| 研究生: |
鄭銚強 Yao-Chiang Cheng |
|---|---|
| 論文名稱: |
焚化系統中抑制戴奧辛生成之初步研究 Investigation of PCDD/PCDF Formation by Inhibitors in Laboratory-scale Experimental System |
| 指導教授: |
張木彬
Moo-Been Chang |
| 口試委員: | |
| 學位類別: |
碩士 Master |
| 系所名稱: |
工學院 - 環境工程研究所 Graduate Institute of Environmental Engineering |
| 畢業學年度: | 92 |
| 語文別: | 中文 |
| 論文頁數: | 125 |
| 中文關鍵詞: | 戴奧辛 、抑制 、硫 、焚化 |
| 外文關鍵詞: | inhibitor, reduce, MSWI, PCDD/Fs |
| 相關次數: | 點閱:12 下載:0 |
| 分享至: |
| 查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報 |
焚化系統中戴奧辛排放控制技術主要採用噴入活性碳吸附及觸媒破壞兩種類型,兩者都能有效去除煙道排氣中之戴奧辛,但這兩項技術皆屬管末處理技術,基於永續發展及源頭減量之考量,有效減少戴奧辛於焚化過程之生成才是治本之道。國外研究指出於廢棄物焚化過程中如添加抑制劑,如含硫、胺、氮及鹼性物質,可有效抑制戴奧辛的生成。本研究結果顯示各項抑制劑對戴奧辛之抑制生成率並非與抑制劑的添加量成一正相關,而是有一最佳添加比例。研究顯示添加硫粉可有效抑制戴奧辛之生成,其中又以S/Cl mole比為2時,其抑制效率最好(54.2﹪),硫粉對於戴奧辛的抑制效果並非隨著硫粉的添加量增加而上升,而是與焚化過程中之氯源含量存有最適的添加量。SO2/HCl濃度比為0.55時,可達50.6﹪的抑制效果,SO2對於PCDF生成的抑制效果較佳,約40~70﹪,而對PCDD則較差,並且在SO2/HCl過低或過高時對戴奧辛之抑制效果皆明顯下降。以氫氧化鈣做為抑制劑時,無論Ca/Cl mole比為0.5、1或2時,其抑制效果皆可高於90﹪以上。氫氧化鈣會與氣流中之HCl反應,形成氯化鈣減少戴奧辛之生成以及氯化能力。尿素在N/Cl mole比為0.1時,抑制率最佳為86.9﹪,尿素易與催化金屬銅形成Cu+-urea錯合物,降低催化金屬之催化能力,尿素遇高溫會自行分解而產生NH3,與氣流中之HCl反應生成NH4Cl,降低氯化反應之進行。抑制劑之抑制效果皆有其最佳之比例,因此於焚化系統中添加抑制劑時,需先了解廢棄物組成中之氯含量並作適度之調整,以達到最佳之抑制效果。成本效益分析結果顯示添加抑制劑技術之成本低於活性碳吸附以及觸媒破壞技術,且國內外研究顯示抑制劑之抑制率可達85~95%,應用抑制劑減少戴奧辛之生成可作為另一項控制戴奧辛排放之源頭控制技術。
Polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) are very toxic compounds mainly emitted from municipal solid waste incinerators(MSWI). These compounds will affect human health when inhaled. Activated carbon injection (ACI) and SCR decompostition are two major end-of-pipe pollution control technologies currently used. It is proved that addition of inhibitors (such as sulfur, SO2, urea, alkaline materials) could decrease formation of dioxins. Experimental results indicate that addition of sulfur in incineration process can reduce PCDD/F formation. PCDD/F formation can be effectively reduced when S/Cl molar ratio is about 2. Dioxins decrease dramatically at SO2/HCl ratio as 0.55. The sulfur component will react with Cl2 and convent it into HCl. In addition, S or SO2 affect dioxin formation by vulcanizating phenolic precursors and catalysis metal, thus inhibiting chlorination reaction. Calcium hydroxide can reduce dioxin formation by more than 90﹪when Ca/Cl molar ratio is over 0.5. Addition of urea can also reduce PCDD/F formation about 50~87﹪when N/Cl mole ratio is about 0.1. The role of urea is to block catalysis metal and to form complex compounds with Cu and to prevent Ullmann reaction. Inhibition of dioxins formation will be the best way to reduce dioxin emissions. The cost of applying inhibitors for reducing dioxin formation is considerably lower than that of using activated carbon injection (ACI) and SCR decompostition. Adding inhibitors technology has a good potential for controling dioxins formation and emission in the future.
1.Lee, W. J., Liow, M. C., Tsai, P. J., Hiseh, L. T., “Emission of Polycyclic Aromatic Hydrocarbons from Medical Waste Incinerators”, Atmospheric Environment, 36, pp.781-790(2002)
2.USPEA,User''s Manual for the Database of Sources of Environmental Releases of Dioxin-like Compounds in the United States: Reference Years 1987 and 1995,(EPA/600/C-01/012, March, 2001)
3.Olie, K., Vermeulen, P. L., Hutzinger, O., “Chlorodibenzo-p-dioxins and Chlorodibenzofurans are Trace Components of Fly Ash and Flue Gas of Some Municipal Incinerators in the Netherlands”, Chemosphere, No.8, pp.455-459(1977)
4.Dickson, C. L., Lenolr, D., Hutzinger, O., “Quantitative Comparison of De Novo and Precursor Formation of Polychlorinated Dibenzo-p-dioxions under Simulated Municipal Solid Waste Incineration Post Combustion Conditions”, Environ. Sci. Technol. Vol.26, pp.1822-1828(1992)
5.Stieglitz, L., Vogg, H., “On Formation Condition of PCDD/PCDF in Fly-ash from Municipal Waste”, Chemosphere, Vol.16, pp.1917-1922(1987)
6.Milligan, M. S., Altwicker, E., “The Relationship between De Novo Synthesis of Polychlorinated Dibenzo-p-dioxin and Dibenzofurans and Low-temperature Carbon Gasification in Fly Ash”, Environ. Sci. Technol., Vol.27, pp.1595-1601(1993)
7.Weber, R., Iino, F., Imagawa, T., Takeuchi, M., Sakurai, T., Sadakata, M., “Formation of PCDF, PCDD, PCB, and PCN in De Novo Synthesis from PAH:Mechanistic Aspects and Correlation to Fluidized Bed Incinerators”, Chemosphere Vol.44, pp.1429-1438(2001)
8.Tuppurainen, K., Halonen, I., Ruokojärvi, P., Tarhanen, J., Ruuskanen, J., “Formation of PCDDs and PCDFs in Municipal Waste Incineration and Its Inhibition Mechanisms:A Review”, Chemosphere, Vol.36, No.7, pp.1493-1511(1998)
9.Ballschmiter, K., Zoller, W., Scholtz, C. and Nottrodt, A., “Destruction of PCDD and PCDF in Bleached Pulp by Chlorine Dioxide Treatment”, Chemosphere, Vol.12, pp.585-597(1983)
10.Hagenmaier, H., Jraft, M., Brunner, H., Haag, R., “Catalytic Effect of Fly Ash from Waste Incineration Facilities on the Formation and Decomposition of Polychlorinated Dibenzo-p-dioxions and Polychlorinated Dibenzofurans”, Environ. Sci. Technol., Vol.21, pp.1080-1084(1987)
11.Luijk, R., Dorland, C., Kapteijn, F., Govers, H. A. J., “The Formation of PCDDs and PCDFs in the Catalyzed Combustion of Carbon:Implications for Coal Combustion”, Fuel, Vol.7, pp.343-347(1993)
12.Ogawa, H., Orita, N., Horaguchi, M., Suzuki, Takumi., Okada, M., Yasuda, S., “Dioxin Reduction by Sulfur Component Addition”, Chemosphere, Vol.32, No1, pp.151-157(1996)
13.Griffin, R. D., “A New Theory of Dioxin Formation in Municipal Solid Waste Combustion”, Chemosphere, Vol.15, No.9-12, pp.1987-1990(1986)
14.Luijk, R., Akkerman, D.M., Slot, P., Olie, K., “Mechanism of Formation of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans in the Catalyzed Combustion of Carbon”, Environ. Sci. Technol., Vol.28, pp.312-321(1994)
15.Stieglitz, L., “Selected Topics on the De Novo Synthesis of PCDD/PCDF on Fly Ash”, Environmental Engineering Science, Vol.15, No1, pp.5-18(1998)
16.Pekárek, V., Grabic, R., Markund, S., Punčochář, M., Ullrich, J., “Effects of Oxygen on Formation of PCB and PCDD/F on Extracted Fly Ash in the Presence of Carbon and Cupric Salt”, Chemosphere, Vol.43, pp.1777-782(2001)
17.Gullett, B. K., Bruce, K. R., Beach, L. O., “Mechanistic Steps in the Production of PCDD and PCDF during Waste Combustion”, Chemosphere, Vol.25 ,No.7-10, pp.1387-1392(1992)
18.Gullett, B. K., Bruce, K. R., Beach, O.L., “Effect of Sulfur Dioxide on the Formation Mechanism of Polychlorinated Dibenzodioxin and Dibenzofuran Municipal Waste Combustors”, Environ. Sci. Technol., Vol.26, pp.1938-1943(1992)
19.Huang, H., and Buekens, A., “On the Mechanisms of Dioxin Formation in Combustion Processes”, Chemosphere, Vol.31, No.9, pp.4099-4117(1995)
20.Addink, R., Cnubben, P. A. J. P., and Olie, K., “Formation of Polychlorinated Dibenzo-p-dioxins/Dibenzofurans on Fly Ash from Precursors and Carbon Model Compounds”, Carbon, Vol.33, Iss.10, pp.1463-1471(1995)
21.Takeuchi, M.,「Reduction and Destruction Technologies of Combustion Derived Dioxins」,戴奧辛生成抑制與破壞去除控制技術研討會,台北,(2002)
22.陳明輝、黃志峰,「中小型焚化爐廢氣重金屬半乾式處理技術介紹」,經濟部工業局工安環保報導,第四期,(2001)
23.Buekens, A. and Huang, H., “Comparative Evaluation of Techniques for Controlling the Formation and Emission of Chlorinated Dioxins/furans in Municipal Waste Incineration”, Journal of Hazardous Materials, Vol.62, pp.1-33(1998)
24.http://www.sciscape.org/news_detail.php?news_id=437
25.Wey, M. Y., Chao, C. Y., Chen, J. C., Yu, L. J., “The Relationship between the Quantity of Heavy Metal and PAHs in Fly Ash”, J. Air & Waste Manage., Assoc.48, pp.750–756(1998)
26.Wey, M. Y ., Chao, C. Y., Wei, M. C., Yu, L. J., Liu, Z. S., “The Influence of Heavy Metals on Partitioning of PAHs during Incineration”, Journal of Hazardous Materials, Vol.77, pp.77–87(2000)
27.Brink, R. W., Louw, R., Mulder, P., “Formation of Polychlorinated Benzenes during the Catalytic Combustion of Chlorobenzene Using a Pt/γ-Al2O3 Catalyst”, Applied Catalysis B:Environmental, Vol.16, pp.219-226(1998)
28.Weber, R., Sakeshi, T., Hagenmaier,H., “Low Temperature Decomposition of PCDD/PCDF, Chlorobenzenes and PAHs by TiO2-based V2O5-WO3 Catalysts”, Applied Catalysis B:Environmental, Vol.20, pp.249-256,(1999)
29.Liljelind, P., Unsworth, J., Maaskant, O., Marklund, S., “Removal of Dioxins and Related Aromatic Hydrocarbons from Flue Gas Stream by Adsorption and Catalytic Destruction”, Chemosphere, Vol.42, pp.615-623(2001)
30.Huang, H. L. and W. M. G. Lee, “Simultaneous Removal of Polycyclic Aromatic Hydrocarbon and Carbon Dioxide by Anionic Surfactant”, J. of Environmental Science and Health-part A, Vol.36, No.7,pp.(2001)
31.Fritaky, K. J., Kumm, J. H., Wilken, M., “Combined PCDD/F Destruction and Particulate Control in a Baghouse:Experience with a Catalytic Filter System at a Medical Waste Incineration Plant”, J. Air & Waste Manage., Assoc.51, pp.1642-1649(2001)
32.Bonte, J. L., Fritsky, K. J., Plink, M. A., and Wilken, M., “Catalytic Destruction of PCDD/F in a Fabric Filter:Experience at a Municipal Waste Incinerator in Belgium”, Waste Management 22, pp.241-246(2002)
33.洪文宗,「氧化鐵觸媒分解戴奧辛技術的新研發」,行政院環境檢驗所通訊雜誌,第三十八期,(2001)
34.Hung, W. T., Lin, C. F., “Use of Regenerated Ferric Oxide for CO Destruction and Suppressing Dioxin Formation in Flue Gas in a Pilot-scale Incinerator”, Chemosphere, Vol.53, pp.727-735 (2003)
35.Stieglitz, L., Vogg, H., Zwick, G., “Thermal Behavior of PCDD/PCDF in Fly Ash from Municipal Incinerators”, Chemosphere, Vol.23, No.8-10, pp.1255-1264(1991)
36.Lippert, T., Wokaun, A., Lenoir, D., “Surface Reaction of Brominated Arenes as a Model for the Formation of Chlorinated Dibenzodioxins and Furans in Incineration:Inhibition by Ethanolamine”, Environ. Sci. Technol., Vol.25, pp.1485-1489(1991)
37.Anthony, E. J., Jia, L. and Granatstein, D. L., “Dioxin and Furan Formation in FBC Boilers”, Environ. Sci. Technol., Vol.35, pp.3002-3007(2001)
38.Takasuga, T., Makino, T., Tsubota, K., Takeda, N., “Formation of Dioxins(PCDD/F) by Dioxin-free Fly Ash as Catalyst and Relation with Several Chlorine-sources”, Chemosphere, Vol.40, pp.1003-1007(2000)
39.張乃斌,垃圾焚化廠:系統工程規劃與設計(上冊),茂昌圖書有限公司,第三版,台北(2001)
40.Weber, R., and Sakurai, T., “Formation Characteristics of PCDD and PCDF during Pyrolysis Processes”, Chemosphere, Vol.45, pp.1111-1117(2001)
41.Ghorishi, S. B., Altwicker, E. R., “Formation of Polychlorinated Dioxins, Furans, Benzenes, and Phenols in the Post-combustion Region of Heterogeneous Combustor:Effect of Bed Material and Post-combustion Temperature”, Environ. Sci. Technol., Vol.29, No.5, pp.1158-1182(1995)
42.Gullett, B. K., Raghunathan, K., Dunn, J. E., “The Effect of Co-firing High-Sulfur Coal with Municipal Waste on Formation of Polychlorinated Dibenzodioxin and Polychlorinated Dibenzofuran”, Environmental Engineering Science, Vol.15, No.1, pp.59-70(1998)
43.Sakai, S. I., “Substance Flow Approach for the Control of PCDD/Fs-recent Development on Emission Control and Abatement of PCDD/Fs in Japan”, Organohalogen Compounds, Vol.14, pp.811-814(1994)
44.Kim, S. C., Jeon, S. H., Jung, H. R., Kim, K. H., Kwon, M. H., Kim, J. H., Yi, J. H., Kim, S. J., You, J. C., and Jung, D. H., “Removal Efficiencies of PCDDs/PCDFs by Air Pollution Control Devices in Municipal Solid Waste Incinerators”, Chemosphere,Vol.43, pp.773-776(2001)
45.Raghunathan, K., Gullett, B. K., “Role of Sulfur in Reducing PCDD and PCDF Formation”, Environ. Sci. Technol., Vol.30, pp.1827-1832(1996)
46.Ruokojärvi, P., Aatamila, M., Tuppurainen, K., Ruuskanen , J., “Effect of Urea on Fly Ash PCDD/F Concentrations in Different Particle Sizes”, Chemosphere, Vol.43, pp.757-762,(2001)
47.Tuppurainen, K., Aatamila, M., Ruokojärvi, P., Halonen, I., Ruuskanen, J., “Effect of Liquid Inhibitors on PCDD/F Formation Prediction of Particle-phase PCDD/F Concentrations Using PLS Modeling with Gas-phase Chlorophenol Concentrations as Independent Variables”, Chemosphere, Vo.l38, pp.2205-2217(1999)
48.Ruokojärvi, P., Asikainen, A., Ruuskanen , J., Tuppurainen, K., Mueller, C., Kilpinen, P., Keturi., N. Y., “ Urea as a PCDD/F Inhibitor in Municipal Waste Incineration”, J. Air & Waste Manage., Assoc.51, pp.422-431(2001)
49.Takacs, L. and Moilanen, G. L., “Simultaneous Control of PCDD/PCDF, HCl and NOx Emissions from Municipal Solid Waste Incinerators with Ammonia Injection”, J. Air & Waste Manage., Assoc.41, pp.716-722(1991)
50.Ruokojärvi, P. H., Halonen, I. A., Tuppurainen, K. A., Ruuskanen, J., Tarhanen, J., “Effect of Gaseous Inhibitors on PCDD/F Formation”, Environ. Sci. Technol., Vol.32, pp.3099-3103(1998)
51.廖萬里、張木彬,「垃圾焚化產生戴奧辛之機制與控制方法」,國立中央大學環境工程學刊,第一期,(1995)
52.Weber, R., Sakurai, T. and Hagenmaier, H., “Formation and Destruction of PCDD/PCDF during Heat-treatment of Fly-ash Samples from Fluidized-bed Incinerators”, Chemosphere, Vol.38, pp.2633-2642(1999)
53.Gullett, B. K., Natschke, D. F. and Bruce, K. R., “Thermal Treatment of 1,2,3,4-tetrachlorodibenzo-p-dioxin by Reaction with Ca-based Sorbents at 23-300℃”, Environ. Sci. Technol., Vol.31, pp.1855-1862 (1997)
54.Raghunathan, K., Brian, K., “Effect of Sulfur on Reducing PCDD/PCDF Formation”, The Proceeding of 1994 International Incineration Conference, pp.255-230(1994)
55.Lee, C. W., Kilgroe, J. D., and Raghunathan, K., “Effect of Soot and Copper Combustor Deposits on Dioxin Emissions”, Environmental Engineering Science, Vol.15, pp.71-84(1998)
56.Olie, K., Addink, R., Schoonenboom, M., “Metals as Catalysts during the Formation and Decomposition of Chlorinated Dioxins and Furans in Incineration Processes”, J. Air & Waste Manage., Assoc.48, pp.101-105(1998)
57.黃彩斐,「焚化過程中溫度與氣流組成對戴奧辛生成之影響初探」,國立中央大學環境工程研究所碩士論文,中壢,(1998)
58.李易晏,「含氯芳香烴化合物於焚化爐飛灰中之形成機制探討」屏東科技大學環境工程與科學系碩士論文,屏東(2001)
59.Addink, R., and Oil, K., “Mechanisms of Formation and Destruction of Polychlorinated Dibenzo-p-dioxin and Dibenzofurans in Heterogeneous System”, Environ. Sci. Technol., Vol.29, pp.1425-1435(1995)
60.賴宏德,「再合成及前驅物催化反應與戴奧辛生成之初步探討」,國立中央大學環境工程研究所碩士論文,中壢,(1999)
61.Sun, R. D., Irie, H., Nishikawa, T., Nakajima, A., Watanabe, T., Hashimoto, K., “Suppressing Effect of CaCO3 on the Dioxins Emission from Poly(vinyl chloride)(PVC) Incineration”, Polymer Degradation and Stability, Vol.79, pp.253-256(2003)
62.Hell, K., Stieglitz, L., Dinjus, E., Segers, P., Buekens, A., “Inhibition of PCDD/F ‘De Novo’ Formation by Addition of Basic Compounds to Dust from Metallurgical Plants:Experiment Results and Discussion of Inhibition Mechanisms”, Organohalogen Compounds, Vol.46, pp.252-255(2000)
63.Altwicker, E. and Millgan, M.S., “Formation of Dioxins: Competing Rates between Chemical Similar Precursors and De Novo Reaction”, Chemosphere, Vol.27, pp.301-307(1993)
64.Schoonenboom, M. H. and Olie, K., “Formation of PCDDs and PCDFs from Anthracene and Chloroanthracene in a Model Fly Ash System”, Environ. Sci. Technol., Vol.29, pp.2005-2009(1995)
65.林敬二、楊惠美、楊寶旺、廖德章、薛敬和,「化學大辭典」,高立圖書公司,(1993)
66.Tsai, W. T. and Chang, C. Y., “Surface Chemistry of Activated Carbons and Its Relevance for Effect of Relative Humidity on Adsorption of Chlorinated Organic Vapors”, Chemosphere, Vol.29, No.12, pp.2507-2515(1994)
67.李崇漢,「一般廢棄物焚化過程中戴奧辛排放特性之初步研究」,國立中央大學環境工程研究所碩士論文,中壢,(1997)
68.江康鈺、紀哲全、許宏銘、陳宜晶、李宏台、吳佩芬、葛家賢,「模擬都市垃圾衍生燃料焚化飛灰中重金屬物種相態分佈特性研究」,第十八屆廢棄物處理研討會,台中,(2003)
69.中興電工機械股份有限公司,新竹市垃圾資源回收廠:92年操作營運評鑑參考資料,(2003)
70.中興電工機械股份有限公司,台北縣八里垃圾焚化廠:九十二年度操作營運輔導查核資料手冊,(2003)
71.台北市環保局,九十二年度已運轉垃圾焚化廠輔導查核及績效評鑑書面資料(內湖垃圾焚化廠),(2003)
72.北投垃圾焚化廠,九十二年度垃圾焚化廠營運績效評鑑,(2003)
73.中興工程顧問有限公司,九十一、九十二、九十三年度建立台灣地區戴奧辛排放清冊及排放資料庫三年工作計畫,九十二年度期中報告,(2003)
74.Vogg, H., Metzger, M. and Stieglitz, L., “Recent Findings on the Formation and Decomposition of PCDD/PCDF in the Municipal Solid Waste Incineration”, Waste Management and Research, Vol. 5, pp.285-294(1987)
75.Addink, R. and Olie, K., “Role of the Oxygen in Formation of Polychlorinated Dibenzo-p-dioxin/Dibenzofurance from Carbon on Fly Ash”, Environ. Sci. Technol., Vol.29, pp.1586-1590(1995)