博碩士論文 953901011 詳細資訊




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姓名 吳曉旻(Hsiao-min Wu)  查詢紙本館藏   畢業系所 化學工程與材料工程學系
論文名稱 氧化鋅-氧化鐵複合擔載金-銀雙金屬觸媒應用於甲醇部分氧化產製氫氣之研究
(Hydrogen production by partial oxidation of methanol over Au-Ag/ZnO-Fe2O3 catalyst)
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摘要(中) 本研究以共沈澱法製備Au-Ag/ZnO-Fe2O3雙金屬觸媒,應用於甲醇部分氧化反應產製氫氣 (CH3OH+0.5O2→2H2+CO2, POM)。利用熱重分析儀 (TGA) 了解觸媒前趨物在煅燒過程中,擔體中的金屬鹽類和擔體本身的熱解特性,發現在540 K左右重量損失最大,是由hydrozincite (Zn5(CO3)2(OH)6) 遇熱分解為ZnO所造成的重量損失。由X-ray繞射儀 (XRD) 鑑定觸媒樣品的成分的晶相,發現煅燒前後皆無法看見金與銀的繞射波峰,僅觀察到擔體中hydrozincite形成結晶良好的ZnO。由程式升溫還原 (TPR) 結果可知,觸媒中的過渡金屬弱化了位於金屬原子附近的Fe-O鍵結力而有利於氧化鐵的還原。穿透式電子顯微鏡 (TEM) 觀察的結果顯示,煅燒程序對於金屬顆粒大小並無顯著影響,因此排除觸媒因為粒徑大小影響催化活性的可能。O2/CH3OH進料比例在0.3,相較於理論值0.5更有利於POM反應的進行,有較少的MD (CH3OH→2H2+CO) 反應發生,一氧化碳選擇率較低。反應溫度低時雖然一氧化碳選擇率低,但是反應以MC (CH3OH+1.5O2→CO2+2H2O) 反應為主,生成太多的水降低了氫氣選擇率。當溫度提升至523 K時,POM反應伴隨WGS (H2O+CO→CO2+H2) 反應發生,於是可得最低的一氧化碳選擇率。
摘要(英) Au-Ag/ZnO-Fe2O3 bimetallic catalysts prepared by co-precipitation method were studied to produce hydrogen from partial oxidation of methanol reaction (CH3OH+0.5O2→2H2+CO2, POM) for fuel cell application. TGA analysis was used to investigate the thermal decomposition of catalyst precursors. During calcination, the main weight loss of catalyst precursor was about 540 K. It was due to the hydrozincite (Zn5(CO3)2(OH)6) decomposed to ZnO. XRD results revealed that no diffraction peak of Au and Ag could be seen before and after calcination; only hydrozincite could be found in the patterns which transformed into the well crystalline ZnO structure. The TPR results showed that the transition-metal of catalyst weakened the Fe-O bond leading to the better reducibility of iron. TEM results revealed that calcination process did not have obvious influence on metal particle size. Thus, the effect of particle size to catalytic activity could be ignored. O2/CH3OH molar ratio of 0.3 exhibited better activity than the ratio of 0.5, theoretical value of POM reaction. Less MD (CH3OH→2H2+CO) reaction occurred resulted in lower CO selectivity. At lower reaction temperature, even it showed lower CO selectivity, the MC reaction predominated which lead to the decrease of H2 selectivity. When the reaction temperature increase to 523 K, POM reaction occurred with WGS (H2O+CO→CO2+H2) reaction, and had the lowest CO selectivity.
關鍵字(中) ★ 甲醇部分氧化
★ 雙金屬觸媒
★ 產氫
關鍵字(英) ★ partial oxidation of reaction
★ produce hydrogen
★ bimetallic catalysts
論文目次 目錄 I
圖索引 IV
表索引 IX
第一章 緒論 1
1.1 前言 1
1.2 燃料電池之簡介 3
1.2.1 燃料電池簡介 3
1.2.2 發展優勢 5
1.2.3 燃料電池之工作原理 6
1.2.4 燃料電池種類 7
1.3 甲醇產製氫氣 10
1.4 研究內容與論文架構 11
第二章 文獻回顧 12
2.1 金與銀的性質 12
2.2 觸媒的製備方法 14
2.3 煅燒程序 16
2.4 擔體效應 18
2.5 活性位置 19
第三章 實驗方法與裝置 22
3.1 雙金屬觸媒的製備 22
3.2 雙金屬觸媒的鑑定分析 25
3.2.1 感應耦合電漿原子放射光譜儀 (ICP-AES) 25
3.2.2 熱重分析 (TGA) 27
3.2.3 X-ray繞射分析 (XRD) 29
3.2.4 程式升溫還原 (TPR) 32
3.2.5 穿透式電子顯微鏡 (TEM) 34
3.3 觸媒活性測試---甲醇部分氧化反應 36
3.4 實驗流程與操作變數 38
3.5 數據的計算與實例 40
3.5.1 轉化率的定義與計算 40
3.5.2 選擇率的定義與計算 43
3.6 藥品、氣體及儀器設備 47
3.6.1 藥品 47
3.6.2 氣體 47
3.6.3 儀器設備 48
第四章 結果與討論 50
4.1 物性分析 50
4.1.1 操作變數對金屬載量的影響 50
4.1.2 熱重分析 (TGA) 52
4.1.3 X-ray繞射分析 (XRD) 56
4.1.4 程式升溫還原分析 (TPR) 62
4.1.5 穿透式電子顯微鏡分析 (TEM) 67
4.2 化性分析 69
4.2.1 雙金屬觸媒對甲醇部分氧化反應的影響 70
4.2.2 擔體比例對觸媒活性的影響 72
4.2.3 共沈澱時pH值對觸媒活性的影響 76
4.2.4 煅燒溫度對觸媒活性的影響 80
4.2.5 進料比例對觸媒活性的影響 85
4.2.6 反應溫度對觸媒活性的影響 90
第五章 結論 96
參考文獻 99
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指導教授 張奉文(Feg-wen Chang) 審核日期 2008-6-30
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