臺灣博碩士論文加值系統

本研究結合活性碳特殊的表面性質與觸媒的高反應特性，製備出以活性碳為擔體之觸媒/吸附劑，並應用於焚化廢氣中酸性氣體的去除，期望能達到高去除率與低化學計量比的目標。所使用之觸媒/吸附劑為經由硝酸氧化處理後的活性碳，再擔持Cu、Ce與Cu-Ce混合等金屬而得到之三種觸媒/吸附劑。
實驗主要利用流體化床焚化爐以產生不同污染源，空氣污染防治設備則為，串聯乾式洗滌塔串聯袋式集塵器，研究探討觸媒/吸附劑對焚化廢氣中酸性氣體的去除效率，實驗操作條件包括(1)觸媒/吸附劑的種類(Cu/A.C.、Ce/A.C.與Cu-Ce/A.C.)；(2)化學劑量比(SR=1與SR=2)與(3)煙道氣組成的影響(SO2，SO2，SO2+Pb與SO2+Cr)。實驗結果並整合觸媒/吸附劑反應前後物化特性的分析，完整評估觸媒/吸附劑應用於煙道氣除硫的可行性。
研究結果指出，經由Cu、Ce與Cu-Ce擔持的三種活性碳觸媒/吸附劑，均會明顯增加SO2的去除效率，其中以Ce/A.C.觸媒/吸附劑具最佳的去除效率。面對較複雜的進氣組成時(SO2+HCl、SO2+Pb)，Cu-Ce/A.C.相較於Cu/A.C.與Ce/A.C.對SO2的去除效率，並不會出現降低的現象，具有穩定的SO2去除效率；煙道氣中含有重金屬Cr時，對於三種觸媒/吸附劑之SO2去除率，均會造成明顯的降低。另一方面，Cu/A.C.、Ce/A.C.與Cu-Ce/A.C.三種觸媒/吸附劑除了對SO2具一定的控制效果外，另外對於其他的污染物包括HCl、Pb與Cr，亦具有同時去除的能力。

The objective of this study is to investigate the possibility of using carbon supporting metals catalyst/sorbents for the removal of SO2 from flue gas, expected to achieve higher SO2 conversion and sorbents utilized efficiently. The catalyst/sorbents were prepared by impregnating the carbon powders with the aqueous solutions of the nitrate of the metals. They are Cu/A.C., Ce/A.C. and Cu-Ce/A.C. catalyst/sorbents, respectively.
A dry scrubber integrated with a frabic filter was employed in the pilot-scale fluidized bed incinerator to demonstrate the performance of catalyst/sorbents for removal of acid gases at selected catalyst/sorbents (Cu/A.C., Ce/A.C. and Cu-Ce/A.C.) and feedstocks (S, S+PVC, S+Pb and S+Cr). The physical and chemical characteristics of catalyst/sorbents prior to and after the experiment were analyzed. The feasibility of the catalyst/sorbents employed in the incineration system was also evaluated.
The results indicated that the removal efficiency of SO2 in flue gas can be enhanced significantly by actived carbon impregnating with Cu, Ce and Cu-Ce, especially for Ce/A.C.. The Cu-Ce/A.C. catalyst/sorbent had a stable removal efficiency of SO2 while it was interfaced with more complicate composition of flue gas (SO2+HCl and SO2+Pb). However, the removal efficiency of SO2 of three indicated catalyst/sorbents decreased obviously when the feedstock contained Cr. Moreover, HCl, Pb, and Cr can be controlled simultaneously by Cu/A.C., Ce/A.C. and Cu-Ce/A.C. catalyst/sorbents during desulfurization process.

摘 要 I
Abstract II
目 錄 III
圖目錄 VI
表目錄 VIII
第一章 前言 1
1-1 研究緣起 1
1-2 研究目的 1
1-3 研究內容與架構 2
第二章 文獻回顧 4
2-1 鈣基吸附劑之酸性氣體的去除 4
2-2 觸媒/吸附劑的探討 5
2-3 觸媒/吸附劑的改良 8
2-3-1 混和金屬之活性相 8
2-3-2 擔體的選用 9
2-3-2-1 擔體影響觸媒/吸附劑的反應特性 10
2-3-2-2 Al2O3的物化特性 10
2-4 活性碳吸附劑 11
2-4-1 活性碳物化特性 11
2-4-2 活性碳對酸性氣體的去除 13
2-4-2-1 活性碳之物理性質對SO2去除探討 14
2-4-2-2活性碳之化學性質對SO2去除探討 15
2-5 活性碳為擔體之觸媒/吸附劑 18
2-5-1 活性碳擔體觸媒/吸附劑對於酸性氣體的探討 18
2-5-2 活性碳觸媒/吸附劑特性分析 20
2-5-3 反應溫度的探討 21
2-5-4 水氣的探討 23
2-6 酸性氣體去除之反應機制 24
2-6-1 NOx去除之反應機制 24
2-6-1-1 SCR觸媒 24
2-6-1-2 活性碳擔體觸媒 24
2-6-2 SO2去除的反應機制 25
2-6-2-1 金屬擔體之觸媒 25
2-6-2-2 金屬擔體之觸媒/吸附劑 25
2-6-2-3 活性碳吸附劑 26
2-7 活性碳擔體之觸媒/吸附劑的再生 27
2-8 觸媒/吸附劑的毒化 28
2-7 文獻總結 30
第三章 實驗設備及方法 31
3-1 觸媒/吸附劑的選用與製備 31
3-1-1 活性金屬的選用 31
3-1-2 製備的溫度 32
3-1-3 擔體的製備 32
3-1-4 觸媒/吸附劑的製備 32
3-1-5 活性碳擔持金屬量的計算 33
3-2 實驗步驟 34
3-2-1 實驗操作條件 34
3-2-2 進料組成之模擬 37
3-2-3 活性碳吸附劑的特性分析 39
3-2-4 實驗設備 42
3-2-5 酸性氣體濃度分析 49
3-3 樣品分析儀器與實驗藥品及材料 50
第四章 結果與討論 52
4-1 觸媒/吸附劑之物化特性分析 52
4-1-1 BET比表面積之分析 52
4-1-2 XRPD表面結晶物種之分析 54
4-1-3 SEM影相表面形態之分析 56
4-2 觸媒/吸附劑對於酸性氣體之去除 57
4-2-1 活性碳擔持金屬前後對SO2去除率之比較 57
4-2-2 化學計量比(SR)對於觸媒/吸附劑去除SO2之影響 62
4-2-3 觸媒/吸附劑對於酸性氣體HCl之去除 63
4-3不同煙道氣組成對於觸媒/吸附劑去除SO2的影響 66
4-3-1 HCl對於觸媒/吸附劑去除SO2的影響 66
4-3-2 重金屬Pb對於觸媒/吸附劑去除SO2的影響 69
4-3-3 重金屬Cr對於觸媒/吸附劑去除SO2的影響 71
4-4 觸媒/吸附劑之評估 73
第五章 結論與建議 77
參考文獻 79
附錄一 觸媒/吸附劑反應前後X光繞射圖譜 86
附錄二 觸媒/吸附劑反應前後孔洞分佈曲線 89
附錄三 觸媒/吸附劑之SEM成像 90
附錄四 不同實驗試程各污染物的入出口濃度 91

Auer, R., Freund, J., Pietsch, J. and Tacke, T., “Carbons as Supports for Industrial Precious Metal Catalysts”, Applied Catalysis A: General, Vol. 173, pp. 259-271, (1998)
Akyurtlu, J. F. and Ates A., “Behavior of Ceria-Copper Oxide Sorbents under Sulfation Conditions”, Chemical Engineering Science, Vol. 54, pp. 2991-2997, (1999)
Atakul, H., Wakker, J. P., Gerritsen, A. W. and van den Berg, P. J., “Regeneration of MnO/r-Al2O3 used for high-temperature desulfurization of fuel gases”, Fuel, Vol. 75, No. 3, pp. 373-378, (1996)
Amblard, M., Burch, R. and Southward, B. W. L., “The Selective Conversion of Ammonia to Nitrogen on Metal Oxide Catalysts under Strongly Oxidising Conditions”, Applied Catalysis B: Environmental, Vol. 22, pp. L159-L166, (1999)
Amblard, M., Burch, R.and Southward, B.W. L., “A Study of The Mechanism of Selective Conversion of Ammonia to Nitrogen on Ni/γ-Al2O3 under Stronly Oxidising Conditions”, Catalysis Today, Vol. 59, pp. 365-371, (2000)
Barton, S. S., Evans, M. J. B., Halliop, E., and MacDonald, J. A. F., “Acidic and Basic Sites on the Surface of Porous Carbon”, Carbon, Vol. 35, No. 9, pp. 1961-1366, (1997)
Bazin, P., Saur O., Lavalley, J. C., Blanchard, G., Visciglio, V. and Touret, O., “Influence of Platinum on Ceria Sulfation”, Applied Catalysis B: Environment, Vol. 13, pp. 265-274, (1997)
Buelna, G. and Lin, Y.S. “Sol-gel-derived Mesoporousγ-Alumina Granules”, Microporous and Mesoporous Materials, Vol. 30, No. 2, pp. 359-369, (1999)
Cal, M.P., Strickler, B.W. and Lizzio, A. A., “High Temperature Hydrogen Sulfide Adsorptioin on Activated Carbon”, Carbon, Vol. 38, pp. 1757-1765, (2000)
Chen, Y., Jiang, Y., Li, W., Jin, R., Tang, S. and Hu, W. “Adsorption and Interaction of H2S/SO2 on TiO2”, Catalysis Today, Vol. 50, pp. 39-47, (1999)
Cudahy, J.J. and Helsel, R.W., “Removal of products of Incomplete Combustion with Carbon”, Waste Management, Vol. 20, pp. 339-345, (2000)
Daley, M.A., Mangun, C.L., DeBarr, J.A., Riha, S. and Lizzo, A.A., “Adsorption of SO2 onto Oxideized and Heat-Treated Activated Carbon Fibers(ACFS)”, Carbon, Vol. 35, pp. 411-417, (1996)
Davini, P., “The Effect of Certain Matallic Derivatives on the Adsorpton of Sulphur Dioxide on Active Carbon”, Carbon, Vol. 39, pp. 419-424, (2001)
Deng, S.G. and Lin, T.S., “Synthesis,Stability,and Sulfation Properties of Sol-Gel-Derived Regenerative Sorbents for Flue Gas Desulfurization”, Ind. Eng. Chem. Res., Vol. 35, pp. 1429-1437, (1996)
Dunn, J.P., Koppula P.R., Stenger, H.G. and Wachs, I.E., “Oxidation of Sulfur Dioxide to Sulfur Trioxide over Supported Vanadia Catalysts”, Applied Catalysis B: Environment, Vol. 19, pp. 103-117, (1998)
Dunn, J.P., Stenger, H.G. and Wachs, I.E., “Oxidation of Sulfur Dioxide over Supported Vanadia Catalysts:Molecular Structure-Reactivity Relationships and Reaction Kinetics”, Catalysis Today, Vol. 51, pp. 301-318, (1999)
Francisco, R.R., “The Role of Carbon Materials in Heterogeneous Catalysis”, Carbon, Vol. 36, No. 3, pp. 159-175, (1998)
Kartheuser, B., Hodnett, B. K., Riva, A., Centi, G., Matralis, H., Ruwet, M., Grange, P. and Passarini, N., “Temperature-Programmed Reduction and X-ray Photoelectron Spectroscopy of Copper Oxide on Alumina Following Exposure to Sulfur dioxide and Oxygen”, Ind. Eng. Chem. Res., Vol. 30, pp. 2105-2113, (1991)
Lisovskii, A., Semiat, R. and Aharoni, C., “Adsorption of Sulfur Dioxide by Active Carbon Treated by Nitric Acid: I.Effect of the Treatment on Adsorption of SO2 and Etractability of the Acid Formed”, Carbon, Vol. 35, No. 10-11, pp. 1639-1643, (1997)
Lisovskii, A., Shter, G.E., Semiat, R. and Aharoni, C., “Adsorption of Sulfur Dioxide Active Carbon Treated by Nitric Acid: II. Effect of Prehearing on the Adsorption Properties”, Carbon, Vol. 35, No. 10-11, pp. 1645-1648, (1997)
Lizzio, A.A. and DeBarr, J.A., “Effect of Surface Aera and Chemisorbed Oxygen on the SO2 adsorption Capacity of Activated Carbon”, Fuel, Vol. 75, No. 13, pp. 1515-1522, (1996)
Li, Y. and Sadakata, M., “Study of Gypsum Formation for Appropriate Dry Desulfurization Process of Flue Gas”, Fuel, Vol. 78, pp. 1089-1095, (1999)
Lu, H., Pradier, C.M. and Flodström, A.S., “Catalytic Reduction pf Nitric Oxide over Copper.Part II: Influence of Sulfur Dioxide”, Journal of Molecular Catalysis A: Chemical, Vol. 112, pp. 459-467, (1996)
Mehandjiev, D., Khristova, M. and Bekyarova, E., “Conversion of NO on Co-Impregnated Active Carbon Catalysis”, Carboon, Vol. 34, No. 6, pp. 757-762, (1996)
Munoz-Guillena, M.J., Macias-Perez, M.C., Linares-Solano, A. and Salinas-Martinez de lecea., “CaO Dispersed on Carbon as an SO2 Sorbent”, Fuel, Vol. 76, No. 6, pp. 527-532, (1996)
Martyniuk, H. and Wieckowska, J., “Adsorbents and Catalysts from Brown Caol for Fuel Gas Desulfurization”, Fuel, Vol. 74, No. 11, pp. 1716-1718, (1995)
Mochida, I., Kuroda, K., Kawano, S., Matsumura, Y. and Yoshikawa, M., “Kinetic Study of the Continuous Removal of SOx on Polyacrylonitrile-based Activated Carbon Fibres”, Fuel, Vol. 76, No. 6, pp. 533-536, (1997)
Mochida, I., Kuroda, K., Kawano, S., Matsumura, Y., Yoshikawa, M., Grulke, E. and Andrews, R., “Kinetic Study of the Continuous Removal of SOx Using Polyacrylonitrile-Based Activated Carbon Fibres”, Fuel, Vol. 76, No. 6, pp. 537-541, (1997)
Nakajima, F. and Hamada, I., “The State-of-Art Technology of Nox Control”, Cayalysis Today, Vol. 29, pp. 109-115, (1996)
Orsenogo, C., Beretta, A., Forzatti P., Svachula, J., Tronconi, E., Bregani, F. and Baldacci, A., “Theoretical and Experimental Study of The Interaction Between NOx Reduction and SO2 Oxidation over DeNOx-SCR Catalysts”, Catalysis Today, Vol. 27, pp. 15-21, (1996)
Orsenigo, C., Lietti, L., Tronconi, E., Forzatti, P. and Bregani, F., “Dynamic Investigation of The Role of The Surface Sulfates in NOx Reduction and SO2 Oxidation over V2O5-WO3/TiO2 Catalysts”, Ind. Eng. Chem. Res., Vol. 37, pp. 2350-2359, (1998)
Park, S.H., McClain, S., Tian, Z.R., Suib, S.L. and Karwacki, C., “Surface and Bulk Measurement of Metals Deposited on Activated Carbon”, Chem. Mater., Vol. 9, pp. 176-183, (1997)
Harriott, P. and Markussen, M., “Kinetic of Sorbent Regeneration in the Copper Oxide Process for Flue Gas Cleanup”, Ind. Eng. Chem. Res., Vol. 31, pp. 373-379, (1992)
Davini, P., “The Effect of Certain Metallic Derivatives on the Adsorption of Sulphur Dioxide on Active Carbon”, Carbon, Vol. 39, pp. 419-424, (2001)
Raymundo-Pinero, E., Cazorla-Amoros, D., Salinas-Martinez de Lecea, C. and Linares-Solano, A., “Factors Controling the SO2 Removal by Porous Carbons: Relevance of the SO2 Oxidation Step”, Carbon, Vol. 38, pp. 335-344, (2000)
Rubel, A.M. and Stencel, J.M., “The Effect of Low-Concentration SO2 on the Adsorption of NO from Gas over Activated Carbon”, Fuel, Vol. 76, No. 6, pp. 521-526, (1996)
Tamon, H. and Okazaki, M., “Influence of Acidic Surface oxides of Activated Carbon on Gas Adsorption Characteristics”, Carbon, Vol. 34, No. 6, pp. 741-746, (1996)
Twu, J., Chung, C.J., Chang, K.I., Yang,C.H. and Chen, K.H., “Raman Spectroscopic Studies on The Sulfation of Cerium Oxide”, Applied Catalysis B: Environmental, Vol. 12, pp. 309-324, (1997)
Vernikovskaya, N.V., Zagoruiko, A.N. and Noskov, A.S., “SO2 oxidation method. Mathematical modeling taking into accont dynamic properties of the catalyst”, Chemical Engineering Science, Vol. 54, pp. 4475-4482, (1999)
Wang, Z.M. and Lin, Y.S., “Sol-Gel-Derived Alumina-Supported Copper Oxide Sorbent for Flue Gas Desulfurization”, Ind. Eng. Chem. Res., Vol. 37, pp. 4675-4681, (1998)
Wang, S. and Lu, G.Q., “Effects of Acidic Treatments on the Pore and Surface Properties of Ni Catalyst Supported on Activated Carbon”, Carbon, Vol. 36, No. 3, pp. 283-292, (1998)
Wey, M.Y., Lu, C.Y., Tseng, H.H. and Fu, C.H., “The Utilization of Catalyst Sorbent in Scrubbing Acid Gases from Incineration Flue Gas”, Air and Management Association, Vol. 52, pp. 449-458, (2002)
Xu, G., Luo, G., Akamatsu, H. and Kato, K., “An Adaptive Sorbent for the Combined Desulfurization/Denitration Process Using a Powder-Particle Fluidized Bed”, Ind. Eng. Chem. Res., Vol. 39, pp. 2190-2198, (2000)
Yoo, K.S., Kim, S.D. and Park, S.B., “Sulfation of Al2O3 in Flue Gas Desulfurization by CuO/r-Al2O3 Sorbent”, Ind. Eng. Chem. Res., Vol. 33, pp. 1786-1791, (1994)
盧啟元，吸附劑/觸媒應用於乾式洗滌法處理焚化廢氣SO2之研究，碩士論文，國立中興大學環境工程系，台中(2001)。
楊文毅，鈀觸媒氧化焚化廢氣中有機物之研究，碩士論文，國立中興大學環境工程系，台中(2000)。
陳志成，焚化過程中重金屬之控制研究，博士論文，國立中興大學環境工程系，台中(1998)。
曾惠馨，介面活性劑添加物應用於乾式洗滌塔串連帶式集塵器處理酸性氣體之研究，國立中興大學環境工程系，台中(2000)。
黃新中，流體化鈀觸媒床氧化處理焚化廢氣中有機物之研究，國立中興大學環境工程系，台中(2001)。
李定粵，觸媒的原理與應用，正中書局印行，台北(1983)。
吳榮宗，工業觸媒概論，國興出版社，新竹(1998)。
張金海，非均勻反應觸媒-特性與實效應用，台灣復文興業股份有限公司，台南(1996)。
許樹恩，吳泰伯，X光繞射處理與材料結構分析，行政院國家科學委員會精密儀器發展中心，台北(1993)。
章裕民 焚化處理技術，文京圖書有限公司，台北(2000)。