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研究生: 陳鴻志
Chen, Hung-Chih
論文名稱: 以La0.58Sr0.4Co0.2Fe0.8O3-δ為觸媒行高溫甲醇蒸氣重組製氫之研究
A study of high temperature steam reforming of methanol over La0.58Sr0.4Co0.2Fe0.8O3-δ catalysts for hydrogen production
指導教授: 黃大仁
Huang, Ta-Jen
口試委員:
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2010
畢業學年度: 98
語文別: 中文
論文頁數: 89
中文關鍵詞: 甲醇蒸氣重組鈣鈦礦
外文關鍵詞: steam reforming of methanol, perovskite
相關次數: 點閱:1下載:0
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  • 本研究主要目的是以鈣鈦礦結構氧化物La0.58Sr0.4Co0.2Fe0.8O3-δ(LSCF)、螢石結構氧化物Ce0.9Gd0.1O2-δ(GDC)為觸媒材料,藉由其具有氧空缺(oxygen vacancy)之特殊結構,進行甲醇蒸氣重組反應(steam reforming of methanol, SRM),希冀作為固態氧化物燃料電池(solid oxide fuel cell)陽極側之觸媒催化層,進行燃料之內部預重組(internal reforming),並透過一氧化碳與水氣產生之水氣轉移反應(water gas shift reaction, WGS),得到更大的氫氣產率,以增進電池效能。
    觸媒實驗結果指出在反應溫度區間600~800℃,GDC-LSCF比傳統之電極材料Ni-YSZ或低溫常用甲醇重組之Cu-GDC觸媒有更好的催化活性,其催化活性不隨反應時間的增加而衰退,具有良好之抗積碳能力,因此有較佳的的甲醇轉化率與氫氣產率。由定溫實驗發現,溫度升高將增進甲醇的裂解,並提升轉化率,但也可能增加或降低WGS反應之發生,導致氫氣產率的增減,與觸媒本身特性有關。
    若以甲醇蒸氣作為SOFC之燃料,將可添加GDC-LSCF於傳統電極Ni-YSZ表面做為催化層,以補足Ni-YSZ催化能力之不足,先於催化層進行燃料重組反應,產生氫氣、一氧化碳供電池使用。


    目錄 第一章 緒論 1 第二章 文獻回顧與理論 3 2-1燃料電池簡介 3 2-2固態氧化物燃料電池之發電原理 5 2-3固態氧化物燃料電池燃料之選擇 7 2-4甲醇產氫 10 2-5甲醇蒸氣重組反應及相關方程式 11 2-6甲醇於觸媒表面之反應機構 18 2-7導氧離子氧化物 22 2-7-1鈣鈦礦型結構 22 2-7-2螢石型結構 23 2-8氧空洞與導氧離子性 24 2-8-1固有氧空洞(intrinsic oxygen vacancy) 24 2-8-2非固有氧空洞(extrinsic oxygen vacancy) 25 第三章 研究構想 26 第四章 實驗方法與步驟 30 4-1實驗藥品 30 4-2實驗氣體 31 4-3觸媒材料製備方法 32 4-3-1 La0.58Sr0.4Co0.2Fe0.8O3-δ (LSCF) 32 4-3-2氧化釓摻雜氧化鈰Ce0.9Gd0.1O2-δ(GDC) 34 4-3-3 GDC- LSCF 之複合觸媒 35 4-3-4 Ni-YSZ 35 4-3-5 GDC擔載銅觸媒 36 4-4分析儀器與實驗裝置 37 4-4-1儀器 37 4-4-2甲醇蒸氣重組實驗裝置 38 4-5實驗方法 40 4-5-1氫氣程溫還原實驗 40 4-5-2氫氣預還原之定溫甲醇蒸氣重組反應 40 4-5-3積碳量的測定 41 4-5-4甲醇轉化率的計算 41 第五章 結果與討論 42 5-1 X光繞射分析(XRD,X-Ray Diffraction) 42 5-1-1 Ce0.9Gd0.1O2-δ 42 5-1-2 La0.58Sr0.4Co0.2Fe0.8O3-δ 44 5-1-3 50GDC-LSCF 45 5-1-4 60Ni-YSZ 46 5-1-5 5Cu-YSZ 47 5-2氫氣程溫還原實驗 (H2-TPR Temperature-programmed reduction) 48 5-2-1 50GDC-LSCF氫氣程溫還原實驗 49 5-2-2 60Ni-YSZ氫氣程溫還原實驗 50 5-2-3 5Cu-GDC氫氣程溫還原實驗 51 5-2-4預還原條件的確立 52 5-3甲醇蒸氣重組之催化活性測試 53 5-3-1 Homogeneous (non catalytic) reaction 53 5-3-2 50GDC-LSCF甲醇蒸氣重組反應 56 5-3-3 60Ni-YSZ甲醇蒸氣重組反應 65 5-3-4 5Cu-GDC甲醇蒸氣重組反應 71 5-3-5綜合比較 79 第六章 結論 85 第七章 未來方向 86 第八章 參考文獻 87

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