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研究生:楊若怡
研究生(外文):Ro-Yi Yang
論文名稱:以反相相轉移觸媒對-二甲基胺砒碇催化合成苯甲醯甘胺酸系統之相轉換特性
論文名稱(外文):Phase Inversion Characteristics of the Synthesis of Hippuric acid Using 4 —(dimethylamino)pyridine as the Inverse Phase Transfer Catalyst
指導教授:江建利
指導教授(外文):Ken-Li Kang
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系碩博士班
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:2002
畢業學年度:90
語文別:中文
論文頁數:92
中文關鍵詞:相轉換反相觸媒
外文關鍵詞:Phase InversionInverse Phase Transfer Catalyst
相關次數:
  • 被引用被引用:1
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  • 下載下載:27
  • 收藏至我的研究室書目清單書目收藏:0
相間轉移觸媒催化反應系統的研究,一直是近年來化工研究的重點。在各種不同的相間轉移觸媒系統中,反相相轉移觸媒的使用亦是其中重要的一環。對於不互溶兩液相的反應系統,在工業界的應用方面,系統的分散穩定性是很重要的設計條件。當分散相越多,質傳面積越大,系統聚合速率越大,即有可能產生相轉換變化,而相轉換的特性會影響系統的反應速率及行為。本文中,我們以對-二甲基胺砒啶做為反相相轉移觸媒,催化有機相中的苯甲醯氯與水相中的甘胺酸合成苯甲醯甘胺酸,藉此探討此類系統的相轉換特性,並與其他反相觸媒系統所得的結果作一比較。
結果顯示,使用對-二甲基胺砒啶的系統中,觸媒較易於使系統成為O/W乳化態,轉速的增加會使系統傾向成為W/O乳化態。而此系統的物性、相轉換Hold-up、液滴結合時間與遲滯相轉換時間等特性,結果均與使用另兩種反相相轉移觸媒,N-氧化-4-甲基砒碇和N-甲基砒碇的結果大致相似,但使用對-二甲基胺砒啶的兩相系統之界面張力值為最低。
在僅添加觸媒的系統中,其容易使系統呈現O/W乳化態的觸媒
依序為N-氧化-4-甲基砒碇、對-二甲基胺砒啶、N-甲基砒碇。在添加觸媒與油相反應物的系統中,此三系統均無法找到相轉換Hold-up的明顯變化趨勢。而在添加觸媒與兩相反應物的系統中,隨反應物濃度的增加,越不容易形成O/W乳化態。上述兩系統在低兩相反應物濃度的狀況下,使用N-氧化-4-甲基砒碇,與在高兩相反應物濃度的狀況下使用對-二甲基胺砒啶,最易使系統產生W/OàO/W的相轉換。而使用對-二甲基胺砒啶的系統,其W/OàO/W的相轉換Hold-up(o)值隨反應物濃度增加的下降趨勢,沒有其他兩系統來地明顯。顯示添加對-二甲基胺砒啶的系統,其相轉換現象對兩相反應物的濃度變化比起其他兩種反相觸媒而言較不敏感。
Recently many researches have been dedicated to the study of phase transfer catalytic (PTC) reaction systems. Inverse phase transfer catalyst (IPTC) is getting more and more important in this field. In view of the industrial applications, the stability of the dispersed system, involving two immiscible liquids, is of much importance in the operations. Increasing the volume fraction of the dispersed phase will result in the increase of the mass transfer areas, promote the drops coalescence rate and eventually lead to the phase inversion, i.e. the dispersed phase becomes the continuous phase and vice versa. The characteristics of phase inversion will affect the reaction rate and the liquid behavior of the system. In this study, we use the synthesis of phenyl hippuric acid from benzoyl choride (organic phase) and glycine (water phase) with 4 —dimethylaminopyridine (DMAP) as the IPTC to study the dispersion stability of this kind of systems, and to compare the results with other IPTC systems.
In those systems with DMAP added , we find that it tends to help water to become the continuous phase, and when the agitated speed increases, it tends to form an O/W emulsion. The results of the physical properties、phase inversion characteristics、droplet coalescence time and delayed inversion time of the systems using DMAP are similar to those obtained by using other two IPTCs, 4 — picoline-N
-oxide and pyridine-N-oxide. However, the interfacial tension is the lowest of these systems by using DMAP.
In those systems with catalysts added only, the sequence of easier to form an O/W dispersion is 4 — picoline-N-oxide、4 —dimethylaminopyridine and pyridine-N-oxide. In systems with the catalyst and organic phase reactant, there is no obvious trends can be found in the phase inversion hold-up. In those systems with catalyst and two phase reactants, with the increase of the reactant concentrations it gets more and more difficult to form an O/W dispersion. These two systems mentioned before are the most easily to make the occurrence of O/W→W/O by using 4 — picoline
-N-oxide at low reactant concentrations; 4 —dimethylaminopyridine at high reactant concentrations and so forth. The tendency of the decrease of the inversion hold-up(o) with the increase of the reactant concentration of the system using DMAP as the catalyst is not so significant as the other two systems; it shows that the system using DMAP is not such sensitive to the reactant concentrations than the others.
表目錄………..…………………………………...………….………….I
圖目錄………..…………………………………...………….…………II
第一章 緒論………….…………………………………….…………1
1.1研究目的………….…………...…..………………….……..1
1.2 相間轉移觸媒簡介….…………………..………………….2
1.3不均勻系統的相轉換……...………………...……………...4
1.4論文架構……...……….……………………………………11
第二章 實驗方法…………………………………………………….13
2.1實驗裝置……………………………………………...……….13
2.2實驗藥品…………………………………………...………….18
2.3實驗步驟……………………………………………...……….18
2.3.1清潔步驟………………………………………..……..……19
2.3.2相轉換Hold-up的測定…………………………..…….…..19
2.3.2.1無觸媒及兩相反應物存在的系統………………….……19
2.3.2.2只有觸媒存在的兩相系統…………………………..…20
2.3.2.3添加觸媒與油相反應物存在的系統………..…………20
2.3.2.4添加觸媒與兩相反應物皆存在的系統…...……...……21
2.3.3液滴結合時間(Tc)的測定….………………………..……21
2.3.4遲滯相轉換時間(Td)的測定….……………………..……21
2.3.4.1無觸媒及兩相反應物存在的系統..…………..……..……21
2.3.4.2添加觸媒與反應物的系統…….……………….…..……22
2.3.5系統物性的量測………………….…………………..…..…22
2.4數據處理……………….…………………………………….23
第三章 結果與討論………………………………………………...…25
3.1純水-純正己烷的系統…...…………………………………..25
3.1.1純相之相轉換現象…………………………………………25
3.1.2純相相轉換Hold-up…………………………….….……...28
3.1.3液滴結合的時間(Tc)………………………………………32
3.1.4遲滯相轉換時間(Td)………………………………………32
3.2添加親水性的反相相轉移觸媒的系統…….….……………..34
3.2.1添加對-二甲基胺砒啶的系統….………….……………...34
3.2.2只添加觸媒的系統……………..…….……….…...…..….34
3.2.3添加反相觸媒與油相反應物的系統….....…….……...…..46
3.2.4添加反相觸媒與兩相反應物的系統….….……...……..…53
3.3三種反相觸媒其相轉換現象的比較……………………..….62
第四章 結論…………………………………………………………...69
參考文獻………………………………………………………………..79
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.ASAI, S., Nakamura, H., Okada, W. and Yamada, M.〝Synthesis of Hippuric Acid with Inverse Phase Transfer Catalyst in a Reaction System〞Chemical Engineering Science, 50, No. 6, 943-949(1995).3.Brooks, B. W. and Richmond, H. N.〝Dynamics of Liquid-Liquid Phase Inversion Using Non-Ionic Surfactant〞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.Chapman, F. S. and Holland, F.A., Liquid Mixing and Processing, Reinhold, New York, 208 (1966).6.Chatzi, E. G. and Kiparissides, C.〝Steady-State Drop-Size Distributions in High Holdup Fraction Dispersion Systems〞AIChE Journal, 41, No. 7, 1640 (1995).7.Coulaloglou, C.A. and Tavlarides,L.L.〝Description of Interaction Processes in Agitated Liquid-Liquid Dispersion〞Chem.Eng.Sci.32, 1289(1976).8.Clarke, S. I. and Sawistowski, H.〝Phase Inversion of Stirred Liquid/Liquid Dispersions Under Mass Transfer Conditions〞Trans IChemE, 56, 50(1978).9.Dickinson, E., 〝Thermodynamic Aspects of Emulsion Phase Inversion〞, J. Colloid Interface Sci., 87, No.2, 416(1982).10.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).11.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).12.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).13.Guilinger, T. R., Grislingas, A. K. and Erga, O.〝Phase Inversion Behavior of Water-Kerosene Dispersion〞, Ind. Eng. Chem. Res., 27, 978(1988).14.Hung S. M., Jwo J. J.,〝Inverse Phase Transfer Catalysis: Kinetics of The Pyridine 1-Oxide-Catalyzed Two-Phase Reactions of Butyl-Benzoyl Chlorides and Benzoate Ions〞,Journal of Molecular Catalysis Che.,154,(2000).15.Kato, S., Nakayama, E. and Kawasaki, J.〝Types of Dispersion in Agitated Liquid-Liquid Systems〞The Canadian Journal of Chemical Engineering, 69, 222 (1991). 16.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).17.Kumar, S.〝On Phase Inversion Characteristic of Stirred Dispersions〞Chemical Engineering Science, 51, No. 5, 831(1996).18.Luhning, R W. and Sawistowski, H., 〝Phase inversion in stirred liquid-liquid mixures〞Proc. ISEC, 712(1971)19.Mathias, K. and R. A. Vaidia,〝Inversion phase Transfer Catalysis. First Report of a New Class of Interfacial Reaction〞America Chem. Society, 108(1986)20.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).21.Nadiv, C. and Semiat, R. 〝Batch Settling of Liquid-Liquid Dispersion〞Ind. Eng. Chem. Res., 34, 2427(1995).22.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).23.Ou J. S., Chen R. H., Jwo J. J.,〝Inverse Phase Transfer Catalysis: Kinetics of the Pyridine 1-Oxide-Catalyzed Two-Phase Reactions of Chlorobenzoyl Chlorides and Chlorobenzoate Ion〞,Journal of Molecular Catalysis Che.,154,(2000).24.Pacek, A. W., Moore, I. P. T. and Nienow, A. W.〝On the Structure of Turbulent Liquid-Liquid Dispersed Flows in an Agitated Vessel〞, Chem. Eng. Sci., 49, No.20, 3485(1994).25.Pacek, A. W., Nienow, A. W., 〝A Problem for the Description of Turbulent Dispersed Liquid-Liquid Systems〞, Int. J. Multiphase Flow, 21, No.2, 323(1995).26.Quinn, J. A. and Sigloh, D. B.〝Phase Inversion in the Mixing of Immiscible Liquid〞The Canadian Journal of Chemical Engineering, 41, 15(1963).27.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).28.Treybal, R. E., AIChE Journal, 4, No.3, 202(1958).29.Vaessen, G. E. J., Stein, H. N., 〝The Applicability of Catastrophe Theory to Emulsion Phase Inversion〞, J. Colloid Interface Sci., 176, 378(1995).30.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).31.李耀昇, 〝利用相間轉移觸媒合成苯甲酸苯酯及其衍生物之研究〞成功大學化工研究所碩士論文(1993).32.吳泓仁, 〝質量傳送造成Marangoni效應對相轉換特性的影響〞 成功大學化工研究所碩士論文(2000).33.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).34.張德興, 〝含PEG相轉移觸媒系統的相轉換特性〞 成功大學化工研究所碩士論文(1999).35.陳怡伶, 〝以對稱型四級銨鹽為觸媒之三液相相間轉移 催化反應系統之相轉換特性〞 成功大學化工研究所碩士論文(1999).36.陳欣鴻, 〝含相間轉移觸媒PEG及其衍生物PEG-MME、PEG-DME系統的相轉換特性〞 成功大學化工研究所碩士論文(2000).37.賴明孝, 〝批示軸槽的相轉換特性〞 成功大學化工研究所碩士論文(1994).38.沈艾霖, 〝以反相相轉移觸媒催化合成苯甲酸苯酯系統之相轉換特性〞 成功大學化工研究所碩士論文(2001).39.石延平, 王茂齡, 〝相間轉移觸媒催化反應在國內研究之現況〞化工雜誌第40卷第3期(1993).
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1. 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.ASAI, S., Nakamura, H., Okada, W. and Yamada, M.〝Synthesis of Hippuric Acid with Inverse Phase Transfer Catalyst in a Reaction System〞Chemical Engineering Science, 50, No. 6, 943-949(1995).3.Brooks, B. W. and Richmond, H. N.〝Dynamics of Liquid-Liquid Phase Inversion Using Non-Ionic Surfactant〞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.Chapman, F. S. and Holland, F.A., Liquid Mixing and Processing, Reinhold, New York, 208 (1966).6.Chatzi, E. G. and Kiparissides, C.〝Steady-State Drop-Size Distributions in High Holdup Fraction Dispersion Systems〞AIChE Journal, 41, No. 7, 1640 (1995).7.Coulaloglou, C.A. and Tavlarides,L.L.〝Description of Interaction Processes in Agitated Liquid-Liquid Dispersion〞Chem.Eng.Sci.32, 1289(1976).8.Clarke, S. I. and Sawistowski, H.〝Phase Inversion of Stirred Liquid/Liquid Dispersions Under Mass Transfer Conditions〞Trans IChemE, 56, 50(1978).9.Dickinson, E., 〝Thermodynamic Aspects of Emulsion Phase Inversion〞, J. Colloid Interface Sci., 87, No.2, 416(1982).10.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).11.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).12.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).13.Guilinger, T. R., Grislingas, A. K. and Erga, O.〝Phase Inversion Behavior of Water-Kerosene Dispersion〞, Ind. Eng. Chem. Res., 27, 978(1988).14.Hung S. M., Jwo J. J.,〝Inverse Phase Transfer Catalysis: Kinetics of The Pyridine 1-Oxide-Catalyzed Two-Phase Reactions of Butyl-Benzoyl Chlorides and Benzoate Ions〞,Journal of Molecular Catalysis Che.,154,(2000).15.Kato, S., Nakayama, E. and Kawasaki, J.〝Types of Dispersion in Agitated Liquid-Liquid Systems〞The Canadian Journal of Chemical Engineering, 69, 222 (1991). 16.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).17.Kumar, S.〝On Phase Inversion Characteristic of Stirred Dispersions〞Chemical Engineering Science, 51, No. 5, 831(1996).18.Luhning, R W. and Sawistowski, H., 〝Phase inversion in stirred liquid-liquid mixures〞Proc. ISEC, 712(1971)19.Mathias, K. and R. A. Vaidia,〝Inversion phase Transfer Catalysis. First Report of a New Class of Interfacial Reaction〞America Chem. Society, 108(1986)20.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).21.Nadiv, C. and Semiat, R. 〝Batch Settling of Liquid-Liquid Dispersion〞Ind. Eng. Chem. Res., 34, 2427(1995).22.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).23.Ou J. S., Chen R. H., Jwo J. J.,〝Inverse Phase Transfer Catalysis: Kinetics of the Pyridine 1-Oxide-Catalyzed Two-Phase Reactions of Chlorobenzoyl Chlorides and Chlorobenzoate Ion〞,Journal of Molecular Catalysis Che.,154,(2000).24.Pacek, A. W., Moore, I. P. T. and Nienow, A. W.〝On the Structure of Turbulent Liquid-Liquid Dispersed Flows in an Agitated Vessel〞, Chem. Eng. Sci., 49, No.20, 3485(1994).25.Pacek, A. W., Nienow, A. W., 〝A Problem for the Description of Turbulent Dispersed Liquid-Liquid Systems〞, Int. J. Multiphase Flow, 21, No.2, 323(1995).26.Quinn, J. A. and Sigloh, D. B.〝Phase Inversion in the Mixing of Immiscible Liquid〞The Canadian Journal of Chemical Engineering, 41, 15(1963).27.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).28.Treybal, R. E., AIChE Journal, 4, No.3, 202(1958).29.Vaessen, G. E. J., Stein, H. N., 〝The Applicability of Catastrophe Theory to Emulsion Phase Inversion〞, J. Colloid Interface Sci., 176, 378(1995).30.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).31.李耀昇, 〝利用相間轉移觸媒合成苯甲酸苯酯及其衍生物之研究〞成功大學化工研究所碩士論文(1993).32.吳泓仁, 〝質量傳送造成Marangoni效應對相轉換特性的影響〞 成功大學化工研究所碩士論文(2000).33.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).34.張德興, 〝含PEG相轉移觸媒系統的相轉換特性〞 成功大學化工研究所碩士論文(1999).35.陳怡伶, 〝以對稱型四級銨鹽為觸媒之三液相相間轉移 催化反應系統之相轉換特性〞 成功大學化工研究所碩士論文(1999).36.陳欣鴻, 〝含相間轉移觸媒PEG及其衍生物PEG-MME、PEG-DME系統的相轉換特性〞 成功大學化工研究所碩士論文(2000).37.賴明孝, 〝批示軸槽的相轉換特性〞 成功大學化工研究所碩士論文(1994).38.沈艾霖, 〝以反相相轉移觸媒催化合成苯甲酸苯酯系統之相轉換特性〞 成功大學化工研究所碩士論文(2001).39.石延平, 王茂齡, 〝相間轉移觸媒催化反應在國內研究之現況〞化工雜誌第40卷第3期(1993).