逆向法测定酮洛芬对映体在Chiralpak AD柱上的吸附等温线

doi:10.3969/j.issn.0438-1157.2012.08.019

化工学报 ›› 2012, Vol. 63 ›› Issue (8): 2469-2476.DOI: 10.3969/j.issn.0438-1157.2012.08.019

逆向法测定酮洛芬对映体在Chiralpak AD柱上的吸附等温线

朱磊，徐进，孙玉高，刘玉明，余卫芳

温州大学化学与材料工程学院，浙江温州 325035

收稿日期:2012-01-05 修回日期:2012-03-17 出版日期:2012-08-05 发布日期:2012-08-05
通讯作者: 余卫芳
基金资助:
国家自然科学基金

Determination of adsorption isotherms of ketoprofen enantiomers on Chiralpak AD column by inverse method

ZHU Lei，XU Jin，SUN Yugao，LIU Yuming，YU Weifang

Received:2012-01-05 Revised:2012-03-17 Online:2012-08-05 Published:2012-08-05
Supported by:
the National Natural Science Foundation

摘要/Abstract

摘要： 模拟移动床（SMB）色谱分离与纯化的操作过程复杂，对其进行设计与优化需要使用数值模拟方法，准确测定竞争型吸附等温线具有重要意义。采用逆向法确定了25℃下酮洛芬对映体在直链淀粉手性固定相（Chiralpak AD）上的竞争吸附等温线，先用高效液相色谱测得酮洛芬对映体在Chiralpak AD 柱上的过载流出曲线，再通过拟合实验测得的流出曲线确定吸附等温线模型及其参数。研究中采用平衡扩散模型描述酮洛芬对映体在色谱柱上流出的瞬态过程。参数拟合过程中，首先用非支配基因算法（NSGA-Ⅱ）在较广的参数空间内搜索吸附等温线模型参数，再以所得结果作为初值，使用Levenberg-Marquardt 算法（LMA）对参数进一步优化。比较了4种不同竞争吸附等温线模型对实验测得的流出曲线的拟合结果，其中五参数的Bi-Langmuir 模型拟合程度最好。测量了不同进料浓度和进料量条件下的流出曲线，并通过与模型预测结果的对照验证了所确定吸附等温线模型和参数。

关键词: 竞争吸附等温线, 酮洛芬对映体, 逆向法, 模拟移动床色谱

Abstract: The determination of competitive adsorption isotherm is of great importance for model-based design and optimization of chromatographic separation processes，especially for the simulated moving bed due to its intrinsic complexity.The competitive adsorption isotherms of ketoprofen enantiomers on an amylose-based chiral stationary phase(Chiralpak AD)at 25℃ were determined in this study by the application of the inverse method.Elution profiles of various racemic feed signals were measured on a preparative chromatography column with a precise temperature control system.The parameters of isotherm models were determined by fitting the experimental elution profiles.The mass balance for component in the column was described by equilibrium-dispersive model.In the fitting procedure，isotherm parameters were searched over a wide range in the parametric space with the non-dominated sorting genetic algorithm(NSGA-Ⅱ)and polished with the Levenberg-Marquardt algorithm.Four competitive adsorption isotherm models were compared based on the fitting to the experimental data.Bi-Langmuir model with 5 parameters gave the best results. In order to validate this model and the model parameters，independent overloaded profiles with different concentrations and amount of feed were measured and compared with the model. Quantitatively good agreement was observed.

Key words: competitive adsorption isotherm, ketoprofen enantiomers, inverse method, SMB

中图分类号:

TQ028.8

朱磊，徐进，孙玉高，刘玉明，余卫芳. 逆向法测定酮洛芬对映体在Chiralpak AD柱上的吸附等温线[J]. 化工学报, 2012, 63(8): 2469-2476.

ZHU Lei，XU Jin，SUN Yugao，LIU Yuming，YU Weifang. Determination of adsorption isotherms of ketoprofen enantiomers on Chiralpak AD column by inverse method[J]. CIESC Journal, 2012, 63(8): 2469-2476.

参考文献 20

[1]	Wei Feng(危凤),Shen Bo(沈波),Chen Mingjie(陈明杰),Zhou Xianbo(周先波),Wu Pingdong(吴平东). Omeprazole resolution by simulated moving bed chromatography[J]. Journal of Chemical Industry and Engineering(化工学报),2005,56(9): 1699-1702
[2]	Zhang Y,Hidajat K,Ray A K. Enantio-separation of racemic pindolol on α1-acid glycoprotein chiral stationary phase by SMB and Varicol[J]. Chem. Eng. Sci.,2007,62(5): 1364-1375
[3]	Wu Xiandong(吴献东),Jin Xiaoming(金晓明),Su Hongye(苏宏业). Multi-objective optimization of simulated moving bed chromatography separation based on NSGA-II algorithm[J]. Journal of Chemical Industry and Engineering(化工学报),2007,58(8): 2038-2044
[4]	Rajendran A,Paredes G,Mazzotti M. Simulated moving bed chromatography for the separation of enantiomers[J]. J. Chromatogr. A,2009,1216 (4): 709-738
[5]	Yu W F,Hidajat K,Ray A K. Modeling,simulation,and experimental study of a simulated moving bed reactor for the synthesis of methyl acetate ester[J]. Ind. Eng. Chem. Res.,2003,42(26),6743-6754
[6]	Lu J G. Numerical simulation of asynchronous simulated moving bed chromatography[J]. Chinese J. Chem. Eng.,2004,12(3): 415-420
[7]	Zhang Z Y,Mazzotti M,Morbidelli M. PowerFeed operation of simulated moving bed units: changing flow-rates during the switching interval[J]. J. Chromatogr. A,2003,1006 (1-2): 87-99
[8]	Schramm H,Kaspereit M,Kienle A,Morgenstern A S. Simulated moving bed process with cyclic modulation of the feed concentration[J]. J. Chromatogr. A,2003,1006(1-2): 77-86
[9]	Lisec O,Hugo P,Seidel-Morgenstern A. Frontal analysis method to determine competitive adsorption isotherms[J]. J. Chromatogr. A,2001,908(1-2): 19-34
[10]	Andrzejewska A,Kaczmarski K,Guiochon G. Theoretical study of the accuracy of the pulse method,frontal analysis,and frontal analysis by characteristic points for the determination of single component adsorption isotherms[J]. J. Chromatogr. A,2009,1216(7): 1067-1083
[11]	Zhang Y,Rohani S,Ray A K. Numerical determination of competitive adsorption isotherm of mandelic acidenantiomers on cellulose-based chiral stationary phase[J]. J. Chromatogr. A,2008,1202(1): 34-39
[12]	Cheng Ming(程明),Li Shuang(李爽),Zhang Fengbao(张凤宝),Zhang Guoliang(张国亮). Determination of competitive adsorption isotherms of tryptphan enantiomers by inverse method[J]. Journal of Chemical Industry and Engineering(化工学报),2006,57(5): 1177-1181
[13]	Araújo J M M,Rodrigues R C R,Mota J P B. Determination of competitive isotherms of enantiomers by a hybrid inverse method using overloaded band profiles and the periodic state of the simulated moving-bed process[J]. J. Chromatogr. A,2008,1189(1-2): 302-313
[14]	Ossipov M H,Jerussi T P,Ren K,Sun H,Porreca F. Differential effects of spinal (R)-ketoprofen and (S)-ketoprofen against signs of neuropathic pain and tonic nociception: evidence for a novel mechanism of action of (R)-ketoprofen against tactile allodynia[J]. Pain,2000,87(2): 193-199
[15]	Liu J T,Liu R H. Enantiomeric composition of abused amine drugs: chromatographic methods of analysis and data interpretation[J]. J. Biochem. Bioph. Meth.,2002,54(1-3): 115-146
[16]	Ribeiro A E,Grac N S,Pais L S,Rodrigues A E. Preparative separation of ketoprofen enantiomers: Choice of mobile phase composition and measurement of competitive adsorption isotherms[J]. Sep. Purif. Technol.,2008,61(3): 375-383
[17]	Migliorini C,Mazzotti M,Morbidelli M. Robust design of countercurrent adsorption separation processes: 5. Nonconstant selectivity[J]. AIChE J.,2000,46(7): 1384-1399
[18]	Ahmad T,Guiochon G. Numerical determination of the adsorption isotherms of tryptophan at different temperatures and mobile phase compositions[J]. J. Chromatogr. A,2007,1142(2): 148-163
[19]	Felinger A,Cavazzini A,Guiochon G. Numerical determination of the competitive isotherm of enantiomers [J]. J. Chromatogr. A,2003,986(2): 207-225
[20]	Dose E V,Jacobson S,Guiochon G. Determination of isotherms from chromatographic peak shapes[J]. Anal.Chem.,1991,63(8): 833-839

逆向法测定酮洛芬对映体在Chiralpak AD柱上的吸附等温线

Determination of adsorption isotherms of ketoprofen enantiomers on Chiralpak AD column by inverse method

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