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系統識別號 U0026-0812200910210873
論文名稱(中文) 碳表面植入氮官能基以增進NH3還原NO時之觸媒效應
論文名稱(英文) Nitrogen-Containing Carbons from Phenol-Formaldehyde Resins and Their Catalytic Activity in NO Reduction with NH3
校院名稱 成功大學
系所名稱(中) 化學工程學系碩博士班
系所名稱(英) Department of Chemical Engineering
學年度 90
學期 2
出版年 91
研究生(中文) 黃媺瓊
研究生(英文) Mei-Chiung Huang
學號 n3689416
學位類別 碩士
語文別 中文
論文頁數 69頁
口試委員 口試委員-翁鴻山
口試委員-王春山
口試委員-何瑞文
口試委員-朱信
指導教授-鄧熙聖
中文關鍵字 氮官能基  碳觸媒  酚醛樹脂  選擇性觸媒還原反應 
英文關鍵字 selective catalytic reduction.  nitrogen functional group  carbon catalyst  phenol-formaldehyde 
學科別分類
中文摘要 本研究主要探討碳觸媒表面之氮官能基對NH3選擇性觸媒還原NO的影響。研究中碳觸媒的製備程序是以合成酚醛樹酯為基材,並於交聯過程摻入含氮之化合物,製得表面含有氮官能基之碳觸媒。實驗中以添加Urea及m-phenylenediamine (MPDA)的方式製得所須之碳觸媒,並且進行觸媒之成份分析及觸媒活性偵測,而添加MPDA的觸媒含氮量隨之提高且觸媒活性有增加的趨勢。
由添加Urea的碳觸媒之表面結構分析得知其有較高的表面積,但由於元素分析得此觸媒並不含氮成份,因此改變製程添加m-phenylenediamine (MPDA)於酚醛樹脂製得含氮碳觸媒。
添加MPDA的製程由實驗得知此樹脂及碳觸媒之化學成份及其活性。而氮的添加對於碳觸媒在NH3還原NO時之觸媒活性有促進的效應,此外由XPS分析得知氮含量對於碳觸媒之活性有密切的關係,且反應主要發生於較大的孔洞。而觸媒活性反應中,對於低溫(< 140℃)系統下反應受吸附作用影響活性隨溫度提高而降低;高溫系統下,反應受吸附氣體與觸媒之親合性影響活性隨溫度提高而增加。本研究發現氮的添加有促進NO的吸附,並且增進吸附氣體與觸媒間的交互作用,因此提高了觸媒於NH3還原NO之反應活性。

英文摘要 Activated carbons with nitrogen functional group will make use of selective catalytic reduction (SCR). Carbons with well-controlled nitrogen contents were prepared from phenol-formaldehyde resins impregnated with different amounts of urea and m-phenylenediamine. The performance of these carbon catalysts for selective catalytic reduction (SCR) of nitric oxide by ammonia were investigated. The chemical compositions of the resin precursors and the resulting carbons well characterized using various analytical techniques. Elemental analysis of the chars from the urea-impregnated resins showed very little presence of nitrogen. For impregnating m-phenylenediamine there are nitrogen functional group in phenol-formaldehyde resins, and in this research we discussed the carbons with m-phenylenediamine in selective catalytic reduction (SCR). The heteroatoms, N and O, in the carbons were found to be more populated in small pores. The catalytic activity of the carbons in NO reduction of NH3 increased because of the nitrogen impregnation. The activity showed a close correlation with the nitrogen content obtained with X-ray photoelectron spectroscopy, indicating that the reaction mainly occurred in larger pores. In the low temperature regime (< 140°C), the reaction was dominated by the adsorption, which rendered a negative apparent energy, while surface interactions controlled the reaction at higher temperatures. The impregnated nitrogen atoms were found to promote the adsorption of NO, as well as to accelerate the interactions between the adsorbed species.

論文目次 中文摘要 Ⅰ
ABSTRACT Ⅱ
誌 謝 Ⅲ
總目錄 Ⅳ
圖目錄 Ⅵ
表目錄 Ⅷ
符號表 Ⅸ
第一章 緒論 1
1-1 前言 1
1-2 含氮官能基之碳觸媒 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碳觸媒製造 6
2-1.1 碳化 7
2-1.2 活化 8
2-2 吸附法分析碳觸媒表面 10
2-2.1 等溫吸附線 10
2-2.2 表面積與孔隙度 12
2-2.3 Dubinin-Radushkevich(D-R)方程式 14
2-2.4 BET方程式 15
2-3 碳觸媒在氨選擇性還原氮氧化物之應用 16
第三章 實驗方法 22
3-1實驗設備 22
3-1.1 氣體 22
3-1.2 藥品 23
3-1.3 表面吸附儀(ASAP 2010) 23
3-1.4 SCR觸媒反應器裝置 24
3-1.5 氮氧化物分析儀(API M200AH) 24
3-1.6 掃描式電子顯微鏡(SEM) 25
3-1.7 紅外線光譜(FTIR)分析 26
3-1.8 核磁共振光譜(13C CP/MAS NMR)分析 26
3-1.9 電子能譜化學分析儀 26
3-2 碳觸媒製備 27
3-2.1 酚醛樹脂的合成 27
3-2.2 高溫爐中進行碳觸媒的製備 28
3-3恆溫選擇性觸媒還原反應 29
3-4 程溫脫附反應(TPD) 30
3-5 程溫脫附一氧化氮(TPD-NO) 31
3-6 動力學實驗設計 31
第四章 結果與討論 38
4-1添加尿素對碳觸媒結構之影響 38
4-1.1 表面積及孔徑分析 38
4-1.2 SEM表面分析 39
4-1.3 Summary 40
4-2添加MPDA對碳觸媒表面及活性分析 41
4-2.1 樹脂及碳觸媒之元素分析 41
4-2.2 樹脂之紅外線光譜(FTIR)分析 42
4-2.3 樹脂之核磁共振光譜(13C CP/MAS NMR)分析 42
4-2.4 含氮碳觸媒之表面特性分析 43
4-2.5 含氮碳觸媒之電子能譜化學分析 44
4-2.6 含氮碳觸媒之SCR反應 45
4-2.7 含氮碳觸媒之動力學探討 46
4-2.7 Summary 48
第五章 結論 65
參考文獻 66
作者自述 69
參考文獻 Ahmed S N, Baldwin R, Derbyshire F, McEnaney B, Stencel J. Fuel 72, 1993, 287.
Boehm H P, Mair G, Stohr T, de Rinc¸on AR, Tereczki B. Fuel 63, 1984, 1001.
Dubinin M M, Stoeckli H F. J Colloid Interface Sci 75, 1980, 34.
Dubinin M M. Carbon 23, 1989, 457.
Dubinin M M.Carbon 23, 1985, 373.
Hsu L-Y, Teng H, Appl Cat B 35,2001, 21.
Huang M C, Hsisheng Teng. Carbon 40, 2002, 955.
Ismail K O, Sirkecioglu J M, Andresen S D, Brown P J Hall, Snape C E, Steedman W. Polymer 37, 1996, 4041.
Izquierdo M T, Rubio B. Environ. Sci. Technol. 32, 1998, 4017.
Jansen R J J, Bekkum Hv, Carbon 33, 1995, 1021.
Jones J M, Thomas K M. Carbon 33, 1995, 1129.
Kaneko K, Fukuzaki N, Ozeki S N, J. Chem. Phys. 87, 1987, 776.
Kapteijn F, Moulijn J A, Matzner S, Boehm H P. Carbon 37, 1999, 1143.
Komatsubara Y, Ida S, Fujitsu H, Mochida I. Fuel 63, 1984, 1738.
Ku B J, Lee J K, Park D, Rhee H K. Ind. Eng. Chem. Res. 33, 1994, 2868.
Kusakabe K, Kashima M, Morooka S, Kato Y. Fuel 67, 1988, 714.
Lahaye J, Nanse G, Bagreev A, Strelko V. Carbon 37, 1999, 585.
Lee J K, Park T J, Park D, Park S. Ind. Eng. Chem. Res. 32, 1993, 1882.
Lee J K, Suh D J, Park S, Park D. Fuel 72, 1993, 935.
Lizzo A A, Radovic L R. Ind Eng Chem Res 30, 1991, 1735.
Mang D, Boehm H P. Extended abstracts, 21st Biennial Conference on Carbon. Buffalo (USA): American Carbon Society, 1993, 521.
Matzner S, Boehm H P, Carbon 36, 1998, 1697.
Mochida I, Ogaki M, Fujitsu H, Komatsubara Y, Idi S, Fuel 64, 1985, 1054.
Mochida I, Ogaki M, Fujitsu H, Komatsubara Y, Ida S. Fuel 62, 1983, 867.
Moreno-Castilla C, Carrasco-Marin F, Maldonado-Hodar, Rivera-Utrilla J, Carbon 36, 1998, 145.
Muñiz J, Marbán G, Fuertes A B. Appl. Catal. B: Environ. 23, 1999, 25.
Oude Lohuis J A, Tromp PJ J, Moulijn J A. Fuel 71, 1992, 9.
Pels J R, Wojtowicz M A, Kapteijn F. Langeveld ADv, Moulijn JA. Extended Carbon ’94. Granada (Spain): Spanish Carbon Group, 1994, 50.
Pels J R, Wojtowicz M A, Kapteijn F, Moulijn J A. Energy Fuels 9, 1995, 743.
Pels J R, Wojtowicz M A, Moulijn J A. Fuel 72, 1993, 373.
Radovic L R, Walker P L Jr, Jenkins R G. Fuel 62, 1983, 849.
Richter E, Schmidt H J, Schecker H G. Chem. Eng. Technol. 13, 1990, 332.
Rodriguez-Mirasol J, Ooms A C, Pels J R, Kapteijn F, Mouli-jn J A. Combust Flame 99, 1994, 499.
Rodriguez-Reinoso F, Molina-Sabio M, Gonzalez M T. Carbon 33, 1995, 15.
Singoredjo L, Kapteijn F, Moulijn JA, Martin-Martinez J M, Boehm H P. Carbon 31, 1993, 213.
Sloss L L, NO emissions from coal combustion, IEA coal x research reports, vol. IEACR/ 36. London: IEA Coal Reprecursor search, 1991, 1.
Stohr B, Boehm H P, Schlogl R. Carbon 29, 1991, 707.
Strelko V Ext. Abstracts Carbone ’90, Intern. Carbon Conf., Paris, 1990, 16.
Suuberg E M, Wójtowicz M, Calo J M. Carbon 27, 1989, 431.
Takeshita M, Sloss L L, Smith I M. N O emissions from coal 2 use, perspectives, vol. IEA PER/ 06. London: IEA Coal Research, 1993,1.
Teng H, Suuberg E M. J. Phys. Chem. 97, 1993, 478.
Teng H, Hsu L Y, Lai Y C. Environ Sci Technol 35, 2001, 2369.
Teng H, Hsu Y F, Tu, Y T. Appl. Catal. B 20, 1999, 145.
Teng H, Ying-Tsung, Yu-Chung Lai, Chi-Cheng Lin. Carbon 39, 2001, 575.
Volkov V B, Michalovsky S V, StrelkoVV. Extended abstracts, International Carbon Conference Carbon ’96. Newcastle (UK): British Carbon Group, 1996, 272.
Wojtowicz M A, Pels J R, Moulijn J A. Fuel 73, 1994, 1416.
Wojtowicz M A, Pels J R, Moulijn J A. Fuel Processing Technol 34, 1993, 1.
Zhu Q, Turner J A, Russell A E, Thomas K M. In: Ziegler A Heek KHv, Klein J, Wanzl W, editors. Proceedings Interna- tional Conference Coal Science, ICCS ’97. DGMK Tagungsberichte, vol. II. Essen: P&W Druck und Verlag, 1997, 1067.
賴育聰, 碳觸媒法氨氣還原一氧化氮之動力學研究, 國立成功大學大學化工研究所碩士論文, 2000.
林吉成, 以不同組成之酚醛樹脂製備多孔性碳材料, 國立成功大學大學化工研究所碩士論文, 2001.
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