反应萃取分离对映体动力学及其传质特性研究

发布时间：2018-06-16 23:37

  本文选题：动力学 + 反应萃取　； 参考：《湘潭大学》2017年硕士论文

【摘要】：本文根据手性萃取中反应发生的位置,建立了均相反应萃取模型和界面反应萃取模型,并研究了反应萃取分离对映体的动力学,得到了相关的动力学参数,为萃取分离对映体的条件优化提供了思路,且为该方法的工业放大提供了依据。本文的主要研究内容及实验结果如下:1.均相反应萃取分离对映体动力学研究体系:在亲水性β-环糊精衍生物反应萃取分离芳香酸及酮康唑对映体的动力学研究中,由于对映体即溶于有机相又溶于水相,而亲水性β-环糊精衍生物溶解在水相,因此采用均相反应模型描述其反应萃取过程。该均相模型基于以下假设:(1)在“坪区”中,忽略反应物在液膜中的传质阻力,即反应物在界面和本体浓度一致;(2)包合反应发生在水相本体中。基于均相反应模型,利用恒界面池分别考察了比界面积、水相中手性选择剂及有机相中对映体的初始浓度等因素对反应萃取分离对映体初始萃取速度的影响。实验结果表明,在278 K下该反应为快速反应。2-苯基丁酸(2-PBA)、托品酸(TA)、α-环戊基扁桃酸(α-CPMA)以及酮康唑(KTZ)对映体反应分级数为1,羟乙基-β-环糊精或羟丙基-β-环糊精(HE-β-CD或HP-β-CD)的反应分级数为2。(+)-2-PBA和( )-2-PBA的反应速率常数分别为2.829×10~(-4) m6/(mol~2·s),1.803×10~(-4)m6/(mol~2·s);(+)-TA和( )-TA的反应速率常数分别为4.041×10-3 m6/(mol~2·s),3.124×10-3 m6/(mol~2·s);(R)-α-CPMA和(S)-α-CPMA的反应速率常数分别为1.459×10-3m6/(mol~2·s),2.056×10-3 m6/(mol~2·s);(+)-KTZ和( )-KTZ的反应速率常数分别为2.067×10-3 m6/(mol~2·s),1.716×10-3 m6/(mol~2·s)。2.界面反应萃取分离对映体动力学研究体系:D-酒石酸异丁酯(DT)和硼酸(BA)协同萃取分离氯丙那林(CPNL)对映体的动力学研究中,由于反应物处在不同的液相中,且不溶于另一相,因此选用界面反应(多相反应)模型描述其反应萃取过程。该界面模型基于以下假设:(1)在“坪区”中,忽略反应物在液膜中的传质阻力,即反应物在界面和本体浓度一致;(2)反应发生在界面上。基于界面反应模型,利用恒界面池主要考察了手性选择剂(BA和DT)的初始浓度以及氯丙那林对映体初始浓度等因素对反应萃取分离对映体初始萃取速度的影响。实验结果表明,在该动力学体系中,硼酸的反应分级数为0.6,氯丙那林对映体的反应分级数为0.8,D-酒石酸异丁酯的反应分级数为0.8。在278 K下,(R)-氯丙那林和(S)-氯丙那林的速率常数分别为2.476×10~(-4) L1.53/(mol1.2 s),1.349×10~(-4)L1.53/(mol1.2 s)。
[Abstract]:In this paper, the homogeneous reaction extraction model and the interface reaction extraction model were established according to the location of the reaction in chiral extraction. The kinetics of separation of enantiomers by reactive extraction was studied, and the related kinetic parameters were obtained. It provides a way to optimize the conditions for extraction separation of enantiomers and provides a basis for the industrial amplification of the method. The main research contents and experimental results are as follows: 1. Homogeneous reaction extraction separation of enantiomers: in the kinetic study of the separation of aromatic acids and ketoconazole enantiomers by reactive extraction of hydrophilic 尾 -cyclodextrin derivatives, the enantiomers were soluble in both organic and aqueous phases. The hydrophilic 尾 -cyclodextrin derivatives were dissolved in the aqueous phase, so the homogeneous reaction model was used to describe the extraction process. The homogeneous phase model is based on the assumption that the mass transfer resistance of reactants in the liquid film is ignored in the "flat area", that is, the reactants are in the same concentration at the interface and the bulk concentration is the same.) the inclusion reaction takes place in the water phase body. Based on the homogeneous reaction model, the effects of specific boundary area, chiral selectivity in water and the initial concentration of enantiomers in organic phase on the initial extraction rate of enantiomers were investigated by using constant interface cell. The experimental results show that, The reaction was rapid at 278K. The enantiomers of 伪 -CPMA, 伪 -CPMA and ketoconazole KTZ were 1, hydroxyethyl- 尾 -cyclodextrin or hydroxypropyl- 尾 -cyclodextrin HE- 尾 -CD or HP- 尾 -CD were classified as HP- 尾 -CDs, and the enantiomers of 伪 -CPMA and ketoconazole KTZ were classified as 1, and hydroxyethyl 尾 -cyclodextrin or hydroxypropyl- 尾 -cyclodextrin HE- 尾 -CD or HP- 尾 -CD were classified as enantiomers. 2.( )-2-PBA鍜，

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