Lithium sorption kinetics on a sorbent based on lithium-aluminum layered double hydroxide

This study presents a detailed analysis of the mechanism of lithium sorption from natural calcium chloride brine with a lithium concentration of 0.24 g/L. Lithium was extracted using a synthesized granular sorbent based on lithium-aluminum layered double hydroxide under static conditions at 25°C. The kinetic data were analyzed using the pseudo-first-order, pseudo-second-order, and Elovich models, as well as the Boyd and Weber–Morris diffusion models. To assess the applicability of the kinetic models, both conventional linearization and rigorous nonlinear regression analysis were employed. The equilibrium sorption capacity of the sorbent was experimentally determined to be 5.5 mg/g. Linearization of the kinetic data using the pseudo-first-order, pseudo-second-order, and Elovich models showed that lithium sorption was best described by the pseudo-second-order model (coefficient of determination R² = 0.9966) and the Elovich model (R² = 0.9847). More rigorous nonlinear regression and subsequent comparison of the Elovich, pseudo-first-order, and pseudo-second-order models identified the Elovich model as providing the best fit to the lithium sorption data. Diffusion analysis of the sorption mechanism revealed two distinct stages. The Weber–Morris model, characterized by two linear segments (R² > 0.98), demonstrated a change in the rate-limiting step: a short initial stage was followed by a longer final stage. The Boyd model (linear relationship, R² = 0.9751) showed that the process was not controlled exclusively by intraparticle diffusion. These results indicate that lithium sorption onto the lithium-aluminum layered double hydroxide sorbent involves a complex mechanism dominated by chemisorption on a heterogeneous surface, with intraparticle diffusion making a substantial contribution, particularly at later stages of the process.

1. Kudryavtsev P.G. Lithium: global reserves and application prospects. Alternative Energy and Ecology. 2016;13- 14(201-202):72-88. (In Russ.). https://doi.org/10.15518/isjaee.2016.13-14.072-088. EDN: WFQKEH.

2. Khokhlatova L.B., Kolobnev N.I., Oglodkov M.S., Mikhaylov E.D. Aluminum-lithium alloys for aircraft building. Metallurgist. 2012;56(5-6):336-341. https://doi.org/10.1007/s11015-012-9580-1. EDN: OLEOMT.

3. Donahue C.J. Lubricating grease: a chemical primer. Journal of Chemical Education. 2006;83(6):862. https://doi.org/10.1021/ed083p862.

4. Blynskiy P., Chikhray Y., Kulsartov T., Gabdullin M., Zaurbekova Z., Kizane G., et al. Experiments on tritium generation and yield from lithium ceramics during neutron irradiation. International Journal of Hydrogen Energy. 2021;46(13):9186-9192. https://doi.org/10.1016/j.ijhydene.2020.12.224. EDN: NKQTGM.

5. Ignatiev V.V., Feynberg O.S., Zagnitko A.V., Merzlyakov A.V., Surenkov A.I., Panov A.V., et al. Molten-salt reactors: new possibilities, problems and solutions articles. Atomic Energy. 2012;112(3):135-143. (In Russ.). EDN: OWOOWX.

6. Kushnir D., Sandén B.A. The time dimension and lithium resource constraints for electric vehicles. Resources Policy. 2012;37(1):93-103. https://doi.org/10.1016/j.resourpol.2011.11.003.

7. Tadesse B., Makuei F., Albijanic B., Dyer L. The beneficiation of lithium minerals from hard rock ores: a review. Minerals Engineering. 2019;131:170-184. https://doi.org/10.1016/j.mineng.2018.11.023. EDN: DRPKWM.

8. Sun Y., Wang Q., Wang Y., Yun R., Xiang X. Recent advances in magnesium/lithium separation and lithium extraction technologies from salt lake brine. Separation and Purification Technology. 2021;256:117807. https://doi.org/10.1016/j.seppur.2020.117807. EDN: GKWRXL.

9. Luo Q., Dong M., Nie G., Liu Z., Wu Z., Li J. Extraction of lithium from salt lake brines by granulated adsorbents. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2021;628:127256. https://doi.org/10.1016/ j.colsurfa.2021.127256. EDN: UCJREX.

10. Zhong J., Lin S., Yu J. Lithium recovery from ultrahigh Mg2+/Li+ ratio brine using a novel granulated Li/Al-LDHs adsorbent. Separation and Purification Technology. 2021;256:117780. https://doi.org/10.1016/j.seppur.2020.117780. EDN: DYMNHS.

11. Isupov V.P., Kotsupalo N.P., Nemudry A.P., Menzeres L.T. Aluminium hydroxide as selective sorbent of lithium salts from brines and technical solutions. Studies in surface science and catalysis. 1999;120:621-652. https://doi.org/ 10.1016/S0167-2991(99)80567-9.

12. Li D., Zhang N., Gao D., Zhuang Z., Zeng D. Phase chemistry for hydration sensitive (de)intercalation of lithium aluminum layered double hydroxide chlorides. ACS Materials Au. 2023;4(1):45-54. https://doi.org/10.1021/ acsmaterialsau.3c00063. EDN: UOSSQO.

13. Zhong J., Lin S., Yu J. Effects of excessive lithium deintercalation on Li+ adsorption performance and structural stability of lithium/aluminum layered double hydroxides. Journal of Colloid and Interface Science. 2020;572:107- 113. https://doi.org/10.1016/j.jcis.2020.03.081. EDN: BHEWSW.

14. Aleynikov S.A., Belousova N.V. Lithium sorption from natural brine. iPolytech Journal. 2025;29(3):376-388. (In Russ.). https://doi.org/10.21285/1814-3520-2025-3-376-388. EDN: YNRNQC.

15. Besserguenev A.V., Fogg A.M., Francis R.J., Price S.J., O’Hare D., Isupov V.P., et al. Synthesis and structure of the gibbsite intercalation compounds [LiAl2(OH)6]X {X = Cl, Br, NO3} and [LiAl2(OH)6]Cl·H2O using synchrotron X-ray and neutron powder diffraction. Chemistry of Materials. 1997;9(1):241-247. https://doi.org/10.1021/ cm960316z. EDN: LEKRWP.

16. Zhang Y., Cheng X., Wu C., Köhler J., Deng S. Electronic structure and lithium diffusion in LiAl2(OH)6Cl studied by first principle calculations. Molecules. 2019;24(14):2667. https://doi.org/10.3390/molecules24142667. EDN: OGQSSN.

17. Lagergren S. Zur theorie der sogenannten adsorption gelöster stoffe. Zeitschrift für Chemie und Industrie der Kolloide. 1907;2(1):15. https://doi.org/10.1007/BF01501332. EDN: LDPCKC. 18. Ho Y.S., McKay G. Pseudo-second order model for sorption processes. Process Biochemistry. 1999;34(5):451- 465. https://doi.org/10.1016/S0032-9592(98)00112-5.

18. Elovich S.Y., Larinov O.G. Theory of contact kinetics of sorption. Doklady Akademii Nauk SSSR. 1949;66(2):401- 404.

19. Peers A.M. Elovich adsorption kinetics and the heterogeneous surface. Journal of Catalysis. 1965;4(4):499- 503. https://doi.org/10.1016/0021-9517(65)90054-0.

20. Akaike H. A new look at the statistical model identification. IEEE Transactions on Automatic Control. 1974;19(6):716-723. https://doi.org/10.1109/tac.1974.1100705.

21. Sugiura N. Further analysis of the data by Akaike’s information criterion and the finite corrections. Communications in Statistics – Theory and Methods. 1978;7(1):13-26. https://doi.org/ 10.1080/03610927808827599.

22. Schwarz G. Estimating the dimension of a model. The Annals of Statistics. 1978;6(2):461-464. https://doi.org/ 10.1214/aos/1176344136.

23. Weber W.J., Morris J.C. Kinetics of adsorption on carbon from solution. Journal of the Sanitary Engineering Division. 1963;89(2):31-59. https://doi.org/10.1061/jsedai.0000430.

24. Boyd G.E., Adamson A.W., Myers L.S. The exchange adsorption of ions from aqueous solutions by organic zeolites. II. Kinetics. Journal of the American Chemical Society. 1947;69(11):2836-2848. https://doi.org/10.1021/ ja01203a066.

25. Wang J., Guo X. Adsorption kinetic models: physical meanings, applications, and solving methods. Journal of Hazardous Materials. 2020;390:122156. https://doi.org/10.1016/j.jhazmat.2020.122156. EDN: PBWIMV.

26. Reichenberg D. Properties of ion-exchange resins in relation to their structure. III. Kinetics of exchange. Journal of the American Chemical Society. 1953;75(3):589-597. https://doi.org/10.1021/ja01099a022.

27. Miftakhova F.R., Nguyen T.K.T., Galimova R.Z., Shaikhiev I.G. The effect of orthophosphoric acid concentration in Earleaf acacia (Acacia auriculiformis) sawdust treatment on sorption characteristics of zinc ions. Herald of Technological University. 2019;22(2):37-43. (In Russ.). EDN: IVJJIF.

28. Caceres-Jensen L., Rodriguez-Becerra J., Escudey M., Joo-Nagata J., Villagra C.A., Dominguez-Vera V., et al. Nicosulfuron sorption kinetics and sorption/desorption on volcanic ash-derived soils: proposal of sorption and transport mechanisms. Journal of Hazardous Materials. 2020;385;121576. https://doi.org/10.1016/ j.jhazmat.2019.121576. EDN: JYZOSF. 30. Krizhanovskaya O.O., Siniaeva L.A., Karpov S.I., Selemenev V.F., Borodina E.V., Roessner F. Application of kinetic models for the description of fat-soluble physiologically active substances adsorption onto highly ordered inorganic siliceous materials. Statute of Roskomnadzor. 2014;14(5):784-794. (In Russ.). EDN: SXLCFF.

29. Sigodina A.B., Nikolaev N.I., Tunitskii N.N. The kinetics of ion exchange on sulphonated cation exchangers. Russian Chemical Reviews. 1964;33(4):440-461. (In Russ.). https://doi.org/10.1070/RC1964v- 033n04ABEH001396.

30. Winiczenko R., Górnicki K., Kaleta A. Evaluation of the mass diffusion coefficient and mass Biot number using a nondominated sorting genetic algorithm. Symmetry. 2020;12(2):260. https://doi.org/10.3390/sym12020260. EDN: EWKJJM.

31. Menzheres L.T., Ryabtsev A.D., Mamilova E.V. Selective sorbent for lithium recovery from highly mineralized chloride brines. Bulletin of the Tomsk Polytechnic University. Geo Assets Engineering. 2004;307(7):76-80. (In Russ.). EDN: HPMUMN.

32. Dong M., Luo Q., Li Ju., Wu Zh., Liu Zh. Lithium adsorption properties of porous LiAl-layered double hydroxides synthesized using surfactants. Journal of Saudi Chemical Society. 2022;26(5):101535. https://doi.org/10.1016/ j.jscs.2022.101535. EDN: ZPPYTO.

33. Simonin J.-P. On the comparison of pseudo-first order and pseudo-second order rate laws in the modeling of adsorption kinetics. Chemical Engineering Journal. 2016;300:254-263. https://doi.org/10.1016/ j.cej.2016.04.079.

34. Zamora F., Sabio E., Román S., González-García C.M., Ledesma B. Modelling the adsorption of p-nitrophenol by the Boyd method in conjunction with the finite element method. Adsorption Science & Technology. 2010; 28(8-9):671-687. https://doi.org/10.1260/0263-6174.28.8-9.671.

35. Al-dhawi B.N.S., Kutty Sh.R.M., Baloo L., Alawag A.M., Almahbashi N.M.Ya., Naji G.M.A., et al. Lithium adsorption from aqueous solution using aluminum hydroxide: Characterization, optimization by response surface methodology, kinetic modelling, and isotherm studies. Case Studies in Chemical and Environmental Engineering. 2023;7:100350. https://doi.org/10.1016/j.cscee.2023.100350. EDN: RVCRQG