反应萃取分离2-苯基丁酸对映体的动力学

doi:10.11949/j.issn.0438-1157.20161190

化工学报 ›› 2017, Vol. 68 ›› Issue (1): 163-169.DOI: 10.11949/j.issn.0438-1157.20161190

反应萃取分离2-苯基丁酸对映体的动力学

蒋盼¹, 张盼良², 曾乐林², 许卫凤², 唐课文²

1 湘潭大学化工学院, 湖南湘潭 411105;
2 湖南理工学院化学化工学院, 湖南岳阳 414006

收稿日期:2016-08-25 修回日期:2016-09-22 出版日期:2017-01-05 发布日期:2017-01-05
通讯作者: 唐课文
基金资助:
国家重点基础研究发展计划项目（2014CB260407）。

Kinetics of reaction extraction separation of 2-phenylbutyric acid enantiomers

JIANG Pan¹, ZHANG Panliang², ZENG Lelin², XU Weifeng², TANG Kewen²

1 College of Chemical Engineering, Xiangtan University, Xiangtan 411105, Hunan, China;
2 Department of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang 414006, Hunan, China

Received:2016-08-25 Revised:2016-09-22 Online:2017-01-05 Published:2017-01-05
Contact: 10.11949/j.issn.0438-1157.20161190
Supported by:
supported by the National Basic Research Program of China (2014CB260407).

摘要/Abstract

摘要：

通过恒界面池法进行了羟乙基-β-环糊精反应萃取2-苯基丁酸对映体的动力学研究。采用双膜理论和均相反应模型描述了萃取过程的相际传质机理，并考察了搅拌速率、界面面积、对映体初始浓度和萃取剂初始浓度等因素对2-苯基丁酸对映体的萃取动力学的影响。实验结果表明羟乙基-β-环糊精与2-苯基丁酸对映体之间的包合反应属于“快反应”；2-苯基丁酸对映体反应分级数为1，羟乙基-β-环糊精反应分级数为2；（+）-2-苯基丁酸和（-）-2-苯基丁酸在278 K下的反应速率常数分别为2.829×10^-4、1.803×10^-4 m⁶·mol^-2·s^-1。该萃取动力学研究为大规模生产中的反应萃取过程的设计和操作以及设备的设计和过程强化提供了科学的依据。

关键词: 动力学, 萃取, 化学反应, 2-苯基丁酸

Abstract:

Kinetics research on the reactive extraction of 2-phenylbutyric acid enantiomers using hydroxyethyl-β-cyclodextrin(HE-β-CD) as extractant was performed in a Lewis cell.A homogeneous reaction model and a two-film theory were employed to describe the mass transfer mechanism of the reactive extraction process.The process parameters affecting the initial extraction rate, including agitation speed, interfacial area, pH value of aqueous phase, initial concentration of 2-phenylbutyric acid(2-PBA) enantiomers and initial concentration of extractant, were separately studied.The results showed that the reaction between hydroxyethyl-β-cyclodextrin and 2-phenylbutyric acid was a fast reaction.It was found that the reaction was first order in 2-phenylbutyric acid and second order in hydroxyethyl-β-cyclodextrin.The forward rate constants for the extraction of(+)-2-phenylbutyric acid and(-)-2-phenylbutyric acid were 2.829×10^-4 and 1.803×10^-4m⁶·mol^-2·s^-1, respectively.The results were useful for the design and operation of reactive extraction process in large-scale production, and provide scientific basis for equipment design and process intensification.

Key words: kinetics, extraction, chemical reactive, 2-phenylbutyric acid

中图分类号:

O643.12

蒋盼, 张盼良, 曾乐林, 许卫凤, 唐课文. 反应萃取分离2-苯基丁酸对映体的动力学[J]. 化工学报, 2017, 68(1): 163-169.

JIANG Pan, ZHANG Panliang, ZENG Lelin, XU Weifeng, TANG Kewen. Kinetics of reaction extraction separation of 2-phenylbutyric acid enantiomers[J]. CIESC Journal, 2017, 68(1): 163-169.

参考文献 37

[1]	HEFNAWY M M, ABOUL-ENEIN H Y. A validated LC method for the determination of vesamicol enantiomers in human plasma using vancomycin chiral stationary phase and solid phase extraction[J]. J. Pharm. Biomed. Anal., 2004, 35(3):535-543.
[2]	GUXMÁN A, YUSTE F, TOSCANO R A, et al. Absolute configuration of (-)-5-benzoyl-1,2-dihydro-3H-pyrrolo[1,2-alpha]-pyrrole-l-carboxylic acid, the active enantiomer of ketorolac[J]. J. Med. Chem., 1986, 29(4):589-591.
[3]	MITSCHER L A., SHARMA P N, CHU D T W, et al. Chiral DNA gyrase inhibitors (Ⅱ):Asymmetric synthesis and biological activity of the enantiomers of 9-fluoro-3-methyl-10-(4-methyl-1-piperazinyl)-7-oxo-2,3-dihydro-7H-pyrido[1,2,3-de]-1,4-benzoxazine-6-carboxylic acid (ofloxacin)[J]. J. Med. Chem., 1987, 30(12):2283-2286.
[4]	PLENGE P, MELLERUP E T, HONORÉ T, et al. The activity of 25 paroxetine/femoxetine structure variants in various reactions, assumed to be important for the effect of antidepressants[J]. J. Pharm. Pharmacol., 1987, 39(11):877-882.
[5]	SHUM W P, CHEN J, CANNARSA M J. Synthesis and enantiomeric purity determination of chiral 3-benzylglycidol, a key synthon for HIV protease inhibitors[J]. Chirality, 1994, 6(8):681-684.
[6]	HALABI A, FERRAYOLI C, PALACIO M, et al. Validation of a chiral HPLC assay for (R)-salbutamol sulfate[J]. J. Pharm. Biomed. Anal., 2004, 34(1):45-51.
[7]	CERLETTI C, MANARINI S, COLOMA M, et al. The (+)-enantiomer is responsible for the antiplatelet and anti-inflammatory activity of (±)-indobufen[J]. J. Pharm. Pharmaco., 1990, 42(12):885-887.
[8]	VIEGAS R M C, AFONSO C A M, CRESPO J G, et al. Racemic resolution of propranolol in membrane contactors:modelling and process optimization[J]. J. Membr. Sci., 2007, 305(1/2):203-214.
[9]	GOURLAY M D, KENDRICK J, LEUSEN F J J. Predicting the spontaneous chiral resolution by crystallization of a pair of flexible nitroxide radicals[J]. Cryst. Growth. Des., 2008, 8(8):2899-2905.
[10]	HUERTA F F, BÄCKVALL J E. Enantioselective synthesis of β-hydroxy acid derivatives via a one-pot aldol reaction-dynamic kinetic resolution[J]. Org. Lett., 2001, 3(8):1209-1212.
[11]	GINESTA X, PERICAS M A, RIERA A. Straightforward entry to the pipecolic acid nucleus. enantioselective synthesis of baikiain[J]. Tetrahedron. Lett., 2002, 43(5):779-782.
[12]	MAKINO K, GOTO T, HIROKI Y, et al. Stereoselective synthesis of anti-β-hydroxy-α-amino acids through dynamic kinetic resolution[J]. Angew. Chem. Int. Ed., 2004, 43(7):882-884.
[13]	SCHURIG V. Separation of enantiomers by gas chromatography[J]. J. Chromatogr. A., 2001, 906(1/2):275-299.
[14]	GUO Z, WANG H Y, ZHANG Y. Chiral separation of ketoprofen on an achiral C8 column by HPLC using norvancomycin as chiral mobile phase additives[J]. J. Pharm. Biomed. Anal., 2006, 41(1):310-314.
[15]	WANG Z, CAI C Q, LIN Y T, et al. Enantioselective separation of ketoconazole enantiomers by membrane extraction[J]. Sep. Purif. Technol., 2011, 79(1):63-71.
[16]	KEURENTJES J T F, NABUURS L, VEGTER E A. Liquid membrane technology for the separation of racemic mixtures[J]. J. Membr. Sci., 1996, 113(2):351-360.
[17]	LOMSADZE K, MARTÍNEZ-GIRÓN A B, CASTRO-PUYANA M, et al. About the role of enantioselective selector-select and interactions and the mobilities of diastereomeric associates in enantiomer separations using CE[J]. Electrophoresis, 2009, 30(16) 2803-2811.
[18]	YU T, DU Y X, CHEN B. Evaluation of clarithromycin lactobionate as a novel chiral selector for enantiomeric separation of basic drugs in capillary electrophoresis[J]. Electrophoresis, 2011, 32(14):1898-1905.
[19]	HOLBACH A, GODDE J, MAHENDRARAJAH R, et al. Enantioseparation of chiral aromatic acids in process intensified liquid-liquid extraction columns[J]. AIChE J., 2015, 61(1):266-276.
[20]	STEENSMA M, KUIPERS N J M, DE HAAN A B, et al. Modelling and experimental evaluation of reaction kinetics in reactive extraction for chiral separation of amines, amino acids and amino-alcohols[J]. Chem. Eng. Sci., 2007, 62(5):1395-1407.
[21]	SCHUUR B, WINKELMAN J G M, HEERES H J. Equilibrium studies on enantioselective liquid-liquid amino acid extraction using a cinchona alkaloid extractant[J]. Ind. Eng. Chem. Res., 2008, 47(24):10027-10033.
[22]	TANG K W, FENG X F, ZHANG P L, et al. Experimental and model study on multistage enantioselective liquid-liquid extraction of ketoconazole enantiomers in centrifugal contactor separators[J]. Ind. Eng. Chem. Res., 2015, 54(35):8762-8771.
[23]	ZHANG X B, GUO C C, LI Z Z, et al. An optical fiber chemical sensor for mercury ions based on a porphyrin dimer[J]. Anal. Chem., 2002, 74(4):821-825.
[24]	PRELOG V, KOVA?EVI? M, EGLI M. Lipophilic tartaric acid esters as enantioselective ionophores[J]. Angew. Chem. Int. Ed., 1989, 28(9):1147-1152.
[25]	LYNAM C, JENNINGS K, NOLAN K, et al. Tuning and enhancing enantioselective quenching of calixarene hosts by chiral guest amines[J]. Anal. Chem., 2002, 74(1):59-66.
[26]	WEBB T H, WILCOX C S. Enantioselective and diastereoselective molecular recognition of neutral molecules[J]. Chem. Soc. Rev., 1993, 22(6):383-395.
[27]	SALEH M I, BARI M F, JAB M S, et al. Kinetics of lanthanum(Ⅲ) extraction from nitrate-acetato medium by Cyanex 272 in toluene using the single drop technique[J]. Hydrometallurgy, 2002, 67(1/2/3):45-52.
[28]	EI-HEFNY N E, EI-DESSOUKY S. Equilibrium and kinetic studies on the extraction of gadolinium(Ⅲ) from nitrate medium by di-2-ethylhexylphosphoric acid in kerosene using a single drop technique[J]. J. Chem. Technol. Biotechnol., 2006, 81(3):394-400.
[29]	YULIZAR Y, OHASHI A, NAGATANI H, et al. Kinetic study of Ni(Ⅱ) and Zn(Ⅱ) complexation with a pyridylazo extractant by a centrifugal liquid membrane method[J]. Anal. Chim. Acta., 2000, 419(1):107-114.
[30]	NAGATANI H, WATARAI H. Direct spectrophotometric measurement of demetalation kinetics of 5,10,15,20-tetraphenylporphyrinatozinc(Ⅱ) at the liquid-liquid interface by a centrifugal liquid membrane method[J]. Anal. Chem., 1998, 70(14):2860-2865.
[31]	PLUCINSKI P, NITSCH W. The calculation of permeation rates through supported liquid membranes based on the kinetics of liquid-liquid extraction[J]. J. Membr. Sci., 1988, 39(1):43-59.
[32]	JÖNSSON J Å, LÖKVIST P, AUDUNSSON G, et al. Mass transfer kinetics for analytical enrichment and sample preparation using supported liquid membranes in a flow system with stagnant acceptor liquid[J]. Anal. Chim. Acta., 1993, 277(1):9-24.
[33]	CICERI D, MASON L R, HARVIE D J E, et al. Extraction kinetics of Fe(Ⅲ) by di-(2-ethylhexyl) phosphoric acid using a Y-Y shaped microfluidic device[J]. Chem. Eng. Res. Des., 2014, 92(3):571-580.
[34]	EI-HEFNY N E. Kinetics and mechanism of extraction and stripping of neodymium using a Lewis cell[J]. Chem. Eng. Process., 2007, 46(7):623-629.
[35]	WASEWAR K L, HEESINK A B M, VERSTEEG G F, et al. Reactive extraction of lactic acid using alamine 336 in MIBK:equilibria and kinetics[J]. J. Biotechnol., 2002, 97(1):59-68.
[36]	BORA M M, BORTHAKUR S, RAO P G, et al. Study on the reactive extraction and stripping kinetics of certain β-lactam antibiotics[J]. Chem. Eng. Process., 2008, 47(1):1-8.
[37]	DORAISWAMY L K. Heterogeneous Reactions:Analysis, Examples and Reactor Design:Vol. 2[M]//SHARMA M M. New York:John Wiley & Sons Inc., 1984:17-45.

反应萃取分离2-苯基丁酸对映体的动力学

Kinetics of reaction extraction separation of 2-phenylbutyric acid enantiomers

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 37

相关文章 15

编辑推荐

Metrics

本文评价

[1]	毕丽森, 刘斌, 胡恒祥, 曾涛, 李卓睿, 宋健飞, 吴翰铭. 粗糙界面上纳米液滴蒸发模式的分子动力学研究[J]. 化工学报, 2023, 74(S1): 172-178.
[2]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[3]	金正浩, 封立杰, 李舒宏. 氨水溶液交叉型再吸收式热泵的能量及分析[J]. 化工学报, 2023, 74(S1): 53-63.
[4]	程成, 段钟弟, 孙浩然, 胡海涛, 薛鸿祥. 表面微结构对析晶沉积特性影响的格子Boltzmann模拟[J]. 化工学报, 2023, 74(S1): 74-86.
[5]	肖明堃, 杨光, 黄永华, 吴静怡. 浸没孔液氧气泡动力学数值研究[J]. 化工学报, 2023, 74(S1): 87-95.
[6]	王俐智, 杭钱程, 郑叶玲, 丁延, 陈家继, 叶青, 李进龙. 离子液体萃取剂萃取精馏分离丙酸甲酯+甲醇共沸物[J]. 化工学报, 2023, 74(9): 3731-3741.
[7]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[8]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[9]	宋明昊, 赵霏, 刘淑晴, 李国选, 杨声, 雷志刚. 离子液体脱除模拟油中挥发酚的多尺度模拟与研究[J]. 化工学报, 2023, 74(9): 3654-3664.
[10]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[11]	汪林正, 陆俞冰, 张睿智, 罗永浩. 基于分子动力学模拟的VOCs热氧化特性分析[J]. 化工学报, 2023, 74(8): 3242-3255.
[12]	杨越, 张丹, 郑巨淦, 涂茂萍, 杨庆忠. NaCl水溶液喷射闪蒸-掺混蒸发的实验研究[J]. 化工学报, 2023, 74(8): 3279-3291.
[13]	曾如宾, 沈中杰, 梁钦锋, 许建良, 代正华, 刘海峰. 基于分子动力学模拟的Fe₂O₃纳米颗粒烧结机制研究[J]. 化工学报, 2023, 74(8): 3353-3365.
[14]	李锦潼, 邱顺, 孙文寿. 煤浆法烟气脱硫中草酸和紫外线强化煤砷浸出过程[J]. 化工学报, 2023, 74(8): 3522-3532.
[15]	何晓崐, 刘锐, 薛园, 左然. MOCVD生长AlN单晶薄膜的气相和表面化学反应综述[J]. 化工学报, 2023, 74(7): 2800-2813.