Research progress on synergistic extraction of typical organophosphorus extractant in solvent extraction

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

Abstract

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

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

CLC Number:

O658.2

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.

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.

Figures/Tables 9

References 67

1	Ye S S, Jing Y, Wang Y D, et al. Recovery of rare earths from spent FCC catalysts by solvent extraction using saponified 2-ethylhexyl phosphoric acid-2-ethylhexyl ester (EHEHPA) [J]. Journal of Rare Earths, 2017, 35(7): 716-722.
2	Thi H N, Lee M S. Recovery of molybdenum and vanadium with high purity from sulfuric acid leach solution of spent hydrodesulfurization catalysts by ion exchanged [J]. Hydrometallurgy, 2014, 147/148: 142-147.
3	Weterings K, Janssen J. Recovery of uranium, vanadium, yttrium and rare earths from phosphoric acid by a precipitation method [J]. Hydrometallurgy, 1985, 15(2): 173-190.
4	Talles Barcelos D C, Meuris G C D S, Melissa G A V. Recovery of rare-earth metals from aqueous solutions by bio/adsorption using non-conventional materials:a review with recent studies and promising approaches in column applications [J]. Journal of Rare Earths, 2019, 38(4): 339-355.
5	Li W, Zhang Y M, Liu T, et al. Comparison of ion exchange and solvent extraction in recovering vanadium from sulfuric acid leach solutions of stone coal [J]. Hydrometallurgy, 2013, 131/132: 1-7.
6	Zhang W S, Zhu Z W, Cheng C Y. A literature review of titanium metallurgical processes [J]. Hydrometallurgy, 2011, 108(3/4): 177-188.
7	Yun C Y, Lee C Y, Lee G G, et al. Modeling and simulation of multicomponent solvent extraction processes to purify rare earth metals [J]. Hydrometallurgy, 2016, 159: 40-45.
8	Dariush A, Larachi F. Behavior of bifunctional phosphonium-based ionic liquids in solvent extraction of rare earth elements-quantum chemical study [J]. Journal of Molecular Liquids, 2018, 263(1): 96-108.
9	Jing Y, Chen J, Su W R, et al. Deep insights into the solution and interface behaviors in heavy rare earth extraction: a molecular dynamics study [J]. Journal of Molecular Liquids, 2019, 296(15): 26-41.
10	Xu D D, Zeb S, Cui Y, et al. Recovery of rare earths from nitric acid leach solutions of phosphate ores using solvent extraction with a new amide extractant (TODGA) [J]. Hydrometallurgy, 2018, 180: 132-138.
11	Wei H Q, Li Y L, Kuang S T, et al. Separation of trivalent rare earths from chloride medium using solvent extraction with heptylaminomethyl phosphonic acid 2-ethylhexyl ester (HEHHAP) [J]. Hydrometallurgy, 2019, 188: 14-21.
12	Chen X Y, Chen Q, Guo F L, et al. Extraction behaviors of rare-earths in the mixed sulfur-phosphorus acid leaching solutions of scheelite [J]. Hydrometallurgy, 2018, 175: 326-332.
13	Wu S X, Wang L S, Zhang P, et al. Simultaneous recovery of rare earths and uranium from wet process phosphoric acid using solvent extraction with D2EHPA [J]. Hydrometallurgy, 2018, 175: 109-116.
14	Tavakoli M R, Dreisinger D B. Separation of vanadium from iron by solvent extraction using acidic and neutral organophosporus extractants [J]. Hydrometallurgy, 2014, 141: 17-23.
15	Kuang S T, Zhang Z F, Li Y L, et al. Synergistic extraction and separation of rare earths from chloride medium by the mixture of HEHAPP and D2EHPA [J]. Hydrometallurgy, 2017, 174: 78-83.
16	Cai Z L, Feng Y L, Zhou Y Z, et al. Selective separation and extraction of vanadium(V) over manganese(II) from co-leaching solution of roasted stone coal and pyrolusite using solvent extraction [J]. JOM, 2013, 65(11): 29-36.
17	Li X B, Wei C, Wu J, et al. Thermodynamics and mechanism of vanadium(IV) extraction from sulphate medium with D2EHPA, EHEHPA and CYANEX272 in kerosene [J]. Transactions of Nonferrous Metals Society of China, 2012, 22(2): 461-466.
18	Deng Z G, Wei C, Fan G, et al. Extracting vanadium from stone-coal by oxygen pressure acid leaching and solvent extraction [J]. Transactions of Nonferrous Metals Society of China, 2010, 20(1): s118-s122.
19	Wang H J, Feng Y L, Li H L, et al. Recovery of vanadium from acid leaching solutions of spent oil hydrotreating catalyst using solvent extraction with D2EHPA (P204) [J]. Hydrometallurgy, 2020, 195: 144-154.
20	Amesh P, Suneesh A S, Venkatesan K A. Preparation and ion exchange studies of cesium and strontium on sodium iron titanate [J]. Separation and Purification Technology, 2019, 238(1): 63-93.
21	Liu Z S, Huang J, Zhang Y M. Separation and recovery of vanadium and aluminum from oxalic acid leachate of shale by solvent extraction with Aliquat 336 [J]. Separation and Purification Technology, 2020, 249(15): 147-148.
22	Chen K H, He Y, Srinivasakannan C, et al. Characterization of the interaction of rare earth elements with P507 in a microfluidic extraction system using spectroscopic analysis [J]. Chemical Engineering Journal, 2019, 56(15): 453-460.
23	Cieszynska A, Wisniwski M. Extractive recovery of palladium(II) from hydrochloric acid solutions with Cyphos^®IL 104 [J]. Hydrometallurgy, 2012, 113/114: 79-85.
24	Kumari A, Panda R, Lee J Y, et al. Extraction of rare earth metals (REMs) from chloride medium by organo-metallic complexation using D2EHPA [J]. Separation and Purification Technology, 2019, 227(15): 56-80.
25	魏昶. 有机磷类萃取剂结构-性能关系及萃取钒基础研究 [R]. 国家自然科学基金结题报告. 昆明: 昆明理工大学. 2015: 10-20.
	Wei C. Study on the relationship between the structure and properties of organophosphorus extractants and the extraction of vanadium [R]. National Natural Science Foundation of China. Kunming: Kunming University of Science and Technology. 2015: 10-20.
26	Zhang Y, Zhang T G, Lü G Z, et al. Synergistic extraction of vanadium(IV) in sulfuric acid media using a mixture of D2EHPA and EHEHPA [J]. Hydrometallurgy, 2016, 166: 87-93.
27	Liu Y, Jeon H S, Lee M S. Solvent extraction of Pr and Nd from chloride solutions using ternary extractant system of Cyanex 272, Alamine 336 and TBP [J]. Journal of Industrial and Engineering Chemistry, 2015, 31(25): 74-79.
28	Atefeh A, Fereshteh R, Ataollah B. Stoichiometry and structural studies of Fe(III) and Zn(II) solvent extraction using D2EHPA/TBP [J]. Separation and Purification Technology, 2016,171(17): 197-205.
29	Cristian T, Yannick M, Dogistein E, et al. Recovery of critical materials from mine tailings: a comparative study of the solvent extraction of rare earths using acidic, solvating and mixed extractant systems [J]. Journal of Cleaner Production, 2019, 218(1): 425-437.
30	Zhang F Y, Wu W Y, Bian X, et al. Synergistic extraction and separation of lanthanum(III) and cerium(III) using a mixture of 2-ethylhexylphosphonic mono-2-ethylhexyl ester and di-2-ethylhexyl phosphoric acid in the presence of two complexing agents containing lactic acid and citric acid [J]. Hydrometallurgy, 2014, 149: 238-243.
31	Mellah A, Benachour D. The solvent extraction of zinc and cadmium from phosphoric acid solution by di-2-ethyl hexyl phosphoric acid in kerosene diluent [J]. Chemical Engineering & Processing: Process Intensification, 2006, 45(8): 684-690.
32	Jin Y, Ma Y J, Weng Y L, et al. Solvent extraction of Fe³⁺ from the hydrochloric acid route phosphoric acid by D2EHPA in kerosene [J]. Journal of Industrial and Engineering Chemistry, 2014, 20(5): 3446-3452.
33	Zhang F Y, Dai J J, Wang A, et al. Investigation of the synergistic extraction behavior between cerium(III) and two acidic organophosphorus extractants using FT-IR, NMR and mass spectrometry [J]. Inorganica Chimica Acta, 2017, 466(1): 333-342.
34	Xiong P, Zhang Y M, Huang J, et al. High-efficient and selective extraction of vanadium(V) with N235-P507 synergistic extraction system [J]. Chemical Engineering Research and Design, 2017, 120: 284-290.
35	Wang L Y, Lee M S. Recovery of Co(II) and Ni(II) from chloride leach solution of nickel laterite ore by solvent extraction with a mixture of Cyanex 301 and TBP [J]. Journal of Molecular Liquids, 2017, 240: 345-350.
36	Shi D, Cui B, Li L J, et al. Lithium extraction from low-grade salt lake brine with ultrahigh Mg/Li ratio using TBP-kerosene-FeCl₃ system [J]. Separation and Purification Technology, 2019, 211(18): 303-309.
37	Hong T, Liu M B, Ma J, et al. Selective recovery of Rhenium from industrial leach solutions by synergistic solvent extraction [J]. Separation and Purification Technology, 2019, 236(1): 62-81.
38	Mishra R K, Rout P C, Sarangi K, et al. A comparative study on extraction of Fe(III) from chloride leach liquor using TBP, Cyanex 921 and Cyanex 923 [J]. Hydrometallurgy, 2010, 104(2): 298-303.
39	Li X B, Wei C, Deng Z G, et al. Selective solvent extraction of vanadium over iron from a stone coal/black shale acid leach solution by D2EHPA/TBP [J]. Hydrometallurgy, 2011, 105(3/4): 359-363.
40	Fatmehsari D H, Darvishi D, Etemadi S, et al. Interaction between TBP and D2EHPA during Zn, Cd, Mn, Cu, Co and Ni solvent extraction: a thermodynamic and empirical approach [J]. Hydrometallurgy, 2009, 98(1/2): 143-147.
41	He Y, Guo S H, Chen K H, et al. Application of microchemical technology in mass transfer behavior contrastive research of rare earth extraction [J]. Microchemical Journal, 2019, 150: 41-80.
42	Zhang G Z, Chen D S, Zhao W, et al. A novel synergistic extraction method for recovering vanadium (V) from high-acidity chloride leaching liquor [J]. Separation and Purification Technology, 2016, 165(13): 166-172.
43	El-Nadi Y A, Awwad N S, Nayl A A. A comparative study of vanadium extraction by Aliquat-336 from acidic and alkaline media with application to spent catalyst [J]. International Journal of Mineral Processing, 2009, 92(1): 115-120.
44	Nayl A A, Aly H F. Solvent extraction of V(V) and Cr(III) from acidic leach liquors of ilmenite using Aliquat 336 [J]. Transactions of Nonferrous Metals Society of China, 2015, 25(12): 4183-4191.
45	Alireza C, Morteza S A, Eskandar K A, et al. Thermodynamics of vanadium (V) solvent extraction by mixture of D2EHPA and TBP [J]. International Journal of Mineral Processing, 2015, 138(10): 49-54.
46	Zhou H Y, Dong Y M, Wang Y B, et al. Recovery of Th(IV) from leaching solutions of rare earth residues using a synergistic solvent extraction system consisting of Cyanex 572 and n-octyl diphenyl phosphate (ODP) [J]. Hydrometallurgy, 2019, 183: 186-192.
47	El-Dessouky S I, El-Nadi Y A, Ahmed I M, et al. Solvent extraction separation of Zn(II), Fe(II), Fe(III) and Cd(II) using tributylphosphate and CYANEX921 in kerosene from chloride medium [J]. Chemical Engineering and Processing: Process Intensification, 2008, 47(2): 177-183.
48	Mehdi N, Fereshteh R, Ataollah B, et al. Selective recovery and separation of nickel and vanadium in sulfate media using mixtures of D2EHPA and Cyanex272 [J]. Separation and Purification Technology, 2014, 136(5): 265-273.
49	Sui N, Huang K. Separation of rare earths using solvent extraction consisting of three phases [J]. Hydrometallurgy, 2019, 188: 112-122.
50	Liu H, Zhang Y M, Huang J, et al. A synergistic approach for separating vanadium and impurities in black shale acid leaching solution using a mixture of Cyanex272 and N235 [J]. Separation and Purification Technology, 2019, 215(15): 335-341.
51	Jiang D D, Song N Z, Liao S F, et al. Study on the synergistic extraction of vanadium by mixtures of acidic organophosphorus extractants and primary amine N1923 [J]. Separation and Purification, 2015, 156(17): 835-840.
52	Liu Y, Lee M S. Separation of Co and Ni from a chloride leach solutions of laterite ore by solvent extraction with extractant mixtures [J]. Journal of Industrial and Engineering Chemistry, 2015, 28(25): 322-327.
53	James E, Quin N, Karin H, et al. Solvent extraction of rare earth elements using phosphonic/phosphinic acid mixtures [J]. Hydrometallurgy, 2015,157: 298-305.
54	Marie C, Hiscox B, Nash K L. Characterization of HDEHP-lanthanide complexes formed in a non-polar organic phase using 31P NMR and ESI-MS [J]. Dalton Transactions, 2012, 41(3): 1054-1064.
55	Maryam M, Kerstin F, Lars K, et al. Separation of ND(III), DY(III) and Y(III) by solvent extraction using D2EHPA and EHEHPA [J]. Hydrometallurgy, 2015, 156: 215-224.
56	Ataollah B, Fereshteh R, Alireza Z, et al. Selective separation of nickel and cadmium from sulfate solutions of spent nickel-cadmium batteries using mixtures of D2EHPA and Cyanex 302 [J]. Journal of Power, 2014, 247(1): 127-133.
57	Shi Q H, Zhang Y M, Huang J, et al. Synergistic solvent extraction of vanadium from leaching solution of stone coal using D2EHPA and PC88A [J]. Separation and Purification Technology, 2017, 181(30): 1-7.
58	Zhao Q, Li Y L, Kuang S T, et al. Synergistic extraction of heavy rare earths by mixture of α-aminophosphonic acid HEHAMP and HEHEHP [J]. Journal of Rare Earths, 2019, 37(4): 422-428.
59	Hu J S, Zou D, Chen J, et al. A novel synergistic extraction system for the recovery of scandium(III) by Cyanex272 and Cyanex923 in sulfuric acid medium [J]. Separation and Purification Technology, 2020, 233(15): 59-77.
60	Hu G P, Chen D S, Wang L N, et al. Extraction of vanadium from chloride solution with high concentration of iron by solvent extraction using D2EHPA [J]. Separation and Purification Technology, 2014, 125(7): 59-65.
61	Ma L, Zhao Z Y, Dong Y M, et al. A synergistic extraction strategy by Cyanex572 and Cyanex923 for Th(IV) separation [J]. Separation and Purification Technology, 2018, 191(31): 307-313.
62	Ma Y Q, Wang X W, Wang M Y, et al. Separation of V(IV) and Fe(III) from the acid leach solution of stone coal by D2EHPA/TBP [J]. Hydrometallurgy, 2015, 153: 8-45.
63	Alexandre S G, Marcel B M. Selection of a synergistic solvent extraction system to remove calcium and magnesium from concentrated nickel sulfate solutions [J]. Hydrometallurgy, 2018, 175: 250-256.
64	Shen L, Chen J, Chen L, et al. Extraction of mid-heavy rare earth metal ions from sulphuric acid media by ionic liquid [A336][P507] [J]. Hydrometallurgy, 2016, 161: 152-159.
65	Fanny M, Guilhem A, Antoine L, et al. Synthesis of organophosphorus ligands with a central oxygen atom and their applications in solvent extraction [J]. Tetrahedron, 2019, 75(30): 3968-3976.
66	Moussa A, Habib S, Safa A A. Solvent extraction of vanadium(IV) with di(2-ethyl-hexyl) phosphoric acid and tri-n-butyl phosphate [J]. Chemical Engineering, 2008, 52(1): 29-33.
67	Seyed M R, Ali H, Ali R K. Thermodynamic modeling of the solvent extraction equilibrium for the recovery of vanadium(V) from acidic sulfate solutions using di-(2-ethylhexyl) phosphoric acid [J]. Fluid Phase Equilibria, 2018, 474(25): 20-31.

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

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

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

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

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