Selective separation of vanadium from the high-acidity leaching liquor through chelating extraction by the ketoxime extractant

doi:10.1016/j.cjche.2025.05.028

Chinese Journal of Chemical Engineering ›› 2025, Vol. 87 ›› Issue (11): 262-272.DOI: 10.1016/j.cjche.2025.05.028

Selective separation of vanadium from the high-acidity leaching liquor through chelating extraction by the ketoxime extractant

Xile Tian^1,2, Fancheng Meng^2,3, Xianglan Zhang¹, Yongchao Wang^2,3, Yahui Liu², Jian Zhang², Shuai Zhao^2,3, Desheng Chen^2,3, Lina Wang^2,3, Tao Qi²

1. School of Chemical & Environmental Engineering, China University of Mining and Technology, Beijing 100083, China;
2. National Engineering Research Center of Green Recycling for Strategic Metal Resources, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
3. School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 101408, China

Received:2025-02-01 Revised:2025-05-07 Accepted:2025-05-08 Online:2025-07-09 Published:2025-11-28
Contact: Fancheng Meng,E-mail:fcmeng@ipe.ac.cn;Lina Wang,E-mail:linawang@ipe.ac.cn
Supported by:
The authors gratefully acknowledge the financial support from Deep Earth Probe and Mineral Resources Exploration – National Science and Technology Major Project, China (2024ZD1003408) and Strategic Priority Research Program of the Chinese Academy of Sciences, China (XDA0430103).

Selective separation of vanadium from the high-acidity leaching liquor through chelating extraction by the ketoxime extractant

Xile Tian^1,2, Fancheng Meng^2,3, Xianglan Zhang¹, Yongchao Wang^2,3, Yahui Liu², Jian Zhang², Shuai Zhao^2,3, Desheng Chen^2,3, Lina Wang^2,3, Tao Qi²

1. School of Chemical & Environmental Engineering, China University of Mining and Technology, Beijing 100083, China;
2. National Engineering Research Center of Green Recycling for Strategic Metal Resources, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China;
3. School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 101408, China

通讯作者: Fancheng Meng,E-mail:fcmeng@ipe.ac.cn;Lina Wang,E-mail:linawang@ipe.ac.cn
基金资助:
The authors gratefully acknowledge the financial support from Deep Earth Probe and Mineral Resources Exploration – National Science and Technology Major Project, China (2024ZD1003408) and Strategic Priority Research Program of the Chinese Academy of Sciences, China (XDA0430103).

Abstract

Abstract: The high-acidity vanadium-containing solution contains high concentrations of iron and aluminum with pH around 0.5, the ketoxime extractant with the active ingredient of 2-hydroxy-5-nonylacetophenone oxime (HNAO, HL) was proposed to extract vanadium from the solution. Under the phase ratio (O/A) of 1:2, HNAO concentration of 0.542 mol·L^-1 at 25 °C for 10 min, 99.06% of vanadium was extracted after a three-stage countercurrent extraction, while the extraction of impurities was less than 1%, with the separation coefficients of vanadium from iron and aluminum were 137050 and 43197, respectively. The antioxidant properties of the extractant were studied. At 25 °C, the extractant basically did not undergo oxidative degradation. Besides, about 91.2% of the loaded vanadium was effectively stripped using 2.5 mol·L^-1 Na₂CO₃ solution. The extraction mechanism of vanadium was investigated through the slope analysis method, the spectral characterizations and density functional theory calculations. It has been observed that VO₂⁺ substitutes the H atom on the phenolic hydroxyl and coordinates with the N atom on the oxime and the O atom on the phenolic hydroxyl to form of a six-membered ring, and the extraction complexes were determined to be VO₂(H₂O)L and VO₂L.

Key words: Vanadium, Solvent extraction, High acidity, Ketoxime extractant, Chelating

摘要： The high-acidity vanadium-containing solution contains high concentrations of iron and aluminum with pH around 0.5, the ketoxime extractant with the active ingredient of 2-hydroxy-5-nonylacetophenone oxime (HNAO, HL) was proposed to extract vanadium from the solution. Under the phase ratio (O/A) of 1:2, HNAO concentration of 0.542 mol·L^-1 at 25 °C for 10 min, 99.06% of vanadium was extracted after a three-stage countercurrent extraction, while the extraction of impurities was less than 1%, with the separation coefficients of vanadium from iron and aluminum were 137050 and 43197, respectively. The antioxidant properties of the extractant were studied. At 25 °C, the extractant basically did not undergo oxidative degradation. Besides, about 91.2% of the loaded vanadium was effectively stripped using 2.5 mol·L^-1 Na₂CO₃ solution. The extraction mechanism of vanadium was investigated through the slope analysis method, the spectral characterizations and density functional theory calculations. It has been observed that VO₂⁺ substitutes the H atom on the phenolic hydroxyl and coordinates with the N atom on the oxime and the O atom on the phenolic hydroxyl to form of a six-membered ring, and the extraction complexes were determined to be VO₂(H₂O)L and VO₂L.

关键词: Vanadium, Solvent extraction, High acidity, Ketoxime extractant, Chelating

Xile Tian, Fancheng Meng, Xianglan Zhang, Yongchao Wang, Yahui Liu, Jian Zhang, Shuai Zhao, Desheng Chen, Lina Wang, Tao Qi. Selective separation of vanadium from the high-acidity leaching liquor through chelating extraction by the ketoxime extractant[J]. Chinese Journal of Chemical Engineering, 2025, 87(11): 262-272.

References

[1] L. Jiang, G.C. Du, J.P. Wang, Z.X. Wu, H.Y. Li, Eco-friendly efficient separation of Cr(VI) from industrial sodium vanadate leaching liquor for resource valorization, Sep. Purif. Technol. 361 (2025) 131673.
[2] A.O. Zyryanov, M.A. Vyboishchik, A.V. Ioffe, T.V. Tetyueva, E.A. Chistopol’tseva, Effect of chromium and vanadium alloying of steels on the intensity of carbon dioxide corrosion, Met. Sci. Heat Treat. 61 (11) (2020) 731-737.
[3] S.H. Long, L. Xu, G.J. Liu, Preparation and modification of heterogeneous vanadium-titanium-based catalysts, Russ. J. Gen. Chem. 91 (3) (2021) 464-487.
[4] K. Lourenssen, J. Williams, F. Ahmadpour, R. Clemmer, S. Tasnim, Vanadium redox flow batteries: a comprehensive review, J. Energy Storage 25 (2019) 100844.
[5] C.Q. Li, T. Jiang, J. Wen, T.X. Yu, F.F. Li, Review of leaching, separation and recovery of vanadium from roasted products of vanadium slag, Hydrometallurgy 226 (2024) 106313.
[6] R.M. Li, T. Liu, Y.M. Zhang, J. Huang, C.B. Xu, Efficient extraction of vanadium from vanadium-titanium magnetite concentrate by potassium salt roasting additives, Minerals 8 (1) (2018) 25.
[7] S. Shakibania, A. Mahmoudi, F. Rashchi, E. Vahidi, Recovery of vanadium from spent refinery catalysts: optimizing the process and analyzing the environmental impact, Clean Technol. Environ. Policy 26 (2) (2024) 291-306.
[8] S.F. Dai, X. Zheng, X.B. Wang, R.B. Finkelman, Y.F. Jiang, D.Y. Ren, X.Y. Yan, Y.P. Zhou, Stone coal in China: a review, Int. Geol. Rev. 60 (5-6) (2018) 736-753.
[9] M.Y. Wang, X.Y. Xiang, L.P. Zhang, L.S. Xiao, Effect of vanadium occurrence state on the choice of extracting vanadium technology from stone coal, Rare Met. 27 (2) (2008) 112-115.
[10] F. Wang, Y.M. Zhang, T. Liu, J. Huang, J. Zhao, G.B. Zhang, J. Liu, A mechanism of calcium fluoride-enhanced vanadium leaching from stone coal, Int. J. Miner. Process. 145 (2015) 87-93.
[11] Y.H. Lu, J.K. Wen, X.L. Mo, X.L. Yang, W.C. Gao, H.Y. Yang, A review of mechanism and technology of vanadium extraction from strategic mineral black shale, Rare Met. 43 (12) (2024) 6183-6200.
[12] Z.J. Ju, C.Y. Wang, F. Yin, Dissolution kinetics of vanadium from black shale by activated sulfuric acid leaching in atmosphere pressure, Int. J. Miner. Process. 138 (2015) 1-5.
[13] M.Y. Wang, L.S. Xiao, Q.G. Li, X.W. Wang, X.Y. Xiang, Leaching of vanadium from stone coal with sulfuric acid, Rare Met. 28 (1) (2009) 1-4.
[14] M.Y. Rao, H.Y. Xia, Y.J. Xu, G.Y. Jiang, Q. Zhang, Y.T. Yuan, L.B. Zhang, Study on ultrasonic assisted intensive leaching of germanium from germanium concentrate using HCl/NaOCl, Hydrometallurgy 230 (2024) 106385.
[15] B.S. Xiong, S.F. Han, S.C. Yang, K.Q. Xie, K.X. Wei, W.H. Ma, Facilitated removal of metal from diamond wire saw silicon powder waste via surfactant-assisted HCl + L-tartaric acid mixed leaching, Chem. Eng. J. 505 (2025) 159632.
[16] Y.L. Yu, S.Y. Li, J.J. Lu, F.S. Xi, X.H. Chen, D.D. Wu, W.H. Ma, R. Deng, Green recycling of end-of-life photovoltaic modules via Deep-Eutectic solvents, Chem. Eng. J. 499 (2024) 155933.
[17] X.B. Li, C. Wei, Z.G. Deng, M.T. Li, C.X. Li, G. Fan, Selective solvent extraction of vanadium over iron from a stone coal/black shale acid leach solution by D2EHPA/TBP, Hydrometallurgy 105 (3-4) (2011) 359-363.
[18] X.B. Zhu, Y. Liu, C. Ma, W. Li, Effective separation of V(IV) and Fe(III) from sulfuric acid solution by solvent extraction with P507 and N₂35, Hydrometallurgy 224 (2024) 106228.
[19] H. Liu, Y.M. Zhang, T. Liu, J. Huang, L.M. Chen, Y.W. Hu, Preparation of vanadium electrolyte from vanadium shale leaching solution with high concentration chloride using D2EHPA, Trans. Nonferrous Met. Soc. China 33 (5) (2023) 1594-1608.
[20] Z.W. Ying, M.X. Huo, G.X. Wu, J. Li, Y. Ju, Q.F. Wei, X.L. Ren, Recovery of vanadium and chromium from leaching solution of sodium roasting vanadium slag by stepwise separation using amide and EHEHPA, Sep. Purif. Technol. 269 (2021) 118741.
[21] J.R. Ju, Y.L. Feng, H.R. Li, C.L. Xu, S.L. Liu, Separation and recovery of vanadium, nickel, and aluminum from acid leaching solution of spent hydrodesulfurization catalyst by a solvent extraction-oxalic acid precipitation process, Min. Metall. Explor. 40 (1) (2023) 65-79.
[22] Z.F. Qin, G.Q. Zhang, Y.J. Xiong, D.M. Luo, C. Li, S.Y. Tang, H.R. Yue, B. Liang, Recovery of vanadium from leach solutions of vanadium slag using solvent extraction with N₂35, Hydrometallurgy 192 (2020) 105259.
[23] X.B. Zhu, Y. Liu, W. Li, Efficient separation and recovery of vanadium(V) from hydrochloric acid solution using N1923 as an extractant, ACS Omega 7 (6) (2022) 5485-5494.
[24] Y.C. Wang, W.J. Wang, F.C. Meng, L.N. Wang, D.S. Chen, T. Qi, Recovery of vanadium from carbonated solution by extraction with transformed aliquat 336 and stripping-precipitation, solvent Extr ion Exch 42 (3) (2024) 216-238.
[25] J. X. Deng, B. Wu, Q. Sun, J.K. Wen, X. Liu, Research progress of poisoning and inhibition of cobalt to hydroxyoxime extractant and its inhibition, Chin. J. Nonferrous Met. 31 (07) (2021) 1922-1932. (in Chinese).
[26] Q.G. Li, L. Xu, Z.S. Qi, X.D. Mo, Y.L. Liao, Extraction of vanadium from high acid leaching solution of stone coal by HBL101, Chin. J. Nonferrous Met. 23 (4) (2013) 1107-1113.
[27] Y. Zhang, T.A. Zhang, D. Dreisinger, W.H. Zhou, F. Xie, G.Z. Lv, W.G. Zhang, Chelating extraction of vanadium(V) from low pH sulfuric acid solution by Mextral 973H, Sep. Purif. Technol. 190 (2018) 123-135.
[28] Y. He, Y.M. Zhang, J. Huang, Q.S. Zheng, H. Liu, Extraction of vanadium(V) from a vanadium-bearing shale leachate through bifunctional coordination in Mextral 984H extraction system, Sep. Purif. Technol. 288 (2022) 120452.
[29] Q.H. Xie, Y. Liu, Q.J. Chen, X.L. Geng, C.Y. Liang, P. Zhang, L.S. Wang, Failure and regeneration of hydroxyoxime in copper solvent extraction process: a review, Hydrometallurgy 221 (2023) 106128.
[30] S.C. Wang, Z.G. Xu, Q. Zou, Y.X. Wang, F. Yang, F.L. Zhou, Effects of sulfuric acid on nitrification resistance of hydroxamate extractant, Hydrometall. China 42 (1) (2023) 95-100. (in Chinese).
[31] X.R. Liu, J.H. Shen, Y.J. Liu, Y.H. Zhu, H. Zhang, Degradation of oxime extractants LIX984N under impact of acid solution and phase disengagement of copper solvent extraction, Chin. J. Nonferrous Met. 27 (4) (2017) 818-824.
[32] C.H. Wang, Z.G. Xu, Q. Zou, J. Li, Q.M. Tang, S.J. Ji, Effect of degradation products on performance of hydroxime extractant, Hydrometall. China 36 (1) (2017) 33-37. (in Chinese).
[33] Z. G. Xu, Q. Zou, J. Li, Q.M. Tang, Y.H. Wang, F. Li, S.J. Ji, M. Yang, Q.H. Yang, Maintenance of performance and quality for copper extractants, Hydrometall. China 35 (3) (2016) 189-195. (in Chinese).
[34] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77 (18) (1996) 3865-3868.
[35] A. Klamt, G. Schuurmann, COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient, J. Chem. Soc., Perkin Trans. 2 (5) (1993) 799-805.
[36] R.S. Mulliken, Intensities of electronic transitions in molecular spectra II. charge-transfer spectra, 7 (1) (1939) 20-34.
[37] K. Fukui, Role of frontier orbitals in chemical reactions, Science 218 (4574) (1982) 747-754.
[38] A.K. Karmakar, Liquid-liquid extraction equilibrium study of vanadium(V) from nitrate medium by technical grade D2EHPA dissolved in kerosene, J. Sci. Eng. Papers 1 (2) (2024) 59-67.
[39] X.M. Chen, H.Y. Li, C.C. Wei, J. Cheng, J. Diao, B. Xie, F.S. Pan, Selective chemical etching of vanadium slag enables highly efficient and clean extraction of vanadium, ACS Sustainable Chem. Eng. 13 (3) (2025) 1327-1335.
[40] S. Gupta, N. Wai, T.M. Lim, S.H. Mushrif, Force-field parameters for vanadium ions (+2, +3, +4, +5) to investigate their interactions within the vanadium redox flow battery electrolyte solution, J. Mol. Liq. 215 (2016) 596-602.
[41] F. Karipcin, B. Dede, M. Cengiz, Synthesis of (2-hydroxo-5-chlorophenylaminoisonitrosoacetyl)phenyl ligands and their complexes: Spectral, thermal and solvent-extraction studies, Russ. J. Inorg. Chem. 55 (4) (2010) 530-540.
[42] A.S. Cattaneo, C. Ferrara, A.M. Marculescu, F. Giannici, A. Martorana, P. Mustarelli, C. Tealdi, Solid-state NMR characterization of the structure and thermal stability of hybrid organic-inorganic compounds based on a HLaNb2O7 Dion-Jacobson layered perovskite, Phys. Chem. Chem. Phys. 18 (31) (2016) 21903-21912.
[43] M.P. Elizalde, M.S. Rua, B. Menoyo, Aggregation equilibria and interactions between components of the extractants based on 2-hydroxy-5-nonylacetophenoneoxime, J. Solut. Chem. 47 (12) (2018) 1953-1964.

Selective separation of vanadium from the high-acidity leaching liquor through chelating extraction by the ketoxime extractant

Selective separation of vanadium from the high-acidity leaching liquor through chelating extraction by the ketoxime extractant

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Bo Pan, Muneeb Ul Hassan Naseer, Hao Du, Shaona Wang, Yeqing Lyu, Biao Liu, Haixu Wang, Lanjie Li. Separation and recovery of V/W/Na from waste SCR catalyst leaching solution using membrane electrolysis—Ion morphology pretreatment solvent extraction-stripping method [J]. Chinese Journal of Chemical Engineering, 2025, 82(6): 153-164.
[2]	Mengxia Liu, Tao Jiang, Jing Wen, Zibi Fu, Tangxia Yu, Changqing Li, Xinyu An. A technological process for extracting vanadium from leaching solution of sodium roasting of vanadium slag by manganese salt pretreatment [J]. Chinese Journal of Chemical Engineering, 2025, 81(5): 219-231.
[3]	Xinyu Liu, Yue Sun, Jing Wen, Tao Jiang, Lan Zhang, Jinchao Yang, Jiayu Dai. Green extraction of vanadium resources: A process for the preparation of vanadium oxide in an ammonia-free system [J]. Chinese Journal of Chemical Engineering, 2025, 88(12): 265-273.
[4]	Bharat Prasad Sharma, Tianzhang Wang, Yufeng Liang, Jinping Xiong, Liangrong Yang, Zheng Li. Synergistic solvent extraction system of bis(pyridin-2-ylmethyl) dodecan-1-amine and dinonylnaphthalene for enhanced selective extraction of nickel and cobalt [J]. Chinese Journal of Chemical Engineering, 2025, 77(1): 10-18.
[5]	Yuwen Wei, Chunling Zhang, Yue Zhang, Lili Wang, Li Xia, Xiaoyan Sun, Shuguang Xiang. Design method of extractant for liquid-liquid extraction based on elements and chemical bonds [J]. Chinese Journal of Chemical Engineering, 2024, 68(4): 193-202.
[6]	Bo Wang, Han Zhou, Shan Jing, Qiang Zheng, Wenjie Lan, Shaowei Li. A data-driven model of drop size prediction based on artificial neural networks using small-scale data sets [J]. Chinese Journal of Chemical Engineering, 2024, 66(2): 71-83.
[7]	Yunchang Fan, Chunyan Zhu, Sheli Zhang, Lei Zhang, Qiang Wang, Feng Wang. Efficient and selective extraction of sinomenine by deep eutectic solvents [J]. Chinese Journal of Chemical Engineering, 2023, 57(5): 109-117.
[8]	Kun Wang, Guoquan Zhang, Linye Li, Yuzhang Li, Xiangxin Liao, Pu Cheng, Mingzhi Luo. Separation of lithium and nickel using ionic liquids and tributyl phosphate [J]. Chinese Journal of Chemical Engineering, 2023, 63(11): 63-70.
[9]	Baibin Yang, Shihong Chen, Haowen Ren, Yang Qiu, Chong Chen, Yong Guo, Chunhui Luo, Qiang Zhao, Wei Yang. Vanadium(V) reduction by using a by-product of the yellow phosphorus industry [J]. Chinese Journal of Chemical Engineering, 2023, 62(10): 150-158.
[10]	Qing Lin, Guoquan Zhang, Kun Wang, Dongmei Luo, Siyang Tang, Hairong Yue. Two-stage cyclic ammonium sulfate roasting and leaching of extracting vanadium and titanium from vanadium slag [J]. Chinese Journal of Chemical Engineering, 2022, 47(7): 39-47.
[11]	Dengke Pang, Zhihong Zhang, Yongquan Zhou, Zhenhai Fu, Quan Li, Yongming Zhang, Guangguo Wang, Zhuanfang Jing. The process and mechanism for cesium and rubidium extraction with saponified 4-tert-butyl-2-(α-methylbenzyl) phenol [J]. Chinese Journal of Chemical Engineering, 2022, 46(6): 31-39.
[12]	Muhammad Faizan, Yingwei Li, Ruirui Zhang, Xingsheng Wang, Piao Song, Ruixia Liu. Progress of vanadium phosphorous oxide catalyst for n-butane selective oxidation [J]. Chinese Journal of Chemical Engineering, 2022, 43(3): 297-315.
[13]	Lingfu Zhu, Zuhong Lin, Jie Tan, Liyang Hu, Tingting Zhang. Application of hydrophobic ionic liquid [Bmmim][PF₆] in solvent extraction for oily sludge [J]. Chinese Journal of Chemical Engineering, 2020, 28(9): 2294-2300.
[14]	Rongrui Deng, Hao Xiao, Zhaoming Xie, Zuohua Liu, Qiang Yu, Geng Chen, Changyuan Tao. A novel method for extracting vanadium by low temperature sodium roasting from converter vanadium slag [J]. Chinese Journal of Chemical Engineering, 2020, 28(8): 2208-2213.
[15]	Bowen Jiang, Lei Hu, Xiaoming Yan, Jiahui Sun, Li Gao, Yan Dai, Xuehua Ruan, Gaohong He. A new long-side-chain sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)/polybenzimidazole (PBI) amphoteric membrane for vanadium redox flow battery [J]. Chinese Journal of Chemical Engineering, 2020, 28(7): 1918-1924.