多级离心连续逆流手性萃取模型及模拟
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摘要
基于单级手性萃取数学模型和质量守恒定律,建立了多级离心手性萃取数学模型,设计了多级离心萃取数学模型程序,并对多级离心萃取分离苯基琥珀酸(PSA)对映体进行了模拟.模拟了相比、萃取剂浓度、对映体浓度、进料位置和萃取级数等工艺参数对萃取效果(产物纯度和产率)的影响.模拟结果表明,考察的工艺参数共同影响萃取相和萃余相的产物纯度及产率;采用中间位置进料和较大的W/F相比有利于对称分离.实验发现:采用中间位置进料,10级离心萃取后萃取相中苯基琥珀酸的光学纯度ee(对映体过量)达到56%以上.模拟结果还表明,采用26级离心萃取器,中间进料,逆流分级萃取,萃取相及萃余相中的光学纯度ee都能达到98%以上.
Based on a single stage equilibrium model and the law of conservation of mass,a multistage mathematical model of enantioselective liquid-liquid extraction was constructed and programmed in the matlab.The influence of changes in process parameters such as phase ratios,stage,extractant concentration([C]) and racemate concentration([AR,S]),the location of feed,extractant excess and number of stages on ee(enantiomeric excess) and Y(yield) were investigated.The simulation results show that the process parameters have the influence on ee and yield in the extract and the raffinate phase.It is conducive to symmetric separation by use of feeding in the middle stage and the larger phase ratio W/F.The ee of 56% in extract phase was obtained for separation of phenylsuccinic acid enantiomers by feeding in the middle stage in a countercurrent cascade of ten centrifugal contactor separators.A cascade of 26 stages is sufficient for symmetric separation of phenylsuccinic acid enantiomers with 98% equal ee(eeeq) in the extract phase and the raffinate phase.
Based on a single stage equilibrium model and the law of conservation of mass,a multistage mathematical model of enantioselective liquid-liquid extraction was constructed and programmed in the matlab.The influence of changes in process parameters such as phase ratios,stage,extractant concentration([C]) and racemate concentration([AR,S]),the location of feed,extractant excess and number of stages on ee(enantiomeric excess) and Y(yield) were investigated.The simulation results show that the process parameters have the influence on ee and yield in the extract and the raffinate phase.It is conducive to symmetric separation by use of feeding in the middle stage and the larger phase ratio W/F.The ee of 56% in extract phase was obtained for separation of phenylsuccinic acid enantiomers by feeding in the middle stage in a countercurrent cascade of ten centrifugal contactor separators.A cascade of 26 stages is sufficient for symmetric separation of phenylsuccinic acid enantiomers with 98% equal ee(eeeq) in the extract phase and the raffinate phase.
引文
1 Steensma M,Kuipers NJM,De Haan AB,Kwant G.Analysis and optimization of enantioselective extraction in a multi-product environment with a multistage equilibrium model.Chem Eng Proc,2007,46:996–1005
2 Roger AS.Organic synthesis—Past,present and future.Chem Industr,1992,7:903–906
3 Aube J,Wang YG,Hammond M,Tanol M,Takusagawa F,Velde DV.Synthetic aspects of an asymmetric nitrogen-insertion process:Preparation of chiral,non-racemic caprolactams and valerolactams.Total synthesis of()-alloyohimbane.J Am Chem Soc,1990,112:4897–4905
4 Jacques J,Collet A,Wilen SH.Enantiomers,Racemates and Resolutions.New York:Wiley,1981
5 Gourlay MD,Kendrick J,Leusen FJJ.Predicting the spontaneous chiral resolution by crystallization of a pair of flexible nitroxide radicals.Cryst Growth Des,2008,8:2899–2905
6 Khan M,Viswanathan B,Rao DS,Reddy R.Chiral separation of frovatriptan isomers by HPLC using amylose based chiral stationary phase.J Chromatogr B 2007,846:119–123
7 Afonso CAM,Crespo JG.Recent advances in chiral resolution through membrane-based approaches.Angew Chem Int Ed,2004,43:5293–5295
8 Kirchner G,Scollar MP,Klicanov AM.Resolution of racemic mixture vialipse catalysis in organic solvents.J Am Chem Soc,1985,107:7072–7076
9唐课文,周春山,蒋新宇.支载液膜双有机相萃取分离氧氟沙星外消旋体.中国科学B辑:化学,2002,6:491–496
10 Ohki A,Miyashita R,Naka K,Maeda S.Enantioselective extraction of di-O-benzoyltartrate anion by ion-pair extractant having binaphthyl-unit.Bull Chem Soc Jpn,1991,64:2714–2719
11 Lacour J,Goujon-Ginglinger C,Torche-Haldimann S,Jodry JJ.Efficient enantioselective extraction of tris(diimine)ruthenium(II)complexes by chiral,lipophilic TRISPHAT anions.Angew Chem Int Ed,2000,39:3695–3697
12 Prelog V,Stojanac Z,Kovacevic K.Separation of enantiomers by partition between liquid-phases.Hel Chim Acta,1982,65:377–384
13 Tsukube H,Shinoda S,Uenishi J,Kanatani T,Itoh H,Shiode M,Iwachido T,Yonemitsu O.Molecular recognition with lanthanide(III)tris(β-diketonate)complexes:Extraction,transport,and chiral recognition of unprotected amino acids.Inorg Chem,1998,37:1585–1591
14 Viegas RMC,Afonso CAM,Crespo JG,Coelhoso IM.Modelling of the enantio-selective extraction of propranolol in a biphasic system.Sep Purif Technol,2007,53:224–234
15 Steensma M,Kuipers NJM,de Haan AB,Kwant G.Influence of process parameters on extraction equilibria for the chiral separation of amines and amino-alcohols with a chiral crown ether.J Chem Technol Biotechnol,2006,81:588–597
16 Koska J,Haynes CA.Modelling multiple chemical equilbria in chiral partition systems.Chem Eng Sci,2001,56:5853–5864
17 Schuur B,Hallett AJ,Heeres HJ,de Vries JG.Scalable enantioseparation of amino acid derivatives using continuous liquid-liquid extraction in a cascade of centrifugal contactor separators.Org Process Res Dev,2009,13:911–914
18 Schuur B,Winkelmam JGM,de Vries JG,Heeres HJ.Experimental and modeling studies on the enantio-separation of3,5-dinitrobenzoyl-(R),(S)-leucine by continuous liquid-liquid extraction in a cascade of centrifugal contactor separators.Chem Eng Sci,2010,65:4682–4690
19 Schuur B,Winkelmam JGM,Heeres HJ.Equilibrium studies on enantioselective liquid-liquid amino acid extraction using a cinchona alkaloid extractant.Ind Eng Chem Res,2008,47:10027–10033
20 Tang KW,Zhang PL,Pan CY,Li HJ.Equilibrium studies on enantioselective extraction of oxybutynin enantiomers by hydrophilicβ-cyclodextrin derivatives.AIChE J,2011,57:3027–3036
21 Tang KW Miao JB,Zhou T,Liu YB,Song LT.Reaction kinetics in reactive extraction for chiral separation ofα-cyclohexyl-mandelic acid enantiomers with hydroxypropyl-β-cyclodextrin.Chem Eng Sci,2011,66:397–404
22 Tang KW,Song LT,Liu YB,Miao JB.Enantioselective partitioning of 2-phenylpropionic acid enantiomers in a biphasic recognition chiral extraction system.Chem Eng J,2012,180:293–298
23 Tang KW,Cai J,Zhang PL.Equilibrium and kinetics of reactive extraction of ibuprofen enantiomers from organic solution by HP-β-CD.Ind Eng Chem Res,2012,51:964–971
24王钟辉,满瑞林,唐课文.HP-β-CD对苯基琥珀酸对映体色谱保留机制及拆分机理的研究.分析测试学报,2009,8:162–167
2 Roger AS.Organic synthesis—Past,present and future.Chem Industr,1992,7:903–906
3 Aube J,Wang YG,Hammond M,Tanol M,Takusagawa F,Velde DV.Synthetic aspects of an asymmetric nitrogen-insertion process:Preparation of chiral,non-racemic caprolactams and valerolactams.Total synthesis of()-alloyohimbane.J Am Chem Soc,1990,112:4897–4905
4 Jacques J,Collet A,Wilen SH.Enantiomers,Racemates and Resolutions.New York:Wiley,1981
5 Gourlay MD,Kendrick J,Leusen FJJ.Predicting the spontaneous chiral resolution by crystallization of a pair of flexible nitroxide radicals.Cryst Growth Des,2008,8:2899–2905
6 Khan M,Viswanathan B,Rao DS,Reddy R.Chiral separation of frovatriptan isomers by HPLC using amylose based chiral stationary phase.J Chromatogr B 2007,846:119–123
7 Afonso CAM,Crespo JG.Recent advances in chiral resolution through membrane-based approaches.Angew Chem Int Ed,2004,43:5293–5295
8 Kirchner G,Scollar MP,Klicanov AM.Resolution of racemic mixture vialipse catalysis in organic solvents.J Am Chem Soc,1985,107:7072–7076
9唐课文,周春山,蒋新宇.支载液膜双有机相萃取分离氧氟沙星外消旋体.中国科学B辑:化学,2002,6:491–496
10 Ohki A,Miyashita R,Naka K,Maeda S.Enantioselective extraction of di-O-benzoyltartrate anion by ion-pair extractant having binaphthyl-unit.Bull Chem Soc Jpn,1991,64:2714–2719
11 Lacour J,Goujon-Ginglinger C,Torche-Haldimann S,Jodry JJ.Efficient enantioselective extraction of tris(diimine)ruthenium(II)complexes by chiral,lipophilic TRISPHAT anions.Angew Chem Int Ed,2000,39:3695–3697
12 Prelog V,Stojanac Z,Kovacevic K.Separation of enantiomers by partition between liquid-phases.Hel Chim Acta,1982,65:377–384
13 Tsukube H,Shinoda S,Uenishi J,Kanatani T,Itoh H,Shiode M,Iwachido T,Yonemitsu O.Molecular recognition with lanthanide(III)tris(β-diketonate)complexes:Extraction,transport,and chiral recognition of unprotected amino acids.Inorg Chem,1998,37:1585–1591
14 Viegas RMC,Afonso CAM,Crespo JG,Coelhoso IM.Modelling of the enantio-selective extraction of propranolol in a biphasic system.Sep Purif Technol,2007,53:224–234
15 Steensma M,Kuipers NJM,de Haan AB,Kwant G.Influence of process parameters on extraction equilibria for the chiral separation of amines and amino-alcohols with a chiral crown ether.J Chem Technol Biotechnol,2006,81:588–597
16 Koska J,Haynes CA.Modelling multiple chemical equilbria in chiral partition systems.Chem Eng Sci,2001,56:5853–5864
17 Schuur B,Hallett AJ,Heeres HJ,de Vries JG.Scalable enantioseparation of amino acid derivatives using continuous liquid-liquid extraction in a cascade of centrifugal contactor separators.Org Process Res Dev,2009,13:911–914
18 Schuur B,Winkelmam JGM,de Vries JG,Heeres HJ.Experimental and modeling studies on the enantio-separation of3,5-dinitrobenzoyl-(R),(S)-leucine by continuous liquid-liquid extraction in a cascade of centrifugal contactor separators.Chem Eng Sci,2010,65:4682–4690
19 Schuur B,Winkelmam JGM,Heeres HJ.Equilibrium studies on enantioselective liquid-liquid amino acid extraction using a cinchona alkaloid extractant.Ind Eng Chem Res,2008,47:10027–10033
20 Tang KW,Zhang PL,Pan CY,Li HJ.Equilibrium studies on enantioselective extraction of oxybutynin enantiomers by hydrophilicβ-cyclodextrin derivatives.AIChE J,2011,57:3027–3036
21 Tang KW Miao JB,Zhou T,Liu YB,Song LT.Reaction kinetics in reactive extraction for chiral separation ofα-cyclohexyl-mandelic acid enantiomers with hydroxypropyl-β-cyclodextrin.Chem Eng Sci,2011,66:397–404
22 Tang KW,Song LT,Liu YB,Miao JB.Enantioselective partitioning of 2-phenylpropionic acid enantiomers in a biphasic recognition chiral extraction system.Chem Eng J,2012,180:293–298
23 Tang KW,Cai J,Zhang PL.Equilibrium and kinetics of reactive extraction of ibuprofen enantiomers from organic solution by HP-β-CD.Ind Eng Chem Res,2012,51:964–971
24王钟辉,满瑞林,唐课文.HP-β-CD对苯基琥珀酸对映体色谱保留机制及拆分机理的研究.分析测试学报,2009,8:162–167