Highly efficient and selective removal of vanadium from tungstate solutions by microbubble floating-extraction

doi:10.1007/s11705-022-2235-2

Front. Chem. Sci. Eng.

2023, Vol. 17

Issue (5) : 581-593 https://doi.org/10.1007/s11705-022-2235-2

RESEARCH ARTICLE

Highly efficient and selective removal of vanadium from tungstate solutions by microbubble floating-extraction

Hanyu Wang, Shengpeng Su, Yanfang Huang, Bingbing Liu, Hu Sun, Guihong Han(

)

School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China

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Abstract

Selective separation of dissolved tungsten and vanadium is of great significance for the utilization of the secondary resources of these elements. In this work, selective removal of vanadium from tungstate solutions via microbubble floating-extraction was systematically investigated. The results indicated that vanadium can be more easily mineralized over tungsten from tungstate solutions using methyl trioctyl ammonium chloride as mineralization reagent under weak alkaline conditions. Owing to the higher bubble and interface mass transfer rates, high-efficiency enrichment and deep separation of vanadium could be achieved easily. Additionally, the deep recovery of tungsten and vanadium from the floated organic phase could be easily realized using a mixed solution of sodium hydroxide and sodium chloride as stripping agents. The separation mechanism mainly included the formation of hydrophobic complexes, their attachment on the surface of rising bubbles, and their mass transfer at the oil–water interface. Under the optimal conditions, the removal efficiency of vanadium reached 98.5% with tungsten loss below 8% after two-stage microbubble floating-extraction. Therefore, the microbubble floating-extraction could be an efficient approach for separating selectively vanadium from tungstate solutions, exhibiting outstanding advantages of high separation efficiency and low consumption of organic solvents.

Keywords tungsten vanadium selective separation reagent mineralization microbubble floating-extraction

Corresponding Author(s): Guihong Han

About author:

*These authors equally shared correspondence to this manuscript.

Online First Date: 28 February 2023 Issue Date: 28 April 2023

Cite this article:

Hanyu Wang,Shengpeng Su,Yanfang Huang, et al. Highly efficient and selective removal of vanadium from tungstate solutions by microbubble floating-extraction[J]. Front. Chem. Sci. Eng., 2023, 17(5): 581-593.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2235-2
https://academic.hep.com.cn/fcse/EN/Y2023/V17/I5/581

Fig.1 Comparison of solvent extraction and microbubble floating-extraction: (a) reaction process, and (b) mass transfer process (k₁ and k₂ are the mass transfer coefficients between the oil–water interface during solvent extraction; K_OW′ and K_OW are the separation equilibrium constants of microbubble floating-extraction and solvent extraction, respectively).

Fig.2 Schematic diagram for separating vanadium from tungstate solutions by microbubble floating-extraction.

Index	Formula	Nomenclature
Mineralization efficiency	$M = 1 ? C M C F × 100 %$	$C F$ , $C M$ , $C R$ , $C S$ , and $C F L$ represent the concentrations of tungsten and vanadium in the feed, supernatant, raffinate, stripping solution, and floated organic phases; $V F L$ and $V S$ are the volumes of the floated organic phase and stripping solution, respectively; D_V and D_W are the distribution coefficient of V and W, respectively.
Flotation efficiency	$F = (1 ? C R C F) × 100 %$
Stripping efficiency	$S T = C S × V S C F L × V F L × 100 %$
Distribution coefficient	$D = C F L C R$
Separation factor	$β V, W = D V D W$

Tab.1 Key indexes of the microbubble floating-extraction process

Tab.2 Equilibrium constants and calculation formulas of relevant ion species

Fig.3 Molar ratio of tungsten and vanadium species as a function of pH in W-V-H₂O system (C_W = 10 g?L^?1, C_V = 1.0 g?L^?1; dash line: tungsten, solid line: vanadium, 25 °C).

Fig.4 Schematic diagram of flotation foam mineralization and reagent mineralization processes.

Fig.5 Effect of solution chemical conditions on the mineralization efficiency of tungsten and vanadium: (a) effect of initial pH (Aliquat336 = 1%, mineralization time = 20 min), (b) effect of mineralization time (Aliquat336 = 1%; pH = 8.67), and (c)–(f) effects of Aliquat336 dosage and initial concentrations (pH = 8.67, mineralization time = 20 min).

Fig.6 Effect of flotation conditions (O/A = 1/5) on flotation efficiency of tungsten and vanadium: (a) effect of different organic solvents (flow rate = 30 mL?min^?1, time = 30 min, 2-octanol = 10%), (b) effect of 2-octanol concentration (flow rate = 30 mL?min^?1, time = 30 min), (c) effect of flow rate (time = 30 min, 2-octanol = 10%), and (d) effect of flotation time (flow rate = 30 mL?min^?1, 2-octanol = 10%).

Fig.7 Effect of different conditions on the stripping process of tungsten and vanadium (O/A = 1): (a) effect of stripping agents, (b) effect of concentrations of sodium hydroxide and sodium chloride, (c) effect of the proportion of sodium hydroxide (A) and sodium chloride (B), and (d) multi-stage stripping efficiency using 1.5 mol?L^?1 sodium hydroxide + 0.25 mol?L^?1 sodium chloride.

Fig.8 FTIR analysis of Aliquat336 before and after mineralization (black line: Aliquat336; red line: Aliquat336 mineralized tungsten and vanadium mixed solution; green line: Aliquat336 mineralized vanadium alone; blue line: Aliquat336 mineralized tungsten alone).

Fig.9 (a) Mass transfer process during the floating-extraction (C_O is the concentration of the target substance in the organic phase at a certain time, and C_W is the concentration of the target substance in the water phase at a certain time), (b) process of bubbles from oil phase to water phase, and (c) aqueous layer and droplets in floating-extraction.

Tab.3 Comparison of the present developed method with earlier reported in related literature on the separation of tungsten and vanadium

Fig.10 (a) Comparison of the separation efficiencies of tungsten and vanadium between microbubble floating-extraction and solvent extraction, and (b) effect of Aliquat336 dosage on two-stage microbubble floating-extraction.

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