摘要

飲用水原水中之天然有機物(natural organic matter, NOM)是一複雜的污染物，在自來水淨水廠加氯消毒程序中，天然有機前驅物質(如腐植質)會和氯作用形成具有致癌性的三鹵甲烷(trihalomethane,THM)，故在加氯消毒程序前預先去除水中天然有機物為必要之處理程序。
本研究旨在探討以氧化鋁及氧化鐵插層(intercalated)進入蒙脫石層間合成柱撐蒙脫石(pillared montmorillonite)，進而應用於淨水處理中作為水中天然有機物吸附劑之可行性。
研究結果顯示，未經提純之蒙脫石其陽離子交換容量(CEC)約為48.6 meq/100g，而將蒙脫石置於水中充分膨潤，再以1000 rpm 轉速(110g) 離心1分鐘，上層液中懸浮之蒙脫石CEC值可提高至約73.8 meq/100g。在合成鋁及鐵插層蒙脫石方面，使用[OH－]/[Al3+]莫耳比為2.5，並以每克蒙脫石配合3 mmol鋁離子進行插層後且經300℃煆燒，可有效增加蒙脫石層間距(d001)與BET比表面積。另一方面，使用[OH－]/[Fe3+]莫耳比為2，以每克蒙脫石配合3 mmol鐵離子進行插層後經300℃煆燒，雖無法產生如鋁插層蒙脫石層間存在之穩定氧化鋁支撐，有效的增加蒙脫石之層間距及BET比表面積，但是仍能在鐵插層蒙脫石層間表面形成非晶質氧化鐵或氫氧化鐵局部覆膜。鋁及鐵插層蒙脫石之Stokes粒徑皆大於未插層之蒙脫石，使得插層之蒙脫石在水中沉降速度變快。又鋁及鐵插層蒙脫石沉降後污泥體積明顯小於未插層之蒙脫石，其固液分離效果較佳。更進一步，鋁及鐵插層蒙脫石由於表面鋁及鐵元素含量增加，而表面鋁及鐵離子可對水中天然有機物分子產生有效的錯合，進而造成其對水中天然有機物的吸附能力明顯提升。
綜合而言，將氧化鋁及氧化鐵插層蒙脫石應用於淨水處理中作為水中天然有機物之吸附劑將是一可行的方法。

Abstract

A large portion of the natural organic matter(NOM) in potable water sources are complex contaminants. During the chlorination procedure in water treatment plane, humus will react with chlorine to form carcinogenic trihalomethane(THM) substances, so it is necessary to remove the NOM in water before chlorination.
The purpose of this study is to synthesis pillared montmorillonite by intercalating Al2O3 and Fe2O3 into the layer space of montmorillonite. Then, the effects of using the pillared montmorillonite as an adsorbent for the removal of NOM from water are evaluated.
The cation exchange capacity(CEC) of unpurified montmorillonite is about 48.6meq/100g. The montmorillonite were purified by centrifuging at 1000rpm(110g) for 1min. The CEC of purified montmorillonite is about 73.8meq/100g. To synthesis Al2O3 and Fe2O3 pillared montmorillonite, the purified montmorillonite suspension was vigorously mixed with hydrolized Al3+ solution at room temperature ( 1g of clay reacted with 3mmol Al3+ in which [OH-]/[Al3+]＝2.5). The final product after 300℃ heat treatment has a basal spacing of 17.7Å and a specific surface area of about 168.93m2/g .In addition, the montmorillonite suspension was vigorously mixed with hydrolized Fe3+ solution at room temperature ( 1g of clay reacted with 3mmol Fe3+ in which [OH-]/[Fe3+]＝2). After calcining at 300℃, the basal spacing and specific surface area of the final product does not increas. The present of Fe2O3 coating film at the interlayer surface of pillared montmorillonite is predicted.
The Stokes particle size of Al2O3 and Fe2O3 pillared montmorillonite is greater than that of unpillared montmorillonite. Thus increase the sedimentation rate of pillared montmorillonite in water. After sedimentation of the pillared montmorillonite, the volume of sludge is smaller than that of unpillared montmorillonite, thus the pillared montmorillonite shows good solid-liquid separation effect. Finally, the sorption capacity of NOM in water progressively increase with the increasing amount of Al2O3 and Fe2O3 intercalated in pillared montmorillonite.
In summary, intercalating of Al2O3 and Fe2O3 into the layers of montmorillonite will form pillared montmorillonite. Experiment results in this study showed that using pillared montmorillonite as an adsorbent for removing NOM from water water is practicable.

1 .蔡宗燕,“納米級無機層材之發展與應用 ”,工業材料,第125期,pp. 120-128,1997.
2 .任磊夫, 黏土礦物與黏土岩,地質出版社,1992.
3 .簡啟恆,“ 純化蒙脫石做為5-FU藥物載體於大腸癌治療之研究”,國立台灣大學材料科學與工程學碩士論文,2000.
4 .唐旭華,“鉑含浸鋁支撐黏土之製備、鑑定及應用”,私立東海大學應用化學碩士論文,1993.
5 .R. Burch and C. I. Warburton,“Pillared clays as demetallisation catalysts”,Applied Catalysis, Vol.33, pp.395-404, 1987.
6 .W. F. Jaynes and G. F. Vance,“BTEX sorption by organo-clay：cosorptive enhancement and equivalence of interlayer complexes”,Soil Sci. Soc. Am. J. , Vol. 60,pp.1742-1749,1996.
7 .林建明,楊正方,普敏莉,吴季懷,“膨潤土/聚丙烯酸鈉鹽吸水性複合物材料研究”,礦物學報,第21卷,第3期,pp.427-430,2001.
8 .張鎮南,許文龍,“原水中腐植酸成分生成消毒副產物特性之探討”,東海學報,第38卷,pp.175-196,1997.
9 .趙杏媛,張有瑜,黏土礦物與黏土礦物分析,海洋出版社,1990.
10 .戴國邦,“ 土壤礦物”,能源、資源與環境,第6卷,第3期,pp16-21,1993.
11 .Kim H. Tan, Environmental soil science, New York, Marcel Dekker, pp40-42,1994.
12 .Murray B. Mcbride, Environmental chemistry of soils, published by Oxford University Press, pp83, 1994
13 .陳培源,“工業用高嶺土的採礦和選礦”,鑛冶, 第15卷,第1期,pp.85-90.
14 .王澤民,周鳳岐,馬小凡,邱立民,“膨潤土的提純及應用研究”,非金屬礦,第22卷,第3期, pp.19-20, 1999.
15 .牛炳昆,“膨潤土提純研究”,化工礦物與加工,第8期, pp.6-8,1999.
16 .王明光譯,鋁的環境化學,國立編譯館出版,1999.
17 .吴平霄,張惠芬,肖文丁,吴金平,“ 柱撐蒙脫石製備與表徵”,礦物學報,第17卷,第2期, pp.200-207,1997.
18 .O.E.W. Vaughan,“Pillared clay- a historical perspective”,Catalysis Today,Vol.2, pp.187-198,1988.
19 .Shoji Yamanaka, Tadahiro Doi and Shuji Sako,“ High surface area solids obtained by intercalation of iron oxide pillars in montmorillonite”,Mat. Res. Bull. , Vol.19, pp.161-168,1984.
20 .R. M. Barrer and D. M. Macleod,“Activation of montmorillonite by ion exchange and sorption complexes of tetra-alkyl ammonium montmorillonites”,Transactions Of The Faraday Society,Vol.51,pp.1290-
1300,1955
21 .N. Lahav and U. Shani,“Cross-linked smectites. I. synthesis and properties of hydroxyl-aluminum-montmorillonite”, Clays and Clay Minerals , Vol.26, No.2, pp.107-115, 1978.
22 .M. L. Occelli and R. M. Tindwa,“ Physicochemical properties of montmorillonite interlayered with cationic oxyaluminum pillars”,Clays and Clay Minerals,Vol.31, No.1, pp.22-28, 1983.
23 .S. Yamanaka, P. B. Malla and S. Komarneni,“ Water adsorption properties of aluminua pillared clay”,Journal Of Colloid And Interface Science,Vol.134, No.1, pp.51-58,1990.
24 .R. A. Schoonheydt,“Pillaring of saponite in concentrated medium”,Clay Minerals, Vol.27, pp.249-252, 1992.
25 .T. Endo and M. M. Mortland,“Intercalation of silica in smectite”, Clays and Clay Minerals, Vol.28, No.2, pp.105-110, 1980.
26 .Shoji Yamanaka, Gunji Yamashita and Makoto Hattori,“ Reaction of hydroxyl-Bismuth polycations with montmorillonite”,Clays and Clay Minerals, Vol.28, No.4, pp.281-284, 1980.
27 .S. Yamanaka and G. W. Brindley,“Hydroxy-Nickel interlayering in montmorillonite by titration method”,Clays and Clay Minerals, Vol.26, No.1, pp.21-24, 1978.
28 .S. Yamanaka and G. W. Brindley,“ High surface area solids obtained by reaction of montmorillonite with zirconyl chloride”,Clays and Clay Minerals, Vol.27, No.2, pp.119-124, 1979.
29 .田淑貴,王冠鑫,林傳易,陳國璽“ 氧化鉻柱支撐蒙脫石的製備研究”,礦物學報,第18卷,第四期, pp.390-395, 1998.
30 .D. H. Doff, N. H. J. Gangas, J. E. M. Allan and J. M. D. Coey, “Preparation and characterization of iron oxide pillared montmorillonite”,Clay Minerals,Vol.23, pp.367-377, 1988.
31 .F. Bergaya, N. Hassoun, J. Barrault and L. Gatineau“ Pillaring of synthetic hectorite by mixed [Al13-xFex] pillars”,Clay Minerals, Vol.28, pp.109-122, 1993.
32 .J.Barrault, M.Abdellaoui, C. Bouchoule, A. Majeste, J. M. Tatibouet,A.Louloudi, N. Papayannakos and N. H. Gangas,“Catalytic wet peroxide oxidation over mixed (Al-Fe) pillared clays”,Applied Catalysis B：Environmental,Vol.27, pp.225-230, 2000.
33 .吴平霄,張惠芬,郭九皋,王輔亞“ 羥基鐵鋁柱撐蒙脫石Keggin結構的穩定性，”礦物學報,第19卷,第2期,pp.132-138,1999.
34 .張信川,“鋁與鋯支撐黏土之製備,鑑定及應用，”私立東海大學應用化學研究所碩士論文,1990.
35 .田淑貴,王冠鑫,王輔亞“ 氧化鉻-鋁混雜柱支撐蒙脫石的製備和性能”,礦物學報,第20卷,第2期, pp.108-111, 2000.
36 .Richard C. Zielke and Thomas J. Pinnavaia, “Modified clays for the adsorption of environmental toxicants：Binding of chlorophenols to pillared , delaminated, and hydroxyl-interlayered smectites”,Clays and Clay Minerals,Vol.36, No.5, pp.403-408, 1988.
37 .吴平霄,張惠芬,郭九皋,王輔亞,劉小勇“無機-有機柱撐蒙脫石對苯酚的吸附”,地球化學,第28卷,第1期, pp.58-69, 1999.
38 .Keeran R. Srinivasan and H. S. Fogler,“ Use of inorgano-organo-clays in the removal of priority pollutants from industrial wastewaters：structural aspects”,Clays and Clay Minerals, Vol.38, No.3, pp.277-286, 1990.
39 .L. J.Michot and T. J. Pinnavaia,“Adsorption of chlorinated phenols from aqueous solution by surfactant-modified pillared clays”,Clays and Clay Minerals,Vol.39, No.6, pp.634-641, 1991.
40 .葉玲,“ 蒙脫石改性及其吸附脫色性能研究”,礦物學報,第21卷,第2期,pp.179-182,2001.
41 .肖子敬,戴勁草, 葉玲,“膨潤土基多孔材料在染液脫色處理中的應用”,礦物學報,第21卷,第3期, pp.419-422, 2001.
42 .范雨珍,廖立兵, 欒兆坤,“ 改性蒙脫石吸附水中氟離子的實驗研究”,礦物學報,第21卷,第1期, pp.34-37, 2001.
43 .劉桂榮,廖立兵, “柱撐蒙脫石吸附水中硫酸根離子的實驗研究 ”,礦物學報,第21卷,第3期, pp.470-472, 2001.
44 .Hinrich L. Bohn, Brian L. Mcneal, George A. O’connor, Soil chemistry,copyright by John Wiley＆Sons, Inc.,1985.
45 .陳立夫,楊秋忠,“ 土壤精華－腐植質”,科學月刊,第24卷,第1期,pp.
53-58,1993.
46 .金相燦,程振華,徐南妮,李海生,環境毒性-有機物污染化學,淑馨出版社,1998.
47 .王明光,環境土壤化學,五南圖書出版,2000
48 .Yun-Hwei Shen,“ Sorption of humic acid to soil：The role of soil mineral composition”,Chemosphere,Vol.38,No.11, pp.2489-2499, 1999.
49 .張有義,郭蘭生,膠體及界面化學入門,高立圖書有限公司,1999.
50 .馮敏,石松,工業水處理技術,海洋出版社,1992.
51 .王一雄, 土壤環境污染與農藥,明文書局出版,1997.
52 .張志純編譯,冷凍乾燥法,徐氏基金會出版,1983.
53 .林正雄,“粒徑分析儀(上)”, 科儀新知,第22卷,第2期,pp.6-20,1998.
54 .E.Molis, F. Thomas, K. Faisandier and I. Bihannic,“ Structural collapse of Al13-intercalated montmorillonite by Na-salicylate solutions”,Clay Minerals, Vol.36,pp.335-344,2001.
55.環境檢測方法彙編,行政院環保署環境檢驗所,1994.
56.選礦學,李文鐘,世界書局,1971.