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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Front. Chem. Sci. Eng.    2023, Vol. 17 Issue (1) : 56-67    https://doi.org/10.1007/s11705-022-2185-8
RESEARCH ARTICLE
Vanadium(IV) solvent extraction enhancement in high acidity using di-(2-ethylhexyl)phosphoric acid with [Cl−] present: an experimental and theoretical study
Hong Liu1,2,3,4(), Yi-Min Zhang1,2,3,4(), Jing Huang1,2,3,4, Tao Liu1,2,3,4
1. School of Resource and Environmental Engineering, Wuhan University of Science and Technology, Wuhan 430081, China
2. State Environmental Protection Key Laboratory of Mineral Metallurgical Resources Utilization and Pollution Control, Wuhan University of Science and Technology, Wuhan 430081, China
3. Hubei Collaborative Innovation Center for High Efficient Utilization of Vanadium Resources, Wuhan University of Science and Technology, Wuhan 430081, China
4. Hubei Provincial Engineering Technology Research Center of High Efficient Cleaning Utilization for Shale Vanadium Resource, Wuhan University of Science and Technology, Wuhan 430081, China
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Abstract

Separation of vanadium from black shale leaching solution at low pH is very meaningful, which can effectively avoid the generation of alkali neutralization slag and the resulting vanadium loss. In this study, coordination mechanism of vanadium in acid leaching solution at low pH was investigated with the intervention of chloride ions. Under the conditions of pH 0.8, di-(2-ethylhexyl)phosphoric acid concentration of 20%, phase ratio of 1:2, and extraction time of 8 min, the vanadium extraction could reach 80.00%. The Fourier transform infrared and electrospray ionization results reveal that, despite the fact that the chloride ion in the leachate could significantly promote vanadium extraction, the chloride ion does not enter the organic phase, indicating an intriguing phenomenon. Among Cl−–V, SO42−–V, and H2O–V, the V–Cl bond is longer and the potential difference between coordinate ions and vanadium is smaller. Therefore, VO2+ gets easily desorbed with chloride ions and enter the organic phase. At the same time, the hydrogen ions of di-(2-ethylhexyl)phosphoric acid also enter the water phase more easily, which reduces the pH required for the extraction reaction.

Keywords vanadium      black shale      solvent extraction      high acidity extraction     
Corresponding Author(s): Hong Liu,Yi-Min Zhang   
About author:

Changjian Wang and Zhiying Yang contributed equally to this work.
Online First Date: 29 August 2022    Issue Date: 21 February 2023
 Cite this article:   
Hong Liu,Yi-Min Zhang,Jing Huang, et al. Vanadium(IV) solvent extraction enhancement in high acidity using di-(2-ethylhexyl)phosphoric acid with [Cl−] present: an experimental and theoretical study[J]. Front. Chem. Sci. Eng., 2023, 17(1): 56-67.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2185-8
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I1/56
Fig.1  Effect of pH on vanadium extraction in different media (extraction conditions: D2EHPA concentration 20%, phase ratio 1:2 (O/A), extraction time 8 min).
Fig.2  Effect of [Cl?] concentration on vanadium extraction (extraction conditions: D2EHPA concentration 20%, feed solution pH 0.8, phase ratio 1:2 (oil/water, O/A), and extraction time 8 min).
Fig.3  Effects of (a) pH, (b) D2EHPA concentration, (c) phase ratio, and (d) extraction time on vanadium extraction.
pH Extraction percentage/% Distribution ratio Separation coefficient
V Fe Al V Fe Al V/Fe V/Al
0.2 46.88 10.52 11.14 1.77 0.24 0.25 7.51 7.04
0.4 60.02 8.56 10.83 3.00 0.19 0.24 16.04 12.36
0.6 77.50 6.77 9.07 6.89 0.15 0.20 47.43 34.52
0.8 80.00 6.65 8.93 8.00 0.14 0.20 56.15 40.79
1.0 83.75 6.32 7.46 10.31 0.13 0.16 76.39 63.91
1.2 85.04 6.16 5.02 11.37 0.13 0.11 86.60 107.57
1.4 87.25 6.02 5.02 13.69 0.13 0.11 106.83 129.47
1.6 88.20 5.88 4.90 14.95 0.12 0.10 119.64 145.04
1.8 88.75 5.65 4.66 15.78 0.12 0.10 131.74 161.40
Tab.1  Separation performance of impurities in vanadium extraction
Fig.4  FTIR spectroscopy analysis of (a) fresh organic phase, (b) loaded organic phase from H2SO4 medium, and (c) loaded organic phase from HCl medium.
Fig.5  ESI-MS analysis of (a) fresh organic phase, (b) loaded organic phase from H2SO4 medium, and (c) loaded organic phase from HCl medium.
Fig.6  Possible major structures in organic phases of (a) fresh organic phase, and (b and c) loaded organic phase from H2SO4/HCl medium.
Classification Reaction ?G/(kJ·mol?1) Equation
Cl– coordinates with vanadium VO2+ + Cl– = VOCl+ –1807.57 (6)
VO2+ + 2Cl– = VOCl2 –2943.53 (7)
VO2+ + 3Cl– = VOCl3– –3396.22 (8)
VO2+ + 4Cl– = VOCl42– –3396.66 (9)
SO42– coordinates with vanadium VO2+ + SO42– = VOSO4 –2102.04 (10)
VO2+ + 2SO42– = VO(SO4)22– –2818.63 (11)
VO2+ + 3SO42– = VO(SO4)34– –1996.77 (12)
H2O coordinates with vanadium VO2+ + H2O = VO(H2O)2+ –498.78 (13)
VO2+ + 2H2O = VO(H2O)22+ –945.52 (14)
VO2+ + 3H2O = VO(H2O)32+ –1326.37 (15)
VO2+ + 4H2O = VO(H2O)42+ –1640.92 (16)
VO2+ + 5H2O = VO(H2O)52+ –1875.10 (17)
Displacement reactions of Cl–, SO42–, and H2O with vanadium complex VO(H2O)2+ + Cl– = VOCl+ + H2O –1280.27 (18)
VO(H2O)22+ + 2Cl– = VOCl2 + 2H2O –1937.41 (19)
VO(H2O)32+ + 3Cl– = VOCl3– + 3H2O –2069.85 (20)
VO(H2O)42+ + 4Cl– = VOCl42– + 4H2O –1755.74 (21)
VOSO4 + 2Cl– = VOCl2 + SO42– –780.90 (22)
VO(SO4)22– + 4Cl– = VOCl42– + 2SO42– –578.02 (23)
SO42– + VO(H2O)22+ = VOSO4 + 2H2O –1156.52 (24)
2SO42– + VO(H2O)42+ = VO(SO4)22– + 4H2O –1177.72 (25)
Tab.2  Main reactions of vanadium ions with different ligands
Fig.7  LUMO analysis of (a) VO2+, (b) VOSO4, (c) VO(SO4)22?, (d) VO(H2O)2+, (e) VO(H2O)22+, (f) VO(H2O)32+, (g) VO(H2O)42+, (h) VOCl+, (i) VOCl2, (j) VOCl3?, and (k) VOCl42?.
Fig.8  Atomic charge and bond length analysis of (a) VOSO4, (b) VO(SO4)22?, (c) VO(H2O)2+, (d) VO(H2O)22+, (e) VO(H2O)32+, (f) VO(H2O)42+, (g) VOCl+, (h) VOCl2, (i) VOCl3?, and (j) VOCl42?.
Fig.9  Mechanism of chloride ion promoting vanadium extraction at low pH.
1 Y Fei, B Zhang, J He, C Chen, H Liu. Dynamics of vertical vanadium migration in soil and interactions with indigenous microorganisms adjacent to tailing reservoir. Journal of Hazardous Materials, 2022, 424 : 127608
https://doi.org/10.1016/j.jhazmat.2021.127608
2 Z S Liu, Y M Zhang, Z L Dai, J Huang, T Liu. Coextraction of vanadium and manganese from high-manganese containing vanadium wastewater by a solvent extraction-precipitation process. Frontiers of Chemical Science and Engineering, 2020, 14( 5): 902– 912
https://doi.org/10.1007/s11705-019-1887-z
3 Z Bian, Y Feng, H Li, R Zhang. New understanding of extraction and separation of vanadium(IV), iron and titanium using iron powder induction-leaching and P204-P507 synergistic extraction. Separation and Purification Technology, 2022, 288 : 120627
https://doi.org/10.1016/j.seppur.2022.120627
4 B Chen, S X Bao, Y M Zhang. Synergetic strengthening mechanism of ultrasound combined with calcium fluoride towards vanadium extraction from low-grade vanadium-bearing shale. International Journal of Mining Science and Technology, 2021, 31( 6): 1095– 1106
https://doi.org/10.1016/j.ijmst.2021.07.008
5 B Hu, C Zhang, Y Dai, X Wang, M Wang. Separation of vanadium and chromium in solution after vanadium precipitation by co-extraction with N263 and selective stripping with NaOH solution. Hydrometallurgy, 2022, 208 : 105798
https://doi.org/10.1016/j.hydromet.2021.105798
6 X Chen, H Wang, B Yan. Sulfuric acid leaching and recovery of vanadium from a spinel concentrate beneficiated from stone coal ore. Hydrometallurgy, 2020, 191 : 105239
https://doi.org/10.1016/j.hydromet.2019.105239
7 H Wang, Y Feng, H Li, H Li, H Wu. Recovery of vanadium from acid leaching solutions of spent oil hydrotreating catalyst using solvent extraction with D2EHPA (P204). Hydrometallurgy, 2020, 195 : 105404
https://doi.org/10.1016/j.hydromet.2020.105404
8 Z Bian, Y Feng, H Li, H Wu. Efficient separation of vanadium, titanium, and iron from vanadium-bearing titanomagnetite by pressurized pyrolysis of ammonium chloride-acid leaching-solvent extraction process. Separation and Purification Technology, 2021, 255 : 117169
https://doi.org/10.1016/j.seppur.2020.117169
9 Y Liu, Q G Li, T Zhang, X S Wu, J W Du, G Q Zhang, L Zeng. New process consisting of oxidative stripping of vanadium from loaded D2EHPA organic solution with H2O2 and direct precipitation with sulfuric acid. Hydrometallurgy, 2021, 203 : 105611
https://doi.org/10.1016/j.hydromet.2021.105611
10 D S Chen, H X Zhao, G P Hu, T Qi, H D Yu, G Z Zhang, L N Wang, W J Wang. An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite. Journal of Hazardous Materials, 2015, 294 : 35– 40
https://doi.org/10.1016/j.jhazmat.2015.03.054
11 T H Nguyen, M S Lee. Solvent extraction of vanadium(V) from sulfate solutions using LIX 63 and PC 88A. Journal of Industrial and Engineering Chemistry, 2015, 31 : 118– 123
https://doi.org/10.1016/j.jiec.2015.06.015
12 X Li, C Wei, J Wu, M Li, Z Deng, C Li, H Xu. Co-extraction and selective stripping of vanadium (IV) and molybdenum (VI) from sulphuric acid solution using 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester. Separation and Purification Technology, 2012, 86 : 64– 69
https://doi.org/10.1016/j.seppur.2011.10.021
13 M R Tavakoli, D B Dreisinger. Separation of vanadium from iron by solvent extraction using acidic and neutral organophosporus extractants. Hydrometallurgy, 2014, 141 : 17– 23
https://doi.org/10.1016/j.hydromet.2013.10.008
14 J Wen, P Ning, H Cao, Z Sun, Y Zhang, G Xu. Recovery of high-purity vanadium from aqueous solutions by reusable primary amines N1923 associated with semiquantitative understanding of vanadium species. ACS Sustainable Chemistry & Engineering, 2018, 6( 6): 7619– 7626
https://doi.org/10.1021/acssuschemeng.8b00445
15 X Jing, Z Wu, J Du, X Wang, X Jing, P Ning. Kinetics of V(V) extraction in V(V)-SO42− (Na+, H+)-primary amine N1923-sulfonated kerosene system using single drop technique. Separation and Purification Technology, 2019, 215 : 473– 479
https://doi.org/10.1016/j.seppur.2019.01.037
16 Z Qin, G Zhang, Y Xiong, D Luo, C Li, S Tang, H Yue, B Liang. Recovery of vanadium from leach solutions of vanadium slag using solvent extraction with N235. Hydrometallurgy, 2020, 192 : 105259
https://doi.org/10.1016/j.hydromet.2020.105259
17 Q Li, J Huang, Y Zhang, Q Zheng. The effect of impurity ions on the pH adjustment for vanadium-bearing acid leaching solution by selective electrodialysis. Journal of Cleaner Production, 2022, 340 : 130801
https://doi.org/10.1016/j.jclepro.2022.130801
18 K Wang, Y Zhang, J Huang, T Liu, J Wang. Recovery of sulfuric acid from a stone coal acid leaching solution by diffusion dialysis. Hydrometallurgy, 2017, 173 : 9– 14
https://doi.org/10.1016/j.hydromet.2017.07.005
19 Y Zhang, T Zhang, D Dreisinger, W Zhou, F Xie, G Lv, W Zhang. Chelating extraction of vanadium(V) from low pH sulfuric acid solution by Mextral 973H. Separation and Purification Technology, 2018, 190 : 123– 135
https://doi.org/10.1016/j.seppur.2017.07.016
20 Y He, Y Zhang, J Huang, Q Zheng, H Liu. Extraction of vanadium(V) from a vanadium-bearing shale leachate through bifunctional coordination in Mextral 984H extraction system. Separation and Purification Technology, 2022, 288 : 120452
https://doi.org/10.1016/j.seppur.2022.120452
21 Q Zheng, Y Zhang, N Xue. Migration and coordination of vanadium separating from black shale involved by fluoride. Separation and Purification Technology, 2021, 266 : 118552
https://doi.org/10.1016/j.seppur.2021.118552
22 Z S Liu, J Huang, Y M Zhang, T Liu, P C Hu, H Liu, D S Luo. Separation and recovery of vanadium and aluminum from oxalic acid leachate of shale by solvent extraction with Aliquat 336. Separation and Purification Technology, 2020, 249 : 116867
https://doi.org/10.1016/j.seppur.2020.116867
23 W Li, X Yan, Z Niu, X Zhu. Selective recovery of vanadium from red mud by leaching with using oxalic acid and sodium sulfite. Journal of Environmental Chemical Engineering, 2021, 9( 4): 105669
https://doi.org/10.1016/j.jece.2021.105669
24 P C Hu, Y M Zhang. Mechanism of vanadium selective separation from iron in shale under an environmentally friendly oxalate ligand system. Separation and Purification Technology, 2021, 276 : 119269
https://doi.org/10.1016/j.seppur.2021.119269
25 W Zhang, D Feng, X Xie, X Tong, Y Du, Y Cao. Solvent extraction and separation of light rare earths from chloride media using HDEHP-P350 system. Journal of Rare Earths, 2022, 40( 2): 328– 337
https://doi.org/10.1016/j.jre.2021.05.003
26 N Tang, L L Liu, C Yin, G P Zhu, Q L Huang, J R Dong, X J Yang, S X Wang. Environmentally benign hydrophobic deep eutectic solvents for palladium(II) extraction from hydrochloric acid solution. Journal of the Taiwan Institute of Chemical Engineers, 2021, 121 : 92– 100
https://doi.org/10.1016/j.jtice.2021.04.010
27 L Cui, L Wang, M Feng, L Fang, Y Guo, F Cheng. Ion-pair induced solvent extraction of lithium (I) from acidic chloride solutions with tributyl phosphate. Green Energy & Environment, 2021, 6( 4): 607– 616
https://doi.org/10.1016/j.gee.2020.05.002
28 C Shen, Y Zhang, J Huang, S Bao, X Yang, P Xiong. Separation of vanadium(V) using N235 by three-phase system in concentrated HCl media. Canadian Journal of Chemistry, 2017, 95( 6): 717– 722
https://doi.org/10.1139/cjc-2016-0669
29 G Hu, D Chen, L Wang, J Liu, H Zhao, Y H Liu, T Qi, C Q Zhang, P Yu. Extraction of vanadium from chloride solution with high concentration of iron by solvent extraction using D2EHPA. Separation and Purification Technology, 2014, 125 : 59– 65
https://doi.org/10.1016/j.seppur.2014.01.031
30 X Zhu, W Li, S Tang, M Zeng, P Bai, L Chen. Selective recovery of vanadium and scandium by ion exchange with D201 and solvent extraction using P507 from hydrochloric acid leaching solution of red mud. Chemosphere, 2017, 175 : 365– 372
https://doi.org/10.1016/j.chemosphere.2017.02.083
31 Y Ma, X Wang, M Wang, C Jiang, X Xiang, X Zhang. Separation of V(IV) and Fe(III) from the acid leach solution of stone coal by D2EHPA/TBP. Hydrometallurgy, 2015, 153 : 38– 45
https://doi.org/10.1016/j.hydromet.2015.02.003
32 G Li, Q Xie, G Ren, J Liu, D Liang. Mass transfer kinetics during the extraction of m-cresol from model coal tar using betaine/glycerol deep eutectic solvents. Chemical Engineering Research & Design, 2022, 177 : 732– 740
https://doi.org/10.1016/j.cherd.2021.11.036
33 Q Shi, Y Zhang, J Huang, T Liu, H Liu, L Wang. Synergistic solvent extraction of vanadium from leaching solution of stone coal using D2EHPA and PC88A. Separation and Purification Technology, 2017, 181 : 1– 7
https://doi.org/10.1016/j.seppur.2017.03.010
34 Y Zhang, T Zhang, G Lv, G Zhang, Y Liu, W Zhang. Synergistic extraction of vanadium(IV) in sulfuric acid media using a mixture of D2EHPA and EHEHPA. Hydrometallurgy, 2016, 166 : 87– 93
https://doi.org/10.1016/j.hydromet.2016.09.003
35 Y Jing, J Chen, W Su, L Chen, Y Liu, D Li. Deep insights into the solution and interface behaviors in heavy rare earth extraction: a molecular dynamics study. Journal of Molecular Liquids, 2019, 296 : 111790
https://doi.org/10.1016/j.molliq.2019.111790
36 Z Ying, M Huo, G Wu, J Li, Y Ju, Q Wei, X Ren. Recovery of vanadium and chromium from leaching solution of sodium roasting vanadium slag by stepwise separation using amide and EHEHPA. Separation and Purification Technology, 2021, 269 : 118741
https://doi.org/10.1016/j.seppur.2021.118741
37 F Zhang, J Dai, A Wang, W Wu. Investigation of the synergistic extraction behavior between cerium (III) and two acidic organophosphorus extractants using FT-IR, NMR and mass spectrometry. Inorganica Chimica Acta, 2017, 466 : 333– 342
https://doi.org/10.1016/j.ica.2017.06.016
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