本文以儲存安全性較佳以及逸散毒性較弱的一氧化碳(CO)替代氨(NH3)作為還原劑，在較廉價的銅活性碳觸媒作用下進行一氧化氮(NO)之還原反應。採用椰殼活性碳為原料，經硝酸處理後含浸於一定濃度的硝酸銅水溶液中，利用化學含浸法製成銅活性碳觸媒(1.1 mmol/g Cu/AC)。再將觸媒置於固定床式反應器中，通入含NO、CO及He之反應氣體，進行NO還原性能測試。
研究結果顯示在無氧條件下進行NO還原反應時，發現添加CO對增加NO轉化率的影響非常明顯，當CO對NO的添加比例增至四比一時(COi：NOi＝1440ppm：360ppm)，在270℃的低溫下NO轉化率即可達97%。添加CO可減少觸媒表面活性基的消耗，有助於觸媒壽命的延長。利用電子顯微鏡(SEM)可觀測到當觸媒喪失活性時，其表面有燒失現象發生而呈現蜂巢狀之構造。於動力學的研究顯示總反應方程式中，各反應物濃度的反應階數與反應溫度有關，其代表NO濃度的反應階數隨反應溫度增加而增加；而代表CO濃度的反應階數則隨反應溫度增加至270℃時達到最大，顯示此時添加CO對反應的助益最大，但當反應溫度達360℃時代表CO濃度的反應階數降為0.06，表示在此溫度下添加CO對反應之影響已可忽略。

The reducer (i.e. NH3) of the nitrogen monoxide (NO) reduction is replaced by carbon monoxide (CO) over a cheaper copper activated carbon catalyst in this study.The purposes are to improve the storage safety and reduce the slipping toxicity of NH3, and to develop a cheaper NO reduction technology. After acid treating with nitric acid, a coconut activated carbon is adding into the solution of copper nitrate, the copper activated carbon catalyst (i.e. 1.1 mmol/g Cu/AC) is then prepared through chemical impregnation. The NO conversion characteristics of the catalyst are testing at a fixed bed reactor with the reacting gases contained NO, CO,and He.
A significant improvement on the NO conversion is discovered when CO is adding into the NO reduction reaction without O2. Under the reaction condition with the ratio of NO to CO equal to 4:1 (i.e, COi：NOi＝1440ppm：360ppm), the NO conversion is found to be 97% on the temperature 270℃. The addition of CO can reduce the consumption of the surface active sites therefore helpful to last the catalyst life. Through using SEM, the burn-off phenomena and honeycomb structures are discovered on the surface of the catalysts which results the catalyst losing its activity. The kinetic study of the overall reaction equation of NO with CO shows that the reaction order of NO is increasing with the temperature, and the reaction order of CO is reaching to a maximum value at the temperature 240℃. More over, the reaction order of CO is decreasing to 0.06 at 360℃, revealing the effect of adding CO is negligible no effect on NO conversion at such temperature.

摘 要 i
Abstract ii
致謝 iii
目 錄 iv
表目錄 vi
圖目錄 vii
第一章 緒論 1
1-1 前言 1
1-2 研究目的 4
第二章 文獻回顧 5
2-1 氮氧化物之特性 5
2-2 氮氧化物之處理方式 5
2-2-1 非選擇性觸媒還原法 6
2-2-2 選擇性觸媒還原法 7
2-3 活性碳之特性 8
2-3-1 活性碳之結構與組成 8
2-3-2 活性碳之官能基 9
2-3-3 活性碳的種類 11
2-3-4 活性碳之製造 12
2-4 活性碳觸媒在NO還原反應之應用 13
2-4-1 活性碳觸媒除NO之反應 13
2-5 觸媒反應動力學模式 15
2-5-1 Power-rate Law 15
第三章 實驗方法 17
3-1 實驗設備及藥品 17
3-1-1 藥品 17
3-1-2 氣體 17
3-1-3 實驗設備 18
3-2 實驗研究方法 23
3-2-1 銅活性碳觸媒製作 23
3-2-2 觸媒性能測試： 26
3-2-3 測試反應前後觸媒表面之變化： 29
3-2-4 反應動力學研究： 30
第四章 結果與討論 32
4-1 無氧反應時CO對NO的添加比例對觸媒的NO轉化率之影響 32
4-2 添加CO對觸媒壽命的影響 34
4-3 觸媒之NO還原反應路徑 35
4-4 反應前後觸媒SEM影像分析 36
4-5 無氧反應且添加CO時的總反應方程式 38
第五章 結論 46
參考文獻 47
附錄A：質量流量計校正圖 51
附錄B：實驗數據 53
附錄C：總反應方程式之實驗套適 57

1. Aarna, I., and E. M. Suuberg, “A review of the kinetics of the nitric oxide-carbon reaction”, Fuel, Vol. 76, p.475-491 (1997).
2. Adlhart, O., S. Hindin, and R. Kenson, “Processing Nitric Acid Tail Gas”,Chemical Engineering Process”, 67(2), p.73, (1971).
3. Ahmed, S.N., R. Baldwin, F. Derbyshire, B. McEnaney, and J. Stencel, “Catalytic Reduction of Nitric Oxides over Activated Carbons”, Fuel, Vol. 72, p.287 (1993).
4. Boehm, H. P., “Some aspects of the surface chemistry of carbon blacks and other carbons”, Carbon, 32, p.759.(1994).
5. Carabineiro, S. A., F. Bras Fernandes, and A. M. Ramos, “Vanadium as a catalyst for NO,N2O, and CO2 reaction with activated carbon”, Catalysis Today, Vol. 57, p.305-312 (2000).
6. Chen, L. C., T. Y. Yen,and G..J. Peng, “ Reduction of NO byActivated Carbon in the Presence of Vanadium ”,Journal of the Chinese Institute Of Chemical Engineers,Vol. 38, p.35-41 (2007).
7. Corapcioglu, M. O., and C. P. Huang, “The surface acidity andcharacterization of some commercial activated carbon”, Carbon, 25, p.569. (1987).
8. Gao, Z., and Y. Wu, “Influences of acid treatments of active carbons on NO reduction over carbon-supported copper oxides”, Reac. Kinet. Catal. Lett., Vol.59, NO.2, p. 359-366 (1996).
9. Gillespie, G.., A. Boyum and M. Collins, “Nitric Acid：Catalytic Purification of Tail Gas”, Chemical Engineering Process, 68(4), p72, (1972).
10. Gohn, G., D. Steele, and H. Andersen, U.S. Patent 2975025, (1961).
11. Hall, C. R, and R. J.Holmes,“The preparation and properties of some activated carbons modified by treatment with phosgene or chlorine, Carbon”,vol.30, p.173,(1992).
12. Illan-Gomez, M.J., A. Linares-Solano, and C. Salinas-Martinez, “NO reduction by activated carbons. 6.catalysis by transition metals”, Energy and Fuels, Vol. 9, p.976-983 (1995).
13. Illan-Gomez, M.J., A. Linares-Solano, L.R. Radovic, and C. Salinas-Martinez, “NO reduction by activated carbons. 7.some mechanistic aspects of uncatalyzed and catalyzed reduction” ,Energy and Fuels, Vol. 10, p. 158-168 (1996).
14. Kristova, M., and D. Mehandjiev, “Conversion of NO on Ni-impregnated active carbon catalyst in the presence of oxygen”, Carbon, Vol.36, NO.9, p.1379-1385 (1998).
15. Lewis, I. C., “Chemistry of Carbonization”, Carbon, 20, p.519, (1982).
16. Mehandjiev, D., M. Kristova, and E. Bekyarova, “Conversion of NO on Co-impregnated active carbon catalysts”, Carbon, Vol.34, NO.6, p.757-762 (1996).
17. Mochida, I., M. Ogaki, H. Fujitsu, Y. Komatsubara, and S. Ida, “Catalytic Activity of Coke Activated with Sulphuric Acid for the Reduction of Nitric Oxide” ,Fuel, Vol. 62, p.867 (1983).
18. Neli B. Stankova, Mariana S. Khristova, and Dimitar R. Mehandjiev, “Catalytic Reduction of NO with CO on Active Carbon-Supported Copper,Manganese, and Copper–Manganese Oxides”, Journal of Colloid and Interface Science 241, p.439–447 (2001).
19. Pârvulescu, V.I.; Grange, P.; Delmon, B. Catal. Today, 46, p.233, (1999).
20. Park, S. J., and Kim, K. D., “Influence of activation temperature on adsorption characteristics of activated carbon fiber composites”, Carbon, 39, p.1741-1746. (2001).
21. Ronald, M.H. and J.F. Robert, “Catalytic Air Pollution Control”, John Wiley and
Sons, (1994).
22. Rodriguez-Reinoso, F., “The Role of carbon materials in heterogeneous catalysis”,
Carbon, 36(3), p159, (1998).
23. Ruckenstein, E., and Y. H. Hu, “Catalytic reduction of NO over Cu/C” ,Ind. Eng. Chem. Res., Vol.36, p.2533-2536 (1997).
24. Salas-Peregrin, M. A., M. Primet , and H. Praliaud, “Nitric oxide reduction over carbon-supported palladium catalysts” , Applied Catalysis B: Environmental, Vol. 8, p.79-100 (1996).
25. Teng, H., Y.F. Hsu, and Y.T. Tu, “Reduction of NO with NH3 over carbon catalysts-the influence of carbon surface and the global kinetics”, Applied Catalysis B,Environmental, Vol. 20, p.145-154 (1999).
26. Tomon, H., and M. Okazaki, “Influence of Acidic Surface Oxides of Activated Carbon on Gas Adsorption Characteristic”, Carbon, 34(6), p.741, (1996).
27. Wang, S. and G.Q. Lu, “Effects of acidic treatments on the pore and surface properties of catalyst supported on activated carbon”, Carbon, Vol. 36, NO. 3, p.283-292 (1998).
28. Zhu, Z., Z. Liu, S. Liu, and H. Niu, “ A novel carbon-supported vanadium oxide catalyst for NO reduction with NH3 at low temperature” ,Applied Catalysis B: Environmental, Vol.23, p.229-233 (1999).
29. Zhu, Z. H., L. R. Radovic, and G..Q. Lu, “ Effects of Acid Treatments of Carbon on and NO Reduction by Carbon-Supported Copper Catalysts” , Carbon, Vol. 38, p.451-464 (2000).
30. 彭冠傑, “高性能銅活性碳觸媒在無氨無氧條件下還原一氧化氮之研究，碩士論文，明新科大化工所,(2006).
31. 黃武章、鄭慶堂, “以椰子纖維製備活性碳之研究，第21屆空氣污染控制技術研討會”,台南成功大學,(2004).
32. 徐禮業, “利用銅在碳及其他載體上為觸媒以NH3還原NO反應之研究”, 國立成功大學化學工程學系博士論文,(2003).
33. 黃龍泰, “以稻殼和花生殼製備高表面積之活性碳與其應用”, 國立台灣科技大學化學工程系碩士論文,(2001).
34. 吳榮宗, “工業觸媒概論”，國興出版社, p.33-250 (1989).
35. 劉曾旭, “活性碳製造技術及應用”，產業調查與技術，127，p.84-97(1998).
36. 曾惠馨, “活性碳擔持銅觸媒對二氧化硫吸附特性之研究”, 國立中興大學環境工程系博士論文, (2002).
37. 曾惠馨、魏銘彥、陳科豪、梁煜申, “活性碳擔持銅、釩、鐵觸媒催化轉換SO2、NO之研究”, 第19屆空氣污染控制技術研討會, (2002).