石化工業製程所排放廢氣中常含有揮發性有機物VOCs(Volatile Organic Compounds)，由於具有高度的光化學反應力，在陽光下經由紫外線照射，容易被氧化形成游離基(radicals)，會再與大氣中的其他成分如NO2、O3反應，形成高濃度的臭氣、空氣污染煙霧(smog)和致癌物質，如醛、酮及PANs等，故一直是石化工業空氣污染事件主要原因。

本實驗室在之前曾經以自行製備觸媒的方式製備Mn2O3/γ-Al2O3來處理工業上常用之揮發性有機污染物三氯乙烯，本論文將延續之前的研究，也將探討觸媒焚化三氯甲烷，並試著加入水氣，探討水氣對反應的影響。論文內容如下：

1.探討Mn2O3/γ-Al2O3觸媒之製備與特性與其衰退現象。在製備Mn2O3/γ-Al2O3的過程中，由XRD之繞射圖我們發現含浸於載體γ-Al2O3上之Mn(NO3)2在經過鍛燒之後變成Mn2O3之晶相，此結晶相應為觸媒活性之主要結構。由BET比表面積實驗知載體γ-Al2O3在含浸Mn(NO3)2之載體，在BET表面積有減少的趨勢，孔洞體積有降低的情形。而鍛燒之後孔洞直徑較γ-Al2O3大，但在觸媒製備的前後其孔洞形狀沒有改變，均為墨水瓶型。

2. 水氣對自製Mn2O3/γ-Al2O3觸媒處理三氯甲烷之影響及產物分佈的
探討。發現當進流氣體加入水氣後會增加Mn2O3/γ-Al2O3觸媒焚化處理三氯甲烷之轉化率。在15小時觸媒衰退之實驗中，我們發現在加入水氣後觸媒衰退的情形有改善，且含氯的副產物以HCl為主。

3. 探討Mn2O3/γ-Al2O3焚化處理三氯乙烯的最佳的動力模式。實驗分析的數據中以Power-rate law與Mars and van Krevelen model所求得之活化能與碰撞因子較適當；而在趨勢預測的部分，則是以Mars and van Krevelen model假設較為符合。故以Mn2O3/γ-Al2O3觸媒焚化三氯乙烯的動力反應探討可能以Mars and van Krevelen model來描述較為合適。

4. 以Sandia 實驗室所發展出來的 CKEMKINIII來探討反應機制。藉由電腦模擬系統，可得到三氯乙烯轉化率與溫度之間的關係，但模擬出來的結果和實驗數據不能完全符合，可能是表面反應敘述的太簡單或數據不太適當。

Volatile organic compounds (VOCs) are the typical pollutants emitted from the petrochemical industrial processing. They can easily release radicals to react with some chemical compounds, such as NOx and Ozone in the atmosphere, to form the photochemical smog. Hence, VOCs are the main targets to prevent air pollution from the petrochemical industry.

Cl-COC decomposed over Mn2O3/γ-Al2O3 catalyst in the fixed bed reactor was conducted in this study. The explanation of results can be divided into four major parts.

1. We can find catalytic pore shape is not changed very much by calcination. The catalytic pore shape of the catalysts are all like “ink bottle” after impregnated, calcined and reduced, From XRD results, we can find the last catalytic crystal becomes Mn2O3.

2. The effects of adding water on the catalytic incineration of TCM were performed. The results show that conversion of TCM increases as adding 10% water. We can’t find any chloric products but HCl in the process of reaction.

3. Three kinetic models, including Power rate law、Mars-Van Krevelen model and Langmuir Hinshelwood model were used to fit the kinetic data of the decomposition of TCE. In the operation range of this experiment, we can find that Mars and van Krevelen model is suitable for the catalytic decomposition of DCE. We obtain the activity energy Ea=43.55 KJ/mole.

4. We use Chemkin III Application PLUG to analyze plug flow reactors in this study. A comprehensive experimental and numerical study has been performed in both the detailed TCE/O2 catalytic decomposition kinetics and the sensitivity analysus. But the result and the experimental data can’t match well . The bad result may produced from that we described the surface reactions too simple.

Atkinson, R.；Baulch, D. L.；Cox , R.F. ；Kerr, J. A.；Troe, J. “Evauluated Kinetic and Photochem. Data for Atmospheric Chemistry：Supplement III ”,J. Phys. Chem. Ref. Data, Vol. 18 ,p.881 ,1989
Arnold E.W.,and Sundaresan S. “Effect of water vapor on activity and selectivity characteristics of a Vanadium phosphate catalyst towards Butane oxidation” Applied Catalysis, 46, p.225-239, 1988.
Anderson, R.B., Stein K.C., Feenan J.J. and Hofer L.J.E. “Industry Engineering Chem.”, 53, 809, 1961.
Baldi Marco, Finocchio, E., Milella, F., and Busca, G., “Catalytic Combustion of C3 hydrocarbons and oxygenates over Mn3O4”, Applied Catalysis B：Environment,Vol 16, p.43-51, 1998
Baldi Marco, Escribano, V.S., Amores, J.M.G., Milella, F., and Busca, G., “Characterization of manganese and iron oxides as combustion catalysts for propane and propene”, Applied Catalysis B：Environment,Vol 17, p.175-182, 1998.
Baulch, D. L. et al. “Evaluated Kinetic Data For High Temperature Reactions Vol.1：Homogeneous Gas Phase Reactions of the H2-O2 systems”, Butterworths, London, 1976.
Baulch, D. L.；Cobos, C. J.；Cox, R. A.；Frank, P.；Hayman, G.；Just, Th；Kerr, J. a.；Murrells, T.；Pilling, M.J.；Troe, J.；Walker, R.W. and Warnatz, J. “Summary Table of Evaluatted Kinetic Data for combustion Modeling Supplement I”,Combust. Flame , vol.98 , p.59-79 ,1994.
Benson, S. W. “Thermochemical kinrtics” , 2nded , wiley ,New York ,p.209-266 ,1976
Benesi, H.A., Bonner, R.V., and Lee, C.F.：Anal. Chem., 27, 195
Bozzelli, J. W. and Dean, A. M. “Chemical Activation Analysis of the Reaction of C2H5 with O2”,J.Phys.Chem. , vol.94,p.3313-3317,1990.
Caracotsios,M. and Stewart, W.E. “Sensitivity Analysis of Initial Value Problems Including ODEs and Algebraic Equations” , Comput. Chem. Eng. ,vol. 9 , p.359-365, 1985.
Chang, C. and Weng, H., "Deep Oxidation of Toluene on Perovskite Catalysts", Ind. Eng. Chem. Res., 32, p.2930-2933, 1993.
Cukier,R. I.；Levine,H. B.；Shuler,K. E. “Nonlinear sensitivity Analysis for Multiparameter Model system ”, J. Comput. Phys., vol.26 , p.1-42 ,1978
Dean, A. M. “Predictions of Pressure and Temperature Effects upon Radical Addiction and Recombination Reactions ”, J. Phys. Chem.,vol. 89 ,p 4600-4608 ,1985.
Dean, A. M. and Westmooreland, P. E."imolecular QRRK Analysis of methyl Radical Reactions ” ,Int. J. Chem. Kinet. , vol. 19 , 207-228 ,1987.
Dean,A.J.；Davidson, D. F.；Hanson, R. K.”A shock tube study of reactions of C atom with H2 and O2 using Eximer photolysis of C3O2 and C atom atomic resonance absorption spectroscopy ”, J. Phys. Chem. Vol.95 , p.183-191 ,1991.
De Boer, J.H., Lippens, B.C., Linsen,B.G, and Broek-hoff, J.C.P., A. van den Heuval, and Th.J. Osinga：J.Colloid Interface Sci., 21, 405, 1966.
Dunker, A. M. “The Direct Decoupled Method for Calculating Sensitivity Coefficients in Chem. Kinetics” , J. Chem. Phys. , vol.81 ,p.2385-2393, 1984.
G. Sinquin , C. Petit “Catalytic destruction of chlorinated C2 compounds on a LaMnO3+δ perovskite catalyst ” , Applied Catalysis B: Environment 32，p.37-47,2001.
Gangwal, S.K., Mullins, M.E., Spivey, J.J. and Caffrey, P.R., "Kinetics and Selectivity of Deep Catalytic Oxidation of n-Hexane and Benzene", Applied Catalysis, 36, p.231-247, 1988.
Gonzalez-Velasco J.R., Aranzabal, A., Gutierrez-Ortiz, J.I., Lopez-Fonseca, R., and Gutierrez-Ortiz M.A., “Activity and product distribution of alumina supported platinum and palladium catalysts in the gas-phase oxidative decomposition of chlorinated hydrocarbons”, Applied Catalysis B：Environment,Vol 19, p.189-197, 1998.
Gonzalez-Velasco, J.R., Aranzabal A., Lopez-Fonseca R., Ferret, R., and Gonzalez-Marcos, J.A. , “Enhancement of the catalytic oxidation of hydrogen-lean chlorinated VOCs in the presence of hydrogen-supplying compounds”, Applied Catalysis B：Environment,Vol 24, p.33-43, 2000.
Heyes, C.J., Irwin, J.G., Johnson, H.A. and Moss, R.L., "The Catalytic Oxidation of Organic Air Pollutants. PartI. Single Metal Oxide Catalysts.", J. Chem. Tech. Biotechnol., 32, p.1025-1033, 1982.
Inkley,F.A., in D.H.Everett and F.S. Stone：Structure and Properties of Porous Materials, Acadenic, New York, p.124, 1958.
James, H. Werner and Tellill, A. cool “The kinetics of the Combustion of Trichloroethylene For Loe Cl/H Ratios” ,Combustion and Flame ,vol. 120 ,p.125-142 ,2000.
K.Ramanathan and J. J. Spivey ,”Catalytic Oxidation of 1,1-Dichloroethane ” , Combust. Sci and Tech. , vol.63 ,p.247-255 , 1989.
Kee, R. J.；Rupley,F. M.；Miller , J. A. “Chemkin II：A Fortran Chem. Kinetics Package for the Analysis of Gas Phase Chem.Kinetics”, Sandia Nationalal Laboratories Report, SAND59-8009B UC-706, 1993.
Kramer, M. A.；Rabitz, H.；Calo. J. M.；Kee, R. J. “Sensitivity Analysis in Chemical Kinetics：Recent Developments and Computantional Comparisons”, International Journal of Chemical Kinetics, vol. 16 ,p. 559-578 ,1984.
Rabitz, H.；Kramer, M. A.；Dacol,D. “Sensitivity Analysis in Chem ” Rund W. van den Brink “Formation of polychlorinated benzenes during the catalytic combustion of chlorobenzene using a Pt/γ-Al2O3 catalyst”， Applied Catalysis B: Environment 19，1998，p.219-226
Ritter, E. R.；Bozzelli ,J. W.；Dean,A. M. “Kinetic Study on Thermal Decomposition of Chlorobenzene Diluted in H2”, J. Phys. Chem. ,vol. 9 , p.2493-2504 ,1990.
Roberts, B.F.：J. Colloid Interface Sci., 23, 266, 1967.
L. M. Gandia, A. Gil, S. A. Korili, “Effects of various alkali-acid additives on the activity of a manganese oxide in the catalytic combustion of ketones ”, Applied Catalysis B：Environment,Vol 33, p.1-8, 2001.
Lutz, A. E.；Kee, R. J.and Miller, J. A. “SENKIN：A Fortran Program for Predicting Homogenerous Gas Phase Chemical Kinetics with Sensitivity Analysis ”, sandia National Laboratories Report , SAND 87-8248, 1992.
M. Kulazynski , J.G. van Ommen “Cataltyic combustion of trechloroethylene over TiO2-SiO2 supported catalysts” Applied Catalysis B：Environmental ,vol. 36 , p.239-247, 2002.
Miller,J. A. and Melius, C. F. ,”Kinetic and Theromdynamic Issues in the Formation of Aromatic Compounds in Flame of Aliphatic Fuels ”,Combust. Flame ,vol. 91 ,p.21-39 ,1992.
N. Coute , J.D.Ortego “Catalytic steam reforming of chlorocarbons：trichloroethanetrichloroethene、perchloroethylene” Applied Catalysis B:Environment 19，1998，p.175-187
Nagata, H., Takakura, T., Tashiro, S., Kishida, M., Mizuno, K., and Wakabayashi, I.T., “Catalytic oxidative decomposition of
chlorofluorocarbons (CFCs) in the presence of hydrocarbons”, Applied Catalysis B：Environment,Vol 5, p.23-31, 1994.
Patterson, M. J., Angove, D.E., Cant, N.W. and Nelson, P.F. “The formation of benzene and chlorobenzene during the oxidation of toluene over rhodium based catalysts”, Applied Catalysis B：Environment, 20 No.2, p.123-131, 1999.
Papaefthomiou, P.,and Verykios, X.E.,“Combustion of nonhalog-Enated volatile organic compounds over group VIII metal catalysts” Applied Catalysis B：Environmental, 13(3-4), p.175-184, 1997.
Papaefthimiou, P., Ioannides, t., and Verykios, X.E., “Performance of doped Pt/TiO2 (W6+) catalysts for combustion of volatile organic
compounds (VOCs)”, Applied Catalysis B：Environment, Vol.15, p.75-92,1998.
Petzod,L.R. “A Description of DASSL：A Differenetial/Algebraic system Solve”, Sandia National Laboratories Report, SAND82-8637, 1982.
Prashant S. Chintawar , Howard L. Greene ,”Decomposition characteristics of chlorinated ethylenes on metal loaded zeolite Y and γ-Al2O3 ” Applied Catalysis B：Environment,Vol 13, p.81-92, 1997.
Robert, JF. , Ronald, M.H. and Barry, K.S. ,”Environment Catalysts” , C＆EN , 7 , p 34-44 , 1992
Senkin, S. M. ,”Converting Methane by Chlorine-Catalyzed Oxidative Pyrolysis”, Chemical Engineering Science. Vol.83 , p.58-61 ,1987.
Spivey, J.J., "Complete Catalytic Oxidation of Volatile Organics", I&EC, Res., 26(11), p.2165-2180, 1987. Spivey, J.J., "Complete Catalytic Oxidation of Volatile Organics", I&EC, Res., 26(11), p.2165-2180, 1987.
Tichenor, A. and Palazzolo, M.A., “Destruction of Volatile Organics componnds via Catalytic Incineration”, Environment Progress, 6(3), p172-176, 1987.
Tiden,J. W.；Costanza, V.；McRae,G.J. “Sensitivity Analysis of Chemically Reacting Systems ”, Modeling of Chem. Reactions Systems,Springer-Verlag, New york ,p.69-91, 1981.
Warnatz J.；Maas U. and Dibble R. E. “Combustion：Physical and chem. Fundamentals, Modeling and Simulation, Experiments,Pollutant Formation ”, 2nd Edition Berlin, New York ,1999.
William C. Garnider, Jr. “Combustion Chemistry ” , Spring-Verlag , New York Inc. ,1984.
Wu Chi-Sheng, and Chang Tai-Yuan, “VOC deep oxidation over catalysts
using hydrophobic supports”, Catalysis Today, 44, p.111-118, 1998.
Wu, Y. P. “Thermal Desorption and Decomposition of Hazardous Organic Compounds. I：Mass Transfer of Benzene and Chlorobenzene in soil Matrices. II：Oxidation and Pyrolysis of 1,1,1-Trichloroethane in Methane/Oxygen/Argon”, Ph.D Dissertation ,New Jersey Institute of Technology, New Jersey ,p. 132-254 ,1992.
Yan Liu, Mengfei Luo, “Catalytic oxidation of chlorobenzene on supported manganese oxide catalysts” Applied Catalysis B：Environment,Vol 29, p.61-67, 2000.
Yan Liu, Zhaobin Wei, Zhaochi Feng ,”Oxidative Destruction of Chlorobenzene and o-Dichlorobenzene on a high active catalyst :
MnOx/TiO2-Al2O3 ”, Journal of Catalysis ,vol.202 , p.200-204 ,2001.
Yuan, T. “Quantitative Measurement of OH Concentrations by LIPF at Atmospheric Pressure ”,中華民國第八屆燃燒科技應用研討會論文集，台南市，p.118-120,1998
丁嘉源，”波洛斯凱特型觸媒用於甲烷還原一氧化氮之研究”, 國立成功大學化學工程研究所碩士論文，六月，1997。
王大中、顧洋、李嘉平，「一甲胺氣體氧化反應之研究」，國立成功大學化學工程研究所碩士論文，六月，1990。
王榮德，「有機溶劑所引起的疾病」，有機廢氣觸媒焚化處理技術研討會，Mar，1989
王清輝，「銅-鉬觸氧化物擔體觸媒運用於氧化分解二硫化二甲基之研究」，國立成功大學化學工程研究所博士論文，六月，1998
化工資訊，「化學品原料商情」，化工資訊，三月，2002
江惠中，「有機廢氣觸媒焚化及廢熱回收」，有機廢氣觸媒焚化處理技術研討會，p.4-1～4-25，三月，1989
李全能，「酸處理對CuO-MoO3/γ-Al2O3觸媒性質及其用於二甲基二硫氧化分解的影響」，國立成功大學化學工程研究所碩士論文，六月, 1997。
李志文，「一氯乙烯在高週波電漿中之反應機制」，國立成功大學環境工程研究所碩士論文，六月，2000。
李學賢，「以觸媒氧化含氯碳氫化合物之研究」，國立中山大學環境工程研究所碩士論文，六月，1994。
李秉傑、邱宏明、王奕凱合譯，「非均勻系催化原理與應用」，渤海堂文化公司印行，二月，1988。
呂立德，「化工動力與化工熱力」，立功出版社，六月，1991。
吳友平，「含氯碳氫化合物氧化反應機構之建立」，國科會計畫，八月，1995。
吳榮宗著，「工業觸媒概論」，國興出版社，1989。
許漢軒，「以Mn2O3/γ-Al2O3觸媒焚化處理三氯乙烯之研究」，國立成功大學環境工程研究所碩士論文，六月，2000。
黃振家，「揮發性有機廢棄處理技術：活性碳吸附」，化工第44卷第3期，p49-59，1997。
黃柳青譯，「化工動力學與反應設計下冊」，科技出版社，p.120-123，1993。
張玉龍，http://www.pcc.vghtpe.gov.tw/docms/50123.htm。
張書豪、張木彬 「科學園區空氣污染物排放特性之探討」，國立中央大學環境工程學刊，第6期，p215-228 ，1999。
陳敏、羅夢飛、袁賢鑫，「載體對負載鈀觸媒催化劑的CO氧化活性的影響」，環境科學學報，第18卷，第四期，p.421-424，1998。
蔡文田、張慶源，「揮發性有機物（VOCS）催化燃燒處理」，環境工程會刊，第四期，p41-58，1992。
蔡文田「含氯溶劑可行減廢技術介紹」，工業汙染防治，第三期，p.171-182，1993
蔡文田、張慶源，「揮發性有機物污染預防技術」，環保資訊，一月，p.35-41，1997
廖渭銅，「乙醚和環氧乙烷於低溫電漿環境中之反應機制」，國立成功大學環境工程研究所博士論文，十二月，2000
賴慶智，化工所八十八年度技術論壇www.epa.gov.tw/F/文宣/固定污 染源/ 工廠輔導成果/page3 /life4.html
劉國棟，「VOC管制趨勢展望」，工業污染防制，第48期，p15-31，1992
盧滄海、賴龍山，「廢溶劑回收可行性探討」，工業污染防治，第29期，p.102-117，1989
環境保護署，環境衛生及毒物管理資料http://www.epa.gov.tw/J/toxic/
環保署環境檢驗所編，「排氣管道中氯化氫檢測方法－硫氫化汞比色法」，空氣檢測方法，A412.70A，一月，1995。