臺灣博碩士論文加值系統

石油及其產品是人類生活上所需之主要來源，常因為人為疏失而造成各種土壤或地下水污染事件。因土壤成分較為複雜，要分離土壤中有機物頗為不易。本論文即利用熱脫附之方法去除土壤中的有機化合物(BTEX：苯、甲苯、乙苯、二甲苯)。
在批式實驗中，所選用的三種溫度為各有機物沸點及其上下各20℃為實驗條件，來探討等溫去除實驗及質傳模式。在等溫去除實驗方面，Modified-Langmuir Model比Langmuir、Freundlich和Jossens et al.三種等溫式更能適切的描述其等溫熱脫附的平衡關係。在質傳模式的探討上，以兩段指數型模式即可表達本實驗之質傳現象。
連續式熱脫附實驗是將受污染土壤經過螺桿式加熱床，達到將有機物與土壤分離的效果。測試此實驗的效能如何，以探討其實用性。本實驗係採桃園縣中壢市內壢里土壤添加有機化合物，針對系統溫度、通氣量、處理時間、污染濃度及土壤量對熱脫附處理效果之影響進行討論。由實驗結果顯示，影響熱脫附效果最大的變因是系統溫度、處理時間以及污染濃度。而通氣量和土壤量這兩組變因，必須在長時間不斷進料，效果才會有較為明顯的變化。
由批式和連續式實驗中發現，BTEX四種有機化合物中，以苯最容易脫附，其次為甲苯，而最不易脫附的是乙苯和二甲苯。由現階段實驗模擬處理成效證明熱脫附系統對於受BTEX污染土壤具有良好之處理能力，對於實際應用於污染現址復育具有相當的可行性與開發潛力。

Petrochemical and other chemical products are important parts of mainstay requires in our life. However, manufacturing of these products very often can cause severe soil or groundwater pollution problems. Due to its complex structure, remediation of soil contaminated by organic compounds has never been easy. In the present experimental research, thermal desorption is considered as a means for remediating soil contaminated by benzene, toluene, ethylbenzene and xylene (BTEX) which are common organic compounds found in the petrochemical industries.
In the batch experimental tests, the desorption temperature were chosen to be around respective boiling points of BTEX. Based on the chosen temperature, experimental tests were conducted to gather data for establish the desorption isothermal Langmuir model was found to describe quiet well the observed data. On the mass transfer aspect, a power type mass transfer model was proposed to represent the mass transfer process.
In the continuous desorption tests, the contaminated soil was transported in a screw heating bed to achieve thermal detachment of organic compounds from soil. Test runs were conducted to investigate the thermal desorption efficiencies of contaminated soil under various operating conditions of temperature, gas flow rate, soil loading and initial organic concentration. Proper conditions were indentified for efficient operation of the thermal desorption process.
The test results idicated that among the four compounds tested, benzene is the easiest to remove from the contaminated soil by xylene, ethylbenzene and toluene. Thermal desorption was found to be a highly efficient process for removal of BTEX or similar compounds.

中文摘要 I
ABSTRACT II
致謝 III
目錄 IV
表目錄 VII
圖目錄 XIII
第一章 緒論 1
1.1前言 1
1.2土壤有機污染來源與危害 2
1.3土壤污染復育技術 3
1.3.1物化處理技術 3
1.3.2生物處理技術 5
1.3.3熱處理技術 5
1.3.4低溫熱脫附技術 6
1.4現行商業化熱脫附系統 7
1.5土壤有機物現行法令規範 8
1.5.1國外法令規範 9
1.5.2我國法令規範 10
1.6文獻回顧 11
1.7研究動機與內容 13
第二章 基本理論 14
2.1土壤有機物之去除 14
2.1.1土壤中有機化合物之吸附機制 15
2.1.2有機化合物與土壤礦物之吸附作用 17
2.1.3有機化合物與土壤有機質之吸附作用 17
2.1.4有機化合物與土壤水份之吸附作用 18
2.2等溫有機物去除模式 19
2.2.1 Langmuir等溫式 20
2.2.2 Freundlich等溫式 20
2.2.3修正型Langmuir等溫式 21
2.2.4 Jossens et al. 等溫式 22
2.3質傳係數模式 24
2.3.1質傳模式 24
2.3.2質傳之溫度效應 26
第三章 土壤理化性質 27
3.1土壤理化性質簡介與分析方法 27
3.1.1 pH值 27
3.1.2有機物含量 28
3.1.3土壤質地 29
3.2.4土壤水份含量 32
3.2分析儀器、設備與藥品 32
3.2.1分析儀器、設備 32
3.2.2實驗藥品 33
3.3結果與討論 35
第四章 批式實驗 36
4.1實驗設備與藥品 36
4.1.1實驗設備與分析儀器 36
4.1.2模擬用有機化合物 38
4.1.3萃取溶劑 40
4.2有機物污染土壤之製備與檢測方法 40
4.2.1有機物污染土壤之製備 40
4.2.2有機物污染土壤之檢測 40
4.2.2.1分析實驗 40
4.2.2.2檢量線製備 41
4.2.2.3溶劑萃取實驗 42
4.3批式實驗步驟 42
4.4結果與討論 42
4.4.1等溫平衡脫附實驗 42
4.4.2脫附質傳實驗 72
4.4.3有機物去除之活化能 91
第五章 連續式實驗 94
5.1實驗設備與藥品 94
5.1.1實驗設備與分析儀器 94
5.1.2模擬用有機化合物 96
5.1.3萃取溶劑 96
5.2連續式實驗步驟 96
5.3結果與討論 97
5.3.1系統溫度對熱脫附處理效果之影響 97
5.3.2系統通氣量對熱脫附處理效果之影響 103
5.3.3土壤處理時間對熱脫附處理效果之影響 103
5.3.4土壤污染濃度對熱脫附處理效果之影響 112
5.3.5土壤量對熱脫附處理效果之影響 112
第六章 結論與建議 121
6.1結論 121
6.2建議 122
參考文獻 123
附錄A 131
附錄B 133
自傳 134

Adamson, A. W., Physical Chemistry of Surfaces, John Wiley and Sons, New York, 1990.
Anderson, W. C., Innovative Site Remediation Technology: Theraml Desorption, American Academy of Environmental Engineers, Annapolis, Maryland, 1993.
Atalay, A. and Hwang, K. J., " Extraction of Light Hydrocarbons from Soil", Water, Air, and Soil Pollution, 90, pp. 451-468, 1996.
Batterman, S., Kulshrestha, A. and Cheng, H. Y., " Hydrocarbon Vapor Transport in Low Moisture Soils", Environmental Science & Technology, 29, pp. 171-180, 1995.
Bird, R. B., Stewart, W. E. and Lightfoot E. N., Transport Phenomena, John Wiley & Sons, Inc., 1960.
Bohn, H. L., McNeal, B. L. and O''Connor, G. A., Soil Chemistry, John Wiley and Sons, New York, 1985.
Bruell, C. J., Segall, B. A. and Walsh, M. T., " Electroosmotic Removal of Gasoline Hydrocarbons and TCE from Clay", Journal of Environmental Engineering, 118, pp. 68-83, 1992.
Bucala, V., Saito, H., Howard, J. B. and Peters, W. A., " Thermal Treatment of Fuel Oil-Contaminated Soils under Rapid Heating Conditions", Environmental Science & Technology, 28, pp. 1801-1807, 1994.
Buttner, W. J., Findlay, M., Vickers, W., Davis, W. M., Cespendes, E. R. Cooper, S. and Adams, J. W., " In Situ Detection of Trinitrotoluene and Other Nitrated Explosives in Soils", Analytica Chimica Acta, 341, pp. 63-71, 1997.
Chiou, C. T. and Shoup, T. D., "Effects of Polar and Nonpolar Groups on the Solubility of Organic Compounds in Soil Organic Matter", Environmental Science & Technology, 28, pp. 1139-1144, 1994.
Chiou, C. T., Porter, P. E. and Schmedding, D. W., " Partition Equilibria of Nonionic Organic Compounds between Soil Organic Matter and Water", Environmental Science & Technology, 17, pp. 227-231, 1985.
Cox, L., Hermosin, M. C. and Cornejo, J., " Sorption of Metamitron on Soils with Low Organic Matter Content", Chemosphere, 32, pp. 1391-1400, 1996.
De Percin, P. R., " Application of Thermal Desorption Technologies to Hazardous Waste Sites", Journal of Hazardous Materials, 40, pp. 203-209, 1995.
Devai, I. and Delaune, R. D., " Evidence for Phosphine Production and Emission from Louisiana and Florida Marsh Soils", Organic Geochemistry, 23, pp. 277-279, 1995.
Doskey, P. V., Costanza, M. S., Hansen, M. C. and Kickels, W. T., " Solid Sorbent Method for The Collection and Analysis of Volatile Halogenated Organic Compounds in Soil Gas", Journal of Chromatography A, 738, pp. 73-81, 1996.
Dural, N. H. and Chen, C. H., " Analysis of Vapor Phase Adsorption Equilibrium of 1,1,1-trichloroethane on Dry Soils", Journal of Hazardous Materials, 53, pp. 75-92, 1997.
Fox, R. D., Alperin, E. S. and Huls, H. H., " Thermal Treatment for The Removal of PCBs and Other Organics from Soil", Environmental Progress, 10, pp. 40-44, 1991.
Gee, G. W. and Bauder, J. W., "Particle-Size Analysis", in Methods of Soil Analysis. II, 2nd ed., ASA and SSSA, Madison, Wl 383, 1986.
Geerdink, M. J., Erkelens, C., Van Dam, J. C., Frank, J. and Luyben, K. Ch. A. M., " Fast Screening of Contaminated Soil Samples Using Thermal Desorption Mass Spectrometry", Analytica Chimica Acta, 315, pp. 159-166, 1995.
George, C. E., Azwell, D. E., Adams, P. A. and Rao, G. V. N., " Evaluation of Steam As a Sweep Gas In Low Temperature Thermal Desorption Processes Used For Contaminated Soil Clean Up", Waster Management, 15, pp: 407-416, 1995.
Goss, K. U., " Effects of Temperature and Relative Humidity on the Sorption of Organic Vapors on Clay Minerals", Environmental Science & Technology, 27, pp. 2127-2132, 1993.
Gunapala, N., Venette, R. C., Ferris H. and Scow K. M., "Effects of Soil Management History on The Rate of Organic Matter Decomposition", Soil Biology and Biochemistry, 30, pp. 1917-1927, 1998.
Hassink, J., Whitmore, A. P. and Kubat, J., "Size and Density Fractionation of Soil Organic Matter and The Physical Capacity of Soils to Protect Organic Matter", European Journal of Agronomy, 7, pp. 189-199, 1997.
Jossens, L., J. M. Prausnitz, W. Fritz, E. U. Schlunder and A. L. Myers, " Thermodynamics of Multi-solute Adsorption from Dilute Aqueous Solutions.", Chemical Engineering Science, 33, p. 1097, 1978.
Keyes, B. R. and Silcox, G. D., " Fundamental Study of The Thermal Desorption of Toluene from Montmorillonite Clay Particles", Environmental Science & Technology, 28, pp. 840-849, 1994.
Khodacloust, A. P., J. A. Wagner, M. T. Suidan and S. I. Safferman., " Solvent Washing of PCP Contaminated Soils with Anaerobic Treatment of Wash Fluids", Environmental Research, Vol. 66,pp. 692-697.
Lee, J. K., Park, D., Kim, B. U., Dong, J. I. and Lee, S., " Remediation of Petroleum-Contaminated Soils by Fluidized Thermal Desorption", Waste Management, 18, pp. 503-507, 1999.
Lighty, J. S., Silcox, G. D., Pershing, D. W., Cundy, V. A. and Linz, D. G., " Fundamental Experiments on Thermal Desorption of Contaminants from soil", Environmental Progress, 8, pp. 57-61, 1989.
Lighty, J. S., Silcox, G. D., Pershing, D. W., V. A. and Linz, D. G., " Fundamentals for the Thermal Remediation of Contaminated Soils. Particle and Bed Desorption Models, Environmental Science & Technology, 24, pp: 750-757, 1990.
Lin, T. F., Michael, D. V. L. and William, W. N., " Gas-phase Transport and Sorption of Benzene in Soil", Environmental Science & Technology, 30, pp. 2178-2186, 1996.
McBride, M. B., Environmental Chemistry of Soils, Oxford University Press, New York, 1994.
Miller, C. E., Turk, L. M. and Foth, H. D., Fundamental of Soil Science, John Wiley and Sons, New York, 1972.
Nelson, D. W. and Sommers L. E., " Total Carbon, Organic Carbon and Organic Matter", in Methods of Soil Analysis Ⅱ, 2nd ed., ASA and SSSA, Madison, WI539, 1982.
Nielson, R. K. and Cosmos, M. G., "Low Temperature Thermal Treatment (LT3) of Volatile Organic Compounds From Soil: A Technology Demonstrated.", Environmental Progress, 8, pp.139-142,1989.
Pavlostathls, S. G. and Mathavan, G. N., " Desorption Kinetics of Selected Volatile Organic Compounds from Field Contaminated Soil", Environmental Science & Technology, 26, pp. 532-538, 1992.
Peters, R. W. and Shem, L., "Adsorption/Desorption Characteristics of Lead on Various Types of Soil", Environmental Progress, 11, pp.234-240, 1992.
Risoul, V., Pichon, C., Trouve, G., Paters, W. A., Patrick, G. and Prado, G., "Thermogravimetric Study of Thermal Decontamination of Soils Polluted by Hexachlorobenzene, 4-Chlorobiphenyl, Naphthalene, or N-decane", Journal of Hazardous Materials, 64, pp. 295-311, 1999.
Rutherford, D. W. and Chiou, C. T., " Effect of Water Saturation in Soil Organic Matter on The Partition of Organic Compounds", Environmental Science & Technology, 26, pp. 964-970, 1992a.
Rutherford, D. W., Chiou, C. T. and Kile, D. E., " Influence of Soil Organic Matter Composition on The Partition of Organic Compounds", Environmental Science & Technology, 26, pp. 336-340, 1992b.
Ruthven, D. M., Principles of Adsorption and Adsorption Processes, John Wiley and Sons, New York, 1984.
Sanchez-Camazano, M., Sanchez-Martin, M. J., Poveda, E. and Iglesians-Jimenez, E., " Study of The Effect of Exogenous Organic Matter on The Mobility of Pesticides in Soils Using Soil Thin-Layer Chromatography", Journal of Chromatography A, 754, pp. 279-284, 1996.
Silcox, G. D., Larsen, F. S., Owens, W. D. and Choroszy-Marshall, M., " Kinetics of Hydrocarbon and Pesticide Removal from Clay Soils During Thermal Treatment in a Pilot-scale Rotary Kiln", Waste Management, 15, pp. 339-349, 1995.
Spencer, M. S., Schmeltzer, J. S. and Kreamer, D. K., "Sorption of Benzene and Trichloroethylene (TCE) on a Soil: Effects of Moisture and Organic Matter", Chemosphere, 33, pp: 961-980, 1996
Stevenson, F. J., Humus Chemistry, John Wiley and Sons, New York, 1982
Stolpe, N. B., McCallister, D. L., Shea, P. J., Lewis, D. T. and Dam, R., " Mobility of Aniline, Benzoic Acid, and Toluene in Four Soils and Correlation with Soil Properties", Environmental Pollution, 81, pp. 287-295, 1993.
Troxler, W. L, Goh, S. K. and Dicks, W. R., " Treatment of Pesticide-Contaminated Soils with Thermal Desorption Technologies", Journal of Air & Waste Management Association, 43, pp. 1610-1619, 1994a.
Troxler, W. L., Cudahy, J. J., Zink, R. P., Yezzi jr., J. J. and Rosenthal, S. I., " Treatment of Nonhazardous Petroleum-contaminated Soils by Thermal Desorption Technologies", Journal of Air & Waste Management Association, 43, pp. 1512-1525, 1994.
U. S. EPA, Engineering Bulletin Separation/Concentration Technology Alternatives for the Remediation of Pesticide-Contaminated Soil, EPA/540/S-97/503, May 1997b.
U. S. EPA, Low Temperature Thermal Treatment(LT3) Technology, Roy F. Weston, Inc:Applications Analysis Report., EPA 540-AR-92-019, 1993.
U. S. EPA, Technology Innovation Office: A Citizen''s Guide to Thermal Desorption, EPA 542-F-96-005 April 1996.
Uzgiris, E. E., Edelstein, W. A., Philipp, H. R. and Iben I. E. T., " Complex Thermal Desorption of PCBs from Soil.", Chemosphere, 30, pp. 377-387, 1995.
Weber, W. J. and Digiano F. A., Process Dynamics in Enviromental Systems., Wiley-Interscience, 1996.
You, S. J., Yin, Y. and Allen, H. E., "Partitioning of Organic Matter In Soils: Effects of pH and Water/Soil Ratio", The Science of the Total Environment, 227, pp: 155-160, 1999.
土壤檢測方法, 行政院環境保護屬環境檢測所, 1997.
王一雄、陳尊賢與李達源，土壤污染學，國立空中大學，台北，1995.
古晏菁，利用熱脫附整合人工合成的油污染土壤，中山大學環境工程系碩士論文，1995.
李森吉，以紅外線熱脫附系統復育受無鉛汽油污染土壤之研究，屏東科技大學，1998.
車明道，土壤復育技術介紹及有效性評估，能源、資源與環境，第六期，第41-46頁，1993.
林瑞崇，氟氯碳化物取代品的吸附與脫附之研究，元智大學化學工程系碩士論文，中壢，1997.
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.
袁菁、高志明、王志哲、劉力群、陳威錦，受BTEX污染壤質砂土之土壤管柱清洗復育研究，第十四屆廢棄物處理研討會，1999.
張添晉，環境工程概論，中華民國環境工程學會，台北，1994.
郭慎賢，以紅外線熱脫附系統復育受BTEX污染土壤，屏東科技大學，1997.
陳武清，酸洗土壤中重金屬之研究，元智大學化學工程系碩士論文，中壢，1999.
陳思曾，受芳香族化合物污染之土壤採現地生物復育影響因子之研究，中興大學環境工程研究所，1995.
黃正宇，大孔徑樹脂吸附水溶液中苯、甲苯、乙苯、二甲苯，元智大學化學工程系碩士論文，中壢，1998.
葉和明，單元操作，三民書局，台北，1991.
葉國樑，原油污染土壤去除方式之研究，中央大學土木工程研究所博士論文，中壢，1999.
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，元智大學化學工程系碩士論文，中壢，1998.