Development of barium@alginate adsorbents for sulfate removal in lithium refining

doi:10.1007/s11705-020-1968-z

Front. Chem. Sci. Eng.

2021, Vol. 15

Issue (1) : 198-207 https://doi.org/10.1007/s11705-020-1968-z

RESEARCH ARTICLE

Development of barium@alginate adsorbents for sulfate removal in lithium refining

Lisa Xu, Kaifei Chen, George Q. Chen, Sandra E. Kentish, Gang (Kevin) Li(

)

Department of Chemical Engineering, The University of Melbourne, Parkville, VIC 3010, Australia

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Abstract

The demand for lithium has been steadily growing in recent years due to the boom of electric cars. High purity lithium is commonly used in the manufacture of battery grade lithium electrolyte. Sulfate residuals originating from acid leaching of lithium ores must be limited to below 20 mg·L⁻¹ during refining. There are methods to remove sulfate such as membrane processing and chemical precipitation using barium salts. However, membrane separation is unable to achieve the required purity while chemical precipitation often causes secondary contamination with barium and requires extra filtration processes that lead to increased processing costs. In this study, we developed a polymeric matrix entrapped with barium ions as a novel adsorbent to selectively adsorb sulfate in aqueous solutions. The adsorbent was prepared by dropwise injection method where alginate droplets were crosslinked with barium to form hydrogel microcapsules. In a typical scenario, the microcapsules had a diameter of 3 mm and contained 5 wt-% alginate. The microcapsules could successfully reduce sulfate concentration in a solution from 100 to 16 mg·L⁻¹, exceeding the removal target. However, the microcapsules were mechanically unstable in the presence of an excess amount of sulfate. Hence, calcium ions were added as a secondary crosslinking agent to improve the integrity of the microcapsules. The two-step Ca/Ba@alginate microcapsules showed an exceptional adsorption performance, reducing the sulfate concentration to as low as 0.02 mg·L⁻¹. Since the sulfate selective microcapsules can be easily removed from the aqueous system and do not result in secondary barium contamination, these Ca/Ba@alginate adsorbents will find applications in ultra-refining of lithium in industry.

Keywords barium@alginate microcapsules dropwise injection sulfate removal lithium

Corresponding Author(s): Gang (Kevin) Li

Just Accepted Date: 25 August 2020 Online First Date: 29 October 2020 Issue Date: 12 January 2021

Cite this article:

Lisa Xu,Kaifei Chen,George Q. Chen, et al. Development of barium@alginate adsorbents for sulfate removal in lithium refining[J]. Front. Chem. Sci. Eng., 2021, 15(1): 198-207.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-1968-z
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I1/198

Fig.1 Methods for preparing Ba@alginate microcapsules: (a) Method 1, pure barium hydroxide Ba@alginate microcapsules; (b) Method 2, two-step Ca/Ba@alginate microcapsules, where the polymerisation reaction first took place by using calcium as the firming agent, followed by barium; (c) Method 3, one step dual-ion Ca-Ba@alginate microcapsules, where both calcium and barium ions were used for the polymerisation reaction at the same time.

Fig.2 Scheme 1 Barium ion crosslinks with carboxyl functional groups.

Fig.3 Optical images of Ba@alginate microcapsules prepared using three methods at different alginate concentrations: (a-e) Ba@alginate microcapsules produced from 2, 3, 4, 5, and 6 wt-% alginate, respectively; (f) Ca/Ba@alginate from 5 wt-% alginate; (g) Ca-Ba@alginate from 5 wt-% alginate. Illustrations of the alginate solution dropwise injection process (h) under the desirable range of viscosity and (i) under high viscosity.

Fig.4 (a) The relationship between the integrity and the concentration of alginate in an 800 mg·L⁻¹ lithium sulfate solution (red line: a line of best fit; inset: optical image of Ba@alginate flakes, scale: mm); (b) the physical strength of calcium@alginate microcapsules under 0.1 and 0.05 mol·L^–1 Ca²⁺ and 60, 3000, 1200 s crosslink time.

Fig.5 SEM/EDS of pure barium hydroxide Ba@alginate microcapsules (a–b) before and (c–d) after sulfate adsorption in 100 mg·L⁻¹ lithium sulfate solution. The distance on the x-axis corresponds to the chord line shown in the microscopy image.

Fig.6 (a) Sulfate removal efficiency of Ba@alginate microcapsules in a 100 mg·L⁻¹ lithium sulfate solution; (b) concentration of sulfate solution after adsorption in a 100 mg·L⁻¹ lithium sulfate solution.

Fig.7 The sulfate removed per gram of Ba@alginate microcapsules in 100 mg·L⁻¹ lithium sulfate solution versus time fitted by (a) the pseudo second order, (b) pseudo first order, and (c) Elovich adsorption kinetic models.

Tab.1 Kinetic parameters of second order pseudo, first order pseudo, and Elovich for Ba@alginate microcapsules in 100 mg·L⁻¹ lithium sulfate solution

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