Ni/Mg-Al-O觸媒於CH4/CO2重組反應之研究

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蔡俊煌(Chun-Huang Tsai) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

Ni/Mg-Al-O觸媒於CH4/CO2重組反應之研究
(CO2 Reforming of Methane on Ni/Mg-Al-O Catalyst)

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摘要(中)

摘要
本研究以共沈澱法製備具有不同Mg/Al比例及不同Ni負載量的hydrotalcite先驅物Ni/HT(x)，經高溫煅燒製得觸媒Ni/HTc(x)。利用X光繞射光譜(XRD)、全表面積測定 (BET) 、X-光電子光譜儀 (XPS) 、氫程溫脫附 (H2-TPD) 、氫程溫還原 (H2-TPR) 對觸媒的物理結構及表面性質做鑑定分析。藉由CH4/CO2重組反應測試，探討不同煅燒溫度、還原溫度、Mg/Al比例、Ni負載量及反應溫度之影響，並進行長時間反應穩定性測試，觀察上述之不同變因對觸媒壽命期之影響，並以程溫氫化反應(H2-TPSR)分析觸媒表面積碳，探討觸媒積碳阻抗的能力。
Ni/HTc(x)於800℃煅燒具有高表面積(125 m2/g以上)，原觸媒先驅物Ni/HT(x)的hydrotalcite層狀結構經高溫煅燒瓦解形成Mg-Al-O共氧化物，隨著煅燒溫度上升，NiO與MgO逐漸形成固溶。Ni/HTc(x)觸媒不易還原，所需的還原溫度較傳統觸媒Ni/γ-Al2O3及Ni/SiO2高出釵h，且隨著煅燒溫度和Mg/Al比例的增加而增加，此外XPS表面組成分析發現Ni/(Mg+Al)莫耳比隨著煅燒溫度上升而下降，進一步證實NiO和MgO確實形成固溶，增加NiO-MgO之間的作用力。
CH4/CO2重組反應結果知CO2轉化率皆高於CH4轉化率，且CO/H2比值介於1.0~1.2之間。RWGS反應是主要的副反應，同時亦發生蒸氣重組反應，使CO/H2比值趨近於理論值1。CH4及CO2轉化率隨Ni負載量、還原及反應溫度上升而增加；隨煅燒溫度及Mg/Al比上升而減小。CH4/CO2重組反應結果以800℃煅燒，500℃還原，Mg/Al比3，8%Ni負載量，700℃反應溫度條件下的8%Ni/HTc(3)觸媒有較好的穩定性。8%Ni/HTc(3)與8%Ni/HTc(3)im(含浸法製備)、8%Ni/γ-Al2O3及8%Ni/SiO2觸媒進行CH4/CO2重組反應比較下，8%Ni/HTc(3)觸媒有最佳穩定性，H2-TPD計算得8%Ni/HTc(3)有最佳分散度，H2-TPSR亦發現8%Ni/HTc(3)觸媒有最佳的積碳阻抗。

摘要(英)

In this study,we prepared different Mg/Al ratios and Ni loading precursor by coprecipitation method,and then calcined at high temperature to prepare Ni/HTc(x) catalysts.
XRD 、BET、XPS、H2-TPR、H2-TPD were used to study the structure and surface properties.
The effect of different calcination temperature、reducing temperature、Mg/Al ratios、Ni loading and reaction temperature was studied by CH4/CO2 reforming.H2-TPSR was used to study coking resistance of catalyst.
Ni/HT(x) has the same structure with hydrotalcite,after calcined at high temperature,the layer stuucture was collased and became Mg-Al-O mixed-oxides,the surface also increased. As the calcined temperature increased NiO and MgO became solid solution.
It is hard to reduce Ni/HTc(x) catalyst,and reducing temperature is higher than Ni/γ-Al2O3 and Ni/SiO2 catalyst. XPS found that Ni/(Mg+Al) ratio reduce as calcination temperature increase,furthre prove NiO and MgO were formed solid solution.
In CH4/CO2 reformimg we found that 8%Ni/HTc(3) catalyst ,calcined at 800℃ ,reduced at 500℃ , Mg/Al ratio is 3,and 700℃ reaction temperature had the best stability than 8%Ni/γ-Al2O3,8%Ni/SiO2. H2-TPSR also found that 8%Ni/HTc(3) had best coking resistance.

關鍵字(中)

★ 合成氣
★ 鎳鎂鋁氧觸媒
★ 重組反應

關鍵字(英)

★ Surported Nickel Catalyst
★ Mg/Al mixed oxide
★ Hydrotalcite
★ Syngas
★ CH4/CO2 reforming

論文目次

目錄
第一章緒論 1
第二章文獻回顧 3
2-1 CH4/CO2在過渡金屬觸媒上之重組反應 ……………….. 3
2-1-1 Ru、Rh觸媒 …………………………………………….. 4
2-1-2 Pt、Pd金屬觸媒 ………………………………………… 9
2-1-3 Ni金屬觸媒 ……………………………………………… 15
2-2 Mg/Al hydrotalcites擔體 ……………………………….… 21
2-2-1 Mg/Al hydrotalcite之製備 ………………………………. 21
2-2-2 Mg/Al hydrotalcite結構性質 ……………………………. 22
2-2-3 Mg/Al hydrotalcite熱處理前後之性質 …………………. 23
2-2-4 Mg/Al hydrotalcite觸媒相關性質 ………………………. 24
第三章實驗方法與設備3-1 Ni/Mg-Al-O(X%Ni/HT(x))先驅物與觸媒之製備 ………...
3-2 Ni/HTc(x)觸媒之加工 ……………………………………... 262627
3-3 其他觸媒之製備 …………………………………………… 28
3-4 氫-程溫還原(H2-TPR) ……………………………………… 28
3-5 氫-程溫脫附(H2-TPD) ……………………….…………….. 30
3-6 全表面積的量測 …………………………………………… 32
3-7 X-射線繞射分析(XRD) ……………………………………. 33
3-8 X-射線光電子光譜(XPS) ………………………………….. 33
3-9 氫-程溫反應 (H2-TPSR) ……………………………………3-10 CH4/CO2於Ni/HTc(x)觸媒之重組反應研究 ………………
3436
3-11 使用藥品 …………………………………….……………... 39
第四章結果與討論 41
4-1 Ni/HT(x)先驅物與Ni/HTc(x)觸媒之製備與鑑定 ………. 41
4-1-1 XRD結構分析 …………………………….…………….. 42
4-1-2 BET表面積測量 ………………………………………… 48
4-2 觸媒表面性質分析 ………………………….……………. 50
4-2-1 氫-程溫還原(H2-TPR) ………………………………….….. 50
4-2-2 氫程溫脫附(H2-TPD) …………….………………………... 56
4-2-3 8%Ni/HTc(3)觸媒表面組成分析(XPS) …………………. 62
4-3 CH4/CO2重組反應 ……………………………………….. 64
4-3-1 不同煅燒溫度之影響 …………………………………….. 64
4-3-2 不同還原溫度的影響 …………………………………….. 69
4-3-3 不同Mg/Al比例之影響 ……………………………….… 73
4-3-4 不同Ni負載量的影響 ……………………………………. 77
4-3-5 不同反應溫度的影響 …………………………………….. 81
4-3-6 不同擔體Ni觸媒反應穩定性的比較 …………………… 85
4-3-7 不同擔體Ni觸媒積碳阻抗之比較(TPSR) ………………. 88
第五章結論 91
總結 92
參考文獻 93
圖目錄
圖2-1 Schematic representation of the proposed mechanism of CO /CH4 reforming over Pt-ZrO2……………………………... 12
圖2-2 Pt/ZrO2於CH4/CO2重組反應機構圖…………………….. 12
圖3-1 氫程溫還原裝置圖………………………………………… 29
圖3-2 氫程溫脫附裝置圖………………………………………… 31
圖3-3 氫程溫反應裝置圖………………………………………… 35
圖3-4 CH4/CO2重組反應實驗裝置示意圖………………………. 38
圖4-1 觸媒先驅物8%Ni/HT(x)之X-ray繞射光譜圖…………… 44
圖4-2 8%Ni/HT(3)經不同溫度煅燒之X-ray繞射光譜圖………. 45
圖4-3 8%Ni/HTc(x)之X-ray繞射光譜圖………………………… 46
圖4-4 x%Ni/HTc(3)之X-ray繞射光譜圖………………………… 47
圖4-5 不同煅燒溫度8%Ni/HTc(3)觸媒之程溫還原圖譜……….. 52
圖4-6 不同擔體Ni觸媒之程溫還原圖譜……………………….. 53
圖4-7 不同Mg/Al比觸媒8%Ni/HTc(x)之程溫還原圖譜……… 54
圖4-8 不同Ni負載觸媒x%Ni/HTc(3)之程溫還原圖譜………….. 55
圖4-9 不同煅燒溫度8%Ni/HTc(3)之氫程溫脫附圖譜…………… 58
圖4-10 8%Ni/HTc(x)之氫程溫脫附圖譜………………………… 59
圖4-11 不同煅燒溫度8%Ni/HTc(3)觸媒之CH4轉化率………… 66
圖4-12 不同煅燒溫度8%Ni/HTc(3)觸媒之CO2轉化率………… 67
圖4-13 不同煅燒溫度8%Ni/HTc(3)觸媒之CO/H2比值………… 68
圖4-14 不同還原溫度8%Ni/HTc(3)觸媒之CH4轉化率………… 70
圖4-15 不同還原溫度8%Ni/HTc(3)觸媒之CO2轉化率………… 71
圖4-16 不同還原溫度8%Ni/HTc(3)觸媒之CO/H2比值………… 72
圖4-17 8%Ni/HTc(x)觸媒之CH4轉化率…………………………. 74
圖4-18 8%Ni/HTc(x)觸媒之CO2轉化率…………………………. 75
圖4-19 8%Ni/HTc(x)觸媒CO/H2比值……………………………. 76
圖4-20 不同Ni負載量之CH4轉化率……………………………. 78
圖4-21 不同Ni負載量之CO2轉化率……………………………. 79
圖4-22 不同Ni負載量之CO/H2比值……………………………. 80
圖4-23 8%Ni/HTc(3)觸媒在不同反應溫度之CH4轉化率………. 82
圖4-24 8%Ni/HTc(3)觸媒在不同反應溫度之CO2轉化率………. 83
圖4-25 8%Ni/HTc(3)觸媒在不同反應溫度之CO/H2比值………. 84
圖4-26 不同擔體Ni觸媒之CH4轉化率………………………….. 86
圖4-27 不同擔體Ni觸媒之CO2轉化率………………………….. 87
圖4-28 不同擔體Ni觸媒TPSR圖譜……………………………... 89
表目錄
表4-1 8%Ni/HT(x)先驅物之表面積………………………………48
表4-2 8%Ni/HTc(3) 經不同溫度煅燒觸媒之表面積…………….49
表4-3 不同Mg/Al比8%Ni/HTc(x)觸媒之表面積……………….49
表4-4 不同煅燒溫度8%Ni/HTc(3)觸媒之氫吸附量與分散度…. 57
表4-5 8%Ni/HTc(x)與傳統觸媒之氫吸附量與分散度…………...60
表4-6 8%Ni/HTc(3)觸媒不同還原溫度之氫吸附量與分散度……60
表4-7 x%Ni/HTc(x)觸媒之氫吸附量與分散度……………………61
表4-8 不同煅燒溫度及不同還原溫度的8%Ni/HTc(3)觸媒之XPS表面分析結果………………………………………………..63
表4-9 不同Ni觸媒之積碳.…………………………………………90

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指導教授

陳吟足(Yn-Zu Chen)

審核日期

2002-6-24

推文