典型有机磷类萃取剂在溶剂萃取中协同萃取的研究进展

doi:10.12034/j.issn.1009-606X.220179

摘要/Abstract

摘要： 协同萃取作为溶剂萃取法的分支被广泛研究。对于协同萃取的机理探索，必须阐明协同效应产生的微观原因，并给出微观与宏观性质的联系，因此从分子的微观结构和内部运动认识协同萃取以及影响因素尤为重要。本工作重点综述了萃取剂之间、萃取剂与金属离子之间的协同作用机理以及影响其作用因素的研究进展，指出协同萃取的本质是氢键的形成导致萃取剂的结构与能量发生变化，进而提高了萃取效果。协同萃取主要包括两个方面，一是更容易生成稳定的萃合物从而提高萃取效率，二是利用萃取剂之间的差异提高分离性能。萃取系统的pH、不同萃取剂的组合及比例、萃取剂的浓度、中性磷类萃取剂的添加等诸多因素显著影响协同萃取过程，且各种因素之间存在交互。运用模拟计算进行理论性预测，通过实验进行验证，并且辅以现代分析化学方法进行表征，是今后化工研究领域行之有效的方法之一，理论推广实际，从而更好地指导生产。

关键词: 计算化学, 离子交换, 溶剂萃取, 模型, 聚合

Abstract: As a branch of solvent extraction, synergistic extraction has been widely studied. In order to explore the mechanism of synergistic extraction, it is necessary to clarify the internal reasons of the extraction system and give the relationship between the micro and macro properties. Therefore, it is important to understand the synergistic extraction system and the influencing factors from the microscopic structure and internal movement of molecules. In this owrk, the mechanism of synergistic action between extractant, extractant and metal ions and the influencing factors were reviewed. It pointed out that the essence of synergistic extraction was the formation of hydrogen bonds, which led to the change of the structure and energy of extractant, thus improving the extraction effect. Synergistic extraction mainly includes two aspects: one is easier to generate stable extraction complex to improve the extraction efficiency; the other is to improve the separation performance by using the difference between extractant. The pH of the extraction system, the combination and proportion of different extractant, the concentration of extractant and the addition of neutral phosphorus extractant significantly affect the synergistic extraction process, and there are interactions among various factors. It will be one of the effective methods in the field of chemical research in the future to carry out theoretical prediction by simulation calculation, verify by experimental means, and characterize with modern analytical chemistry method. The theory is popularized to practice, so as to better guide the production.

Key words: computational chemistry, ion exchange, solvent extraction, model, polymerization

中图分类号:

O658.2

张豪, 叶国华, 陈子杨, 谢禹, 左琪. 典型有机磷类萃取剂在溶剂萃取中协同萃取的研究进展[J]. 过程工程学报, 2021, 21(7): 741-751.

Hao ZHANG, Guohua YE, Ziyang CHEN, Yu XIE, Qi ZUO. Research progress on synergistic extraction of typical organophosphorus extractant in solvent extraction[J]. The Chinese Journal of Process Engineering, 2021, 21(7): 741-751.

图/表 9

图1 典型有机磷类萃取剂结构简图

Fig.1 Structure diagram of typical organic phosphorus extractants

表1 三种酸性萃取剂与其二聚体主要键长比较(单位：nm)[25]

Table 1 Comparison of main bond lengths of three acid extractants in dimers (Unit: nm)[25]

Bond shape	P204 single molecule	P204 dimer	P507 single molecule	P507 dimer	Cyanex272 single molecule	Cyanex272 dimer
P=O	0.1485	0.1608	0.1493	0.1622	0.1501	0.1633
P-O	0.1600	0.1697	0.1616	0.1721	0.1653	0.1696
O-H	0.0968	0.1038	0.0968	0.1038	0.0972	0.1046

表2 三种酸性萃取剂与其二聚体主要中心原子电荷比较(单位：C)[25]

Table 2 Comparison of the charge of three acid extractants at the main center of dimer (Unit: C)[25]

Atom	P204 single molecule charge	P204 dimer charge	P507 single molecule charge	P507 dimer charge	Cyanex272 single molecule charge	Cyanex272 dimer charge
P	2.259	1.501	1.904	1.428	1.430	1.225
O (hydroxyl)	-0.761	-0.742	-0.731	-0.724	-0.681	-0.764
O (phosphoryl group)	-0.738	-0.744	-0.705	-0.775	-0.684	-0.746
H	0.385	0.490	0.383	0.441	0.382	0.486

表3 三种酸性萃取剂与其二聚体能量比较(单位：kJ/mol)[25]

Table 3 Energy comparison of three acid extractants and dimers(Unit: kJ/mol)[25]

Extractant	Energy	ΔE
P204-P204	-6683328.863	-418.801
P204 monome	-3341455.030
P507-P507	-6288551.753	-687.303
P507 monome	-3143932.228
Cyanex-Cyanex	-5996893.000	-104152.000
Cyanex monome	-2946370.000

图2 磷类萃取剂协同萃取结合形式示意图[33]

Fig.2 Schematic diagram of combined forms of synergistic extraction of phosphorus extractants[33]

表4 三种酸性萃取剂二聚体分子前线轨道与能量比较(单位：eV)[25]

Table 4 Comparison of molecular frontier orbitals and energies of dimers of three acid extractants(Unit: eV)[25]

Orbital	P204 dimer	P507 dimer	Cyanex dimer
HOMO-1	-7.983	-7.508	-7.006
HOMO	-7.920	-7.486	6.836
LUMO	-0.756	0.152	1.006
LUMO+1	-0.103	0.713	1.494
ΔE_HOMO-LUMO	7.164	7.638	7.842

图3 中性萃取剂与萃取电子轨道

Fig.3 Neutral extractant and extraction electron orbit

图4 Zn参与协萃反应

Fig.4 Co-extraction of Zn

图5 Fe参与协萃反应

Fig.5 Co-extraction of Fe

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