Recovery of Lithium from Brine with a High Mg/Li Ratio Using Hydroxyl-Functionalized Ionic Liquid and Tri-n-butyl Phosphate

Abstract

In this study, a hydroxyl-functionalized ionic liquid 1-hydroxyethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide ([OHEMIM][NTf2]) and tri-n-butyl phosphate (TBP) were used as co-extraction reagent and extractant, respectively, to improve the extraction efficiency of Li+ and the separation factor of Li–Mg from brine with a high Mg/Li ratio. The extraction efficiency of Li+ is 94.2% and the separation factor of Li–Mg is 539 under the optimal condition. The washing efficiency of Mg2+ and K+ is close to 100% using 0.6 mol L−1 LiCl and 1.8 mol L−1 NaCl as the washing solution at an organic-to-aqueous phase ratio (O/A) of 4, and the stripping efficiency of Li+ is about 98.0% using 1.0 mol L−1 HCl as the stripping agent at an O/A phase ratio of 1. The extraction efficiency of Li+ is reduced by less than 4.4% after seven cycles, indicating that the extraction system is stable and reusable.

Graphical Abstract

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig. 13

References

  1. 1.

    Pozio A, Carewska M, Santucci A, Tosti S (2017) Behavior of hydrogenated lead–lithium alloy. Int J Hydrog Energy 42:1053–1062. https://doi.org/10.1016/j.ijhydene.2016.08.166

    CAS  Article  Google Scholar 

  2. 2.

    Sun CW, Liu J, Gong YD, Wilkinson DP, Zhang JJ (2017) Recent advances in all-solid-state rechargeable lithium batteries. Nano Energy 33:363–386. https://doi.org/10.1016/j.nanoen.2017.01.028

    CAS  Article  Google Scholar 

  3. 3.

    Swain B (2017) Recovery and recycling of lithium: a review. Sep Purif Technol 172:388–403. https://doi.org/10.1016/j.seppur.2016.08.031

    CAS  Article  Google Scholar 

  4. 4.

    Siekirka A, Tomaszewska B, Bryjak M (2018) Lithium capturing from geothermal water by hybrid capacitive deionization. Desalination 436:8–14. https://doi.org/10.1016/j.desal.2018.02.003

    CAS  Article  Google Scholar 

  5. 5.

    Li Z, Binnemans K (2020) Selective removal of magnesium from lithium-rich brine for lithium purification by synergic solvent extraction using β-diketones and Cyanex 923. AIChE J 66:e16246. https://doi.org/10.1002/aic.1624612

    CAS  Article  Google Scholar 

  6. 6.

    Liu G, Zhao ZW, Ghahreman A (2019) Novel approaches for lithium extraction from salt-lake brines: a review. Hydrometallurgy 187:81–100. https://doi.org/10.1016/j.hydromet.2019.05.005

    CAS  Article  Google Scholar 

  7. 7.

    Hamzaoui AH, Jamoussi B, M’nif A (2008) Lithium recovery from highly concentrated solutions: response surface methodology (RSM) process parameters optimization. Hydrometallurgy 90(1):1–7. https://doi.org/10.1016/j.hydromet.2007.09.005

    CAS  Article  Google Scholar 

  8. 8.

    Nie Z, Bu LZ, Zheng MP, Huang WN (2011) Experimental study of natural brine solar ponds in Tibet. Sol Energy 85(7):1537–1542. https://doi.org/10.1016/j.solener.2011.04.011

    CAS  Article  Google Scholar 

  9. 9.

    Xu ZH, Zhang HJ, Wang RY, Gui WJ, Liu GF, Yang Y (2014) Systemic and direct production of battery-grade lithium carbonate from a saline lake. Ind Eng Chem Res 53(42):16502–16507. https://doi.org/10.1021/ie502749n

    CAS  Article  Google Scholar 

  10. 10.

    Wang L, Meng CG, Ma W (2009) Preparation of lithium ion-sieve and utilizing in recovery of lithium from seawater. Front Chem Sci Eng 3(1):65–67. https://doi.org/10.1007/s11705-009-0105-9

    CAS  Article  Google Scholar 

  11. 11.

    Zhou ZY, Qin W, Chu YF, Fei WY (2013) Elucidation of the structures of tributyl phosphate/Li complexes in the presence of FeCl3 via UV–visible, Raman and IR spectroscopy and the method of continuous variation. Chem Eng Sci 101:577–585. https://doi.org/10.1016/j.ces.2013.07.020

    CAS  Article  Google Scholar 

  12. 12.

    Li Z, Mercken J, Li XH, Riaño S, Binnemans K (2019) Efficient and sustainable removal of magnesium from brines for lithium/magnesium separation using binary extractants. ACS Sustain Chem Eng 7:19225–19234. https://doi.org/10.1021/acssuschemeng.9b05436

    CAS  Article  Google Scholar 

  13. 13.

    Bi QY, Xu SA (2018) Separation of magnesium and lithium from brine with high Mg2+/Li+ ratio by a two-stage nanofiltration process. Desalin Water Treat 129:94–100. https://doi.org/10.5004/dwt.2018.23062

    CAS  Article  Google Scholar 

  14. 14.

    Shi CL, Jing Y, Xiao J, Wang XQ, Yao Y, Jia YZ (2017) Solvent extraction of lithium from aqueous solution using non-fluorinated functionalized ionic liquids as extraction agents. Sep Purif Technol 172:473–479. https://doi.org/10.1016/j.seppur.2016.08.034

    CAS  Article  Google Scholar 

  15. 15.

    Wang Y, Liu HT, Fan JH, Liu XT, Hu YF, Hu YL, Zhou ZY, Ren ZQ (2019) Recovery of lithium ions from salt lake brine with a high magnesium/lithium ratio using heteropolyacid ionic liquid. ACS Sustain Chem Eng 7:3062–3072. https://doi.org/10.1021/acssuschemeng.8b04694

    CAS  Article  Google Scholar 

  16. 16.

    Zhou ZY, Qin W, Fei WY (2011) Extraction equilibria of lithium with tributyl phosphate in three diluents. J Chem Eng Data 56:3518–3522. https://doi.org/10.1021/je200246x

    CAS  Article  Google Scholar 

  17. 17.

    Sun SY, Ye F, Song XF, Li YZ, Wang J, Yu JG (2011) Extraction of lithium from salt lake brine and mechanism research. Chin J Inorg Chem 27:439–444

    CAS  Google Scholar 

  18. 18.

    Su H, Li Z, Zhang J, Liu WS, Zhu ZW, Wang LA, Qi T (2020) Combining selective extraction and easy stripping of lithium using a ternary synergistic solvent extraction system through regulation of Fe3+ coordination. ACS Sustain Chem Eng 8(4):1971–1979. https://doi.org/10.1021/acssuschemeng.9b06432

    CAS  Article  Google Scholar 

  19. 19.

    Yang LX, Wu SX, Liu XL, He J, Chen WG (2013) Lithium and magnesium separation from salt lake brine by tributyl phosphate under action of co-extraction reagent ClO4. Chem J Chin Univ 34(1):55–60. https://doi.org/10.7503/cjcu20120171

    CAS  Article  Google Scholar 

  20. 20.

    Sun XQ, Luo HM, Dai S (2012) Ionic liquids-based extraction: a promising strategy for the advanced nuclear fuel cycle. Chem Rev 112(4):2100–2128. https://doi.org/10.1021/cr200193x

    CAS  Article  Google Scholar 

  21. 21.

    Patil AB, Pathak PN, Shinde VS, Alyapyshev MY, Babain VA, Mohapatra PK (2015) A novel solvent system containing a dipicolinamide in room temperature ionic liquids for actinide ion extraction. J Radioanal Nucl Chem 305(2):521–528. https://doi.org/10.1007/s10967-015-4028-2

    CAS  Article  Google Scholar 

  22. 22.

    Xiao J, Jia YZ, Shi CL, Wang XQ, Wang S, Yao Y, Jing Y (2017) Lithium isotopes separation by using benzo-15-crown-5 in eco-friendly extraction system. J Mol Liq 241:946–951. https://doi.org/10.1016/j.molliq.2017.06.119

    CAS  Article  Google Scholar 

  23. 23.

    Dutta B, Ruhela R, Yadav M, Singh AK, Sahu KK, Padmanabhan NPH, Chakravartty JK (2017) Liquid–liquid extraction studies of gadolinium with N-methyl-N,N,N-trioctyl ammonium-bis-(2-ethylhexyl) phosphonate-task specific ionic liquid. Sep Purif Technol 175:158–163. https://doi.org/10.1016/j.seppur.2016.11.033

    CAS  Article  Google Scholar 

  24. 24.

    Ma L, Zhao ZY, Dong YM, Sun XQ (2017) A synergistic extraction strategy by [N1888][SOPAA] and Cyphos IL 104 for heavy rare earth elements separation. Sep Purif Technol 174:474–481. https://doi.org/10.1016/j.seppur.2016.10.046

    CAS  Article  Google Scholar 

  25. 25.

    Quijada-Maldonado E, Torres MJ, Romero J (2017) Solvent extraction of molybdenum(VI) from aqueous solution using ionic liquids as diluents. Sep Purif Technol 177:200–206. https://doi.org/10.1016/j.seppur.2016.12.045

    CAS  Article  Google Scholar 

  26. 26.

    Parmentier D, Metza SJ, Kroon MC (2013) Tetraalkylammonium oleate and linoleate based ionic liquids: promising extractants for metal salts. Green Chem 15:205–209. https://doi.org/10.1039/C2GC36458A

    CAS  Article  Google Scholar 

  27. 27.

    Hu QY, Zhao JM, Wang FC, Huo F, Liu HZ (2014) Selective extraction of vanadium from chromium by pure [C8mim][PF6]: an anion exchange process. Sep Purif Technol 131:94–101. https://doi.org/10.1016/j.seppur.2014.05.003

    CAS  Article  Google Scholar 

  28. 28.

    Gao DL, Yu XP, Guo YF, Wang SQ, Liu MM, Deng TL, Chen YW, Belzile N (2015) Extraction of lithium from salt lake brine with triisobutyl phosphate in ionic liquid and kerosene. Chem Res Chin Univ 31(4):621–626. https://doi.org/10.1007/s40242-015-4376-z

    CAS  Article  Google Scholar 

  29. 29.

    Shi CL, Duan DP, Jia YZ, Jing Y (2014) A highly efficient solvent system containing ionic liquid in tributyl phosphate for lithium ion extraction. J Mol Liq 200:191–195. https://doi.org/10.1016/j.molliq.2014.10.004

    CAS  Article  Google Scholar 

  30. 30.

    Shi CL, Jing Y, Jia YZ (2016) Solvent extraction of lithium ions by tri-n-butyl phosphate using a room temperature ionic liquid. J Mol Liq 215:640–646. https://doi.org/10.1016/j.molliq.2016.01.025

    CAS  Article  Google Scholar 

  31. 31.

    Fan YC, Dong X, Li Y, Zhong YY, Miao J, Hua SF, Sun YC (2015) Extraction of l-tryptophan by hydroxyl-functionalized ionic liquids. Ind Eng Chem Res 54:12966–12973. https://doi.org/10.1021/acs.iecr.5b03651

    CAS  Article  Google Scholar 

  32. 32.

    Hawkins CA, Rud A, Garvey SL, Dietz ML (2012) Evaluation of hydroxyalkyl-functionalized imidazolium-based ionic liquids as solvents for the extraction of metal ions. Sep Sci Technol 47:1993–2001. https://doi.org/10.1080/01496395.2012.697527

    CAS  Article  Google Scholar 

  33. 33.

    Li ZJ, Zhang XP, Dong HF, Zhang XC, Gao HS, Zhang SJ, Li JW, Wang CM (2015) Efficient absorption of ammonia with hydroxyl-functionalized ionic liquids. RSC Adv 5:81362–81370. https://doi.org/10.1039/C5RA13730F

    CAS  Article  Google Scholar 

  34. 34.

    Yang SC, Liu GW, Wang JF, Cui L, Chen YM (2019) Recovery of lithium from alkaline brine by solvent extraction with functionalized ionic liquid. Fluid Phase Equilib 493:129–136. https://doi.org/10.1016/j.fluid.2019.04.015

    CAS  Article  Google Scholar 

  35. 35.

    Shi CL, Jing Y, Jia YZ (2017) Tri-n-butyl phosphate–ionic liquid mixtures for Li+ extraction from Mg2+-containing brines at 303–343 K. Russ J Phys Chem A 91:692–696. https://doi.org/10.1134/S0036024417040033

    CAS  Article  Google Scholar 

  36. 36.

    Su H, Li Z, Zhu ZW, Wang LA, Qi T (2019) Extraction relationship of Li+ and H+ using tributyl phosphate in the presence of Fe(III). Sep Sci Technol 55(9):1677–1685. https://doi.org/10.1080/01496395.2019.1604759

    CAS  Article  Google Scholar 

  37. 37.

    Shen SF, Chang ZD, Liu J, Sun XH, Hu X, Liu HZ (2007) Separation of glycyrrhizic acid and liquiritin from Glycyrrhiza uralensis Fisch extract by three-liquid-phase extraction systems. Sep Purif Technol 53:216–223. https://doi.org/10.1016/j.seppur.2006.07.003

    CAS  Article  Google Scholar 

  38. 38.

    Fatmehsari DH, Darvishi D, Etemadi S, Hollagh ARE, Alamdari EK, Salardini AA (2019) Interaction between TBP and D2EHPA during Zn, Cd, Mn, Cu, Co and Ni solvent extraction: a thermodynamic and empirical approach. Hydrometallurgy 98(1–2):143–147. https://doi.org/10.1016/j.hydromet.2009.04.010

    CAS  Article  Google Scholar 

  39. 39.

    Nguyen VT, Lee J, Jeong J, Kim BS, Cote G, Chagnes A (2015) Extraction of gold(III) from acidic chloride media using phosphonium-based ionic liquid as an anion exchanger. Ind Eng Chem Res 54:1350–1358. https://doi.org/10.1021/ie5045742

    CAS  Article  Google Scholar 

  40. 40.

    Ao YY, Peng J, Yuan LY, Cui ZP, Li C, Li JQ, Zhai ML (2013) Identification of radiolytic products of [C4mim][NTf2] and their effects on the Sr2+ extraction. Dalton Trans 42:4299–4305. https://doi.org/10.1039/c2dt32418k

    CAS  Article  Google Scholar 

Download references

Acknowledgments

This research is financially supported by the National Natural Science Foundation of China (52063025) and the Foundation from Qinghai Science and Technology Department (2020-HZ-808).

Author information

Affiliations

Authors

Corresponding author

Correspondence to Shiai Xu.

Ethics declarations

Conflict of interest

On behalf of all authors, the corresponding author states that there is no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

The contributing editor for this article was Hongmin Zhu.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Zhou, W., Xu, S. & Li, Z. Recovery of Lithium from Brine with a High Mg/Li Ratio Using Hydroxyl-Functionalized Ionic Liquid and Tri-n-butyl Phosphate. J. Sustain. Metall. (2021). https://doi.org/10.1007/s40831-020-00331-1

Download citation

Keywords

  • Lithium extraction
  • Magnesium/lithium separation
  • High Mg/Li ratio brine
  • Tri-n-butyl phosphate
  • Ionic liquid