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研究生: 吳信賢
Wu, Hsin-Hsien
論文名稱: 氧化錳-氧化鈰擔載銀觸媒應用於揮發性有機物完全氧化之研究
Deep oxidation of volatile organic compounds using manganese oxide - cerium oxide supported silver catalysts
指導教授: 周更生
Chou, Ken-Sen
談駿嵩
Tan, Chung-Sung
口試委員: 陳郁文
Chen, Yu-Wen
沈克鵬
Shen, Keh-Perng
黃國柱
Hwang, Kuo-Chu
學位類別: 博士
Doctor
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2017
畢業學年度: 105
語文別: 中文
論文頁數: 131
中文關鍵詞: 揮發性有機物銀觸媒氧化錳氧化鈰奈米銀絲中孔洞氧化矽洗塗
外文關鍵詞: Volatile Organic Compounds, silver catalysts, Manganese oxide, Cerium oxide, Silver nanowire, SBA-15, Wash-coating
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  • 本研究成功製備氧化錳-氧化鈰擔載銀觸媒,並藉由觸媒分析和活性測試,掌握作為VOCs完全氧化反應觸媒的特性。
    首先利用沉積沉澱法和共沈澱法製備金屬氧化物(鈰、錳和鐵等)擔載銀觸媒,結果顯示金屬氧化物擔載銀觸媒,其活性皆高於銀觸媒,其中以Ag/MnOx-CeO2應用於低溫VOCs觸媒氧化反應之可行性最高,可在175℃將丙酮(1000 ppm)完全氧化。
    此外奈米銀絲,因具有特殊晶面結構,本研究證明奈米銀絲作為VOCs觸媒具有優於一般銀粒子的催化活性,兩者將異丙醇完全氧化的溫度分別為200℃(奈米銀絲)及310℃(一般銀粒)。並進一步以多元醇法披覆金屬氧化物殼層之方式,合成核殼結構銀觸媒,並探討核殼結構對奈米銀絲的結構及活性的幫助程度。研究結果顯示,此方式讓奈米銀絲的結構特徵在披覆金屬氧化物殼層後,不會發生顯著變化,而且異丙醇(125 ppm)完全氧化的溫度可進一步降低至175℃。
    中孔洞氧化矽SBA-15具有高表面積、高熱穩定性及孔洞大小具一致性的優點。本研究利用TEOS為粘著劑將SBA-15洗塗於陶瓷紙,利用超音波測試其粘著效果發現SBA-15損失率極低。再將其含浸觸媒後應用於廢氣處理結果顯示,可有效減少觸媒用量20%。
    從工業廢氣處理的角度,上述觸媒研究結果各有其特點。核殼結構銀觸媒活性高,但目前的製備程序較複雜而不易實施。以SBA-15洗塗於陶瓷紙並含浸觸媒的方式相對簡單,而且陶瓷紙相較於堇青石蜂巢陶瓷具有達93%之輕量化效果,更具有放大實施之優勢。


    A catalyst, Ag/MnOx-CeO2 was successfully prepared in this study. The characterization and activity test of catalyst were also conducted to understand the reactivity for the treatment of VOCs.
    The catalyst with metal oxide (such as Ce, Mn, and Fe) and Ag were prepared by deposition-precipitation method and co-precipitation method. Our results showed that the catalytic activity of this Ag/MnOx-CeO2 catalyst were higher than the Ag catalyst. Ag/MnOx-CeO2 showed a very high removal efficiency for VOCs at low temperature. Acetone (1000 ppm) can be completely oxidized at 175 °C.
    In addition, we also tried silver nanowire as the catalyst, its catalytic activity was higher than the Ag particles due to the special crystal structure of the nanowire. The temperatures for complete oxidation of isopropanol were 200 °C and 310 °C for Ag nanowire and Ag particles, respectively.
    The synthesis of core-shell structure of silver nanowire by polyol method was also conducted in this study. The results indicated that the structure of silver nanowire did not change after the polyol process and the temperature for complete oxidation of isopropanol (125 ppm) was further reduced to 175 °C from 200 °C.
    The advantages of SBA-15 as support are high surface area, high thermal stability, and homogeneous pore size. In this study, SBA-15 was wash-coated on ceramic paper with TEOS as the adhesive agent. The results showed that the lost rate of SBA-15 was extremely low by an ultrasonic test. Using impregnation method to prepare SBA-15 supported catalyst and used it to treat VOCs exhaust, the results show the amount of catalyst could be reduced by 20%.
    From the perspective of industrial waste gas treatment, the various catalysts show their own characteristics from the test results of this study. The silver nanowire with core-shell structure shows a high activity, but it requires a complex preparation process, and might be difficult result to implement industrially. On the other hand, the use of SBA-15 coated on ceramic paper and subsequent impregnation method to prepare SBA-15 catalyst is relatively easy. The weight of ceramic paper was light than the cordierite honeycomb-like ceramic by 93%, which should be advantageous to the scale up for industrial waste gas treatment.

    第一章、緒論 1 1.1 前言 1 1.2 研究動機 2 1.3 研究架構 5 第二章、文獻回顧 8 2.1 銀觸媒的應用 8 2.1.1 VOCs完全氧化反應 8 2.1.2 助觸媒對活性的影響 13 2.2 銀的氧化活性 20 2.2.1 不同晶面的氧化活性 20 2.2.2 奈米核殼結構觸媒 26 2.3 SBA-15擔載銀觸媒的應用 29 2.3.1 SBA-15洗塗方式及應用 31 2.3.2 實驗設計法用於觸媒合成條件探討 34 第三章、實驗方法與裝置 37 3.1 觸媒合成步驟及方法 37 3.1.1 製備Ag/MnOx-CeO2 觸媒 37 3.1.1.1 共沈澱法製備MnOx-CeO2 37 3.1.1.2 沉積沈澱法製備Ag/MnOx-CeO2 38 3.1.2 製備核殼結構銀觸媒 38 3.1.2.1 奈米銀絲製備 38 3.1.2.2 沉積沈澱法製備核殼結構銀觸媒(以氧化鐵殼層為例) 39 3.1.2.3 多元醇法製備核殼結構銀觸媒 39 3.1.3 利用含浸及沉積沈澱等法製備SBA-15擔載觸媒 40 3.1.3.1 SBA-15製備 40 3.1.3.2 一步合成法製備Ag/SBA-15觸媒 40 3.1.3.3 沉積沈澱法製備Ag/SBA-15觸媒 41 3.1.3.4 初濕含浸法製備AgMnCe/SBA-15觸媒 42 3.1.3.5 製備SBA-15洗塗漿料(TEOS為黏著劑) 42 3.1.3.6 製備SBA-15洗塗漿料(AS-30為黏著劑) 43 3.2 儀器設備 44 3.2.1 BET比表面積、孔隙體積及孔徑大小分佈的分析 44 3.2.2 X-射線繞射分析(XRD) 45 3.2.3 氧氣程式升溫脫附(O2-TPD) 46 3.2.4 穿透式電子顯微鏡(TEM) 47 3.2.5 掃描式電子顯微鏡(SEM) 47 3.2.6 觸媒活性測試 48 3.3 藥品及氣體 51 3.3.1 藥品 51 3.3.2 氣體 52 第四章、結果與討論 53 4.1 Ag/MnOx-CeO2應用於VOCs觸媒氧化反應 53 4.1.1 觸媒合成和物性分析 53 4.1.2 金屬氧化物助觸媒對反應性的影響 58 4.1.3 鍛燒溫度對VOCs完全氧化的影響 62 4.1.4 擔載銀觸媒應用於丙烯腈完全氧化反應 64 4.1.5 結論 69 4.2 Ag nanowire/MnOx-CeO2應用於VOCs觸媒氧化反應 70 4.2.1 奈米銀絲及核殼結構觸媒合成與物性分析 71 4.2.2 奈米銀絲及多晶銀粒子觸媒活性分析 82 4.2.3 核殼結構觸媒活性分析 83 4.2.4 結論 84 4.3 SBA-15擔載銀觸媒及VOCs觸媒氧化反應 85 4.3.1 SBA-15擔載銀觸媒 85 4.3.2 以部分因子實驗設計法探討觸媒之製備條件 97 4.3.3 SBA-15洗塗於陶瓷紙及擔載觸媒之特性分析 106 4.3.4 結論 117 第五章、總結 118 第六章、未來展望 120 參考文獻 121 發表著作 130

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