臺灣博碩士論文加值系統

本研究是利用萃取法去除廢水中重金屬的污染，其中包括用乳液萃取廢水中的六價鉻，用液液萃取法去除鋅及鎘。探討萃取過程及回收再利用的最佳條件。
液膜分離法是以批式實驗進行各項變因的探討，實驗結果以廢水中六價鉻的去除率為判斷依據。探討的變因包括萃取時間、pH值、製乳轉速、萃取時的擋板及攪拌速度、界面活性劑及載劑的濃度、內水相NaOH的濃度、乳液用量及液膜中油相與內水相的比，另外還有溫度的影響也一併討論。
將乳液分離法以共流多級程序操作，以吸附理論Langmuir及Freundlich等溫式描述乳液萃取的等溫平衡關係曲線，利用此等溫曲線在乳液總量一定的情況下比較一級操作及二極操作的影響。
液液萃取部份是利用D2EHPA萃取含鋅廢水，用McCabe-Thiele圖解法求理論級數，並實際求得中間濃度，印證逆向多級操作的可行性。另一部份是以HEHEHP萃取淋洗土壤後含鎘的酸洗液，實驗探討將酸洗液中重金屬去除的最佳條件，以更經濟的方式處理土壤污染。

The objectives of this study are to utilize extraction method for removal of
heavy metals from wastewater. Water/oil/water (W/O/W) emulsion liquid
membrane (ELM) and Liquid-liquid-extraction methods were, respectively,
employed for extracting Cr6+ and zinc and cadmium ions from aqueous
solution.
Batch extractions by liquid membrane were conducted to investigate the
effects of all operating variables on the Cr6+ removal efficiency so as to enable
considered included extraction time, pH, impeller speed of emulsion
preparation, baffles and impeller speed during extraction, surfactant and carrier
concentrations, sodium hydroxide concentration, temperature and the amount
of emulsion relative to the amount of wastewater.
Multistage operation of liquid membrane extraction was performed with an
aim of improving the overall Cr6+ extraction efficiency. Using the Langmuir
and Freundlish isotherm, the Cr6+ removal for the two-stage extraction was
experimentally and theoretically invertigated. The test results indicated that the
two-stage extraction is a more efficient process that the single-stage operation
in terms saving of the amount of extraction emulsion for the same extraction
duty.
D2EHPA (Di-(2-ethyl-hexyl) phosphoric acid) was observed to be a good
extraction agent for zinc removal from wastewater in the liquid-liquid
extraction process. Another extraction agent, HEHEHP (2-ethyl-hexyl
phosphonic acid mono-2-ethyl-hexyl ester), was seen to be good one for
extracting cadmium from wastewater. The McCabe-Thiele method was
employed to determine the number of ideal stage of these liquid-liquid
extraction processes. Both experimental and theoretical investigations were
conducted to compare the efficiency of countercurrent multistage extraction in
comparison with the single-stage operation. Finally, the optimum operating
conditions were determined for effective heavy metal removal removal by the extraction
processes.

第一章 緒論
1.1 前言………………………………………………………………. 1
1.2 液膜方法簡介……………………………………………………. 1
1.2.1 液膜的種類和結構…………………………………….. 1
1.2.2 液膜分離之機構與應用……………………………….. 6
1.2.3 液膜分離操作…………………………………………..14
1.2.4 液膜體系的組成………………………………………. 14
1.3 研究動機與內容………………………………………………… 26
1.4 鉻、鋅及鎘的探討……………………………………………… 31
第二章 乳化液膜分離方法之理論………………………. 41
2.1 反應系統與化學平衡…………………………………………… 41
2.2 質傳數學模式…………………………………………………… 41
2.3 共流多級程序…………………………………………………… 44
2.4 逆向多級萃取…………………………………………………… 46
2.4.1逆向多級萃取原理……………………………………… 46
2.4.2單批次萃取……………………………………………… 50
2.4.3逆向二級操作…………………………………………… 50
2.4.4最小萃取劑使用量……………………………………… 51
第三章 實 驗 部 份……………………………………… 53
3.1儀器與藥品………………………………………………………… 53
3.2實驗裝置及步驟…………………………………………………… 55
3.2.1 實驗裝置………………………………………………… 55
3.2.2乳化液膜萃取……………………………………………. 57
3.2.3液液萃取…………………………………………………. 57
第四章 批次液膜與萃取實驗結果………………………… 58
4.1 各種變因對液膜萃取的影響……………………………….…… 58
4.1.1萃取時間…………………………………………….……. 58
4.1.2 pH值……………………………………………………… 58
4.1.3擋板的影響…………………………………………….…. 58
4.1.4 製乳轉速……………………………………………….… 61
4.1.5 攪拌速度……………………………………………….… 61
4.1.6 界面活性劑濃度……………………………………….… 65
4.1.7 NaOH濃度…………………………………………….…. 65
4.1.8 乳液用量……………………………………………….… 70
4.1.9 乳液內溶液含量……………………………………….… 70
4.1.10 載劑用量……………………………………………….. 70
4.1.11 溫度的影響…………………………………………… 70
4.2 破乳與回收…………………………………………………….… 78
4.2.1高壓靜電破乳方法簡介與解離機構………………….… 78
4.2.2實驗裝置………………………………………………….. 81
4.2.3破乳結果………………………………………………….. 81
第五章 共流液膜萃取法………..………………………….. 84
5.1 共流液膜萃取法簡介……….………….……………………….... 84
5.2 實驗方法…………………………..……………………………… 84
5.3 結果與討論……………………………………………………….. 86
第六章 以液液萃取法萃取重金屬………………..…….... 102
6.1 以D2EHPA萃取鋅…………………………………………….…102
6.1.1 逆向多級萃取………………………………………….…102
6.1.2 反萃取………………………………………………….…104
6.2 以HEHEHP萃取鎘……………………………………….….105
6.2.1 各種變因對萃取的影響……………………………..106
6.2.2 反萃取………………………………………………..110
第七章 結論與建議………………………..………………..…...116
7.1 結論…………………………………………………..116
7.2 建議…………………………………………………..117
參考文獻………………………………………………………….….118

Amanatidou, E., Stefanut, M. N. and Grozav, A. "A Method of Cobalt Ion Concentration from Dilute Aqueous-Solution," Separation Science and Technology, 31, 655-664 (1996)
Baillod, C. R., Faith, B. M. and Masi, O. "Fatenof Specific Pollutants during Wet Oxidation and Ozonation," Evironmental Progress, 1(3), 217(1982)
Bailes, P. J. and Larkai, S. K. L. "An Experimental Investigation into the use of High Voltage D.C. Fields for Liquid Phase Separation," Transactions of the Institute of Chemical Engineers, 59, 229(1981)
Bailes, P. J. and Stitt, E. H. "Column Liquid Contacting with Vigorous Agitation Balanced by Electrostatic Coalescence," Chemical Engineering Research and Design, 65, 514(1987)
Bock, J. and Vallnt, P. L. Jr. "Uranium Extraction from Wet Process Phosphoric Acid. A Liquid Membrane Approach," Industrial and Engineering Chemistry Fundamentals, 21, 417 (1982)
Biehl, M. P., Izatt, R. Ming., Lamb, J. D. and Christensen, J. J. "Use of a Macrocyclic Crown Ether in an Emulsion (Liquid Surfactant) Membrane to Effect Rapid Separation of Pb2+ from Vation Mixtures," Separation Science and Technology, 17, 289 (1982)
Beltrame, P. L., and Carniti, P. "Inhibiting Action of Chlorophenol on Biodegradation of Phenol and its Correlation with Structural Properties of Inhibitors," Biotechnology and Bioengineering, 31, 821(1988)
Casamatta, G., Chavarie, C. and Angelino, H. "Hydrocarbon Separation Through a Liquid Water Membrane: Modeling of Permeation in an Emulsion Drop," AIChE Journal, 24, 945 (1978)
Cahn, R. P. and Li, N. N. "Separation of Phenol from Waste Water by the Liquid Membrane Technique," Separation Science and Technology, 9, 505 (1974)
Chakraborty, R. and Datta, S. "Determination of Membrane Thickness for Emulsion Liquid Membrane - A New Approach," Journal of Membrane Science, 115, 129-132 (1996)
Chan, C. C. and Yang, J. F. "Separation and Concentration of Phenylalanine by Emulsion Liquid Membrane in CSTR Extraction Process," Separation Science and Technology, 30, 3001-3024 (1995)
Datta, S., Mukhopadhyay, A. and Sanyal, S. K. "Facilitated Transport through Liquid Surfactant Membrane with Continuous Phase Resistance: Role of Drop-Size Distribution," Separation Science and Technology, 28, 1327 (1993)
Devlin, H. R. and Harrls, I. J. "Mechanism of the Oxidation of Aqueous Phenol with dissolved Oxygen," Industrial and Engineering Chemistry Fundamentals, 23, 387(1984)
Eroglu, I., Kalpakei, R. and Gunduz, G. "Extraction of Strontium Ions with Emulsion Liquid Membrane Technique," Journal of Membrane Science, 80, 319-325 (1993)
Frankenfeld, J. W., Cahn, R. P. and Li, N. N. "Extraction of Copper by Liquid Membranes," Separation Science and Technology, 16, 385 (1981)
Garti, N. and Kovas, A. "Facilitated Emulsion Liquid Membrane Separation of Complex Hydrocarbon Mixtures," Journal of Membrane Science, 56, 239 (1991)
Goswami, A. N., Sharma, A. and Sharma, S. K. "A Reappraisal of Modeling in a Liquid Surfactant Membrance Waste-water Cleanup Process," Journal of Membrane Science, 70, 283 (1992)
Hano, T., Matsumoto, M., Kawazu, T. and Ohtake, T. "Separation of Di- and Tripeptides with Solvent Extraction and an Emulsion Liquid Membrane," Journal of Chemical Technology and Biotechnology, 62, 60 (1995)
Hayworth, H. C., Ho, W. S., Burns, W. A. Jr. and Li, N. N. "Extraction of Uranium from Wet Process Phosphoric Acid by Liquid Membranes," Separation Science and Technology, 18, 493 (1983)
Hatton, T. A. and Lightfoot, E. N "An Internal Recycle Mixer for Solvent Extraction. Mass Transfer Characterization with Liquid Membranes," Industrial and Engineering Chemistry Fundamentals, 22, 27 (1983)
Hirai, T., Kobayashi, J. and Komasawa, I. "Preparation of Composite Sr-Pb Oxalate Fine Particles Using Emulsion Liquid Membrane System," Journal of Chemical Engineering of Japan, 31, 787-794 (1998)
Hirai, T., Okamoko, N. and Komasawa, I. "Preparation of Spherical Oxalate Particles of Rare-Earths in Emulsion Liquid Membrane System," AIChE Journal, 44, 197-206 (1998)
Hu, S. B. and Wiencek, J. M. "Emulsion-Liquid-Membrane Extraction of Copper Using a Hollow-Fiber Contactor," AIChE Journal, 44, 570-581 (1998)
Ho, W. S., Hatton, T. A. Lightfood, E. N. and Li, N. N. "Batch Extraction with Liquid Surfactant Membranes: A Diffusion Controlled Model," AIChE Journal, 28, 662 (1982)
Kakoi, T., Goto, M., Natsukawa, S., Ikemizu, K., Makashio, F., Matsumoto, M., and Hano, T. "Recovery of Phenols Using Liquid Surfactant Membranes Prepared with Newly Synthesized Surfactants," Separation Science and Technology, 31, 107 (1996)
Kim, K. S., Choi, S. J. and Ihm, S. K. "Simulation of Phenol Removal from Wastewater by Liquid Membrane Emulsion," Industrial and Engineering Chemistry Fundamentals 22, 167 (1983)
Kondo, K. and Matsumoto, M. "Solvent-Extraction of Europium with Diisostearylphosphoric Acid and Its Application to an Emulsion Liquid Membrane Technique," Separation Science and Technology, 31, 557-567 (1996)
Lee, S. C., Ahn, B. S. and Lee, W. K. "Mathematical-Modeling of Silver Extraction by an Emulsion Liquid Membrane Process," Journal of Membrane Science, 114, 171-185 (1996)
Lee, S. C., Lee, K. H., Hyun, G. H. and Lee, W. K. "Continuous Extraction of Penicillin-G by an Emulsion Liquid Membrane in a Countercurrent Extraction Column," Journal of Membrane Science, 124, 43-51 (1997)
Li, N. N. "Separation of Hydrocarbons by Liquid Membrane Permeation," Industrial and Engineering Chemistry Process Development and Process Design 10, 215 (1971)
Li, Q. M., Liu, Q., Zhang, Q. F., Wei, X. J. and Guo, J. Z. "Separation Study of Cadmium Through an Mobile Liquid Membrane Using Triisooctlamine as Mobile Carrier," Talanta, 46, 927-932 (1998)
Li, L. Q., Wang, C. and Li, Y. D. "Separation of Cobalt and Nickel by Emulsion Liquid Membrane with the Use of EDTA as Masking Reagent," Journal of Membrane Science, 135, 173 (1997)
Li, W. X. and Shi, Y. J. "Water-Permeation Swelling of Emulsion Liquid Membrane," Separation Science and Technology, 28, 241-254 (1993)
Lin, C. C. and Long, R. L. "Removal of Nitric-Acid by Emulsion Liquid Membrane Experimental Results and Model Prediction," Journal of Membrane Science, 134, 33-45 (1997)
Liu, X. R. and Zhang, X. J. "Simplified Model for Extraction of Rare-Earth Ions Using Emulsion Liquid Membrane," Journal of Membrane Science, 128, 223 (1997)
Ma, X. S. and Shi, Y.J. "Study of Operating Condition Affecting Mass Transfer Rate in Liquid Surfactant Membrane Process," Separation Science and Technology 22, 819 (1987)
Ma, G., Jiang Y., and Kun S. C.,"A General Mass Transfer Model for Liquid Surfactant Membranes," Chemical Engineering Science, 52, 433 (1997)
Nakano, K., Kato, S., Noritomi, H. and Nagahama, K. "Extraction of Polyunsaturated Fatty-acid Ethyl-Esters from Sardine Oil Using Ag+-Containing O/W/O Emulsion Liquid Membrane," Journal of Membrane Science, 110, 219-227 (1996)
Nakano, K., Kato, S., Noritomi, H. and Nagahama, K. "Extraction of Eicosapentaenoic Ethyl-Ester from a Model Media Using Ag(I)-Containing O/W/O-Type Emulsion Liquid Membranes," Journal of Membrane Science, 136, 127-139 (1997)
Nakatsuji, Y., Inoue, M., Matsumoto, M., Masuyama, A. and Kida, T. "Selective Transport of Lithium Ion Using Noncyclic Proton-Ionizable Ionophores Through Bulk and Emulsion Liquid Membranes," Journal of Membrane Science, 140, 165-172 (1995)
Nii, S., Tanaka, K. and Takeuchi, H. "Application of Ferromagnetic Particles to Emulsion Liquid Membranes," Separation Science and Technology, 60, 3253-3263 (1995)
Ohki, A., Matsuno, S., Takeada, M. and Ueno, K. "Bathocuproine-Mediated Copper Transport through Liquid Membrane by Driven Redox potential ," Separation Science and Technology, 17, 1273 (1982)
People R. F., Krishana. P., and Simonsen, R. N., "Nobiological Treatment of Refinery Wastewater," Journal of Water Pollution Control Federation, 44, 2120 (1972)
Pruden, B. B. and Le, H., "Wet Air Oxidation of Soluble Component In Waste Water," Canadian Journal of Chemical Engineering, 54, 319 (1976)
Pickering, P. J. and Chaudhuri, J. B. "Enantioselective Extraction of (D)-Phenylalanine from Racemic (D/L)-Phenylalanine Using Chiral Emulsion Liquid Membranes," Journal of Membrane Science, 127, 115 (1997)
Shen, J. Q., Yin, W. P., Zhao, Y. X. and Yu, L. J. "Extraction of Alanine Using Emulsion Liquid Membranes Featuring a Cationic Carrier," Journal of Membrane Science,120, 45-53 (1996)
Shinnar, R., "On the Behavior of Liquid Dipersions in Mixing Vessels," Journal of Fluid Mechanics, 10, 259(1960)
Strzelbicki, J. and Charewicz, W. "Separation of Cobalt by Liquid Surfactant Membranes," Separation Science and Technology, 13, 141 (1978)
Teramoto, M. and Matsuyama, H. "Effect of Facilitated Diffusion in internal Aqueous Droplets on Effective diffusivity and Extraction Rate if Phenol in Emulsion Liquid Membranes," Journal of Chemical Engineering of Japan, 19, 469 (1986)
Teramoto, M., Sakai, T., Yanagawa, K., Ohsuga, M and Miyake, Y. "Modeling of the Permeation of Copper through Liquid Surfactant Membranes," Separation Science and Technology, 18, 735 (1988)
Teramoto, M., Takihana, H., Shibutani, M., Yuasa, T. and Hara, N. "Extraction of Phenol and Cresol by Liquid Surfactant Membrane," Separation Science and Technology, 18, 397 (1983)
Teramoto, M., Matsuyama, H. and Izumo, O. "Effective Diffusivity in W/O Emulsion," Journal of Membrane Science, 68, 169 (1992)
Walpole, R. E. and Myers, H. R. "Probability and Statistics for Engineers and Scientists", Macmillan Publishing Company, New York (1993)
Wang, K. C., Huang, C. R. and Shiau, C. Y. "Mathematical Modeling of Phenol Removal with Dispersed Liquid Membrane," Journal of the Chinese Institute of Chemical Engineers, 21, 115 (1990)
Wan, Y. H., Wang, X. D. and Zhang, X. J. "Treatment of High-Concentration Phenolic Waste-Water by Liquid Membrane with N-503 as Mobile Carrier," Journal of Membrane Science, 135, 263-270 (1997)
Wang, X. D.,Zhu, B., Wan, Y. H. and Zhang, X. J. "A New Technique for Quick Production of Ammonium Paratungstate (Apt) Crystals by a Liquid Membrane," Journal of Membrane Science, 105, 55 (1995)
Wang, S. S., Lee, C. J. and Chan, C. C. "Demulsification of Water-in-Oil Emulsion by Use of a High-Voltage AC Field," Separation Science and Technology, 29, 157-170 (1995)
Yamaguchi, M., Kobayashi, A., Ohbori, K. and Katayama, T. "Continuous Separation of an Emulsion of Water in Oil by Applying a DC Electric Field," International Chemical Engineering, 27, 506(1987)
Yan, N. X., Huang, S. A., and Shi, Y. J. "Removal of Acetic Acid from Wastewater with Liquid Surfactant Membranes: An External Boundary Layer and Membrane Diffusion Controlled Model," Separation Science and Technology, 22, 801 (1987)
Yan, Z., Li, S., Yu, Y. and Zheng, X. "An Investigation into the Breaking-down of Water-in-oil Type Emulsions by Means of Pulsed Voltage," Desalination, 62, 323 (1987)
Yan, N., Shi Y. and Su, Y. F. "A Mass Transfer Model for Type ⅠFacilitated Trandport in Liquid Membranes," Chemical Engineering Science, 47, 4365 (1992)
Treybal, R. E., Mass-Transfer Operations, McGraw-Hill Book Company, New York (1980)
Winston Ho, W. S. and Sirkar, K. K., Membrane Handbook, Van Nostrand Reinhold, New York (1992)