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研究生(外文):Yu, Shen-Wei
論文名稱(外文):Evaluation for Oxygen Vacancy on Co-Ce-Y Composite Oxides and Steam Reforming of Ethanol
指導教授(外文):Wang, Chen-Bin
口試委員(外文):Yeh, Chuin-TihShiu, Feng-JangWu, Ren-JangWang, Chen-BinWu, Kuo-Hui
外文關鍵詞:Steam reforming of ethanolUltrasonic-assistedOxygen storage capacityAccessible oxygen
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本研究探討Co3O4-CeO2及Co3O4-CeO2-Y2O3觸媒中之移動氧對乙醇蒸氣重組(SRE)之影響。分別以水熱共沉澱法(Hydrothermal Co-precipitation, H)及超音波輔助水熱共沉澱法(Ultrasonic-assisted Hydrothermal Co-precipitation, UH)製備莫耳比為1:1之Co3O4-CeO2觸媒,之後再利用同UH法分別加入2.5、5及10 wt %的Y2O3進行修飾。所有觸媒均利用X光繞射儀(XRD)、程溫還原/程溫氧化(TPR/TPO)、電子能譜儀(XPS)、高解析TEM (HR-TEM)、元素分析(EA)、二氧化碳程溫脫附(CO2-TPD)等方式對觸媒進行特性鑑定。實驗結果顯示Co離子進入CeO2的晶格中可增加觸媒之分散性、氧空缺及提升CeO2的儲/釋氧能力,其中以超音波所製備之Co3O4-CeO2觸媒較顯著,其較多之移動氧在乙醇蒸氣重組反應及抑制積碳中拌演重要角色。Co-Ce(UH)觸媒具較高之活性,在400 oC時乙醇可完全轉換且氫氣選擇率(SH2)達90 %,另此觸媒之高儲氧能力(Oxygen Storage Capacity, OSC)及高移動氧可在積碳生成同時將之氧化/氣化。然而,添加Y使Co2+不易進入CeO2晶格,且未進入CeO2晶格中的Y易堆積在表面而覆蓋活性金屬,並減少氧空缺的生成,故隨Y含量增加而導致活性降低,且易生成積碳。
The effect of accessible oxygen on the steam reforming of ethanol (SRE) over Co3O4-CeO2 and Co3O4-CeO2-Y2O3 catalysts was investigated. Both equal molar ratio of Co3O4-CeO2 catalysts were prepared by hydrothermal co-precipitation (H) and hydrothermal ultrasonic-assisted co-precipitation (UH) methods, and finally the UH method was applied to prepare 2.5, 5, and 10 wt % of yttrium-doped Co3O4-CeO2 catalysts, respectively. All catalysts were characterized through X-ray diffraction (XRD), temperature programmed reduction/temperature programmed oxidation (TPR/TPO), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HR-TEM), elemental analysis (EA) and CO2 - temperature programmed desorption (CO2-TPD) techniques at various stages. The results indicated that the incorporation of cobalt ion into the ceria lattice could increase the dispersion of ceria, oxygen vacancies and promote the oxygen-storing and releasing capability of ceria, especially over the catalyst prepared by ultrasonic-assisted method. The accessible oxygen played an important role on the SRE reaction and resistant to carbon deposition. The Co-Ce(UH) catalyst was more active and selective, i.e., ethanol conversion achieved complete and hydrogen selectivity (SH2) approached 90% at 400 C. The high oxygen storage capacity (OSC) and high accessible oxygen for the Co-Ce(UH) catalyst allowed oxidation/gasification of deposited carbon as soon as it formed, and less coke was detected. However, cobalt ions were not easily incorporated into CeO2 lattice with less formation of oxygen vacancies when the yttrium was added, which led to decrease of activity and more formation of carbonaceous deposits.
誌謝 ii
摘要 iii
目錄 v
表目錄 ix
圖目錄 x
1. 緒論 1
1.1 前言 1
1.2 產氫技術 3
1.2.1 碳氫化合物為燃料 4
1.2.2 非碳氫化合物為燃料 5
1.3 乙醇產氫 6
1.3.1 生質乙醇 6
1.3.2 乙醇製氫方法 7
1.3.3 積碳之生成 9
1.4 文獻回顧 10
1.4.1 活性金屬 10
1.4.2 載體 11
1.4.3 促進劑 12
1.4.4 觸媒製備方式 13
1.5 研究動機與方向 14
2. 實驗 15
2.1 實驗藥品 15
2.2 觸媒之製備 15
2.2.1 氧化鈷之製備 16
2.2.2 氧化鈰之製備 16
2.2.3 鈷鈰複合氧化物觸媒之製備 17
2.2.4 鈷鈰釔複合氧化物觸媒之製備 18
2.3 觸媒之特性鑑定 24
2.3.1 X光繞射儀(XRD) 24
2.3.2 感應耦合電漿原子放射光譜儀(ICP-AES) 25
2.3.3 高解析穿透式電子顯微鏡(HR-TEM) 25
2.3.4 氮氣等溫吸/脫附測試(BET) 25
2.3.5 元素分析儀(EA) 27
2.3.6 程溫還原/氧化裝置(TPR/TPO) 27
2.3.7 電子能譜儀(XPS) 28
2.3.8 二氧化碳程溫脫附(CO2-TPD) 29
2.4 乙醇蒸氣重組活性測試 31
2.4.1 活性測試裝置 31
2.4.2 活性測試數據分析 31
3. 結果與討論 35
3.1 Co3O4觸媒及CeO2載體之特性鑑定及SRE反應活性評估 35
3.1.1 反應前之特性鑑定 35
3.1.2 反應活性評估 43
3.1.3 反應後之特性鑑定 50
3.2 Co3O4-CeO2觸媒之特性鑑定及SRE反應活性評估 54
3.2.1 反應前之特性鑑定 54
3.2.2 反應活性評估 71
3.2.3 反應後之特性鑑定 76
3.2.4 長時間穩定性測試 79
3.2.5 穩定性測試後之特性鑑定 81
3.3 Co3O4-CeO2-Y2O3觸媒之特性鑑定及SRE反應活性評估 84
3.3.1 反應前之特性鑑定 84
3.3.2 反應活性評估 94
3.3.3 反應後之特性鑑定 98
3.3.4 長時間穩定性測試 102
3.3.5 穩定性測試後之特性鑑定 104
4. 結論 107
參考文獻 109
附錄A 氫氣檢量線建立 117
附錄B 氧氣檢量線建立 119
附錄C 重疊峰之分峰(I) 121
附錄D 重疊峰之分峰(II) 126
論文發表 130
自傳 132

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