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標題: 奈米碳管擔持銅/氧化鈰觸媒之製備及其催化甲醇蒸汽重組反應之研究
Preparation of Cu/CeO2 Catalysts Supported on Carbon nanotubes for Steam Reforming of Methanol
作者: 陳志維
Chen, Zhi-Wei
關鍵字: carbon nanotubes
steam reforming of methanol
cerium oxide
precipitation and reduction method
出版社: 化學工程學系所
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摘要: 本論文之研究目的為將活性金屬銅與促進劑氧化鈰擔持於奈米碳管表面,將其應用於甲醇蒸汽重組反應。觸媒製備的變數包括不同的製備方法、不同載體、不同活性金屬與促進劑之重量比、不同活性金屬與促進劑總擔持量、不同第二促進劑添加、主要促進劑氧化鈰與第二促進劑氧化鋅不同重量比、不同第二活性金屬的添加等。甲醇蒸汽重組反應變因包含有不同水量對甲醇莫耳數比、不同重量空間流速與觸媒穩定性測試。 實驗結果顯示,利用沉澱與還原法製備之觸媒反應活性較高。使用管徑40~60 nm的奈米碳管其氫氣產率最高。添加促進劑氧化鈰與活性金屬銅重量比為1:1時,氫氣產率與二氧化碳選擇率都較高。活性金屬與促進劑總擔持量為50 %時,反應溫度在320 ℃,有很高的反應活性。添加少量氧化鋅為第二促進劑時,氫氣產率在280 ℃,即達到接近100 %,而添加第二活性金屬鉑、鐵與鈀則會抑制反應活性。 在甲醇蒸汽重組反應變因中,當水與甲醇莫耳數比為1.3 mol/mol與反應溫度為280 ℃時,氫氣產率為98 %,其單位觸媒產氫速率可達117.05 mmol/s*。在100小時之活性穩定測試過程中,反應時間超過34小時後,其單位觸媒產氫速率即保持在84 mmol/s*。 本研究成功利用沉澱與還原法將促進劑氧化鈰與活性金屬銅擔持於奈米碳管上,應用於甲醇蒸汽重組反應中有相當好的效果。
In the thesis, the purpose of this study is to prepare nanocatalyst Cu/CeO2 supported on carbon nanotubes (CNTs) and to apply it on steam reforming of methanol. The parameters catalyst preparation include the different Cu/CeO2 deposition method, types of support of catalyst, weight ratio of Cu/ CeO2, Cu/ CeO2 content, different second promoters, weight ratio of CeO2/ZnO and additions of different metals . Operating conditions in steam reforming of methanol are molar ratio of H2O/CH3OH, weight hourly space velocity, and stability of catalysts. The results show that the catalyst prepared by precipitation and reduction method has a higher activity than co-precipitation method. The highest hydrogen yield with carbon nanotubes(40~60 nm) as support for catalysts was obtained. A high hydrogen yield and selectivity of CO2 were achieved at weight ratio of Cu to CeO2 being 1:1. The catalyst with 50 wt% Cu/ CeO2/CNTs showed high activities at 320 ℃, and by adding ZnO as second promoter to Cu/ CeO2/CNTs catalyst, the hydrogen yield was obtained near 100 % at 280 ℃. The addition of second active metal (Pt、Fe and Pd) reduces the catalytic activity. In methanol steam reforming with 1.3 of molar ratio of water to methanol, the hydrogen yield was 98 % and hydrogen production rate was 117.05 mmol/s* at 280 ℃. In 100-hour duration of test, after 34 hr, the hydrogen production rate kept at 84 mmol/s* In this study, we successfully prepared Cu/ CeO2 catalyst supported on carbon nanotubes with precipitation and reduction method, and applied it in steam reforming of methanol efficiently.
其他識別: U0005-2406200816142200
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