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研究生：	劉啟徵 Liu, Chi-Cheng
論文名稱：	在銅/中孔洞分子篩觸媒上以NH3還原NO的研究 Catalytic NO Reduction with NH3 over Mesoporous Molecular Sieve Loaded with Copper
指導教授：	鄧熙聖 Teng, Hsisheng
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：	2004
畢業學年度：	92
語文別：	中文
論文頁數：	66
中文關鍵詞：	SCR 催化反應、MCM-41 、一氧化氮、銅
外文關鍵詞：	Ammonia, Selective Catalytic Reduction, Nitric oxide, Cu/MCM-41
相關次數：	點閱：62 下載：1
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　　在利用MCM-41 當載體負載Cu 當觸媒，進行氨還原一氧化氮的實驗中，我們發現活性基Cu 的化學結構對反應活性會造成影響。實驗中以傳統的離子交換法和模板離子交換法製備的兩種觸媒(分別簡稱HMCu和TMCu)中，HMCu 觸媒的活性較大。我們利用CO 的程溫還原實驗和NO吸附後的程溫脫附實驗可知，HMCu 觸媒還原能力較好而且NO的吸附量較多，所以對SCR 反應之催化活性較高。再進一步的利用同步輻射，發現TMCu 觸媒的活性基Cu 本身的配位數高，和載體的鍵結數多，因此造成對SCR 反應之催化活性比HMCu 觸媒差。在動力學實驗方面，發現Mars-van Krevelen 能套適HMCu 觸媒催化SCR 反應中的反應機制。

　　Copper supported on MCM-41, through the template-ion exchange and the conventional hydroxyl group-ion exchange and incipient-wetness impregnation, were employed for selective catalytic NO reduction with NH3 within a temperature range of 200−450°C. Cu/MCM-41 catalysts with a low Cu content (ca. 0.7 wt%) from the template-ion and hydroxyl group-ion exchange methods, i.e. TMCu and HMCu respectively, showed high activities in the NO reduction. Further increase of the Cu content did not obviously improve the activity of the catalysts. HMCu has a higher activity than TMCu,　especially at temperatures lower than 350°C. The Cu species on HMCu exhibited stronger tendencies towards reduction and oxidation, an indication　that both reduction and oxidation of the active species controlled the NO reduction rate. The Mars-van Krevelen kinetic model gave a satisfactory　simulation of the experimental data, which supported the argument that the NO reduction was governed by a cyclic redox of the Cu species. The reaction orders with respect to NO and NH3 were of a fraction (between 0.5 and unity) and of ca. zero, respectively. The activation energies were similar for reactions over these two catalysts, whereas the reactions over HMCu were seen to have larger values of the frequency factor, a parameter closely related to the intrinsic chemical structure. XANES spectra reflected that the catalysts were mainly composed of CuO. The coordination number of Cu−O analyzed by EXAFS reflected that HMCu had a larger content of CuI, which has been suggested to facilitate NO attack on active sites.

總目錄
中文摘要..................................... I
Abstract......................................II
致謝......................................... III
總目錄....................................... IV
圖目錄........................................VII
表目錄....................................... VIII
第一章 緒論...................................1
1.1. 前言.................................................................................................. 1
1.2. 氮氧化物對環境的影響.................................................................. 1
1.3. 氮氧化物的處理技術...................................................................... 2
1.4. 研究動機.......................................................................................... 3
第二章理論說明..........................................................................6
2.1. 選擇性觸媒還原氮氧化物的應用.................................................. 6
2.2. 分子篩MCM-41.............................................................................. 7
2.2.1 MCM41 的生成機構................................................................................ 7
2.2.2 MCM-41 的應用....................................................................................... 9
2.3. 氮氣吸附........................................................................................ 10
2.3.1 等溫吸附曲線........................................................................................... 11
2.3.2 BET 理論................................................................................................. 12
2.3.4 BJH 理論................................................................................................. 13
V
2.4. 同步輻射分析................................................................................ 17
2.4.1 X 光近緣結構(XANES) ......................................................................... 17
2.4.2 延伸X 光吸收精細結構(EXAFS)......................................................... 18
2.4.3 測試方法................................................................................................. 20
2.5. 觸媒反應動力學模式研究............................................................ 21
2.5.1. Power-rate Law 模式............................................................................. 22
2.5.2. Langmuir-Hinshelwood 模式................................................................ 22
2.5.3. Mars-van Krevelen 模式....................................................................... 24
2.5.4. 反應速率常數與活化能之關係............................................................ 25
第三章實驗藥品設備與實驗.....................................................28
3.1. 實驗藥品與設備............................................................................ 28
3.1.1. 實驗用氣體............................................................................................ 28
3.1.2. 實驗用藥品............................................................................................ 28
3.1.3. 表面吸附儀（ASAP2010）.................................................................. 29
3.1.4. SCR 觸媒反應裝置................................................................................ 29
3.1.5. 氮氧化物分析儀（API M200AH） ..................................................... 29
3.1.6. 碳氧化物分析儀.................................................................................... 30
3.1.7. 原子吸收光譜（Atomic Absorption Spectrophotometer）.................. 30
3.1.8. 同步輻射................................................................................................ 31
3.2. 實驗步驟........................................................................................ 31
3.2.1. MCM-41 的合成.................................................................................... 31
3.2.2. 觸媒製作................................................................................................ 32
3.2.3. 觸媒活性測試........................................................................................ 32
3.2.4. 一氧化氮程溫脫附實驗(NO -TPD).................................................... 33
3.2.5. 程溫還原實驗(TPR) ............................................................................ 34
3.2.6. 動力學實驗設計.................................................................................... 34
3.2.7. 觸媒同步輻射分析................................................................................ 35
第四章結果與討論....................................................................38
4.1. 觸媒的物理特性............................................................................ 38
4.2. 觸媒活性測試................................................................................ 38
4.3. 動力學分析.................................................................................... 40
Power-rate law 模式：....................................................................................... 40
Langmuir-Hinshelwood 模式：.......................................................................... 41
Mars-van Krevelen 模式： ................................................................................. 42
4.4. NO-TPD ......................................................................................... 43
4.5. 觸媒表面結構分析........................................................................ 44
第五章結論..............................................................................58
參考文獻........................................................................................59
附錄................................................................................................62
自述................................................................................................66
                                    

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校內：2005-08-03公開
校外：2005-08-03公開

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