臺灣博碩士論文加值系統

本研究在於使用共沉澱法製備CuO-CeO2的觸媒、微濕含浸法製備Cu/Ce/γ-Al2O3觸媒，以及使用微濕含浸將銅搭載於Ce-MCM-41載體上合成Cu/Ce-MCM-41觸媒。使其應用在過量氫氣環境中，進行選擇性一氧化碳氧化的反應，探討其觸媒對於CO的移除或轉化為CO2的活性為何，而對於合成的觸媒進行觸媒特性分析以及活性測試。特性分析方面使用XRD測量觸媒結構，BET量測觸媒表面積，ICP檢測觸媒的含量，而活性測試方面則於反應溫度50〜350oC下模擬重組器出口的氣體：1vol%的CO和2vol%的O2以及50vol%的H2，額外加入15%的CO2和3%的H2O，探討其CO的轉化率和選擇率。
實驗結果顯示銅、鈰莫爾比3:7的CuO-CeO2觸媒在反應溫度170〜230oC，CO的轉化率可達100%。而在相同的銅、鈰莫爾比情況下，Cu/Ce/γ-Al2O3觸媒的CO轉化率優於CuO-CeO2觸媒，其中銅、鈰莫爾比6:4的Cu/Ce/γ-Al2O3觸媒於230 oC下CO轉化率可達99.50%。然而，Cu/Ce-MCM-41觸媒CO轉化率卻遠不如CuO-CeO2及Cu/Ce/γ-Al2O3，由BET及ICP結果斷定，Cu/Ce-MCM-41表面積大幅度的下降，造成觸媒活性點減少，以及觸媒中Ce的含量不足所致。

This study is focused to optimize the selective oxidation of carbon monoxide reaction process over three types of the lab-prepared catalysts to remove CO or convert into CO2 in the presence of excess hydrogen.The proposed catalysts, Cu/Ce/γ-Al2O3 and Cu/Ce-MCM-41 were prepared by incipient wetness method, and CuO-CeO2 was made by co-precipitation. These catalysts were characterized by XRD, BET, and ICP. The activity of catalysts was tested in an environment of 1vol% CO, 2vol%O2 50vol% H2, 15vol% CO2, and 3vol%H2O.
The experimental results showed that the CO conversion achieved 100% at 170 oC ~230oC when the CuO-CeO2 catalyst with Cu to Ce molar ratio is 3:7. At the same molar ratio, the CO conversion of Cu/Ce/γ-Al2O3 was higher than those by CuO-CeO2 catalysts.The CO conversion achieved 99.5% at 230°C when the Cu/Ce/γ-Al2O3 catalyst with Cu to Ce molar ratio was 6:4. According to the BET and ICP results showed that surface area of Cu/Ce-MCM-41 decrease significantly.The active centers decreased and the ceria content was insuffucuent as well.

目 錄
摘要 I
Abstract II
圖目錄 I
表目錄 IV
第一章 導論 1
1-1 前言 1
1-2 孔洞觸媒載體的介紹 1
1-2-1 MCM-41 2
1-2-2 Al2O3 4
1-3文獻回顧 5
1-3-1 導氧離子氧化物 5
1-3-2 界面活性中心 7
1-3-3 CuO-CeO2觸媒簡介 8
1-3-4 ㄧ氧化碳的選擇性氧化 11
1-4 本文研究目的 13
第二章 實驗方法與步驟 15
2-1 觸媒的合成 15
2-1-1 CuO-CeO2觸媒的合成 15
2-1-2 Cu/Ce/γ-Al2O3觸媒的合成 16
2-1-3 MCM-41系列觸媒的合成 18
2-1-3-1載體MCM-41的合成 18
2-1-3-2 Ce-MCM-41的合成 19
2-1-3-3 Cu/Ce-MCM-41觸媒的合成 20
2-1-4 CeO2觸媒的合成 21
2-2觸媒的特性分析 21
2-2-1 BET表面積測試 21
2-2-2 X-ray粉末繞射儀晶體結構的檢測 22
2-2-3感應耦合電漿光譜儀的檢測 23
2-3 觸媒活性測試實驗 24
2-3-1 觸媒在固定床反應器的程序升溫反應 24
第三章 結果與討論 27
3-1觸媒BET的結果分析 27
3-1-1 CuO-CeO2和Cu/Ce/γ-Al2O3觸媒的表面積 27
3-1-2 Cu/Ce-MCM-41觸媒的表面積 29
3-2 X-ray粉末繞射圖譜的結果分析 31
3-2-1 CuO-CeO2觸媒與Cu/Ce/γ-Al2O3觸媒的比較 31
3-2-2 MCM-41系列觸媒XRD的分析結果 33
3-2-3 XRD圖譜下觸媒的晶粒大小 35
3-3感應耦合電漿光譜儀的結果分析 36
3-4 動力學研究的結果討論 37
3-4-1 固定床反應器程序升溫反應的結果分析 37
3-4-1-1觸媒中Cu-Ce的成分比例對於選擇性CO氧化活性的影響 38
3-4-1-2 IWP與COP合成的觸媒對於選擇性CO氧化活性的探討 41
3-4-1-3 CO2對於選擇性CO氧化活性的影響 42
3-4-1-4 H2O對於選擇性CO氧化活性的影響 48
3-4-1-5同時加入CO2和H2O對於選擇性CO氧化活性的影響 55
3-4-1-6反應後出口的CO濃度探討 57
第四章 結論與展望 60
附錄 63
附錄A 實驗儀器及裝置 63
附錄B 藥品 64
附錄C XRD晶格 65
附錄D XRD Databank 66
附錄E 氣相層析儀實驗相關資料 69
E-1 檢量線 69
E-2 實驗參數 70
附錄F BET吸/脫附等溫曲線的形式 71
附錄G 微濕含浸法前驅溶液的製備 74
附錄H MCM-41系列觸媒合成方式文獻之整理 75
附錄I CeO2系列觸媒合成方式文獻之整理 81
參考文獻 84

圖目錄
圖1-1 四級氨鹽的化學結構式 3
圖1-2 MCM-41的生成機制 4
圖1-3 螢石型氧化物之結構 7
圖1-4 CuO-CeO2觸媒CO氧化表面反應路徑圖 10
圖2-1 共沉澱法實驗流程圖 16
圖2-2 微濕含浸法實驗流程圖 18
圖2-3 感應耦合電漿光譜儀 23
圖2-4 程序升溫反應實驗流程圖 26
圖3-1 CuO-CeO2 觸媒BET恆溫吸/脫附曲線圖 28
圖3-2 Cu/Ce/γ-Al2O3觸媒和γ-Al2O3載體BET恆溫吸/脫附曲線圖 29
圖3-3 MCM-41系列的觸媒BET恆溫吸/脫附曲線圖 30
圖3-4 CuO/CeO2觸媒的XRD晶相結構圖譜(A)銅、鈰莫爾比2:8(9wt%的銅)(B)銅、鈰莫爾比3:7(12wt%的銅)(C)銅、鈰莫爾比 6:4(30wt%的銅)(D)銅、鈰莫爾比8:2(50wt%的銅) 32
圖3-5 銅、鈰莫爾比6:4 Cu-CeO2與Cu/Ce/γ-Al2O3 XRD圖譜 33
圖3-6 MCM-41和Ce/MCM-41小角度XRD圖譜 34
圖3-7 廣角度XRD Cu/Ce/MCM-41觸媒的訊號圖譜 35
圖3-8 於不同銅、鈰比例下的CuO-CeO2觸媒，CO轉化率與反應溫度的關係圖(表格2-3中B種的進料方式) 39
圖 3-9 氧氣的反應路徑圖 40
圖3-10 於不同銅、鈰比例下的CuO-CeO2觸媒，CO選擇率與反應溫度的關係圖(表格2-3中B種的進料方式) 41
圖3-11 CuO-CeO2、Cu/Ce/γ-Al2O3觸媒，CO轉化率與反應溫度比較圖(表格2-3中B種的進料方式) 42
圖3-12 銅、鈰莫爾比2:8的CuO-CeO2觸媒，加CO2和未加CO2情況 下，CO轉化率與反應溫度關係圖(實線為表格2-3中B種的進料方式，虛線則為表格2-3中D種的進料方式) 44
圖3-13 銅、鈰莫爾比3:7的CuO-CeO2觸媒，加CO2和未加CO2情況下，CO轉化率與反應溫度關係圖(實線為表格2-3中B種的進料方式，虛線則為表格2-3中D種的進料方式) 44
圖3-14 銅、鈰莫爾比6:4的CuO-CeO2觸媒，加CO2和未加CO2情況下，CO轉化率與反應溫度關係圖(實線為表格2-3中B種的進料方式，虛線則為表格2-3中D種的進料方式) 45
圖3-15 銅、鈰莫爾比8:2的CuO-CeO2觸媒，加CO2和未加CO2情況下，CO轉化率與反應溫度關係圖(實線為表格2-3中B種的進料方式，虛線則為表格2-3中D種的進料方式) 45
圖3-16 當CO轉化率小於零時，不同銅、鈰比例的CuO-CeO2觸媒對於反應溫度的分布圖 46
圖3-17 銅、鈰莫爾比6:4的Cu/Ce/γ-Al2O3觸媒，加CO2和未加CO2情況下，CO轉化率與反應溫度關係圖(實線為表格2-3中B種的進料方式，虛線則為表格2-3中D種的進料方式) 46
圖3-18 銅、鈰莫爾比8:2的Cu/Ce/γ-Al2O3觸媒，加CO2和未加CO2情況下，CO轉化率與反應溫度關係圖(實線為表格2-3中B種的進料方式，虛線則為表格2-3中D種的進料方式) 47
圖3-19 CuO-CeO2、Cu/Ce/γ-Al2O3觸媒加入CO2情況下，CO轉化率與反應溫度比較圖(表格2-3中D種的進料方式) 47
圖3-20 反應模擬氣加入15vol%的CO2時，不同比例的觸媒，CO選擇率相對於反應溫度的比較圖(表格2-3中D種的進料方式 48
圖3-21 銅、鈰莫爾比2:8的CuO-CeO2觸媒，加H2O和未加H2O情況下，CO轉化率與反應溫度關係圖(實線為表格2-3中B種的進料方式，虛線則為表格2-3中C種的進料方式) 50
圖3-22 銅、鈰莫爾比3:7的CuO-CeO2觸媒，加H2O和未加H2O情況下，CO轉化率與反應溫度關係圖(實線為表格2-3中B種的進料方式，虛線則為表格2-3中C種的進料方式) 50
圖3-23 銅、鈰莫爾比6:4的CuO-CeO2觸媒，加H2O和未加H2O情況下，CO轉化率與反應溫度關係圖(實線為表格2-3中B種的進料方式，虛線則為表格2-3中C種的進料方式) 51
圖3-24 銅、鈰莫爾比8:2的CuO-CeO2觸媒，加H2O和未加H2O情況下，CO轉化率與反應溫度關係圖(實線為表格2-3中B種的進料方式，虛線則為表格2-3中C種的進料方式) 51
圖3-25 銅、鈰莫爾比6:4的Cu/Ce/γ-Al2O3觸媒，加H2O和未加H2O情況下，CO轉化率與反應溫度關係圖(實線為表格2-3中B種的進料方式，虛線則為表格2-3中C種的進料方式) 52
圖3-26 銅、鈰莫爾比6:4的Cu/Ce/γ-Al2O3觸媒，加H2O和未加H2O情況下，CO轉化率與反應溫度關係圖(實線為表格2-3中B種的進料方式，虛線則為表格2-3中C種的進料方式) 52
圖3-27 CuO-CeO2系列觸媒加入H2O時，CO轉化率相對於反應溫度比較圖(表格2-3中C種的進料方式) 53
圖3-28 CuO-CeO2、Cu/Ce/γ-Al2O3觸媒加入H2O時，CO轉化率相對於反應溫度比較圖(表格2-3中C種的進料方式) 53
圖3-29 於不同比例下的觸媒加入3%的H2O時，CO選擇率相對於反應溫度比較圖(表格2-3中C種的進料方式) 54
圖3-30 加入H2O和CO2 情況下，不同比例的觸媒，反應溫度相對於CO轉化率比較圖(表格2-3中A種的進料方式) 56
圖3-31 加入H2O和CO2 情況下，不同類型的觸媒，反應溫度相對於CO轉化率比較圖(表格2-3中A種的進料方式) 56
圖F-1 氮氣恆溫吸附/脫附曲線類型 73
圖F-2 氮氣恆溫吸附/脫附曲線遲滯回圈的類型 73


表目錄
表格1-1 氧化鋁在各種溫度的相變化 5
表格2-1 共沉澱法合成觸媒所使用的金屬量 15
表格2-2 Cu/Ce/γ-Al2O3 觸媒成分 17
表格2-3 反應進料條件 25
表格3-1 CuO-CeO2和Cu/Ce/γ-Al2O3觸媒BET資料表 28
表格3-2 MCM-41系列表面積、孔洞體積、平均粒徑大小比較表 31
表格3-3 各觸媒中CuO(111)、CeO2(111)的晶粒大小 36
表格3-4 ICP成分分析結果 37
表格3-5 銅、鈰莫爾比例與觸媒活性關係表 39
表格3-6 CuO-CeO2和Cu/Ce/γ-Al2O3觸媒活性關係表 42
表格3-7 在未加CO2和加CO2的情況下，CO轉化溫度的比較 48
表格3-8 在未加H2O和加H2O的情況下，CO轉化溫度的比較 54
表格3-9 共沉澱合成的CuO-CeO2觸媒，在加入CO2和H2O的情況下，出口CO濃度比較 58
表格3-10 微溼含浸法合成的Cu-Ce/γ-Al2O3觸媒，在加入CO2和H2O的情況下，出口CO濃度比較 59
表D-1 氧化鈰CeO2 Databank 66
表D-2 氧化銅CuO Databank 66
表D-3 二氧化矽SiO2 Databank 67
表D-4 氧化鋁γ-Al2O3 Databank 67
表D-5 氧化亞銅Databank 68
表E-1 甲烷CH4檢量線 70
表E-2 水H2O檢量線 70
表G-1 前趨溶液配置成份表 74

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