本文選題：動力學(xué) + 反應(yīng)萃取��； 參考：《湘潭大學(xué)》2017年碩士論文

【摘要】：本文根據(jù)手性萃取中反應(yīng)發(fā)生的位置,建立了均相反應(yīng)萃取模型和界面反應(yīng)萃取模型,并研究了反應(yīng)萃取分離對映體的動力學(xué),得到了相關(guān)的動力學(xué)參數(shù),為萃取分離對映體的條件優(yōu)化提供了思路,且為該方法的工業(yè)放大提供了依據(jù)。本文的主要研究內(nèi)容及實(shí)驗(yàn)結(jié)果如下:1.均相反應(yīng)萃取分離對映體動力學(xué)研究體系:在親水性β-環(huán)糊精衍生物反應(yīng)萃取分離芳香酸及酮康唑?qū)τ丑w的動力學(xué)研究中,由于對映體即溶于有機(jī)相又溶于水相,而親水性β-環(huán)糊精衍生物溶解在水相,因此采用均相反應(yīng)模型描述其反應(yīng)萃取過程。該均相模型基于以下假設(shè):(1)在“坪區(qū)”中,忽略反應(yīng)物在液膜中的傳質(zhì)阻力,即反應(yīng)物在界面和本體濃度一致;(2)包合反應(yīng)發(fā)生在水相本體中�；诰喾磻�(yīng)模型,利用恒界面池分別考察了比界面積、水相中手性選擇劑及有機(jī)相中對映體的初始濃度等因素對反應(yīng)萃取分離對映體初始萃取速度的影響。實(shí)驗(yàn)結(jié)果表明,在278 K下該反應(yīng)為快速反應(yīng)。2-苯基丁酸(2-PBA)、托品酸(TA)、α-環(huán)戊基扁桃酸(α-CPMA)以及酮康唑(KTZ)對映體反應(yīng)分級數(shù)為1,羥乙基-β-環(huán)糊精或羥丙基-β-環(huán)糊精(HE-β-CD或HP-β-CD)的反應(yīng)分級數(shù)為2。(+)-2-PBA和( )-2-PBA的反應(yīng)速率常數(shù)分別為2.829×10~(-4) m6/(mol~2·s),1.803×10~(-4)m6/(mol~2·s);(+)-TA和( )-TA的反應(yīng)速率常數(shù)分別為4.041×10-3 m6/(mol~2·s),3.124×10-3 m6/(mol~2·s);(R)-α-CPMA和(S)-α-CPMA的反應(yīng)速率常數(shù)分別為1.459×10-3m6/(mol~2·s),2.056×10-3 m6/(mol~2·s);(+)-KTZ和( )-KTZ的反應(yīng)速率常數(shù)分別為2.067×10-3 m6/(mol~2·s),1.716×10-3 m6/(mol~2·s)。2.界面反應(yīng)萃取分離對映體動力學(xué)研究體系:D-酒石酸異丁酯(DT)和硼酸(BA)協(xié)同萃取分離氯丙那林(CPNL)對映體的動力學(xué)研究中,由于反應(yīng)物處在不同的液相中,且不溶于另一相,因此選用界面反應(yīng)(多相反應(yīng))模型描述其反應(yīng)萃取過程。該界面模型基于以下假設(shè):(1)在“坪區(qū)”中,忽略反應(yīng)物在液膜中的傳質(zhì)阻力,即反應(yīng)物在界面和本體濃度一致;(2)反應(yīng)發(fā)生在界面上�；诮缑娣磻�(yīng)模型,利用恒界面池主要考察了手性選擇劑(BA和DT)的初始濃度以及氯丙那林對映體初始濃度等因素對反應(yīng)萃取分離對映體初始萃取速度的影響。實(shí)驗(yàn)結(jié)果表明,在該動力學(xué)體系中,硼酸的反應(yīng)分級數(shù)為0.6,氯丙那林對映體的反應(yīng)分級數(shù)為0.8,D-酒石酸異丁酯的反應(yīng)分級數(shù)為0.8。在278 K下,(R)-氯丙那林和(S)-氯丙那林的速率常數(shù)分別為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 偽 -CPMA, 偽 -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 偽 -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，

本文編號：2028530