Vanadium(IV) solvent extraction enhancement in high acidity using di-(2-ethylhexyl)phosphoric acid with [Cl⁻] present: an experimental and theoretical study

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.

Graphical abstract

Keywords

vanadium / black shale / solvent extraction / high acidity extraction

References

[1] Fei Y, Zhang B, He J, Chen C, Liu H. Dynamics of vertical vanadium migration in soil and interactions with indigenous microorganisms adjacent to tailing reservoir. Journal of Hazardous Materials, 2022, 424 : 127608

[2] Liu Z S, Zhang Y M, Dai Z L, Huang J, Liu T. 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

[3] Bian Z, Feng Y, Li H, Zhang R. 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

[4] Chen B, Bao S X, Zhang Y M. 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

[5] Hu B, Zhang C, Dai Y, Wang X, Wang M. 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

[6] Chen X, Wang H, Yan B. Sulfuric acid leaching and recovery of vanadium from a spinel concentrate beneficiated from stone coal ore. Hydrometallurgy, 2020, 191 : 105239

[7] Wang H, Feng Y, Li H, Li H, Wu H. Recovery of vanadium from acid leaching solutions of spent oil hydrotreating catalyst using solvent extraction with D2EHPA (P204). Hydrometallurgy, 2020, 195 : 105404

[8] Bian Z, Feng Y, Li H, Wu H. 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

[9] Liu Y, Li Q G, Zhang T, Wu X S, Du J W, Zhang G Q, Zeng L. 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

[10] Chen D S, Zhao H X, Hu G P, Qi T, Yu H D, Zhang G Z, Wang L N, Wang W J. An extraction process to recover vanadium from low-grade vanadium-bearing titanomagnetite. Journal of Hazardous Materials, 2015, 294 : 35– 40

[11] Nguyen T H, Lee M S. Solvent extraction of vanadium(V) from sulfate solutions using LIX 63 and PC 88A. Journal of Industrial and Engineering Chemistry, 2015, 31 : 118– 123

[12] Li X, Wei C, Wu J, Li M, Deng Z, Li C, Xu H. 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

[13] Tavakoli M R, Dreisinger D B. Separation of vanadium from iron by solvent extraction using acidic and neutral organophosporus extractants. Hydrometallurgy, 2014, 141 : 17– 23

[14] Wen J, Ning P, Cao H, Sun Z, Zhang Y, Xu G. 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

[15] Jing X, Wu Z, Du J, Wang X, Jing X, Ning P. 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

[16] Qin Z, Zhang G, Xiong Y, Luo D, Li C, Tang S, Yue H, Liang B. Recovery of vanadium from leach solutions of vanadium slag using solvent extraction with N235. Hydrometallurgy, 2020, 192 : 105259

[17] Li Q, Huang J, Zhang Y, Zheng Q. 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

[18] Wang K, Zhang Y, Huang J, Liu T, Wang J. Recovery of sulfuric acid from a stone coal acid leaching solution by diffusion dialysis. Hydrometallurgy, 2017, 173 : 9– 14

[19] Zhang Y, Zhang T, Dreisinger D, Zhou W, Xie F, Lv G, Zhang W. Chelating extraction of vanadium(V) from low pH sulfuric acid solution by Mextral 973H. Separation and Purification Technology, 2018, 190 : 123– 135

[20] He Y, Zhang Y, Huang J, Zheng Q, Liu H. 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

[21] Zheng Q, Zhang Y, Xue N. Migration and coordination of vanadium separating from black shale involved by fluoride. Separation and Purification Technology, 2021, 266 : 118552

[22] Liu Z S, Huang J, Zhang Y M, Liu T, Hu P C, Liu H, Luo D S. 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

[23] Li W, Yan X, Niu Z, Zhu X. 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

[24] Hu P C, Zhang Y M. Mechanism of vanadium selective separation from iron in shale under an environmentally friendly oxalate ligand system. Separation and Purification Technology, 2021, 276 : 119269

[25] Zhang W, Feng D, Xie X, Tong X, Du Y, Cao Y. Solvent extraction and separation of light rare earths from chloride media using HDEHP-P350 system. Journal of Rare Earths, 2022, 40( 2): 328– 337

[26] Tang N, Liu L L, Yin C, Zhu G P, Huang Q L, Dong J R, Yang X J, Wang S X. 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

[27] Cui L, Wang L, Feng M, Fang L, Guo Y, Cheng F. Ion-pair induced solvent extraction of lithium (I) from acidic chloride solutions with tributyl phosphate. Green Energy & Environment, 2021, 6( 4): 607– 616

[28] Shen C, Zhang Y, Huang J, Bao S, Yang X, Xiong P. Separation of vanadium(V) using N235 by three-phase system in concentrated HCl media. Canadian Journal of Chemistry, 2017, 95( 6): 717– 722

[29] Hu G, Chen D, Wang L, Liu J, Zhao H, Liu Y H, Qi T, Zhang C Q, Yu P. Extraction of vanadium from chloride solution with high concentration of iron by solvent extraction using D2EHPA. Separation and Purification Technology, 2014, 125 : 59– 65

[30] Zhu X, Li W, Tang S, Zeng M, Bai P, Chen L. 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

[31] Ma Y, Wang X, Wang M, Jiang C, Xiang X, Zhang X. Separation of V(IV) and Fe(III) from the acid leach solution of stone coal by D2EHPA/TBP. Hydrometallurgy, 2015, 153 : 38– 45

[32] Li G, Xie Q, Ren G, Liu J, Liang D. 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

[33] Shi Q, Zhang Y, Huang J, Liu T, Liu H, Wang L. Synergistic solvent extraction of vanadium from leaching solution of stone coal using D2EHPA and PC88A. Separation and Purification Technology, 2017, 181 : 1– 7

[34] Zhang Y, Zhang T, Lv G, Zhang G, Liu Y, Zhang W. Synergistic extraction of vanadium(IV) in sulfuric acid media using a mixture of D2EHPA and EHEHPA. Hydrometallurgy, 2016, 166 : 87– 93

[35] Jing Y, Chen J, Su W, Chen L, Liu Y, Li D. Deep insights into the solution and interface behaviors in heavy rare earth extraction: a molecular dynamics study. Journal of Molecular Liquids, 2019, 296 : 111790

[36] Ying Z, Huo M, Wu G, Li J, Ju Y, Wei Q, Ren X. 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

[37] Zhang F, Dai J, Wang A, Wu W. 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

Acknowledgements

This study was supported by the National Key R&D Program of China (Grant No. 2020YFC1909700) and the Project of National Natural Science Foundation of China (Grant Nos. 51974207 and 51774215).

RIGHTS & PERMISSIONS

2022 Higher Education Press