臺灣博碩士論文加值系統

重金屬在現今的工業上使用很普遍，一旦造成污染可能經年累月也無法改善。由於重金屬不像有機物會分解且消滅，使本來的毒害作用完全消失，雖然經過物理及化學變化，重金屬仍是重金屬。因此對於受重金屬污染的土壤，我們必須尋求一個有效且經濟的處理對策。
近年來，土壤污染案例層出不窮，例如桃園縣蘆竹鄉中福社區的鎘污染，乃是當年基力化工廠含重金屬廢水處理不當的結果，而本文乃是針對此一污染土壤，提供一個復育土壤的技術。在中福土壤中，重金屬鎘及鋅均超過標準值甚多，且大部分以水溶性及交換性形態居多，而此兩種形態最易為農作物吸收而威脅人類健康，因此欲處理亦需以此兩種形態物種為主要目標。
在批次實驗中，我們使用了三種不同形式的萃取劑（HCl、EDTA、CaCl2）來去除中福土壤中的鎘及鋅，探討何種萃取劑對去除效果最好，結果發現CaCl2溶液萃取出的鎘量最多，可能是因為Ca2+與土壤的吸附選擇性大於H+與土壤的吸附選擇性的結果，且經由氯化鈣溶液處理過後的土壤不會破壞土壤結構，仍可繼續種植。而在恆溫去除實驗方面，經驗式的中Freundlich 比 Langmuir 較適切描述此等溫去除現象，而修正的Langmuir 及 Jossens et al. 也都有不錯的契合效果。在質傳模式的探討上，以簡單的平方動力模式對於三種試劑皆能適切的表示出質傳現象。
在連續淋洗實驗上是採用管柱淋洗方式，主要以交換性萃取劑為主，探討的變因包括萃取劑的種類、pH、通量、濃度、價數、土壤粒徑、回收液淋洗次數及萃取劑純度。在理論方面，則使用General Logistic、Hill、Weibull等方程式模擬其淋洗去除貫穿曲線，發現三種模式皆能適切的表示出淋洗系統的行為。
在使用小規模管柱淋洗後，我們將規模放大為長30公分寬30公分的管柱，實際模擬現場操作行為，探討是否會因規模放大而對重金屬的去除效率有所影響，結果發現，氯化鈣及氯化鈉皆有不錯的效果。而在後續的土壤廢液處理問題上，離子交換法及沈澱法也都能有效的將重金屬自淋洗廢液中分離出來，此流程可作為日後處理類似土壤污染問題的一個參考指標。

Heavy metals are widely used in various in industrial processes nowadays. However, these industrial processes very often generate different types of wastes that contain toxic heavy metals. Unlike the organic or inorganic compounds that can be decomposed, heavy metals remain the polluted environment for quite long time. Therefore, effective and economic methods are needed to tackle the heavy metal pollution problem.
In the past decade, the farmland in Chung Fu area, Lu Tsu, Taoyuan Country was found to be seriously contaminated by cadmium and zinc. Such a heavy metal contamination of soil stemmed from improper handling of heavy metal-containing wastewater produced by Chi-Lee chemical plant. Various methods have been proposed for cleaning up the contaminated soil. In the present study, acid and calcium salt solution washings were explored as potential methods for effective removal of heavy metal from the contaminated farmland. Experimental tests were conducted to determine the heavy metal removal efficiencies under different operating conditions.
In the batch tests, three kinds of extractants (HCl, EDTA, CaCl2) were examined to remove cadmium and zinc in contaminated soils. Both soil artificially contaminated with heavy metals as prepared in the laboratory and contaminated soil obtained from the field were tested in the extraction tests. It was found that calcium chloride was more efficient than the other two extractants in removing cadmium from the contaminated soil. This may be due to that the adsorptive selectivity of Ca2+ was stronger than H+. Extensive equilibrium extraction tests were performed to collect data for the equilibrium adsorption of heavy metal in soil. Different adsorption isotherms were attempted for describing the equilibrium adsorption relationship. The empirical Freundlich model was found to represent the observed data better than the Langmuir model. The modified Langmuir and Jossens models also were to describe the equilibrium adsorption well. In the mass transfer aspect, a simple model based on the sequared-driving principle was adopted and found to describe well the overall mass transfer process.
Continuous column washing tests were also conducted to determine the effects of operating variables, including the type of extractant, pH, flow rate, extractant concentration, valence, soil particle size, extraction time, etc. on the heavy metal removal efficiency. Various empirical or semi-empirical equations, like general logistic, Hill and Weibull models, were employed to represent the soil washing breakthrough curves. The column models were be helpful in accurate estimation of the washing tome.
After soil washing tests using a small column, test runs were also conducted in a much bigger pilot column of 30 cm (W) x 30 cm (L) x 100 cm (H) to simulate the in-situ operation and to determined effectiveness of two calcium salts, i.e. calcium chloride and sodium chloride. One important aspect considered in the present investigation was the reuse of washing solution. The washing solution after soil washing contained significant amounts of heavy metals and chemicals. Chemical precipitation offerred good heavy metal removal from wastewater and the treated washing solution can be readily recycled for reuse in the washing process.

第一章 緒 論...........................................1
1.1前 言..............................................1
1.2土壤污染來源與重金屬的危害..........................3
1.2.1土壤污染的定義.................................3
1.2.2土壤污染之產生.................................3
1.2.3土壤污染物.....................................3
1.2.4土壤污染之途徑.................................4
1.2.5土壤污染物之來源...............................4
1.2.6土壤重金屬的危害...............................7
1.3土壤污染整治技術....................................9
1.4文獻回顧............................................18
1.4.1重金屬在土壤中的行為...........................18
1.4.2重金屬在土壤中的型態...........................19
1.4.3土壤pH對重金屬的影響...........................20
1.4.4土壤復育技術...................................20
1.4.5理論模式應用...................................22
1.5研究動機與目的......................................23
第二章 基本理論........................................25
2.1土壤重金屬之去除....................................25
2.1.1吸附現象.......................................25
2.1.2土壤吸附特性...................................26
2.1.3萃取劑種類與作用原理...........................28
2.2恆溫重金屬去除模式..................................34
2.3質傳係數模式........................................37
2.3.1質傳模式.......................................37
2.3.2質傳之溫度效應.................................39
2.4連續淋洗重金屬去除模式..............................40
2.4.1連續淋洗重金屬之去除...........................40
2.4.2連續淋洗理論模式...............................42
第三章 現地土壤簡介及基本性質..........................45
3.1中福地區土壤污染概況................................45
3.2土壤基本性質及分析方法..............................52
3.2.1pH值...........................................52
3.2.2陽離子交換容量.................................52
3.2.3有機質含量.....................................54
3.2.4土壤質地.......................................57
3.2.5游離氧化鐵、鋁.................................59
3.2.6可交換性鹽基...................................59
3.3土壤重金屬含量基本分析..............................60
3.3.1鹽酸抽出法.....................................60
3.3.2王水消去法.....................................61
3.4分析儀器、設備與藥品................................62
3.5土壤理化分析結果....................................65
第四章 批次實驗........................................66
4.1實驗設備與藥品66
4.1.1實驗設備與分析儀器.............................66
4.1.2實驗藥品.......................................67
4.2重金屬污染土壤之製備................................68
4.3重金屬污染土壤之檢測................................68
4.4批次實驗步驟........................................69
4.5結果與討論...........................................70
4.5.1萃取劑種類與濃度的影響..........................70
4.5.2 pH的影響.......................................73
4.5.3震盪速率的影響..................................77
4.5.4溫度的影響......................................78
4.5.5質傳模式........................................78
4.5.6恆溫重金屬去除之溫度效應動力模式................85
4.5.7重金屬去除之活化能..............................87
4.5.8恆溫重金屬去除平衡模式..........................90
第五章 連續淋洗實驗.....................................96
5.1實驗設備與藥品.......................................96
5.1.1實驗設備與分析儀器..............................96
5.1.2實驗藥品........................................97
5.1.3實驗裝置........................................98
5.1.4初始濃度分析方法................................98
5.2連續淋洗實驗步驟.....................................98
5.2.1小規模管柱淋洗實驗步驟..........................98
5.2.2大規模管柱淋洗實驗步驟..........................100
5.3小管柱淋洗實驗結果與討論..........................101
5.3.1萃取劑種類的影響................................102
5.3.2濃度的影響......................................108
5.3.3 pH的影響.......................................112
5.3.4通量的影響......................................112
5.3.5價數的影響......................................124
5.3.6土壤粒徑的影響..................................124
5.3.7回收液淋洗次數的影響............................129
5.3.8 NaCl純度的影響.................................134
5.3.9連續淋洗理論模式................................140
5.4大管柱淋洗實驗結果與討論.............................152
5.4.1 CaCl2淋洗實驗結果...............................152
5.4.2NaCl淋洗實驗結果.................................152
5.4.3連續淋洗理論模式.................................161
5.4.4經濟效益評估.....................................167
第六章 土壤廢液回收實驗..................................170
6.1樹脂吸附法............................................170
6.1.1離子交換之應用...................................170
6.1.2離子交換的基本原理...............................170
6.1.3批次式吸附.......................................172
6.1.4連續式吸附.......................................172
6.2實驗裝置及藥品........................................174
6.3 IRC-718簡介..........................................176
6.4樹脂之前處理與再生....................................176
6.5結果與討論............................................176
6.5.1樹脂種類對飽和吸附量的影響.......................176
6.5.2樹脂再生與吸附次數的影響.........................177
6.5.3貫穿吸附進料流速的影響...........................177
6.5.4連續式樹脂再生...................................178
6.5.5貫穿吸附理論模式.................................184
6.6沈澱法................................................189
第七章 結論與建議.........................................190
7.1結論...................................................190
7.2建議...................................................192
參考文獻..................................................193
附錄......................................................201
自傳......................................................205

Adamson, A. W., Physical Chemistry of Surfaces, John Wiley and Sons, New York（1990）
Alloway, B. J. ,Heavy Metals in Soils, John Wiley and Sons, New York (1990)
Bohn, H. L., McNeal, B. L. and O’Connor, G. A., Soil Chemistry, John Wiley and Sons, New York（1985）
Bruemmer, G. W., Gerth , J. and Herms, U. , “Heavy Metal Species, Mobility and Availability in Soil,” Zeitschrift fur Pflanzenernahrung und Bodenk, 149, 382-398 (1986)
Caruana, C. M., “New Soil-cleaning Routes Tackle Metals,” Chemical Engineering Progress, 93, 11-30 (1997)
Cline, S. R. and Reed, B. E., “Lead Removal from Soils via Bench-scale Soil Washing Techniques,” Journal of Environmental Engineering, ASCE, 121,700-705（1995）
Davis, A. P. and Hotha, B. V., “Washing of Various Lead Compounds from a Contaminated Soil Column,” Journal of Environmental Engineering, ASCE, 124, 1066-1075（1998）
Davis, A. P. and Singh, I., “Washing of Zinc(II) from Contaminated Soil Column,” Journal of Environmental Engineering, ASCE,121, 174-185（1995）
Doner, H. E., “Chlorid as a Factor in Mobilities of Ni(Ⅱ),Cu(Ⅱ) and Cd(Ⅱ) in Soil,” Soil Science Society of America Journal, 42, 882-885 (1978)
Ellito, H. A. and Denneny, C. M., “Soil Adsorption of Cadmium from Solutions Containing Organic Ligands,” Journal Environmental Quality, 11, 658-663 (1982)
Enfield, G. C., Harlin, JR. C. C. and Bledsoe, E. B., “Comparison of Five Kinetic Models for Orthophosphate Reactions in Mineral Soils,” Soil Science Society of America Journal, 40, 243-249 (1976)
Gerritse, R. G., “Dispersion of Cadmium in Columns of Saturated Sandy Soils, Journal of Environmental Quality, 25, 1344-1349（1996）
Gibson, A. M., Bratchell, N. and Roberts, T. A., “The Effect of Sodium Chloride and Temperature on the Rate and Extent of Growth of Clostridium Botulinum Type A in Pasteurized Pork Slurry,” Journal of Applied Bacteriology, 62, 479-490（1987）
Kabata-Pendias, A. and Kakuzo, K. and Ichiro, Y., “Heavy metal pollution in soils of Japan,” Japan Scientific Societies Press, Tokyo（1981）
Kabata-Pendias, A., “Behavioral Properties of Trace Metals in Soils,” Applied Geochemistry, 2, 3-9 (1993)
Kakuzo, K., Ichiro, Y., Heavy Metal Pollution in Soils of Japan, Japan Scientific Societies Press, Tokyo (1981)
Keller, C. and Vedy, J. C., “Distribution of Copper and Cadmium Fractions in two Forest Soils,” Journal Environmental Quality, 23, 987-999（1994）
Levin, S. A., Biomathematics,Spriger-Verlag, Beerlin, Germany（1993）
Lin, S. H. and Lin, R. C., “Adsorption and Mass Transfer Characteristics of Pent and Cyclopentane by Various Adsorptions,” Environmental Technology, 20, 11-19（1999）
Lindsay, W. L. and Norvell, W. A., “Development of a DTPA micronutrient soil test,” Agronomy Abstr, American Society of Agronomy, Madison. WI, 84 (1969)
Lindsay, W. L. and Norvell, W. A., “Development of a DTPA Soil Test for Zine, Iron, Manganese, and Copper,” Soil Science Society of America Journal, 42, 421-428 (1978)
Lindsay, W. L., Chemical Equilibrian in Soils, Wiley-Interscience, New York (1979)
Ma, L. Q. and Rao, G. N., “Effect of Phosphate Rock on Sequential Chemical Exactration of Lead in Contaminated Soils,” Journal Environmental Quality, 26, 788-794（1997）
McBride, M. B. and Blasiak, J. J., “Zinc and Copper Solubility as a Function of pH in an Acid Soil,” Soil Science Society of America Journal. 43, 866（1979）
McBride, M. B., “Chemisorption of Cd(Ⅱ) on Calcite Surfaces.,” Soil Science Society of America Journal, 44, 26-28（1980）
McCabe, W. L., Smith, J. C. and Harriot, P., Unit Operation of Chemical Engineering, McGraw-Hill, New York（1986）
Mclaren, R. G. and Grawford, D. V., “Studies on Soil Copper: I. The Fractionation of Copper in Soils,” Journal of Soil Science, 24, 172-181（1973）
Miller, C. E., Turk, L. M. and Foth, H. D., Fundamental of Soil Science, John Wiley , New York（1972）
Naidu, R., Bolan, N. S., Kookana, R. S., and Tiller, K. G., “Ionic-Strength and pH Effects on the Sorption of Cadmium and the Surface Charge of Soils,” European Journal of Soil Science, 45, 419-429（1994）
Neale, C. N., Bricka, R. M. and Chao, A. C., “Evaluating Acids and Chelating Agents for Removing Heavy Metals from Contaminated Soils,” Environmental Progress, 16, 274-280（1997）
Nelson, D. W. and Sommer, L. E., “Total Carbon, Organic Carbon, and Organic Matter,” In Page, A. L. et al. (ed.) Meyhods of soil analysis, Part 2. Chemical and microbiological properties., 2nd ed. Agronomy monograph 9 , 539-577 (1982)
Pearl, R., The Biology of Population Growth, Alfred A. Knopf, New York（1925）
Peters, R. W. and Shem, L., “Adsorption/Desorption Characteristics of Lead on Various Types of Soil,” Environmental Progress, 11, 234-240（1992）
Ramos, L. L. M. Hernandez and M. J. Gonzalez, “Sequential Fractionation of Copper, Lead, Cadmium and Zine in Soils form or near Donana National Park,” Journal Environmental Quality, 23, 50-57（1994）
Ratkowsky, D. A., Nonlinear Regression Modeling, Marcel Dekker, New York（1983）
Reed, B. E., Carriere, P. C., and Moore, R., “Flushing of a Pb(Ⅱ) Contaminated Soil Using HCl, EDTA, and CaCl2,” Journal of Environmental Engineering, 122, 48-50（1996）
Ruthven, D. M., Principles of Adsorption and Adsorption Processes, John Wiley and Sons, New York（1984）
Santiallan-Medrano, J. and Jurinak, J. J., “The Chemistry of Lead and Cadmium in Soil: Soild Phase Formation,” Soil Science Society of America Journal, 39 , 851-856（1975）
Seber, G. A. F. and Wild, C. J., Nonlinear Regression, John Wiley and Sons, New York（1989）
Skoog, D. A., West, D. M. and Holler, F. J., Fundamentals of Analytical Chemistry, 6th ed., Saunders College Pub., Londen (1992)
Stevenson, F. J., Humus Chemistry, John Wiley , New York（1982）
Tampouris, S., Papassiopi, N. and Paspaliaris, I., “Removal of Contaminant Metals form Fine Grainrd Soils, Using Agglomeration, Chloride Solutions and Pile Leaching Techniques,” Journal of Hazardous Materials, 84, 297-319 （2001）
Tejowulan, R. S. and Hendershot, W. H., “Removal of Trace Metals from Contaminated Soils Using EDTA Incorporating Resin Trapping Techniques,” Environmental Pollution, 103, 135-142 (1998)
Tessier, A., and Campbell, P. G. C., “Partitioning of Trace Metals in Sediments.” in J.R. Kramer and H. E. Allen(ed.) Metal speciation: Theory, Analysis, and Application. Lewis Publishers, Chelsea, MI.（1988）
Thornton, I, Applied Environmental Geochemistry, Academic Press, London（1983）
Tiller, K. G., Gerth, J. and Bruemmer, G. W., “The Relative Affinities of Cd, Ni, and Zn for Different Clay Fraction and Goethite.,”Geoderma, 34, 17-35 (1984)
Tomas, G. W., Exchangeable cation, In Page, A. L. et al. (ed.) Methods of soil analysis, Part 2. Chemical and microbiological properties, 2nd ed., Agronomy Monograph (1982)
Wang, W. Z., Brusseau, M. L. and Artiola, J. F., “The use of Calcium to Facilitate Desorption and Removal of Cadmium and Nickel in Subsurface Soils,” Journal of Contaminant Hydrology, 25, 325-336（1997）
Wheeler, A. and Robell, A. J., “Performance of Fixed-Bed Catalytic Reactors with Poison in the Feed,” Journal of Catalysis, 13, 299-305（1969）
Yoon, Y. H. and Nelson, J. H., “Application of Gas Adsorption Kinetics I. A Theoretical Model for Respirator Cartridge Service Life,” American Industrial Hygiene Association Journal, 45, 509-516（1984）
王一雄，土壤環境污染與農藥，明文書局（1997）
王一雄、高玉燦與陳玉麟，”重金屬鎘、鉻、銅及鋅在土壤中移動性之預測”，中國農業化學會誌，23，119-126（1985）
王一雄、陳尊賢、李達源，土壤污染學，國立空中大學（1995）
王光明，土壤環境化學，國立編譯館（1997）
王銀波，”台灣地區重金屬污染之一些實況”，危害性物質處理管制研習會，中央大學編印（1987）
王銀波等，土壤品質基準－土壤重金屬含量分級基準之建立，行政院環境保護署研究報告（1991）
何念祖、孟賜福，植物營養原理, 上海科學技術出版社 （1987）
李方胤、廖秋榮，”鎘、鉛在污染土壤中之聚積形態、性質與分佈情況”，第二屆土壤防制研討會論文集，台大農化系編印（1990）
李左江、賀福與王茂章，”PAN基活性碳纖維床層上有機溶劑蒸氣的穿透特性”，離子交換與吸附（1997）
李豔祺、王銀波，”台灣農耕土壤之千萃取與作物體濃度之關係”，第四屆土壤污染防制研討會論文集（1993）
林淇松，化纖至程廢水處理與回收再利用之研究，私立元智大學化學工程系碩士論文（1997）
林福全，EDTA淋洗受重金屬污染土壤之研究，國立台灣大學農業工程學研究所碩士論文（1990）
姜志新、諶竟清與宋正孝，離子交換分離工程，天津大學出版社，天津（1992）
高秋實與袁書玉，環境化學，科技圖書股份有限公司，台北（1989）
張如燕，銅、鋅、鎘、鉛在受污染土體中之移動即在土壤各組成中之分
佈，國立台灣大學農業化學研究所碩士論文（1989）
張坤森，重金屬鎘之土壤污染及其溶質移動吸附模擬研究，台大農工所碩士論文（1985）
張明暉，鎘、鉛在砂質與粘質污染土壤中移動的模擬，國立台灣大學農業化學研究所碩士論文（1991）
張添晉，”台北市土壤污染監測站設置規劃之研究”，台北市政府環境保護局（1993）
張嵩林、陳嘉裕、劉思聰，”台灣農業土壤及作物受重金屬污染情形之調查研究”，台灣環境保護，8，1-14（1988）
莊祈龍、許俊男，”土壤分析與重金屬除污之基礎研究”，核子科學，319-325（1993）
陳台煇，土壤中鎘、鉛交換之研究，國立中興大學碩士論文（1996）
陳泰成，利用螯合劑清洗人工合成污染土壤之研究，國立中山大學碩士論文（1995）
傅崇德、劉康成、葉金明、邱林鑫、許鼎居、何鴻哲、周錦東、王成財與
王美雪，桃園縣環境保護白皮書，私立萬能工商專科學校環境工程科（1998）
溫一倉，以化學萃取配合物理連續沉澱法復育受鎘、銅及鉛污染土壤之研究，國立屏東科技大學環境工程與科學系碩士論文（1999）
劉原宏、李芳胤、廖秋榮，”幾種台灣土壤對銅與鎘吸附性的探討”，中國農業化學會誌，35，671-682 （1997）
劉覲銘、張尊國、徐玉標與吳先琪，”以螯合劑淋洗受重金屬污染土壤之研究”，第三屆土壤污染防治研討會論文集（1992）
賴旭亮，離子交換樹脂測定水飽和土壤之重金屬生物有效性，私立元智大學化學工程系碩士論文（1998）