Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3856
標題: 銅-氧化鋯觸媒擔持於鏑-鋁混合氧化物之製備及其用於甲醇蒸氣重組產氫之研究
Preparation of Copper-Zirconia Catalyst Supported on Dysprosium-Aluminum Mixed Oxides for Hydrogen Production by Methanol Steam Reforming
作者: 高楚昀
Kao, Chu-Yun
關鍵字: steam reforming of methanol
蒸氣重組反應
copper catalysts
dysprosium oxide
chemical reduction method
氧化鏑
銅觸媒
化學還原法
出版社: 化學工程學系所
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摘要: 本論文研究目的為將活性金屬銅與氧化鋯擔持於鏑-鋁混合氧化物載體,將其應用於甲醇蒸氣重組反應。觸媒製備變數包含不同製備方法及煅燒溫度、不同促進劑、不同促進劑及活性銅含量、不同製備溶劑、不同前驅物溶液濃度、不同還原劑及分散劑、鏑-鋁混合氧化物比例,觸媒活性則以填充床反應器在水對甲醇莫耳比為1.3下於溫度200℃至400℃間測試。甲醇蒸汽重組反應變因包含不同水量與甲醇莫耳比、不同重量空間流速與觸媒穩定測試。 實驗結果顯示,利用沉澱與化學還原法製備觸媒反應比共沉澱法來的好,在Cu/Dy2O3 觸媒中添加10%不同促進劑(Zn、Sm、Ce、Zr) 皆能提升觸媒的分散性及活性,於280°C下大致都可提升5%的氫氣產率及降低CO濃度,其中以氧化鋯具有最佳的氫氣產率約92%。隨著促進劑氧化鋯含量的增加超過20%,過多的促進劑反而會包覆活性銅,使觸媒活性下降。製備觸媒過程中,溶液濃度對銅晶粒大小有明顯的影響,在低濃度時粒子間距過大,促進劑及分散劑效應減弱而使晶粒變大。此外,經由不同分散劑的添加都能有效使銅分散,提高觸媒表面積及催化活性。在載體中摻混氧化鋁,能提升催化效率,在穩定性測試結果中,Cu(25)/Dy2O3(75)觸媒於反應20小時活性下降為76%、Cu(25)ZrO2(10)/Dy2O3(65)觸媒於反應30小時仍維持在87%,而摻混氧化鋁之觸媒於100小時反應後氫氣產率僅下降約10%,最佳觸媒比例為Cu(25)ZrO2(10)/ [Dy2O3(75)-Al2O3(25)](65)。
In this dissertation, the purpose of this study is to prepare copper -zirconia catalyst supported on dysprosium-aluminum mixed oxides and to apply it on steam reforming of methanol. The catalysts were tested by packed-bed reactor between 200℃ to 400℃. The parameters of catalyst preparation include the different deposition methods and calcination temperature, ratios of promoter and copper to support, different solvents, concentration of precursor solution, types of reductant and dispersant, ratios of dysprosium-aluminum mixed oxides. Operating conditions in steam reforming of methanol included molar ratio of H2O/CH3OH, weight hourly space velocity, and stability of catalysts. The results revealed that the catalyst prepared by chemical reduction method is better than that prepared by co-precipitation method for this system. Doping of 10% amounts of metal oxide promoters (Zn, Sm, Ce, Zr) to the Cu/Dy2O3 catalyst enhanced the dispersion, activity of the catalyst and improved about 5% yield at 280°C. The catalyst added ZrO2 has the best hydrogen yield of about 92%. With the addition content of ZrO2 more than 20%, promoters would be too much and hide copper to decrease the activity of catalyst. Concentration of solution also significantly affect the copper of the grain size in the process of preparation of catalyst, because at low concentration distance between particles is larger, the effect of promoter and dispersant is weaker and lead larger grains. In addition, different dispersants can effectively improve the dispersion of copper and also improve the surface area and activity of the catalyst. Mixing the alumina in the support can improve the catalytic efficiency. In the stability test, the activity of Cu(25)/Dy2O3(75) catalyst remained 76% in the reaction of 20 hours, and the Cu(25)ZrO2(10)/Dy2O3(65) catalyst maintained at 87%. While the hydrogen yield of the catalyst added alumina almost decreased about 10% in the reaction of 100 hours, the best ratio of Cu(25)ZrO2(10)/[Dy2O3(75)-Al2O3(25)](65) catalyst.
URI: http://hdl.handle.net/11455/3856
其他識別: U0005-0407201116125400
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