水比例與溫度對催化反應的影響…..........51
3-4-1-1氧氣比例與溫度對催化反應的影響.....................52
3-4-1-2金屬對催化反應的影響..............................60
3-4-1-3氧化物支撐物對催化反應的影響.......................68
3-4-2  最佳催化劑Rh/BZDy與Rh/CeO2的最佳條件測試比較…......76
3-4-3  長時間測試.......................................78
3-5  反應後XRD測試結果….................................81
3-6  反應後Energy dispersive X-ray spectroscopy (EDS) 鑑定結果…..................................................83
3-5  O2-Temperature-Programmed Oxidation (O2-TPO) 鑑定結果.....................................................84
第四章 : 結論
4-1  結論..............................................86
4-2  未來研究方向.......................................86
參考文獻................................................87

                                

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