臺灣博碩士論文加值系統

本研究以商業用之活性氧化鋁（γ- Al2O3）和兩種新穎奈米級磁性氧化鋁（分別以沉澱法合成之磁性氧化鋁（MAP）、及溶膠凝膠法合成之磁性氧化鋁（MASG））等三種鋁型吸附劑吸附處理含氟水溶液，研究內容包含了吸附劑之物理化學特性鑑定分析、等溫吸附行為、吸附動力學分析、小型管柱動力實驗等。此外，亦針對操作因子如pH值、離子強度、氟離子初始濃度、管柱實驗操作參數等對處理效果之影響進行探討。
以共沉澱法製備奈米級Fe3O4超順磁性顆粒、並以緩慢加酸法於Fe3O4表面包覆SiO2，得到(SiO2/Fe3O4)磁性載體；再分別經由沉澱法（Precipitation method）及溶膠凝膠法（Sol-Gel method）於磁性載體表面合成氧化鋁，可製備得奈米級磁性氧化鋁吸附劑（即MAP和MASG）。Fe3O4、磁性載體、MAP、及MASG之顆粒粒徑（dp,NMD）分別為：7 nm、31.3 nm、37.5 nm及33 nm；飽和磁化強度分別為59.24、8.16、8.69和8.73 emu/g，皆具有超順磁性；XRD之鑑定結果顯示MAP及MASG表面之鋁氧化物為三羥氧化鋁（Bayerite）結構。
等溫吸附試驗之研究結果顯示以Langmuir與Freundlich等溫吸附方程式皆能有效的模擬氟離子吸附在氧化鋁、MAP和MASG等三種吸附劑表面之行為。MAP和MASG對氟離子之吸附行為亦適用線性（linear）等溫吸附方程式模擬。單就單層飽和吸附量（qL）而言，MASG為本研究中所使用三種吸附劑中對氟離子吸附效果最佳者。假性二階動力程序（pseudo-second-order equation）及Elovich rate equation可有效的模擬MASG於CSTR中對氟離子之吸附動力。
小型吸附管柱貫穿實驗中，所求出之最適操作條件為：溶液之初始pH值為4、再生液（NaOH）強度為0.01N、及再生後之氧化鋁中和至pH=4以進行下一循環之吸附，此系統之吸附能力可維持長時間（14個完整循環以上）之穩定。當溶液之初始pH值越低，其吸附氟之能力越強，應是表面具有帶正電之官能基（S-OH2+）有效的增加，促進提升對氟離子的吸附容量。實驗中無法得到一氟離子完全貫穿之曲線，顯示氧化鋁具有緩衝之特性，並使溶出之Al3+可以持續生成氫氧化鋁膠羽，而達到氟吸附去除之目的，故此系統之吸附行為應可分為氧化鋁之吸附及氫氧化鋁膠羽之吸附，後者作用最顯著的地方應於高原遲緩期（plateau）處。
本研究期以表面複合模式（Surface complex formation model）為基礎，預測氧化鋁對含氟溶液之吸附貫穿曲線動力，但因模式仍於開發測試階段，目前尚無法進行貫穿曲線動態模擬。現階段以表面複合理論中兩性離子交換器之多重單價離子系統描述氧化鋁對氟離子之等溫吸附行為，並求出與等溫吸附相關之表面複合理論參數（ 與m(H,F)），以作為將來預測氧化鋁對含氟溶液之吸附貫穿曲線動力之基礎。
半導體製造廠LSR系統中，WA樹脂塔進流廢水成分主要為氟離子，濃度約為54 mg/L，其餘陰離子包括Cl-、BrO3-、NO3-和SO42-等濃度分別為2.2、1.1、9.2和1.5mg/L，且pH值偏低（=3.6），初步認為此股廢水應適合以活性氧化鋁或磁性氧化鋁等鋁型吸附劑，進行溶液中氟之吸附去除處理，且其操作條件可以本研究小型管柱實驗所得之最適操作條件為基礎。

The adsorption process applied in the removal of fluoride from aqueous solutions was investigated in this study. Commercial activated alumina (γ-Al2O3) and two novel magnetic alumina adsorbents, which were synthesized by precipitation method (MAP) and sol-gel method (MASG), were used as the alumina-type adsorbents. The physicochemical characteristics of three adsorbents and factors affecting the adsorption equilibrium and kinetics were further examined in this study.
The Langmuir and Freundlich isotherms were successfully used to predict the adsorption behavior of fluoride onto γ-Al2O3, MAP, and MASG, in which the monolayer adsorption capacity (qL) of MASG is the highest among three adsorbents. Furthermore, the linear isotherm also well described the adsorption behavior of fluoride onto both novel magnetic nano-adsorbents, MAP and MASG. Therefore, the novel magnetic nano-adsorbents, which were prepared by Fe3O4 coated with SiO2 and sequentially synthesized by means of precipitation and sol-gel methods in this study, can successfully be applied in the removal of fluoride from solutions. Regarding the adsorption kinetics of fluoride from solutions, among the tested kinetics models in this study (e.g. pseudo-first-order equation, pseudo-second-order equation and Elovich rate equation), both the pseudo-second-order equation and Elovich rate equation can well predict the adsorption kinetics of fluoride onto MASG in CFSTR.

The removal of fluoride by commercial Al2O3 was also carried out in the fixed-bed adsorber. The optimal operating conditions were the pH value of 4 for the fed fluoride solution, the regeneration agent (NaOH) of 0.01 N, and the neutralization pH of 4 by means of 3.16×10-4 N HNO3. Under the optimal conditions, the removal efficiency of fluoride from solutions was not reduced for at least fourteen runs. In addition, the fluoride adsorption capacity increased with decreasing pH of fluoride solution and can be divided into two parts: adsorbed by alumina and by aluminum hydroxide, in which the former might be the major mechanism in the whole adsorption process and the latter mainly influenced the adsorption in the plateau area.
The main composition and pH value of the aged scrubbing solution in the semiconductor manufacturing industries are fluoride of 40~ 60 mg/L, and 3.6, respectively. Therefore, on the basis of the data obtained from this study it is deduced that Al2O3, MAP and MASG possess high potential as the adsorbents for the application of adsorption process in the defluoridation from aged scrubbing solution.

頁 次
中文摘要 …………………………………………………………… I
英文摘要 …………………………………………………………… III
目錄 …………………………………………………………… V
表目錄 …………………………………………………………… IX
圖目錄 …………………………………………………………… X
符號說明 …………………………………………………………… XV

第一章 緒論…………………………………………………… 1
1-1 研究背景……………………………………………… 1
1-2 研究目的……………………………………………… 3

第二章 文獻回顧……………………………………………… 5
2-1 氟化物………………………………………………… 5
2-1-1 氟化物對人體之影響………………………………… 5
2-1-2 氟化物之處理方法…………………………………… 6
2-1-3 氟離子與鋁離子之錯合水化學……………………… 11
2-2 吸附理論……………………………………………… 13
2-2-1 基本理論……………………………………………… 13
2-2-2 等溫吸附方程式……………………………………… 13
2-2-3 表面複合理論………………………………………… 15
2-2-4 吸附動力學…………………………………………… 26
2-2-4-1 整體性動力分析(global kinetic expressions)………… 26
2-2-5 影響吸附之因素……………………………………… 29
2-3 鋁氧化物……………………………………………… 33
2-3-1 鋁氧化物特性………………………………………… 33
2-3-2 鋁氧化物之水化學…………………………………… 36
2-4 磁性技術……………………………………………… 40
2-4-1 磁性分離技術………………………………………… 40
2-4-2 磁性載體製備與應用………………………………… 41
2-4-3 磁性吸附劑製備……………………………………… 44
2-4-3-1 均勻沉澱法（Homogenous precipitation method）…… 45
2-4-3-2 溶膠凝膠法（Sol-gel method）……………………… 46
2-5 半導體製造廠排氣洗滌(LSR)系統…………………… 48

第三章 實驗設備與研究方法………………………………… 51
3-1 藥品…………………………………………………… 51
3-2 設備…………………………………………………… 52
3-3 實驗步驟……………………………………………… 55
3-3-1 商業用氧化鋁之前處理……………………………… 55
3-3-2 磁性氟選擇性氧化鋁之合成………………………… 55
3-3-2-1 包覆SiO2之Fe3O4磁性載體………………………… 59
3-3-2-2 均勻沉澱法…………………………………………… 59
3-3-2-3 溶膠凝膠法…………………………………………… 60
3-3-3 吸附劑之物理化學特性分析………………………… 60
3-3-4 等溫吸附實驗………………………………………… 65
3-3-5 動力管柱試驗………………………………………… 68
3-3-6 完全混合反應槽實驗………………………………… 74

第四章 結果與討論…………………………………………… 75
4-1 吸附劑之基本性質…………………………………… 75
4-1-1 商業用氧化鋁………………………………………… 75
4-1-2 磁性氧化鋁…………………………………………… 81
4-2 商業用氧化鋁之吸附………………………………… 105
4-2-1 吸附平衡……………………………………………… 105
4-2-1-1 氟離子與鋁離子吸附之空白試驗…………………… 105
4-2-1-2 平衡時間之探討……………………………………… 105
4-2-1-3 等溫吸附曲線………………………………………… 109
4-2-1-4 氧化鋁之鋁離子溶出探討…………………………… 110
4-2-2 動力管柱試驗………………………………………… 116
4-2-2-1 連續流式反應槽……………………………………… 116
4-2-2-2 最適操作參數………………………………………… 118
4-2-3 貫穿曲線動力模擬…………………………………… 136
4-3 磁性氧化鋁之吸附…………………………………… 140
4-3-1 吸附平衡……………………………………………… 140
4-3-1-1 平衡時間之探討……………………………………… 140
4-3-1-2 等溫吸附曲線………………………………………… 140
4-3-1-3 等溫吸附曲線綜合比較……………………………… 143
4-3-2 吸附動力探討………………………………………… 146
4-4 實廠廢水特性分析…………………………………… 155

第五章 結論與建議…………………………………………… 157
5-1 結論…………………………………………………… 157
5-2 建議…………………………………………………… 161

參考文獻 …………………………………………………………… 162

附錄
附錄A 微波消化方法與步驟………………………………… A-1
附錄B 磁性顆粒粒徑分佈直方圖、自然對數分佈圖………… B-1
附錄C XRD標準圖譜………………………………………… C-1
附錄D 表面複合理論之 與m(H,F) 計算過程…………
D-1
附錄E 追蹤劑試驗(Tracer test) E-1
附錄F 動力學分析數據(MASG) …………………………… F-1

Abe, I., S. Iwasaki, T. Tokimoto, N. Kawasaki, T. Nakamura and S. Tanada, “Adsorption of Fluoride Ions onto Carbonaceous Materials,” J. Colloid Interface Sci., 275, 35, (2004).
Bahena, J. L. R., A. R. Cabrear, A. L. Valdivieso and R. H. Urbina, “Fluoride adsorption onto alpha-Al2O3 and its Effect on the Zeta Potential at the Alumina-aqueous Electrolyte Interface,” Sep. Sci. Technol., 37(8), 1973, (2002).
Benfield, L. D., J. F. Judkins and L. W. Barron, Process Chemistry for Water and Wastewater Treatment. Prentice-Hall, USA, (1982).
Benson, D. L., D. L. Porth and O. R. Seweeny, Proc. IOWA Academy of Science, 47, 221, (1940).
Bhargava, D. S. and S. D. J. Killedar, “Batch Studies of Water Defluoridation Using Fishbone Charcoal,” Res. J. Water Pollut. Control Fed., 63, 848, (1991).
Butler, J. N., Ionic Equilibrium: A Mathematical Approach. Addison-Wesley Publishing Co., Inc., USA, (1964).
Carroll, W. M., M. Murphy and C. B. Breslin, “The Corrosion Dissolution Behavior of Aluminum in Solutions Containing Both Chloride and Fluoride Ions,” Corros. Sci., 34(9), 1495, (1993).
Chang, C. F., C. Y. Chang, K. H. Chen, W. T. Tsai, J. L. Shie and Y. H. Chen, “Adsorption of Naphthalene on Zeolite from Aqueous Solution,” J. Colloid Interface Sci., (in press), (2004).
Cheung, C. W., J. F. Porter and G. Mckay, “Sorption Kinetic analysis for the removal of Cadmium Ions from Effluents Using Bone Char,” Wat. Res., 35(3), 605, (2001).
Chikuma, M. and M. Nishimura, “Selective Sorption of Fluoride Ion by Anion Exchange Resin Modified with Alizarin Fluorine Blue-praseodymium(III) Complex,” Reactive Polymers, 13(1-2), 131, (1990).
Choi, W. W. and K. Y. Chen, “The Removal of Fluoride from Waters by Adsorption,” J. Am. Water Works Assoc., 71, 562, (1979).
Ciccone, V. J., Inc. Associates and V. A. Woodbridge, “Technologies and Costs for the Removal of Fluoride from Potable Water Supplies,” Prepares for Environmental Protection Agency, Washington, D. C., (1984).
Dixon, J. B. and S. B. Weed, Minerals in Soil Environments, 2nd ed., Soil Science Society of America Book Series, Madison, Wisconsin, USA, 1989.
Ertl, G. H. KÖzinger, and J. Weitkamp, Preparation of Solid Catalysts, Wiley, Germany, (1999).
Farrah, H., J. Slavek, and W. F. Pickering, “Fluoride Interactions with Hydrous Aluminum Oxides and Alumina,” Aust. J Soil Res., 25, 5, (1987).
Reimers, G. W. and S. E. Khalafalla, “Production of Magnetic Fluids by Peptization Techniques,” U. S. Patent No. 3843540, (1974).
Garrison Sposito, Ph.D., The Environmental Chemistry of Aluminum, CRC Press, Inc., USA, (1996).
Gilles, D. G. and R. C. Loehr, “Waste Generation and Minimization in Semiconductor Industry,” J. Environ. Eng. ASCE, 120(1), 72, (1994).
Gribanov, N. M., E. E. BiBik, O. V. Buzunov and V. N. Naumov, “Physico-chemical Regularities of Obtaining Highly Dispersed Magnetite by the Method of Chemical Condensation,” J. Magn. Magn. Mater., 85, 7, (1990).
Hao, O. J. and C. P. Huang, “Adsorption Characteristics of Fluoride onto Hydrous Alumina,” J. Environ. Eng., 112, 1054, (1986).
Haron, M. J., W. M. Z. Wan Yunus, S. A. Wasay, A. Uchiumi and S. Tokunaga, “Sorption of Fluoride Ions from Aqueous Solutions by a Yttrium-loaded Poly(Hydroxamic Acid) Resin,” Int. J. environ. Stud., 48(3/4), 245, (1995).
Hingston, F. J., A. M. Posner and J. P. Quirk, “Anion Adsorption by Goethite and Gibbsite: I. The Role of the Proton in Determining Adsorption Envelopes,” J. Soil Sci., 23, 177, (1972).
Ho, Y. S. and G. Mckay, “Sorption of dye from aqueous solution by peat,” Chemical Engineering Journal, 70, 115, (1998).
Hohl, H. and W. Stumn, “Interaction of Pb2+ with Hydrousγ-Al2O3,”J. Colloid Interface Sci., 55(2), (1976).
Horst, J. and W. H. Höll, “Application of the Surface Complex Formation Model to Ion Exchange Equilibria,” J. Colloid Interface Sci., 195, 250, (1997).
Huang, C. D. and W. Stumn, “Specific Adsorption of Cations on Hydrous γ-Al2O3,” J. Colloid Interface Sci., 43, 409, (1973).
Huang, C. J. and J. C. Liu, “Precipitate Flotation of Fluoride-Containing Wastewater from a Semiconductor Manufacturer,” Water Res., 33(16), 3403, (1999).
Iler, R. K., The Chemistry of Silica-solubility, Polymerization, Colloid and Surface Prosperities, and, Biochemistry, Wiley, New York, (1979).
Kanesato, M., T. Yokoyama and T. M. Suzki, “Selective Adsorption of Fluoride Ions by La(III)-loaded Chelating Resin Having phosophono- methylamino groups,” Chem. Letters, 2, 207, (1988).
Ku, Y. and H.M. Chiou, “The Adsorption of Fluoride Ion form Aqueous Solution by Activated Alumina,” Water Air and Soil Pollution, 133(1/4), 349, (2002).
Lai Y. D. and J. C. Liu, “Fluoride Removal from Water with Spent Catalyst,” Sep. Sci. Technol., 31(20), 2791, (1996).
Lee, H. C. and T. C. Chou, “Electrochemical Techniques in Industrial Waste-water Management - A Review,” J. Chin. Inst. Chem. Eng., 25(4), 239, (1994).
Levenspiel, O., Chemical Reaction Engineering, 2nd Ed., Wiley, New York, (1972).
Luther, E. P., F. F. Lange and D. S. Pearson, “˝Alumina˝ Surface Modification of Silicon Nitride for Colloidal Processing,” J. Am. Cerm. Soc., 78(8), 2009, (1995).
Mukherjee, D., A. Kulkarni and W. N. Gill, “Membrane Based System for Ultra-pure Hydrofluoric Acid Etching Solutions”, J. Membr. Sci., 109, 205, (1996).
Popat, K. M., P. S. Anad and B. D. Dasare, “Selective Removal of Fluoride on from Water by the Aluminum Form of the Aminomethylphosphonic Acid Type Ion Exchanger” Reactive Polymer, 23(1), 23, (1994).
Reimers, G. W. and S. E. Khalafalla, “Production of Dilution-stable Aqueous Magnetic Fluids,” IEEE Transactions on Magnetics, 16(2), 178, (1980).
Rubel, F. Jr. and R. D. Woosley, “The Removal of Excess Fluoride from Drinking Water by Activated Alumina,” Journal AWWA, 20(6), 667, (1979).
Staebller, C. J. Jr., “Treatment and Recovery of Fluoride Industrial Wastes,” U.S. EPA-660/2-73-024, (1974).
Stumm, W., Chemistry of the Solid-Water Interface, Wiley, New York, (1992).
Sujana, M.G., R. S. Thakur, and S. B. Rao, “Removel of Fluoride from Aqueous Solution Alum Sludge,” J. Colloid Interface Sci., 206, 94, (1998).
Teng H. and C. Hsieh, “Activation Energy for Oxygen Chemisorption on Carbon at Low Temperatures,” Ind. Eng. Chem. Res., 38, 292, (1999).
Wang, C. M., “High Green Compact Strength of coated Si3N4 powder,” J. Mater. Sci. Lett., 14, 1256, (1995).
Wright, J. D. and Sommerdijk, M. A. J. M., Sol-Gel Materials: Chemistry and Applications, Taylor & Francis Books Ltd, U.K., 2001.
Wu, Y. C. “Activated Alumina Removes Fluoride Ions from Water,” Water & Sewage Works, 125(6), 76, (1978).
Wu, Y. C., M. ASCE and A. Nitya, “Water Defluoridation with Activated Alumina,”J. Environ. Eng. Div., ASCE, 105, 357, (1979).
下飯坂達, 「粉体液相中凝集分散」， 粉体粉末冶金, 12(6), 263, (1966).
中國技術服務社工業污染防治技術服務團，「半導體製造業污染防治輔導專案綜合報告」，1993。
行政院環境保護署，「台灣地區氟的污染分佈及其對人體牙齒及健康影響之研究」， 1995。
吳忠信，「二價陰離子在氧化鋁表面之吸附研究」，國立台灣大學環工所博碩士論文，1999。
周珊珊、曹連桂、黃森元、李茂松、彭淑惠，「含氟廢水之流體化床結晶處理技術」，第十九屆廢水處理技術研討會論文集，1994。
邱作基，「積體電路積體電路工業清潔生產技術指標探討」，清潔生產資訊，第14期，1997。
邱惠美，「以吸附式程序處理含氟水溶液反應行為之研究」，國立台灣科技大學化學工程技術研究所碩士論文,，1997。
高大華，「印刷電路板製造業含氟廢水與含銅污泥之處理」，臺灣工業技術學院化學工程系碩士論文，1996。
張俊彥、鄭晃忠，「積體電路製程及設備技術手冊」，中華民國經濟部技術處， 1997。
張冠東、官月平、單國彬、安振濤、劉會洲，「納米Fe3O4顆粒的表面包覆及其在磁性氧化鋁載體製備中的應用」， 過程工程學報，2(4)，319，2002。
張冠東、官月平、單國彬、安振濤、劉會洲，「製備工藝對磁性球形氧化鋁催化劑載體性能的影響 」，中國稀土學報，20（in pressed），285，2002。
莊子傑，「以溶解空氣氟除法處理半導體製造業含氟廢水之研究」，國立台灣科技大學化學工程研究所碩士論文，2000。
莊永豐，「Wastewater Treatment Recycle and Reuse in UMC」，專題演講，國立台灣科技大學化工系，2001。
許明華、馬念和、阮國棟，「氟化物水污染處理技術及管理策略」，工業污染防治，第60 期， 1997。
陳其華、李弘，「以LSR處理回收半導體業全氟化物衍生含氟廢液實例介紹」，2001產業環保工程實務研討會論文集，2001。
陳建忠，「奈米粉體的合成與應用」，奈米科技於環境領域應用及相關議題論壇(VI)，行政院環保署，2003。
陳澄佑 ，「磁性流體的研製」，國立清華大學碩士論文，1993。
黃忠良，「磁性流體理論應用」， 復漢出版社，1989。
蔡長益，「以鐵被覆廢觸媒去除水中氟離子之研究」，臺灣工業技術學院化學工程系碩士論文，1997。
蔡煥修，「磁性流體製程與性質之基礎研究」，國立成功大學礦冶及材料科學研究所碩士論文，1992。
顏雅侖，「錳鋅鐵氧化物磁性流體之製備及分散研究」，國立成功大學資源工程研究所碩士論文，2002。