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研究生:陳怡伶
研究生(外文):Chen,I-Ling
論文名稱:以對稱型四級銨鹽為觸媒之三液相相轉移催化反應系統之相轉換特性
論文名稱(外文):Phase inversion characteristics of three-liquid-phase phase transfer catalytic systems using symmetric quaternary ammonium salts as the catalysts
指導教授:江建利
指導教授(外文):Chiang,Chien-Lih
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:1999
畢業學年度:87
語文別:中文
論文頁數:146
中文關鍵詞:對稱型四級銨鹽相轉換特性
外文關鍵詞:Symmetric Quaternary Ammonium SaltPhase Inversion Characteristics
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三液相相間轉移催化反應系統為化工界具有潛力的一個研究領域。第三液相的生成,可使得反應速率大幅增加。另一方面,第三液相也使得產物及觸媒的分離步驟簡化,因此觸媒可以重複被使用。在工業界的應用方面,這類含不均勻相系統的分散特性也是很重要的設計資料。本文以常用的對稱型四級銨鹽,包括親水性(溴化四丙基銨、溴化四丁基銨與溴化四戊基銨)和親油性(溴化四己基銨),來催化溴正丁烷與酚鈉的反應系統,在批次攪拌槽內,透過電導度法來探討三液相相間轉移催化反應系統的相轉換特性。
我們發現在只添加觸媒的系統中,無論是親水性或親油性的觸媒,系統的相轉換過渡區都會隨著觸媒濃度的增加而變寬。而親水性越強的觸媒,相轉換過渡區越小。在W/O轉換成O/W時,在系統中添加親油性觸媒,對系統的相轉換Hold-up(o)值影響不大。當添加親水性觸媒的系統出現第三液相時,不論是W/O轉換成O/W或是O/W轉換成W/O,系統的相轉換Hold-up(o)值會比沒有第三液相生成時為低。當添加親油性觸媒的系統生成第三液相時,在W/O轉換成O/W的部份,其相轉換Hold-up(o)值比純相系統為高。
在影響第三液相生成的因素方面,無論是親水性或是親油性觸媒,第三液相生成量皆隨著觸媒及酚鈉的濃度增加而增加。增加溴正丁烷的濃度會使親油性觸媒的第三液相生成量增加,而對親水性觸媒的第三液相生成量沒有影響。NaOH的存在對親水性觸媒生成第三液相與否有直接的關係,而對親油性觸媒則沒有直接的關係。綜合上述因素可知,親水性和親油性觸媒形成第三液相的機制不同。
一般而言,有第三液相生成的系統和添加NaOH的系統,它們的Tc值比其他系統為大。對大部份系統而言,O/W分散型態的Tc值比W/O分散型態為大。
The system with three-liquid phase transfer catalysis reaction is one of the research fields of great potential in the chemical engineering industries. The formation of the third liquid phase (TLP) can increase the reaction rate substantially. In another aspect, the TLP can simplify the steps of separation, thus the catalyst can be reused. For the applications in the industries, dispersion characteristics of this kind of heterogeneous system is very important in the equipment design. In this article, some common symmetric quaternary ammonium salts, including hydrophilic (tetrapropyl ammonium bromide, tetrabutyl ammonium bromide, tetrapentyl ammonium bromide) and hydrophobic catalysts (tetrahexyl ammonium bromide), are used as catalysts to catalyze the reaction between n-butyl bromide and sodium phenolate trihydrate which takes place in a batch agitation. Also we study the phase inversion characteristics of this kind of systems by the conductivity-measuring method.
We found that adding catalyst to the system, no matter the catalyst added is hydrophilic or hydrophobic, the ambivalent region of the system will become broader as the catalyst concentration increases. And the more hydrophilic the catalyst, the more narrow the ambivalent region. For W/O inverses to O/W, the addition of hydrophobic catalyst has no significant effect on the phase inversion hold-up(o) value of the system. The phase inversion hold-up(o) values of the systems contain hydrophilic catalysts become smaller if the TLP occurs, no matter the inversion is from W/O to O/W or from O/W to W/O. For W/O inverses to O/W, the phase inversion hold-up(o) values of the systems which contain hydrophobic catalysts and have the TLP formed are higher than those of the pure-pure system.
For the factors which affect the formation of the third liquid phase, no matter the catalyst added is hydrophilic or hydrophobic, the amount of the TLP formed increases with the increasing concentrations of catalyst and sodium phenolate trihydrate. The increase of the concentration of n-butyl bromide increases the amount of the TLP for the system contains hydrophobic catalysts but has no effect on the amount of the TLP for the system contains hydrophilic catalysts. The existence of NaOH is directly related to the formation of the TLP for the system contains hydrophilic catalysts, but has no direct relation to the formation of the TLP for the system contains hydrophobic catalysts. From the above reasons, we know that the mechanisms of the formation of the TLP for the system with hydrophilic and hydrophobic catalyst are different.
Generally speaking, the Tc values of the systems contain the TLP or NaOH are higher than those of the other systems. For the most systems, the Tc values of the O/W dispersion type are higher than those of the W/O dispersion type.
第一章 緒論
1.1 不均勻系的相轉換
1.2 文獻回顧
1.3 研究目的
1.4 論文架構
第二章 實驗部份
2.1 實驗裝置
2.2 實驗藥品
2.3 實驗步驟
2.4 數據處理
第三章 結果與討論
3.1 純水-純正己烷的系統
3.2 添加親水性觸媒的系統
3.2.1 添加溴化四丙基銨的系統
3.2.1.1 只添加觸媒的系統
3.2.1.2 添加觸媒和兩相反應物的系統
3.2.1.3 有第三液相生成的系統
3.2.2 添加溴化四丁基銨的系統
3.2.2.1 只添加觸媒的系統
3.2.2.2 添加觸媒和兩相反應物的系統
3.2.2.3 有第三液相生成的系統
3.2.3 添加溴化四戊基銨的系統
3.2.3.1 只添加觸媒的系統
3.2.3.2 添加觸媒和兩相反應物的系統
3.2.3.3 有第三液相生成的系統
3.2.4 親水性觸媒的比較
3.3 添加親油性觸媒的系統
3.3.1 添加溴化四己基銨的系統
3.3.1.1 只添加觸媒的系統
3.3.1.2 添加觸媒和兩相反應物的系統
3.1.1.3 有第三液相生成的系統
3.4 親水性與親油性觸媒的比較
第四章 結論
參考文獻
1. Arashmid, M. and Jeffreys, G. V.〝Analysis of the Phase Inversion Characteristics of Liquid-Liquid Dispersions,〞 AIChE Journal,26,No.1,51 (1980).
2. Becher, P., Emulsions : Theory and Practice,150(1965).
3. Brooks, B. W. and Richmond, H. N.〝Dynamics of Liquid-Liquid Phase Inversion Using Non-Ionic Surfactants,〞 Colloids and Surfaces,58,131(1991).
4. Brooks, B. W. and Richmond, H. N.〝Phase Inversion in Non-Ionic Surfactant -Oil-Water System-Ⅰ.The Effect of Transitional Inversion on Emulsion Drop Sizes,〞Chemical Engineering Science,49,No.7,1053(1994).
5. Chatzi, E. G. and Kiparissides, C.〝Steady-State Drop-Size Distributions in High Holdup Fraction Dispersion Systems,〞 AIChE Journal,41,No.7,1640 (1995).
6. Clarke, S. I. and Sawistowski, H.〝Phase Inversion of Stirred Liquid/Liquid Dispersions Under Mass Transfer Conditions,〞Trans IChemE,56,50(1978).
7. Coulaloglou, C. A. and Tavlarides, L. L.〝Drop Size Distribution and Coalescence Frequencies of Liquid-Liquid Dispersion in Flow Vessels,〞AIChE Journal,22,No.2,289(1976).
8. Efthimiadu, I. and Moore, I. P. T.〝Phase Inversion of Liquid-Liquid Dispersions Produced Between Parallel Shearing Plates,〞Chemical Engineering Science,49,No.9,1439(1994).
9. Gilchrist, A., Dyster, K. N., Moore, I. P. T., Nienow, A. W. and Carpenter, K. J.〝Delayed Phase Inversion in Stirred Liquid-Liquid Dispersions,〞Chemical Engineering Science,44,No.10,2381(1989).
10. Godfrey, J. C., Hanson, C., Slater, M. J. and Tharmalingam, S.〝Studies of Entrainment in Mixer Settlers,〞The American Institute of Chemical Engineers,74,No.173,127(1978).
11. Groeneweg, F., Agterof, W. G. M., Jaeger, P., Janssen, J. J. M., Wieringa, J. A, and Klahn, J. K.〝On the Mechanism of the Inversion of Emulsions,〞Trans IChemE,76,part A,55(1998).
12. Guilinger, T. R., Grislingas, A. K. and Erga, O.〝Phase Inversion Behavior of Water-Kerosene Dispersion,〞Ind. Eng. Chem. Res.,27,978(1988).
13. Hwu, D. H., Hwang, C., Shih, Y. P., Yeh, M. Y. and Chao, C. L.〝Kinetics of the Synthesis of Benzyl Ethers Using Tertiary Amines as Catalysts,〞Ind. Eng. Chem. Res.,31,177(1992).
14. Kato, S., Nakayama, E. and Kawasaki, J.〝Types of Dispersion in Agitated Liquid-Liquid Systems,〞The Canadian Journal of Chemical Engineering,69,222(1991).
15. Kumar, S., Kumar, R. and Gandhi, K. S.〝Influence of the Wetting Characteristics of the Impeller on Phase Inversion, 〞Chemical Engineering Science,46,No.9,2365(1991).
16. Kumar, S.〝On Phase Inversion Characteristic of Stirred Dispersions,〞 Chemical Engineering Science,51,No.5,831(1996).
17. Mason, D., Magdassi, S. and Sasson, Y.〝Role of a Third Liquid Phase in Phase-Transfer Catalysis,〞J. Org. Chem.,56,No.26,7229(1991).
18. McClarey, M. J. and Mansoori, G. A.〝Factors Affecting the Phase Inversion of Dispersed Immiscible Liquid-Liquid Mixtures,〞The American Institute of Chemical Engineers,74,No.173,134(1978).
19. Nadiv, C. and Semiat R.〝Batch Settling of Liquid-Liquid Dispersion,〞Ind. Eng. Chem. Res.,34,2427(1995).
20. Nikolov, A. D., and Wasan, D. T.〝Effects of Surfactant on Multiple Stepwise Coalescence of Single Drops at Liquid-Liquid Interfaces,〞Ind. Eng. Chem. Res.,34,3653(1995).
21. Norato, M. A., Tsouris C. and Tavlarides L. L.〝Phase Inversion Studies in Liquid-Liquid Dispersions,〞The Canadian Journal of Chemical Engineering,76,486(1998).
22. Pacek, A. W., Moore, I. P. T. and Nienow, A. W.〝On the Structure of Turbulent Liquid-Liquid Dispersed Flows in an Agitated Vessel,〞Chemical Engineering Science,49,No.20,3485(1994a).
23. Pacek, A. W., Moore, I. P. T. and Nienow, A. W.〝Video Technique for Measuring Dynamics of Liquid-Liquid Dispersion During Phase Inversion,〞 AIChE Journal,40,No.12,1940(1994b).
24. Quinn, J. A. and Sigloh, D. B.〝Phase Inversion in the Mixing of Immiscible Liquid,〞The Canadian Journal of Chemical Engineering,41,15(1963).
25. Selker, A. H. and Sleicher, Jr. C. A.〝Factors Affecting which Phase Disperse when Immiscible Liquids are Stirred Together,〞The Canadian Journal of Chemical Engineering,43,298(1965).
26. Skelland, A. H. P. and Jeffrey, S. K.〝Transient Drops Size in Agitated Liquid-Liquid Systems, As Influenced by the Direction of Mass Transfer and Surfactant Concentration,〞Ind. Eng. Chem. Res.,31,2566(1992).
27. Smith, D. V. and Davies, G. A.〝Coalescence in Droplet Dispersions,〞The Canadian Journal of Chemical Engineering,48,628(1970).
28. Starks, C. M., Journal of the American Chemical Society,93,195(1971).
29. Starks, C. M. and Owens, R. M.〝Phase-Transfer Catalysis. Ⅱ. Kinetic Details of Cyanide Displacement on 1-Halooctanes,〞Journal of the American Chemical Society,95,No.11,3613(1973).
30. Tobin, T. and Ramkrishna, D.〝Coalescence of Charged Droplets in Agitated Liquid-Liquid Dispersions,〞AIChE Journal,38,No.8,1199(1992)
31. Treybal, R. E., AIChE Journal,4,No.3,202(1958).
32. Wang, D. H. and Weng, H. S.〝Preliminary Study on the Role Played by the Third Liquid Phase in Phase Transfer Catalysis,〞Chemical Engineering Science,43,No.8,2019(1988).
33. Wang, D. H. and Weng, H. S.〝Solvent and Salt Effects on the Formation of Third Liquid Phase and the Reaction Mechanisms in the Phase Transfer Catalysis System-Reaction Between N-Butyl Bromide and Sodium Phenolate,〞Chemical Engineering Science,50,No.21,3477(1995).
34. 王鵬為,〝以對稱型四級銨鹽為相間轉移觸媒形成第三液相及催化正溴丁烷-酚化鈉反應,〞成功大學化工研究所碩士論文(1998).
35. 何美玲,〝Marangoni效應對相轉換現象的影響,〞成功大學化工研究所碩士論文(1996).
36. 李珠瑤,〝三液相相轉移催化反應系統的相轉換現象,〞成功大學化工研究所碩士論文(1996).
37. 陳美玲,〝三液相相轉移催化反應的研究-以正己烷為有機相溶劑由溴正丁烷和酚化鈉合成正丁基苯基醚,〞成功大學化工研究所碩士論文(1993).
38. 張炯宏,〝相間轉移觸媒反應系統的相轉換現象研究,〞成功大學化工研究所碩士論文(1995).
39. 趙承琛,〝界面科學基礎,〞復文書局(1996).
40. 賴明孝,〝批示軸流萃取槽的相轉換特性,〞成功大學化工研究所碩士論文(1994).
41. 謝詮晟,〝觸媒構造對相間轉移觸媒反應系統相轉換特性的影響,〞成功大學化工研究所碩士論文(1997).
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