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研究生: 林新茹
Lin, Shin-Ru
論文名稱: 金屬(Rh, Ni)附載於不同載體(CeO2, BZDy)對乙醇氧化蒸氣重組反應影響
Mechanistic study of oxidative steam reforming of ethanol (OSRE) on CeO2 and Dy-doped BaZrO3 supported Rh and Ni catalysts
指導教授: 王禎翰
Wang, Jeng-Han
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2016
畢業學年度: 104
語文別: 中文
論文頁數: 116
中文關鍵詞: 乙醇氧化蒸氣重組反應氧化鈰鈣鈦礦結構
英文關鍵詞: oxidative steam reforming of ethanol, cerium oxide, perovskite, rhodium, nickle
DOI URL: https://doi.org/10.6345/NTNU202203634
論文種類: 學術論文
相關次數: 點閱:129下載:2
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  • 本篇論文利用銠(10 wt% Rh)及鎳(30 wt% Ni)金屬分別附載於具有氧空缺之氧化鈰(CeO2)及具有親水性之鋯酸鋇摻雜鏑(Dy-doped BaZrO3, BZDy),於300℃環境下進行乙醇氧化蒸氣重組反應,探討氧氣量多寡以及乙醇及水比例不同對催化劑之影響。實驗以PVP法及含浸法合成顆粒狀及粉末狀催化劑,進行物化性質鑑定以及催化反應活性。催化劑之晶相以及確認金屬存在、含量鑑定、還原性質、表面物種組成分別利用X光粉末繞射儀(XRD)、能量散射光譜(EDX)、程序升溫還原反應(TPR)、X光光電子能譜儀(XPS)鑑定以及利用原位漫反射紅外線傅立葉轉換光譜(in situ DRIFTS)推測反應路徑及中間產物。在實驗結果中,隨著氧氣量以及乙醇及水比例增加,提升乙醇轉換效率,乙醛選擇率下降並有助於氫氣生成,在過高氧氣條件下促進二氧化碳生成以及氫氣減少形成水。從四個催化劑(Rh,Ni)/(CeO2,BZDy)可以發現,銠及鎳金屬皆具有斷乙醇C-C鍵之特性並生成氫氣、甲烷、一氧化碳、二氧化碳。除此之外,鎳金屬可以斷來自水的OH鍵促使氫氣產率提升,並具有含碳溶解性,因此生成之碳氫產物與氫氣反應生成甲烷,具有較高之甲烷選擇率。以具有親氧性之氧化鈰以及親水性之鋯酸鋇摻雜鏑為載體之催化劑在高氧化境下皆具有高氫氣產率。最後,鎳金屬催化劑在乙醇比水1:7時,C/O ratio為0.8之條件下,有最好的氫氣產率140%。

    The present work systematically examined oxidative steam reforming of ethanol (OSRE) on oxygen-active CeO2 and hydrophilic Dy-doped BaZrO3 (BZDy) supported Rh (10%) and Ni (30%) catalysts in various ethanol/oxygen/steam compositions at 300oC to investigate the environmental (oxygen and steam ratios) and catalyst (metal and oxide) effects on OSRE. The catalysts were initially synthesized by PVP and impregnation methods and characterized by powder X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), temperature programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS) for their crystallinity, chemical composition and oxidation states. The catalytic products were analyzed by gas chromagraphy (GC) and the key intermediates were identified by diffuse reflectance infrared fourier transform spectroscopy (DRIFTS). The experimental results with varied oxygen and steam compositions found that increases of oxygen or steam ratios can efficiently enhance the ethanol conversion and block the dehydrogenation pathway to reduce the acetaldehyde selectivity and improve hydrogen yield. The influence of oxygen is more significant than that of steam. Also, higher oxygen and steam ratios will promote full oxidation to raise the CO2 selectivity and diminish hydrogen yield. The experiments on the four catalysts (Rh,Ni)/(CeO2,BZDy) concluded that both Rh and Ni are highly active for C-C bond breaking of ethanol and produce mainly H2, CH4, CO and CO2. Additionally, Ni can better cleavage O-H bond to utilize the hydrogen from water for hydrogen production. Also, Ni can easily dissolve carbon to boost the high CH4 selectivity. The oxygen-active CeO2 and hydrophilic BZDy are highly sensitivity to the oxygen and steam ratios, but the effects from the two oxides are quite similar. Finally, the optimized condition correspond to Ni-based catalysts in ethanol/steam ratio of 1/7 and C/O ratio of 0.8 and give the best hydrogen yield at 140%.

    目錄 III 圖目錄 VI 表目錄 VIII 第一章 緒論 1 1.1 前言 1 1.2 乙醇催化製氫介紹 2 1.3 催化劑反應介紹 4 1.4 催化劑介紹 6 1.4.1 螢石結構 (Fluorine ,AO2) 6 1.4.2 鈣鈦礦結構 (Perovskite, ABO3) 8 1.5 研究目的 9 第二章 實驗方法 10 2.1 實驗藥品、氣體及儀器 12 2.1.1 實驗藥品 12 2.1.2 實驗氣體 14 2.1.3 實驗器材 15 2.2 催化劑合成製備 16 2.2.1 製備顆粒狀載體 17 2.2.2 製備粉末狀載體 18 2.2.3 製備顆粒狀催化劑 22 2.2.4 粉末狀催化劑 22 2.3 催化劑特性鑑定 25 2.3.1 X光繞射分析儀(X-ray diffraction analysis ,XRD) 25 2.3.2 能量散射光譜儀 (Energy Dispersive X-ray Spectroscopy, EDX) 27 2.3.3 程序升溫還原反應 (Temperature Programmed Reduction , TPR) 28 2.3.4 X光光電子表面能譜儀 (X-ray photoelectron spectroscopy ,XPS) 30 2.4 催化劑反應活性測試 31 2.4.1 氣相層析儀 (Gas Chromatography ,GC) 31 2.4.2 乙醇氧化蒸氣重組反應 (Oxidative Steam Reforming of Ethanol) 31 2.4.3 數據計算 35 2.4.4 原位漫反射紅外線傅立葉轉換光譜儀 (Diffuse Reflectance Infrared Fourier Transform Spectroscopy , in situ DRIFTS) 37 第三章 結果與討論 40 3.1 X光粉末繞射儀分析 (XRD) 40 3.2 能量散射光譜儀分析 (EDX) 44 3.3 程序升溫還原反應分析 (H2-TPR) 46 3.3.1 不同載體之程序升溫還原反應分析 46 3.3.2 不同金屬於載體之程序升溫還原反應分析 46 3.3.3 金屬於不同載體間之程序升溫還原反應分析 47 3.4 X光光電子能譜儀表面分析 (XPS) 52 3.5 乙醇氧化蒸氣重組反應 (OSRE) 56 3.5.1 氮氧比(N2 / O2)對催化反應之影響 56 3.5.2 水及乙醇比例對催化反應之影響 57 3.5.3 不同金屬附載於載體之催化反應影響 75 3.5.4 金屬附載於不同載體之催化反應影響 85 3.6 原位漫反射紅外線傅立葉轉換光譜儀分析 (in situ DRIFTS) 95 3.6.1 溫度及氮氧比對載體之影響 95 3.6.2 溫度及氮氧比對催化劑之影響 99 3.6.3 金屬附載對催化劑之影響 100 3.6.4 溫度及不同金屬於載體之影響 103 3.6.5 不同乙醇及水比例對催化劑之影響 107 第四章 結論 110 4.1 結論 110 4.2 未來展望 111 第五章 參考資料 112

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