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研究生:譚誠明
研究生(外文):Chen-Ming Tan
論文名稱:以冷媒R134a萃取金屬螯合物
論文名稱(外文):Metal Extraction in Refrigerant R134a
指導教授:余艇
指導教授(外文):Tiing Yu
學位類別:碩士
校院名稱:國立交通大學
系所名稱:應用化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:中文
中文關鍵詞:冷媒萃取金屬螯合物介面活性劑
相關次數:
  • 被引用被引用:2
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  • 下載下載:32
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水溶性的金屬離子在添加適當的有機螯合劑作用後,可用有機溶劑從水中萃取出,然而萃取過後的大量有機溶劑,變成新的問題待處理。超臨界流體可以取代傳統有機溶劑進行萃取,並且在收集的過程一經洩壓便可氣化與萃取物分離,達到濃縮的效果,大幅地減少樣品處理體積。本實驗嘗試以液態冷媒R134a(1,1,1,2-tetrafluoroethane)取代受到廣泛應用的超臨界二氧化碳,將操作壓力條件降低了100個大氣壓以上,同時保有足夠的溶解能力。超臨界二氧化碳對極性物質的溶解力不高,必須使用氟化的樣品才有顯著的溶解力,或是加入修飾劑以提升萃取物的溶解度,這個問題在使用R134a時獲得改善。近來有研究指出添加介面活性劑能夠增進萃取效益,甚至可以由介面活性劑與水形成的微乳液直接萃取金屬離子,而不必添加螯合劑,在本研究中亦證實可行,這對於萃取複雜基質中的金屬離子具有重要的意義。由吸收光譜測得的收集液濃度,經過計算完成定量工作,得到的資訊包括溶解度、分配係數,以及樣品中的萃取回收比例。
Hydrophilic metal ions can be extracted from aqua by organic solvent with proper organic chelating agent. Nevertheless, a new problem comes from the great volume of organic solvent containing metal ions. Supercritical fluids can replace conventional organic solvents in extraction process. When degassing at collecting, such fluids separate from extracts suddenly and concentrate them, which can reduce the waste volume. We try to use R134a (1,1,1,2-tetrafluoroethane) instead of supercritical carbon dioxide, a widely utilized solvent, and recognize that R134a has appreciable solvency while the working pressure is 100 atm lowered. Polar compounds showed low solubility in SF-CO2, unless fluorinated compounds or modifier are used, but this drawback is overcome in using R134a. Recent researches show that adding surfactant during extraction improves efficiency and even metal ions can be extracted through microemulsion without chelating agent, we also prove this idea in our experiment. This is momentous for metal ions extraction from a complicated matrix. Quantitative calculation is based on UV/Vis absorbance data; information herein includes solubility, partition coefficient and recovery of sample extraction.
目錄
中文摘要…………….…………………………………………………………………i
英文摘要…………………………………………………………………...………….ii
謝誌………………………………………………………………………………...…iii
目錄………………………………………………………………………….………..iv
表目錄………………………. ……………………………………………………….vi
圖目錄………………………………………………………………………………..vii
第一章 緒論………………………………………………………………………....1
第二章 研究背景……….. ………………………………………………………….4
2.1 螯合劑………………………. ……………………………………………..4
2.1.1 螯合劑簡介……………………. …………………………………..4
2.1.2 螯合劑分類………………………………………………………....4
2.1.3 螯合反應機制………….. ………………………………………….4
2.2 介面活性劑…………………….. ………………………………………….4
2.2.1 介面活性劑分類…………………….. ……………………………...5
2.2.2 介面活性劑作用……………….. …………………………………...5
2.2.3 反微胞萃取法……….. ……………………………………………...6
2.3 冷媒R134a…………………….. ………………………………………….6
2.3.1 冷媒介紹………….. ………………………………………………...6
2.3.2 冷媒R134a簡介………….. ………………………………………...7
2.3.3 R134a的物理性質………. ………………………………………...9
2.4 核廢料處理………………………………………………...………………9
2.4.1 核能原理…………………….. ……………………………………...9
2.4.2 核燃料簡介……………….. ……………………………………….11
2.4.3 核廢料處理 ………….. …………………………………………...12
2.4.4 Purex process簡介……….. ………………………………………12
2.4.5 超臨界流體結合Purex process………….. ………………………..13
第三章 實驗…………………….. ………………………………………………...15
3.1 試藥…………………….. ………………………………………………..15
3.1.1 金屬…………………….. ………………………………………….15
3.1.2 螯合劑…………………….. ……………………………………….15
3.1.3 介面活性劑…………………….. ………………………………….15
3.1.4 溶劑…………………….. ………………………………………….16
3.1.5 固態基質…………………….. …………………………………….16
3.2 裝置設備…………………….. …………………………………………..16
3.3 儀器…………………….. ………………………………………………..17
3.4 實驗步驟……………………………………………………………….....17
3.4.1 合成金屬螯合物…………………….. ………………………….…17
3.4.2 可溶性判斷…………………………………………..……………..17
3.4.3 測量螯合物溶解度……………………………………………..…..18
3.4.4 修飾劑與助溶劑……………………. ……………………………..18
3.4.4.1 修飾劑對溶解度效應之實驗…………………….. ……………..18
3.4.4.2 助溶劑對溶解度效應之實驗…………………………………….19
3.4.5 溶解度之計算………………….. ………………………………….19
3.4.6 從水樣品中萃取金屬-靜態萃取………. ………………………….19
3.4.7 從水樣品中萃取金屬-動態萃取……...………...………………….20
3.4.8 從固態基質萃取金屬螯合物…………………….. ……………….21
3.4.9 從植物內萃取金屬………………………………………………....21
3.4.10 酸性條件下的金屬萃取………………………. ………………....21
3.4.11 從硝酸溶液中進行鈾之萃取…...…. …………………………….22
3.4.12 測量稀土金屬錯合物之分配係數………………………………..22
第四章 結果討論…………………….. …………………………………………...23
4.1 螯合結構鑑定……………………………………………………………..23
4.1.1 質譜………………………………………………………………....23
4.1.2 核磁共振光譜……………………. ………………………………..23
4.2 可溶性判斷…………………………………………………………...…..24
4.3 影響溶解度之因素…………………………………………………….....25
4.3.1 溫度…………………………………………………………..……..25
4.3.2 壓力……………………………………………………………..…..25
4.4 修飾劑……………………. ……………………………………………...26
4.5 助溶劑……………………………………………………...……………..26
4.6 金屬螯合物在SF-CO2和R134a中溶解度之比較………………………27
4.7 從水樣品中萃取金屬-靜態萃取……………………………………..…..27
4.8 從水樣品中萃取金屬-動態萃取……………………………………...….27
4.9 固態基質萃取………………………………………………………….....28
4.10 植物體內金屬之萃取………………………………………………….....28
4.11 從硝酸溶液中進行鈾之萃取………………………………………….....29
第五章 結論………………………………………………………………………..30
參考文獻……………………………………………………………………………..31
1. A. E. Martell, M. Calvin, ”Chemistry of the Metal Chelate Compounds”, Prentice-Hall Inc., Englewood Cliffs, N. J., (1952), 2-50
2. Sidgwick, ” The Electron Theory of Valency”, Oxford University Press, New York, (1927), 116
3. Feigl, ”Chemistry of Specific, Selective and Sensitive Reactions”, Academic Press, Inc., New York, (1949), 25
4. F. P. Dwyer, D. P. Mellor, ”Chelating Agents and Metal Chelates”, Academic Press, Inc., New York, (1964), 7
5. F. P. Dwyer, D. P. Mellor, ”Chelating Agents and Metal Chelates”, Academic Press, Inc., New York, (1964), 21-22
6. V. Lewis, ”Valence and the Structure of Atoms and Molecules”, The Chemical Catalog Company Inc., New York, (1923)
7. R. F. Heck, ”Organotransition Metal Chemistry”, Academic Press, Inc., (1974), 1
8. A. E. Martell, M. Calvin, ”Chemistry of the metal chelate compounds”, Prentice-Hall Inc., New York, (1952), 512-513
9. 台北市政府環境保護局,’’台北市土壤污染優先地區重金屬含量調查研究’’,(民國八十三年六月),14-15
10. 行政院勞工委員會安全衛生研究所,’’重金屬對勞工免疫功能影響之初步調查’’,(民國八十五年),3-38
11. O. Tomioka, Y. Enokida, L.Yamamoto, T. Takahashi, ”Cleaning of Materials Contaminated with Metal Oxides through Supercritical Fluid Extraction with CO2 Containing TBP”, Prog. Nucl. Energy, 37 (2000), 417-422
12. C. Kersch, M. van der Kraan, G. F. Woerlee, G. J. Witkamp, ”Municipal Waste Incinerator Fly Ash: Supercritical Fluid Extraction of Metals”, J. Chem. Technol. Biotechnol., 77 (2002), 256-259
13. C. M. Wai, S. Wang, ”Separation of metal chelates and organometallic compounds by SFC and SFE/GC”, J. Biochem. Biophys. Methods, 43 (2000), 273-293
14. S. Wang, C. M. Wai, ”Separation of metal chelates and organometallic compounds by supercritical fluid chromatography”, Chinese J. Anal. Chem., 29 (2001), 725-730
15. K. E. Laintz, J. Yu, C. M. Wai, ”Separation of Metal Ions with Sodium Bis(trifluoroethyl)dithiocarbamate Chelation and Supercritical Fluid Chromatography”, Anal. Chem., 64 (1992), 311-315
16. H. Wu, Y. Lin, N. G. Smart, C. M. Wai, ”Separation of Lanthanidesβ-Diketones via Organophosphorus Adduct Formation by Supercritical Fluid Chromatography”, Anal. Chem., 68 (1996), 4072-4075
17. Y. Lin, C. M. Wai, ”Supercritical Fluid Extraction of Lanthanides with Fluorinated β-Diketones and Tributyl Phosphate”, Anal. Chem., 66 (1994), 1971-1975
18. J. Chrastil, ”Solubility of Solids and Liquids in Supercritical Gases”, J. Phys. Chem., 86 (1982), 3016-3021
19. K. E. Laintz, C. D. Hale, P. Stark, C. L. Rouquette, J. Wikinson, ”A Comparison of Liquid and Supercritical Carbon Dioxides as an Extraction Solvent for Plating Bath Treatment”, Anal. Chem., 70 (1998), 400-404
20. Y. Lin, R. D. Brauer, K. E. Laintz, C. M. Wai, ”Supercritical Fluid Extraction of Lanthanides and Actinides from Solid Materials with a Fluorinated β-Diketones”, Anal. Chem., 65 (1993), 2549-2551
21. C. M. Wai, Y. Lin, R. D. Brauer, S. Wang, W. F. Beckert, ”Supercritical Fluid Extraction of Organic and Inorganic Mercury from Solid Materials”, Talanta, 40 (1993), 1325-1330
22. E. J. Roggeman, A. M. Scurto, J. F. Brennecke, ”Spectroscopy, solubility, and modeling of cosolvent effects on metal chelate complexes in supercritical carbon dioxide solutions”, Ind. Eng. Chem. Res., 40 (2001), 980-989
23. C. M. Wai, S. Wang, Y. Liu, V. Lopez-Avila, W. F. Beckert, ”Evaluation of dithiocarbamates andβ-diketones as chelating agents in supercritical fluid extraction of Cd, Pb, and Hg from solid samples”, Talanta, 43 (1996), 2083-2091
24. J. Liu, W. Wang, G. Li, ”A new strategy for supercritical fluid extraction of copper ions”, Talanta, 53 (2001), 1149-1154
25. M. Z. Yates, D. L. Apodaca, M. L. Campbell, E. R. Birnbaum, T. M. McCleskey, ”Metal Extractions Using Water in Carbon Dioxide Microemulsions”, Chem. Eng. Commun., (2001), 25-26
26. M. L. Campbell, D. L. Apodaca, M. Z. Yates, T. M. McCleskey, E. R. Birnbaum, ”Metal Extraction from Heterogeneous Surfaces Using Carbon Dioxide Microemulsions”, Langmuir, 17 (2001), 5458-5463
27. Z. J. Cui, J. C. Liu, L. C. Gao, Y. Q. Wei, J. Z. Zhang, ”Study on a New Method of Extraction of Metal Ions from Solid Matrices by Supercritical Fluid”, Chin. Chem. Lett., 10 (1999), 525-528
28. Y. S. Tang, J. H. Saling, ”Radioactive waste management”, Hemisphere Publishing Corporation, New York, (1990), 102-106
29. D. D. Sood, S. K. Patil, ”Chemistry of Nuclear Fuel Reprocessing: Current Status”, J. Radioanal. Nucl. Chem., 203 (1996), 547-573
30. M. Z. Ozel, K. D. Bartle, A. A. Clifford, M. D. Burford, ”Extraction, solubility and stability of metal complexes using stainless steel supercritical fluid extraction system”, Anal. Chim. Acta., 417 (2000), 177-184
31. C. M. Wai, B. Waller, ”Dissolution of metal species in supercritical fluids - Principles and applications”, Ind. Eng. Chem. Res.,39 (2000), 4837-4841
32. J. R. Davis, ”Stainless Steels”, ASM International, Materials Park, Ohio, (1994), 152
33. A. J. Sedriks, ”Corrosion of stainless steels”, Wiley, New York, (1979), 226
34. S. Gronowitz, ”Thiophene and Its Derivatives”, Wiley, New York, (1985), 427-428
35. 坤詮工程塑膠有限公司,”常用工程塑膠特性表”
36. A. E. Martell, M. Calvin, ”Chemistry of the metal chelate compounds”, Prentice-Hall Inc., New York, (1952), 514-558
37. J. J. Eisch, R. B. King, ”Organometallic syntheses”, Academic Press, New York, 3 (1965), 1-19
38. J. A. Darr, M. Poliakoff, ”New Directions in Inorganic and Metal-organic Coordination Chemistry in Supercritical Fluids”, Chem. Rev., 99 (1999), 495-541
39. N. G. Smart, T. Carleson, T. Kast, A. A. Clifford, M. D. Burford, C. M. Wai, ”Solubility of chelating agents and metal-containing compounds in supercritical fluid carbon dioxide”, Talanta, 44 (1997), 137-150
40. M. Bourrel, R. S. Schechter, ”Microemulsions and Related Systems.” Marcel Dekker, INC., New York and Basel, (1988)
41. D. Myers, ”Surfactant Science and Technology.” VCH Publisher, Inc., (1988)
42. M. E. Leser, G. Wei, P. Lüthi, G. Haering, A. Hochkoeppler, E. Blochliger, P. L. Luisi, ”Application of Enzyme-Containing Reverse Micelles.” J. de Chimie. Physique., 84 (1987), 1113-1118
43. M. J. Pires, M. R. Aires-Barros, J. M. S. Cabral, ”Liquid-Liquid Extraction of Proteins with Reverse Micelles.” Biotechnol. Prog., 12 (1996), 290-301
44. T. G. Statt, ”Potential ozone-safe refrigerants for centrifugal chillers”, ASHARE J., (Sep., 1990), 46-51
45. H. O. Spauschus, ”Emerging HVAC & R issues: energy, environment and economics”, ASHARE J., (Feb., 1991), 23-27
46. J. R. Dean, B. Liu, R. Price, ”Extraction of Tanshinone IIA from Salvia miltiorrhiza bunge using supercritical fluid extraction and a new extraction technique, phytosol solvent extraction”, J. Chromatogr. A, 799 (1998), 343-348
47. Y-L. Tasi, T. Yu, ”Feasibility Study of Using Refrigerant 1,1,1,2-Tetrafluoroethane As the Mobile Phase in High-Speed Counter- Current Chromatography.” J. Chromatogr. A, 835 (1999), 237-242
48. J. A. Blackwell, R. W. Stringham, ”Characterization of 1,1,1,2-Tetrafluoroethane and Carbon Dioxide Binary Mobile Phases with Polymeric Columns Using Linear Solvation Energy Relationships”, Anal. Chem., 69 (1997), 4608-4614
49. M. Sorner, K. H. U. Storm, ”Estimation of equation of state parameters for 1,1,1,2-tetrafluoroethane in a modified Benedict-Webb-Rubin equation”, Can. J. Chem. Eng., 73 (1995), 854-861
50. A. P. Abbott, C. A. Eardley, ”Solvent Properties of Liquid and Supercritical 1,1,1,2-Tetrafluoroethane.” J. Phys. Chem. B, 102 (1998), 8574-8578
51. 美國杜邦公司,”Aerosol propellants-Dymel 134a 介紹資料”
52. Y. S. Tang, J. H. Saling, ”Radioactive waste management”, Hemisphere Publishing Corporation, New York, (1990), 95-99
53. ”環華百科全書”, 彭園出版社,9(民國七十三年七月),401-415
54. Y. S. Tang, J. H. Saling, ”Radioactive Waste Management”, Hemisphere Publishing Corporation, New York, (1990), 96-98
55. Y. Enokida, S. A. El-Fatah, C. M. Wai, ”Ultrasound-Enhanced Dissolution of UO2 in Supercritical CO2 Containing a CO2-Philic Complexant of Tri-n-butylphosphate and Nitric Acid”, Ind. Eng. Chem. Res., 41 (2002), 2282-2286
56. R. S. Addleman, M. J. Carrott, C. M. Wai, ”Determination of Solubilities of Uranium Complexes in Supercritical CO2 by On-Line Laser-Induces Fluorescence”, Anal. Chem., 72 (2000), 4015-4021
57. Y. Meguro, S. Iso, Z. Yoshida, ”Correlation between Extraction Equilibrium of Uranium(Ⅵ) and Density of CO2 Medium in a HNO3/Suoercritical CO2-Tributyl Phosphate System”, Anal. Chem., 70 (1998), 1262-1267
58. M. Wisniewski, A. Jakubiak, J. Szymanowski, ”Interfacial phenomena in solvent extraction of metals: Extraction of palladium(II)”, J. Radioanal. Nucl. Chem., 228 (1998), 109-111
59. J. A. Gawenis, J. F. Kauffman, S. S. Jurisson, ”Ion pairing as a strategy for extraction by modified supercritical carbon dioxide: Extraction of radioactive metal ions”, Anal. Chem., 73 (2001), 2022-2026
60. M. Baaden, R. Schurhammer, G. Wipff, ”Molecular Dynamics Study of the Uranyl Extraction by tri-n-Butylphosphate (TBP): Demixing of Water/"Oil"/TBP Solutions with a Comparison of Supercritical CO2 and Chloroform”, J. Phys. Chem. B, 106 (2002), 434-441
61. A. A. Al-Manaseer, D. M. Roy, ”Concrete and Grout in Nuclear and Hazardous Waste Disposal”, American Concrete Institute, Detroit, Mich., (1995), 44-46
62. M. Ashraf-Khorassani, M. T. Combs, L. T. Taylor, ”Solubility of metal chelates and their extraction from an aqueous environment via supercritical CO2”, Talanta, 44 (1997), 755-763
63. M. Ashraf-Khorassani, M. T. Combs, L. T. Taylor, ”Supercritical Fluid Extraction of Metal Ions and Metal Chelates from Different Environments”, J. Chromatogr. A, 774 (1997), 37-49
64. Y. Takeshita, Y. Sato, S. Nishi, ” Study of extraction of metals from CCA-treated wood with supercritical CO2 containing acetylacetone: Extraction of Cu by continuous addition of acetylacetone”, Ind. Eng. Chem. Res., 39 (2000), 4496-4499
65. A. Zhang, J. Hu, X. Zhang, F. Wang, ” Hydroxylamine derivative in Purex Process II. Study on the kinetics and mechanism of redox reaction between N,N-diethylhydroxylamine and vanadium(V)”, J. Radioanal. Nucl. Chem., 247, (2001), 525-530
66. A. E. Comyns, B. M. Gatehouse, E. Wait, ”The Chemistry of Uranyl Acetylacetone Complex”, J. Chem. Soc., (1958), 4655-4665
67. A. E. Martell, M. Calvin, ”Chemistry of the metal chelate compounds”, Prentice-Hall Inc., New York, (1952), 47-50
68. J. M. Murphy, C. Erkey, ”Thermodynamics of Extraction of Copper(Ⅱ) from Aqueous Solutions by Chelation in Supercritical Carbon Dioxide”, Environ. Sci. Technol., 31 (1997), 1674-1679
69. O, Tomioka, Y. Enokida, I.Yamamoto, ”Selective Recovery of Neodymium from Oxides by Direct Extraction Method with Supercritical CO2 Containing TBP-HNO3 Complex”, Sep. Sci. Technol., 37 (2002), 1153-1162
70. A. Zhang, Y. Liu, ”Hydroxylamine derivative in Purex Process III. The kinetics of oxidation-reduction reaction between N,N-diethylhydroxylamine and neptunium(VI)”, J. Radioanal. Nucl. Chem., 245 (2000), 357-361
71. Y. Lin, H. Wu, C. M. Wai, N. G. Smart, ”Separation of divalent transition metal β-diketones and their adducts by supercritical fluid chromatography”, Talanta, 52 (2000), 695-701
72. W. Cross, Jr., A. Akgerman, C. Erkey, ”Determination of Metal-Chelate Complex Solubilities in Supercritical Carbon Dioxide”, Ind. Eng. Chem. Res., 35 (1996), 1765-1770
73. 李介仁,”測量介面活性劑於1,1,1,2-Tetrafluoroethane之溶解度”,國立交通大學,碩士論文,(民國八十九年六月)
74. C. M. Wai, S. Wang, J. J. Yu, ”Solubility Parameters and Solubilities of Metal Dithiocarbamates in Supercritical Carbon Dioxide”, Anal. Chem., 68 (1996), 3516-3519
75. S. Wang, C. M. Wai, ”Supercritical Fluid Extraction of Bioaccumulated Mercury from Aquatic Plants”, Environ. Sci. Technol., 30 (1996), 3111-3114
76. P.S. Dhami, R. Kannan, V. Gopalakrishnan, A. Ramanujam, N. Salvi, S.R. Udupa, ”Sorption of plutonium, americium and fission products from reprocessing effluents using Rhizopus arrhizus”, Biotechnol. Letters, 20 (1998), 869-872
77. K. L. Toews, R. M. Shroll, C. M. Wai, N. G. Smart, ”pH-Defining Equilibrium between Water and Supercritical CO2. Influence on SFE of Organics and Metal Chelates”, Anal. Chem., 67 (1995), 4040-4043
78. Ed. V. Renard, A. A. Chizhov, V. S. Vlasov, ”The Purex thermodynamics of plutonium(IV) and uranium(VI) macroconcentrations coextraction into tri-n butylphosphate: new data and new models”, J. Nucl. Mater., 223 (1995), 90-93
79. Y. Lin, N. G. Smart, C. M. Wai, ”Supercritical Fluid Extraction of Uranium and Thorium from Nitric Acid Solutions with Organophosphorus Reagents”, Environ. Sci. Technol., 29 (1995), 2706-2708
80. M. I. El-Dessouky, M. M. A. El-Aziz, E. H. El Mossalamy, H. F. Aly, ”Wet-oxidation of spent organic waste tributyl phosphate/diluents”, J. Radioanal. Nucl. Chem., 249 (2001), 643-647
81. A. S. Teja, C. A. Eckert, ”Commentary on Supercritical Fluids: Research and Applications”, Ind. Eng. Chem. Res., 39 (2000), 4442-4444
82. D. C. Grant, T. Lemke, G. Duepner, D. Wilkes, N. Powell, ”Measurement of inorganic contaminant extraction from fluid handling components by dynamic extraction”, J. Inst. Environ. Sci., 39 (1996), 29-37
83. 魏明通,”核化學”,五南圖書出版公司,(民國八十九年四月)
84. 劉東山,蔡昭明,”放射性廢料管理”,曉園出版社,(1993)
85. P. C. Simões, O. J. Catchpole, ”Fractionation of Lipid Mixtures by Subcritical
R134a in a Packed Column”, Ind. Eng. Chem. Res., 41 (2002), 267-276
86. O. J. Catchpole, K. Proells, ”Solubility of Squalene, Oleic Acid, Soya Oil, and
Deep Sea Shark Liver Oil in Subcritical R134a from 303 to 353 K”, Ind. Eng. Chem. Res., 40 (2001), 965-972
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