臺灣博碩士論文加值系統

本研究主要探討UV/TiO2程序在連續式填充床反應器中的效果, 所用的TiO2載體為玻璃珠, 氣相污染物為甲基乙基酮(MEK), 實驗的變因包括UV光波長、初始濃度、溫度、流速、滯留時間等效應, 並利用Langmuir-Hinshelwood吸附理論與Fick質傳理論結合推導出適用於此實驗系統的動力方程式, 求出L-H反應速率常數(k)、MEK吸附平衡常數(Ka)、活化能(E)與頻率因子(k0)等參數。實驗結尾並結合光觸媒與臭氧程序, 觀察兩者協同反應的效果。
由實驗結果可以歸納出, 波長254nm的UV光對MEK的分解效果比波長365nm的UV光效果更好。當初始濃度提高時, 光觸媒對MEK的去除率越低且越容易產生失活現象。滯留時間對光觸媒的MEK去除效率影響分為兩階段, 當滯留時間小於30秒時去除率與滯留時間成正比, 當滯留時間大於30秒時去除率與滯留時間無關。在動力參數方面可以發現k值會隨著溫度提高而增大, 代表反應速率加快, Ka值會隨著溫度增高而減小, 代表不利於反應物吸附。
對三種程序TiO2/UV、O3/TiO2、O3/TiO2/UV而言, 在滯留時間相同的條件下, MEK去除效率為O3/TiO2/UV > TiO2/UV > O3/TiO2。而在高初始濃度與低滯留時間的環境中, O3/TiO2/UV程序的處理效果最佳。

This research discuss mainly UV/TiO2 process in the continuous packed bed reactor. We use glass pearls for loading TiO2.The gaseous phase pollutant is Methyl Ethyl Ketone (MEK) .The changes of this experiment includes such effects as wavelength of UV light , initial concentration, system temperature, flow rate and retention time, etc. Then we combine Langmuir-Hinshelwood adsorption theory with Fick mass transfer theory for examining the kinetic equation suitable for this experimental system. Find out several parameter such as L-H reaction rate constant (k) , MEK adsorption constant (Ka) , activate energy(E) , frequency factor (k0).At the end of our experiment we combine photocatalytic process with ozone process, and observe the effect of synergy reaction.
From the experimental result we can conclude several points. Use UV light of wavelength 254nm to decompose MEK is better than UV light of wavelength 365nm.When we raise MEK initial concentration, it will induce to decrease the MEK conversion ratio and make photocatalyst more easily deactivate. The retention time effects for MEK photolysis can divide into two stages. When retention time is smaller than 30 seconds, the getting rise of retention time is in direct proportion to MEK conversion ratio. When retention time is greater than 30 seconds, the getting rise of retention time have nothing to do with MEK conversion ratio. The aspect of kinetic parameters, we can find k value will increase as temperature improves. It represents that reaction rate speeds up. Ka value will be reduced as temperature increases. It represents an unfavorable effect for the reactant to adsorb.
As to three process of TiO2/UV, O3/TiO2, O3/TiO2/UV, under the same condition of retention time, decomposing efficiency of MEK is O3/TiO2/UV> TiO2/UV> O3/TiO2. Under the conditions of high initial concentrations and low retention times, the treatment result of O3/TiO2/UV process is the best.

目 錄
圖目錄…………………………………………………………………VIII
表目錄………………………………………………………………….XII
第一章 緒論
1-1 前言…………………………………………….........................1
1-2 研究目的……………………………………………………….3
第二章 文獻回顧
2-1 揮發性有機化合物(VOCS)…………………………………….4
2-1-1 揮發性有機物的種類……………………………………4
2-1-2 揮發性有機物的危害……………………………………7
2-1-3 傳統揮發性有機物之處理技術…………………………9
2-1-4 發展中的VOC處理技術介紹…………………………12
2-2 二氧化鈦光觸媒……………………………………………..16
2-2-1光觸媒基本原理…………………………………………16
2-2-2 n-型與p-型半導體………………………………………18
2-2-3二氧化鈦的晶型…………………………………………20
2-2-4二氧化鈦的物化特性……………………………………24
2-2-5二氧化鈦光觸媒的製備方法……………………………25
2-2-6光觸媒的光催化反應機制………………………………29
2-2-7商品奈米晶體光觸媒……………………………………33
2-3光催化反應器的種類…………………………………………34
2-4影響UV/TiO2光催化程序氧化的因素………………………37
2-4-1紫外線光強度效應………………………………………37
2-4-2反應溼度效應…………………………………………....38
2-4-3反應溫度效應……………………………………………39
2-4-4反應氣體含氧量效應……………………………………41
2-4-5光觸媒的負載量效應……………………………………42
2-4-6反應滯留時間效應………………………………………42
2-5 UV/TiO2反應動力模式建立………………………….............43
2-6臭氧(Ozone)…………………………………………………...47
2-6-1臭氧的發現與製造………………………………………47
2-6-2臭氧的性質與毒性……………………………………....47
2-6-3臭氧的性質與毒性………………………………………51
2-6-4臭氧在空氣中的自解……………………………………51
第三章 研究材料與方法
3-1研究流程………………………………………………………52
3-2實驗藥品與材料……………………………………………….54
3-2-1反應氣體…………………………………………………54
3-2-2光觸媒……………………………………………………54
3-3光觸媒之物化特性分析……………………………………….57
3-3-1物理特性分析……………………………………………57
3-3-2化學特性分析……………………………………………62
3-4實驗方法……………………………………………………….64
3-4-1背景實驗…………………………………………………64
3-4-2異相光催化反應…………………………………………65
3-4-3臭氧濃度測定……………………………………………69
第四章 實驗結果與討論
4-1光觸媒基本性質分析…………………………………………73
4-1-1 BET表面孔隙分析……………………………………...73
4-1-2 XRD(X-ray diffraction)表面晶型分析………………….75
4-1-3 ICP-AES(Inductively Coupled Plasma-Atomic Emission Spectroscopy)金屬元素分析……………………………77
4-1-4 SEM(Scaning electron microscope)觸媒外觀分析……..78
4-1-5 EDS(Energy dispersive spectroscopy) 觸媒表面元素分析………………………………………………………...80
4-2背景實驗……………………………………………………….81
4-2-1光觸媒活性的再現性……………………………………81
4-2-2光觸媒活性耐久度實驗………………………………....83
4-2-3光觸媒活性驗證…………………………………………84
4-3 實驗參數探討………………………………………………...88
4-3-1各濃度下長時間反應濃度曲線........................................88
4-3-2溫度效應探討....................................................................91
4-3-3溫度與流速效應綜合探討................................................94
4-4動力模式探討…………………………………………...........100
4-4-1 動力參數分析…………………………………………100
4-4-2 動力模式預測…………………………………………107
4-5臭氧與光觸媒協同反應……………………………………...107
4-5-1各濃度下光觸媒與臭氧協同處理效果………………..109
4-5-2三種程序處理效果綜合比較…………………………..115
4-5-3利用臭氧能力比較……………………………………..117
第五章 結論與建議
5-1結論…………………………………………………………...119
5-2建議…………………………………………………………...120
參考文獻……………………………………………………………….121

1.劉希平，台北縣固定污染源VOC濃度調查及空污費徵收方式研究計畫，台北縣環保局，民國八十八年三月。
2. 蘇世昌, 溫溼度協同效應對四氯乙烯光催化分解反應影響之探討,民國92年七月。
3.行政院環境保護署網站，http://www.epa.gov.tw/。
4.鍾美華、黃思篿、張淑芬，有機性有害空氣污染物列管名單篩選方法之探討，第十屆空氣污染控制技術研討，民國八十二年十二月。
5.J.J Spivey,Complete Catalytic Oxidation of Volatile Organics, Ind. Eng. Chem. Res.,26(1987)2165
6.張志平, 以光觸媒對加油站油氣污染物控的探討, 民國94年7月
7. Linsebigier, A. L., Lu, G., and Yates, J.T., “Photocatalysis on TiO2
Surface: Principles, Mechanism, and Selected Results,” Chem. Rev.,
95: pp.735-758, 1995.
8. 盧明俊，“毒性化學物質經二氧化鈦催化之光氧化反應”，博士論文，國立交通大學土木工程研究所，1993。
9.Amyl. Linsebigler.Guangquan Lu and John T. Yates. Jr., 1995,Chem.Rev.,Vol.95.pp.735-758.
10. Burdett J. K., Hughbanks T., Miller G. J., Richardson J. W. and Smith J V. (1987)Structural-electronic relationships in inorganic solids: powder neutron diffractionstudies of the rutile and anatase polymorphs of titanium dioxide at 15 and 295 K. J. Am. Chem. Soc. 109, 3639.
11. Fox, M. A.; Dulay, M. T., “Hetergeneous photocatalysis”, Chem Rev 3, 93, p.341 (1989)
12. 黃鈺惠，“二氧化鈦光觸媒之製備及分解室內揮發性有機物質之研究”，碩士論文，中國文化大學研究所，2001。
13. Kato, K., “Synyhesis of TiO2 photocatalyst with high activity by the
alkoxide method”, in Photocatalytic Purification and Treatment of
Water and Air, Ollis, D.F., Al-Ekabi, H., Eds., Elsevier: Amsterdam,
p.809 (1993)
14. Anderson, M. A., Yamazaki-Nishida, A., Cervera-March, S.,
“Photodegradation of trichloroethylene in the gas phase using TiO2
porpous ceramic membranes”, in Photocatalytic Purification and
Treatment of Water and Air, Ollis, D. F., Al- Ekabi, H., Eds., Elsevier: Amsterdam, p.405 (1993)
15. Hung, C. H., Marinas, B. J., “Role of chlorine and oxygen in the
photocatalytic degradation of trichloroethylene vapor on TiO2 films”,
Environ. Sci. Technol. 31(2), p.562 (1997)
16. Kishimoto H., Takahama K., Hashimoto N., Aoi Y. and Deki S. (1998) Photocatalyticactivity of titanium oxide prepared by liquid phase deposition (LPD). J. Mater. Chem.8, 2019-2024.
17. Richardson T.J. and Rubin M.D. (2001) Liquid phase deposition of electrochromic thin films. Electrochim. Acta 46, 2119-2123.
18. Howe, R. F., “EPR Spectroscopy in Surface Chemistry: Recent
Developments,” Advances in Colloid and Interface Science, Vol.18
pp.1, 1982.
19. Howe, R. F., and Gratzel, M., “EPR Study of Hydrated Anatase under UV Irradiation,” J. Phys. Chem., Vol.91, pp.3906-3909, 1987.
20. Cundall, R. B., Rudham, R., and Salim, M. S., “Photocatalytic
Oxidation of Propan-2-ol in the Liquid Phase by Rutile,” J. Chem.
Soc. Faraday Trans. I., Vol.72, pp.1642, 1976.
21. Izumi, I., Dunn, W. W., Wilbourn, K. O., Fan, F. R., and Bard, A. J.,“Heterogeneous Photocatalytic Oxidation of Hydrogens on Platinized TiO2 Powders,” J. Phys. Chem., Vol.84, No.24, pp.3207, 1980.
22. Fukuzawa, K. S., and Kwan, T., “Photoadsorption and
Photodesorption of Oxygen on Titanium Dioxide,” J. Catalysis, Vol.11, pp.364, 1968.
23. Jaeger, C. D., and Bard, A. J., “Spin Trapping and Electron Spin
Resonance Detection of Radical Intermediates in the
Photodecomposition of Water at TiO2 Particulate System,” J. Phys.
Chem., Vol.83, No.24, pp.3146, 1979.
24. Naccache, C., Meriaudeau, P., Che, M., and Tench, A., “Identification of Oxygen Species Adsorbed on Reduced Titanium Dioxide,” J. Trans. Faraday Soc., Vol.67, pp.506, 1971.
25. Nair, M. R., Jacoby, W. A., Blake, D. M., and Milne, T. A.,
“Detection of Intermediates from the Gas-phase Photocatalytic
Oxidation of Trichlorothylene,” Proceeding of the 1st International
Conference on TiO2 Photocatalytic Purification and Treatment of
Water and Air, London, Ontario, Canada, 8-13 November 1992.
26. William, J. C., Meacham, D. E., Nickelsen, M. G., and Lin, K., “The Removal of Trichloroethylene (TCE) and Tetrachloroethylene (PCE) from Aqueous Solution Using High Energy Electrons,” Air and Waste Management Association Annual Meeting,43: pp.1358-1366, 1993.
27. Gratson, D. A., Nimos, M. R., and Wolfrum, E. J., “Photocatalytic
Oxidation of Gas-Phase BTEX-Contaminated Waste Streams,” The
88th Air＆Waste Management Association Annual Meeting, June,
1995.
28. Ibusuki, T., and Takeuchi, K., “Toluene Oxidation on UV-Irradiated Titanimn Dioxide with and without O2, NO2, or H2O at Ambient Temperature,” Atmospheric Environment,20: pp.1711, 1986.
29. Hung, C. H., and Marinas, B. J., “Role of Chlorine and Oxygen in the Photocatalytic Degradation of Trichloroethylene Vapor on TiO2
Films,” Envirion. Sci. Technol 31(2): pp.562-568, 1997.
30. Ibusuki, T., Kutsuna, S., Takeuchi, K., Shin-Kai, K., Sasamoto, T.,
and Miyamoto, M., “Removal of Low Concertration Air Pollutionts
through Photoassisted Heterogeneous Catalysis,” in Phototcatalytic
Purification and Treatment of Water and Air, pp.375, 1993.
31. Anderson, M. A., Aeltner, M., Fu, X., and Tompkins, D., “Chamber Studues Comparing the Effectiveeness of Photocatalytic Degradation and Activated Carbon for the Treatment of Indoor Air,” Air＆Waste Management Assoication Annual Metting, June, 1996.
32. Zeltner, W. A., Fu, X., and Anderson, M. A., “Photocatalytic Ceramic Membrances Reactors: The Chemists Perspective,” The 88th Air＆Waste Management Association Annual Meeting, June, 1995.
33. Jordan, P. H., and Yue, P. L., “Photocatalytic Abatement of Nitrogen Oxide,” in Photocatalytic Purification and Treatment of Water and Air, pp.727-732, 1993.
34. Murabayashi, M., Itoh, K., Kawashima, K., Masunda, R., and Suauki, S., “Photocatalytic Degradation of Chloroform with TiO2 Coated Glass Fiber Cloth,” in Photocatalytic Purification and Treatment of Water and Air, pp.783-788, 1993.
35. Peral, J., and Ollis, D. F., “Heterogeneous Photocatalytic Oxidation of Gas-Phase Organics for Air Purification: Acetone, 1-Butanol,
Butyaldehyde, Formaldehyde, and m-Xylene Oxidation,” J.
Catal.,134: pp.554-565, 1992.
36. Dibble, L. A., and Raupp, G. B., “Fluidized-Bed Photocatalytic
Oxidation of Trichloroethylene in Contaminated Air Streams,”
Envirion. Sci. Technol, 1992.
37. Hofstadler, K., Bauer, R., Novalle, S., and Heisler, G., “New Reactor Design for Photocatalytic Wastewater Treatment with TiO2
Immobilized on Fused-Silica Glass Fibers: Photomineralization of
4-Chlorophenol,” Envirion. Sci. Technol, pp.670-674, 1994.
38. Peill, N. J., and Hoffmann, M. R., “Chemical and Physical
Characterization of a TiO2-Coated Fiber Optical Cable Reactor,”
Envirion. Sci. Technol, pp.2806-2812, 1996.
39.Racehl A,Subrahmanyam M,Boule P.Appl. Catal. A,2002 37:301~308
40 .Racehl A,Subrahmanyam M,Sakakha M, et al. Appl. Catal. B,2002 37:293~300
41. Dibble, L. A., and Raupp, G. B., “Fluidized-Bed Photocatalytic
Oxidation of Trichloroethylene in Contaminated Air Streams,”
Envirion. Sci. Technol, 1992.
42. Dibble, L. A., “The Gas-Solid Heterogeneous Photocatalytic
Oxidation of Trichloroethylene by Near Ultraviolet Illuminated
Titanium Dioxide,” Ph. D. Dissertation Arizona State University,
1989.
43. Raupp, G. B., and Junio, C. T., “Photocatalytic Oxidation of
Oxygenated Air Toxics,” Appl. Sur. Sci.,72: pp.321, 1993.
44. Jacoby, W. A., Nimlos, M. R., and Blake, D. M., “Products
Intermediates Mass Balances and Reaction Pathways for the
Oxidation of Trichloroethylene in Air via Heterogeneous
Photocatalysis,” Envirion. Sci. Technol,28: pp.1661, 1994.
45. Peterson, M. W., Turner, J. A., Nozik, A. J., “Mechanistic Studies of the Photocatalytic Behavior of TiO2 Particles in a
Photoelactrochemical Slurry Cell and Relevance to
Photodetoxification Reactions,” J. Phys. Chem., Vol.95, pp.221,
1991.
46. 顧洋, 江立偉, “以紫外線/二氧化鈦程序處理氣相苯、甲苯及二甲苯污染物反應行為之研究,” 第十六屆空氣污染控制技術研討會論文集, pp.704-714, 1999。
47. Obee, T. N., and Brown, R. T., “TiO2 Photocataltsis for Indoor Air
Applications: Effect of Humidity and Trace Contaminant Levels on
the Oxidation Rates of Formaldehyde,Toluene,and 1,3-Butadiene,”
Environ. Sci. Technol.,29, pp.1223-1231, 1995.
48. Jacoby, A. M., Blake, D. M., Fennell, J. A., Boulter, J. E., and Vargo,L. M., “Hetergeneous Photocatalysis for Control of Volatile OrganicCompounds in Indoor Air,” The 88th Air＆Waste Management Association,46: pp.891-898, 1996.
49. Fu, X. F., Clark, L. A., Zeltner, W. A., Anderson, M.A., “Effect of reaction temperature and water vapor content on the heterogeneous
photocatalytic oxidation of ethylene”. J. Photochem. Photobiol. 97,
p.181 (1996)
50. Wang, K. M., and Marinas, B. J., “Control of VOC Emissions from
Air-Stripping Towers: Development of Gas-Phase Photocatalytic
Process,” in Photocatalytic Purification and Treatment of Water and Air, pp.733-737, 1993.
51.V.Augugliaro,L.Palmisano,M.schiavello,A.Sclafani, Applied Catalysis, 69,323-340(1990).
52.Obee T.N.and Brown R.T.,TiO2 Photocatalysis for Indoor Air Application,Effect of Humidity and Trace Contaminant Levels on the Oxidation Rates of Formaldehyde, Toluene, and 1,3-Butadiene. Environ.Sci,&Technol.1995;29:1223-1231.
53. Al-Ekabi H.,Butters B.,Delany D.,Holden W.,Powell T. and story J.:Photocatalytic Destruction of Gaseous Trichloroethylene and Tetrachloroethylene Over Immobilized Titanium Dioxide Photocatalytic Purification and Treatmert of Water and Air.1993:719-725.
54. 袁中新,蕭德福,吳政峰及洪崇軒:二氯化鈦光觸媒改質及四氯乙烯去除率及礦化率之探討。空氣污染,控制技術研討會論文集, 2000:268-272.
55. 溫添進、張家欽, 臭氧之應用及其電解法製造, 化工, Vol 41, No 3, pp.60~71 (1994).
56. 戴正光, 臭氧處理養殖水質之基礎研究, 國立中興大學農業機械工程學系碩士論文 (2002).
57. Razumovskii, S. D.; Zaikov, G. E. Ozone and its reactions with orangic compounds; Elsevier Science Publishing Company, Inc.: New York, 1984.
58. Langlias, B., D.A. Reckhow and D.R. Brink, Ozone in Water
Treatment Application and Engineering , Lewis publishers ,
Michigan, U.S.A Inc. (1991).
59. Prengle, H. W. and C.E. Mauk, ”New technology ozone/UV chemical oxidation wastewater process for metal complex, organic species and disinfection,” AIChE Sym., Vol 74, pp.228 (1978).
60. Pichat, P., J. Disdier, C. Hoang-Van, D. Mas, G. Goutailler, C. Gaysse, “Purification / deodorization of indoor air and gaseous effluents by TiO2 photocatalysis”, Catalysis Today, Vol. 63, pp.362-369 (2000)
61. Al-Ekabi, H., Butters, B., Delany, D., Holden, W., Powell, T., Story, J., Photocatalytic Purification and Treatment of Water and Air, Elsevier Science Publishers B.V. Amsterdam, pp.719-725 (1993)
62. Pengyi Zhang,Juan Liu, “Photocatalytic degradation of trace hexane in the gas phase with and without ozone addition:kinetic study”,Journal of photochemistry and photobiology,Chemistry 167(2004)
63. Jeng-Fong Wu, Chung-Hsuang Hung,, Chung-Shin Yuan,” Kinetic modeling of promotion and inhibition of temperature on photocatalytic degradation of benzene vapor”, Journal of Photochemistry and Photobiology A: Chemistry 170 (2005) 299–306
64. 曾熠焜，“以紫外線/光觸媒程序處理氣相丙酮反應行為之研究”，碩士論文，台灣科技大學化學工程研究所，2003。
65. 馬志明，“以紫外線/二氧化鈦程序處理氣相三氯乙烯污染物反應行為之研究”，碩士論文，台灣科技大學化學工程研究所，1998。