本研究利用錳砂為吸附劑，除了分析其特性外，更進一步探討錳離子在其表面之吸附、脫附作用及自媒催化情形，並利用不同水質條件測試其對錳離子吸附效果之影響。
人造錳砂特性分析方面，在X光繞射分析結果顯示人造錳砂上之錳氧化物並非單一物種，其物種包括三氧化二錳(Mn2O3)、氧化錳(MnO2)及氫氧化錳(Mn(OH)4)，而在顯微結構分析中，可觀察到人造錳砂表面為一粗糙不平及佈滿大小顆粒狀之錳氧化物及許多孔隙之濾料。另外，由SEM/EDS分析結果中，可知人造錳砂上之錳氧化物與石英砂間之界面型態為機械界面層，並且也觀察到錳離子有擴散至石英砂內部，導致披覆在人造錳砂上之錳氧化物為一薄層，但也間接強化錳氧化物覆膜在石英砂表面之強度。批次實驗方面，在無錳砂之溶氧實驗中，顯示系統pH＜9時，二價錳之氧化速率非常緩慢；吸附動力試驗結果，錳離子在初期吸附非常快速，吸附反應2小時已有85%以上之吸附率，並且在4小時後吸附反應已達平衡，總吸附量約在96.7%；吸附邊緣曲線試驗則顯示錳吸附量隨pH值上升而增加，而且在pH=2.75時，錳吸附量仍有50%，係因人造錳砂之pHzpc為1.26所致；恆溫吸附曲線之研究結果中，錳離子在人造錳砂表面呈現多層吸附型態，推測為錳離子之自媒催化反應(autocatalysis)，且經迴歸模擬後，遵循非線性之多層模式。另外，在溫度影響下，其多層吸附量隨溫度上升而增加；由競爭吸附結果，可知亞鐵離子確實與二價錳離子產生競爭，且亞鐵離子濃度愈高，競爭效果愈顯著；最後在脫附實驗中，可得到初期錳離子脫附非常快速，但在30分鐘後脫附速率已趨於平緩，總脫附率約在88%，而在不同吸附接觸時間之影響方面，則顯示吸附時間愈長，錳總脫附量愈少。

"Manganese-coated sand" is a type of coated silica medium with manganese oxides, which formed from the sorption of manganese oxides during long-term filtration via the process of rapid sand filtration, followed by aeration in water treatment plant. Locally available manganese-coated sand, both of packing and byproduct of filtration process for water treatment plants in Taiwan, was found to be a low-cost and promising adsorbent for removal of Mn2+ from raw water. This study was conducted to build the basic data for coating hydrated manganese oxide on the sand surface to utilize adsorbent properties of the coating and filtration properties of sand. In this study, gas adsorption porosimetry and scanning electron microscope (SEM) analyses were used to investigate the surface properties of the coated layer. An energy dispersive X-ray (EDAX) technique of analysis was used for characterizing metal adsorption sites on a manganese-coated sand surface. Results indicated manganese-coated sand had more micropores and higher specific surface area, owing to attachment of manganese sand. Manganese ions penetration into the micropores and mesopores of manganese oxide on a sandy surface; regeneration of manganese-coated sand could be achieved by soaking with pH＜2.0 acid solution. Results of EDAX analysis showed that mechanism interfacial layer constructing the interface of manganese-coated sand. Acid- and alkali-resistance tests interpret a wide application range of pH for manganese-coated sand, and general temperature conditions do not affect the performance of this sand. Manganese-coated sand is potentially suitable for application to a packed bed for treatment of heavy metal from water. The results of this study can also benefit plant operational capacity data for engineering design.

摘要 Ⅰ
目錄 Ⅲ
表目錄 Ⅶ
圖目錄 Ⅷ
第一章 緒論 1
1-1 研究緣起 1
1-2 研究目的與內容 1
1-2-1 研究目的 2
1-2-2 研究內容 2
第二章 文獻回顧 3
2-1 錳之物化特性 3
2-2 錳氧化物之化學性質 3
2-3 錳氧化物之種類及結構 4
2-4 水中錳之來源 4
2-5 錳之水化特性 6
2-6 錳之氧化動力學 11
2-7 錳對人體健康影響與飲用水及工業用水之規定 13
2-8 吸附理論 14
2-9 吸附速率 16
2-10 影響吸附之因素 17
2-11 等溫吸附模式 18
2-12 金屬氧化物表面特性 21
2-13 水化金屬氧化物對重金屬吸附 24
2-14 離子強度對吸附反應影響 25
2-15 覆膜基本理論 26
2-15-1 物質表面特性 26
2-15-2 基質與薄模形成界面層之分類 26
2-15-3 形成界面層之鍵結形式 28
第三章 實驗材料、設備與方法 30
3-1 實驗架構流程 30
3-2 實驗材料 31
3-3 實驗設備 31
3-4 吸附、脫附批次試驗 33
3-4-1 吸附試驗 33
3-4-1-1 恆溫動力吸附試驗 33
3-4-1-2 恆溫吸附邊緣曲線試驗 33
3-4-1-3 恆溫吸附曲線試驗 33
3-4-1-4 水質參數探討 34
3-4-2 脫附試驗 34
3-4-2-1 吸附接觸時間影響 34
3-4-2-2 吸附接觸時間影響 34
3-5 錳砂來源 35
3-6 人造錳砂表面之分析 35
3-6-1 界達電位分析 35
3-6-2 X光繞射分析(XRD) 35
3-6-3 表面型態分析 36
3-6-4 界面分析及界面元素分析 37
3-6-5 比表面積及孔隙大小測定 37
3-6-6 錳砂之抗酸鹼試驗 38
3-6-7 錳離子之測定 38
第四章 結果與討論 40
4-1濾砂及其表面氧化錳形態之鑑定 40
4-1-1 石英砂之型態 40
4-1-2錳砂型態 40
4-2 濾砂表面及氧化錳顯微結構之觀察 43
4-2-1 石英砂表面之觀察 43
4-2-2錳砂表面之觀察 43
4-3比表面積及孔隙直徑尺寸 47
4-4覆膜氧化錳量、厚度及抗酸鹼性測定 48
4-4-1錳砂表面元素分析與氧化錳量 48
4-4-2氧化錳覆膜厚度 49
4-4-3錳砂表面氧化錳之抗酸鹼性 51
4-5氧化錳覆膜於濾砂表面之機制 52
4-5-1人造錳砂界面分析 52
4-5-2實場錳砂界面分析 53
4-6錳砂之界達電位 55
4-7錳離子吸附試驗 56
4-7-1背景實驗 56
4-7-2恆溫動力吸附試驗 58
4-7-3 吸附邊緣曲線 61
4-7-4 恆溫吸附曲線 63
4-7-5 等溫吸附模式模擬 65
4-7-6錳離子吸附機制推估 67
4-8水質參數對於錳離子吸附之影響 68
4-8-1 背景離子強度之影響 68
4-8-2 pH值影響 69
4-8-3 溫度影響 70
4-8-4 競爭吸附 72
4-9錳氧化物於界面反應中之消長 74
4-9-1 錳總量於批次反應中之變化 74
4-9-2 錳離子濃度於批次反應中之變化 77
4-9-3 高價錳氧化物濃度於披次反應中之變化 78
4-10 脫附試驗 80
4-10-1 恆溫動力脫附試驗 80
4-10-2 不同吸附接觸時間對錳離子脫附之影響 80
第五章 結論與建議 82
5-1 結論濾砂性質與表面分析 82
5-2 建議 83
參考文獻 84

Appelo, C. A. J., and Postma, D., “A Consistent Model for Surface Complexation on Birnessite (-MnO2) and its Application to a Column Experiment,” Geochim. et Cosmochim. Acta., Vol 63, pp. 3039-4048 (1999).
Barrow, N. J., Bowden, J. W., Posner, A. M., and Quirk, J. P., “Describing the Effects of Electrolyte on Adsorption of Phosphate by A Variable Charge Surface,” Aust. J. Soil Res., Vol. 18, pp. 395-404 (1980).
Driehaus, W., Seith, R., and Jekel, M., “Oxidation of Arsenate(III) with Manganese Oxides in Water Treatment,” Wat. Res., Vol 29, pp. 297-305 (1995).
Engelbrecht, R. S., “Significance and Removal of Iron in Water Supplies, Fourth Annul Environmental Engineering and Water Resources,” Vanderblit University, Nashville, TN (1965).
Ellis, D., Bouchard, C., and Lantagne, G., “Removal of Iron and Manganese from Goundwater by Oxidation and Microfiltration,” Desalination, Vol 130, pp. 255-264 (2000).
Floroiu, R. M., Davis, A. P., and Torrents, A., “Cadmium Adsorption on Aluminum Oxide in the Presence of Polyacrylic Acid,” Environ. Sci. Technol., Vol 35, pp. 348-353 (2001).
Healy, T. W., A. P. Herring, and D. W. Fuerstenau, “The Effect of Crystal Structure on the Surface Properties of a Series of Manganese Dioxides,” Colloid Interface Sci., Vol 21, pp. 435-444 (1966).
Hohl, M., and Stumm, W.,“Interaction of Pb2+ with Hydrous γ-Al2O3,” J. Colloid Interface Sci., Vol 55, pp. 281-288 (1976).
Huang, C. P., “The Surfaces Acidity of Hydrous Soilds,” in Anderson, M. A., and Rubin, A. J., Ed., “Adsorption of Inorganic at Soild / Liquid Interfaces,” Ann Arbor Sci. (1981).
Hayes, K. F., Papelis, C., and Leckie, J. O., “Modeling Ionic Strength Effect on Anion Adsorption at Hydrous/Solution Interfaces,” J. Colloid Interface Sci., Vol.125, pp. 717-726 (1988).
Hayes, K. F., and Leckie, J. O., “Modeling Ionic Strength Effect on Anion Adsorption at Hydrous Solids/Solution Interfaces,” J. Colloid Interface Sci., Vol. 115, pp. 564-572 (1987).
James, W. M., John, G. D., Rudolf, G., Harald, M., and Werner, S., “Oxidation of Mn(II): Initial Mineralogy, Oxidation State and Ageing,” Geochim. et Cosmochim. Acta., Vol 49, pp. 463-470 (1985).
Klewicki, J. K., and Morgan, J. J., “Dissolution of β-MnOOH Particles by Ligands:Pyrophosphate, Ethylenediaminetetraacetate, and Citrate,” Geochim. et Cosmochim. Acta., Vol 63, pp. 3017-3024 (1999).
Lovley, D. R., and Lonergan, D. J.,“Hydrogenand Formate Oxidation Coupled to Dissimilatory Reduction of Iron or Manganese by Alteromonas putrefaciens,”Environ. Microbiol., Vol 56, 1856 (1990).
Morgan, J. J., and Stumn, W., “The Role of Multivalent Metal Oxides in Limnological Transformations, as Exemessed by Iron and Manganese,”Conf. on Water Pollution Research, New York (1964).
Morgan, J. J., “Chemical Equilibria and Kinetic Properties of Manganese in Natural Waters,” Principles and Applications in Water Chemisty, pp. 561-624 (1967a).
Morgan, J. J., “Applications and Limitations of Chemical Thermodynamics in Water System in Equilibrium Concepts in Natural Water System,” American Chemical Society, Washington (1967b).
Morgan, J. J. and Kessick, M. A., “Mechanism of Autoxidation of Manganese in Aqueous Solution,” Environ. Sci. Technol., Vol 9, pp. 157-159 (1975).
Morgan, J. J., “Applications and Limitations of Chemical Thermodynam-ics in Water System in Equilibrium Concepts in Natural Water System,” American Chemical Society (1976).
Morrill, L. G., Mahilum, B. C., and Mohiuddin, S. H., “Sorption Degradation and Persistence,” Organic Compounds in Soils, Ann Arbor Sci. Publishers (1982).
Mesuere, K., and Fish, W., “Chromate and Oxalate Adsorption on Goethite 2. Surface Complexation Modeling of Competitive Adsorption,” Environ. Sci. Technol., Vol. 26, pp. 2365-2370 (1992).
Scott, M. J. and Morgan, J. J., “Reactions at Oxides Surface. 1. Oxidation of As(III) by Synthetic Birnessite,” Environ. Sci. Technol., Vol 29, pp. 1898-1905 (1995).
Scott, M. J., and Morgan, J. J., “Reactions at Oxides Surface. 2. Oxidation of Se(IV) by Synthetic Birnessite,” Environ. Sci. Technol., Vol 30, pp. 1990-1996 (1996).
O''Conner, J. T., “Iron and Manganese in Water Quality and Treatment”, AWWA, Inc. Denver, CO (1971).
Posselt, H. S., Anderson, F. J., and Weber, W. J. Jr., “Cation Sorption on Colloidal Hydrous Manganese Dioxide”, Enviorn. Sci. Technol., Vol. 2, pp. 1087-1093 (1968).
Pulker, H. K., “Coatings on Glass,” Elsveier, New York (1984).
Peter, J. L., Kenneth, S. J., Kenneth, H. C. and Virginia, A. E., “Oxidation Kinetics of Manganese(Ⅱ) in Seawater at Nanomolar Concentrtions,” Geochim. et Cosmochim. Acta., Vol 61, pp. 4945-4954 (1997).
Stumm, W., Hohl, H., and Dalang, F.,“Interaction of Metal Ions with Hydrous Oxide Surfaces,” Groatica Chemica Acta., Vol 48, pp. 491-504 (1976).
Swallow, K. C., Hume, D. N., and Morel, F. M. M., “Sorption of Copper and Lead by Hydrous Ferric Oxide,” Environ. Sci. Technol., Vol. 14, pp. 1326-1331 (1980).
Stumm, W., and Morgan, J. J.,“Aquatic Chemistry,” John Wiley & Sons, Inc, New York (1981).
Sundstrom, D. W., and Klei, H. E., Wastewater Treatment, Prentice-Hall, Inc. Englewood Cliffs, NJ (1979).
White, W. C., Handbook of Chlorination, Van Nostrand Reinhold Company, New York (1972).
Wang, J., C. P. Huang, H.E. Allen, L. R. Takiyama, I. Poesponegoro, and D. Pirestani, “Acid Characteristics of Dissolved Organic Matter in Wastewater,” Water Environ. Res., Vol 70, 1042-1048 (1998).
許樹恩、吳泰伯，「X光繞射原理與材料結構分析」，行政院國家科學委員會精密儀器發展中心 (1993)。
洪世政，「去除原水中二價鐵、錳時其生成顆粒粒徑的影響與控制研究」，碩士論文，國立中興大學環境工程研究所，台中 (1993)。
賴進興，「氧化鐵覆膜濾砂吸附過濾水中銅離子之研究」，博士論文，國立台灣大學環境工程學研究所，台北 (1995)。
黃肇隆，「快濾去除地下水鐵錳影響因素之模廠研究」，碩士論文，國立中興大學環境工程研究所，台中 (1996)。
蕭蘊華，傅崇德譯，「環境工程化學」，第四版，滄海書局，第94-99頁 (1997)。
王明光，「土壤環境化學」，編譯館，初版，台北 (1997)。
黃如菊，「錳砂氧化吸附去除水中二價鐵錳之研究」，碩士論文，國立中興大學環境工程研究所，台中 (1998)。
王明光，「土壤環境礦物學」，藝軒圖書，第141-160頁，台北 (2000)。
翁誌煌、蔡鑫位，「生物污泥灰對染料（new coccine）的吸附特性研究」，第25屆廢水處理技術研討會論文集，794-801 (2000)。
陳維政，「自來水工程設計與處理技術」，文笙書局，初版，台北 (2000)。