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Hydrometallurgy of lithium: Selective separation from geothermal brines using chitosan-lithium ion sieve composite

Year 2025, Volume: 7 Issue: 2, 140 - 153, 31.05.2025

Yaşar Kemal Recepoğlu , Aslı Yüksel Özşen

https://doi.org/10.51435/turkjac.1629713

Abstract

This study investigates the selective recovery of lithium (Li) from geothermal brines using a chitosan-coated lithium manganese oxide composite (CTS/LMO). Geothermal brines from Germencik and Tuzla in Türkiye, characterized by distinct physicochemical properties, were used to evaluate adsorption performance. The Freundlich isotherm provided the best fit for the adsorption data, indicating heterogeneous and multilayer adsorption, with maximum adsorption capacities of 3.622 mg/g for Germencik and 3.556 mg/g for Tuzla derived from the Langmuir isotherm. Kinetic studies revealed that lithium adsorption followed a pseudo-first-order model for Germencik (R2 = 0.992) and a pseudo-second-order model for Tuzla (R2 = 0.914). The intraparticle diffusion model identified boundary layer diffusion as a significant rate-limiting step, with diffusion rate constants of 0.365 mg/g·h0.5 for Germencik and 0.588 mg/g·h0.5 for Tuzla. Mechanistic studies demonstrated ion exchange as the dominant adsorption mechanism, supported by adsorption energy values of 8.64 kJ/mol for Germencik and 9.13 kJ/mol for Tuzla. Optimal conditions yielded lithium recovery efficiencies of 95% for Germencik and 80% for Tuzla, with the differences attributed to variations in salinity and ionic composition. CTS/LMO effectively retained Li up to 241 BV with 69.03% efficiency, while desorption peaked at 43 mg/L at 9 BV, achieving 76% elution efficiency in column operation with a model solution. These findings demonstrate the potential of CTS/LMO as an efficient and sustainable adsorbent for Li recovery from geothermal brines, contributing to the growing demand for Li in renewable energy applications.

Keywords

adsorption geothermal water hydrometallurgy lithium separation

Ethical Statement

This study was financially supported by the Research Universities Support Program of the Higher Education Council of Türkiye (Grant No: 2022IYTE-2-0009).

Supporting Institution

Higher Education Council of Türkiye

Project Number

2022IYTE-2-0009

Thanks

This study was financially supported by the Research Universities Support Program of the Higher Education Council of Türkiye (Grant No: 2022IYTE-2-0009).

References

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  • Y.K. Recepoğlu, N. Kabay, K. Yoshizuka, S. Nishihama, İ. Yılmaz-Ipek, M. Arda, M. Yüksel, Effect of Operational Conditions on Separation of Lithium from Geothermal Water by λ-MnO2 Using Ion Exchange–Membrane Filtration Hybrid Process, Solvent Extr Ion Exch, 36 (2018) 499–512.
  • Y.K. Recepoğlu, N. Kabay, İ. Yılmaz-Ipek, M. Arda, M. Yüksel, K. Yoshizuka, S. Nishihama, Elimination of boron and lithium coexisting in geothermal water by adsorption-membrane filtration hybrid process, Sep Sci Technol, (Philadelphia) 53 (2018) 856–862.
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Lityumun hidrometalurjisi: Kitosan-lityum iyon elek kompoziti kullanılarak jeotermal tuzlu sulardan seçici ayırma

Year 2025, Volume: 7 Issue: 2, 140 - 153, 31.05.2025

Yaşar Kemal Recepoğlu , Aslı Yüksel Özşen

https://doi.org/10.51435/turkjac.1629713

Abstract

Bu çalışmada, kitosan kaplı lityum manganez oksit kompoziti (CTS/LMO) kullanılarak jeotermal tuzlu sulardan lityumun (Li) seçici olarak geri kazanılması araştırılmıştır. Türkiye'deki Germencik ve Tuzla'dan elde edilen ve farklı fizikokimyasal özelliklerle karakterize edilen jeotermal tuzlu sular, adsorpsiyon performansını değerlendirmek için kullanılmıştır. Freundlich izotermi, adsorpsiyon verileri için en iyi uyumu sağlayarak heterojen ve çok katmanlı adsorpsiyonu göstermektedir ve Langmuir izoterminden elde edilen Germencik için maksimum adsorpsiyon kapasiteleri 3.622 mg/g ve Tuzla için 3.556 mg/g'dır. Kinetik çalışmalar, lityum adsorpsiyonunun Germencik için psödo-birinci dereceden bir model (R2 = 0.992) ve Tuzla için psödo-ikinci dereceden bir model (R2 = 0.914) izlediğini ortaya koymuştur. Parçacık içi difüzyon modeli, sınır tabakası difüzyonunu önemli bir hız sınırlayıcı adım olarak tanımlanmıştır ve Germencik için 0,365 mg/g·h0,5 ve Tuzla için 0,588 mg/g·h0,5 difüzyon hız sabitleri elde edildi. Mekanistik çalışmalar, iyon değişiminin baskın adsorpsiyon mekanizması olduğunu göstermiştir ve Germencik için 8,64 kJ/mol ve Tuzla için 9,13 kJ/mol adsorpsiyon enerji değerleri ile desteklenmiştir. Optimal koşullar, Germencik için %95 ve Tuzla için %80 lityum geri kazanım verimliliği sağlamıştır. Farklılıkların tuzluluk ve iyonik bileşimdeki değişikliklerden kaynaklandığı düşünülmektedir.. CTS/LMO, Li'yi %69,03 verimlilikle 241 BV'ye kadar etkili bir şekilde tutarken, desorpsiyon 9 BV'de 43 mg/L'de zirveye ve bir model çözeltiyle kolon çalışmasında da %76 elüsyon verimliliğine ulaşmıştır. Bu bulgular, CTS/LMO'nun jeotermal tuzlu sulardan Li geri kazanımı için etkili ve sürdürülebilir bir adsorban olarak potansiyelini ortaya koyarak, yenilenebilir enerji uygulamalarında Li'ye olan talebin artmasına katkıda bulunmaktadır.

Keywords

adsorpsiyon jeotermal su hidrometalurji lityum ayırma

Project Number

2022IYTE-2-0009

References

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  • D. Chandrasekharam, M.F. Şener, Y.K. Recepoğlu, T. Isık, M.M. Demir, A. Baba, Lithium: An energy transition element, its role in the future energy demand and carbon emissions mitigation strategy, Geothermics 119 (2024) 102959.
  • G. Calvo, A. Valero, A. Valero, Assessing maximum production peak and resource availability of non-fuel mineral resources: Analyzing the influence of extractable global resources, Resour Conserv Recycl 125 (2017) 208–217.
  • Y.K. Recepoğlu, Optimized Lithium (I) Recovery from Geothermal Brine of Germencik, Türkiye, Utilizing an Aminomethyl phosphonic Acid Chelating Resin, Solvent Extr Ion Exch, (2024) 1–22.
  • P. Christmann, E. Gloaguen, J.-F. Labbé, J. Melleton, P. Piantone, Global lithium resources and sustainability issues, in: Lithium Process Chemistry, Elsevier, 2015: pp. 1–40.
  • R. Millot, A. Hegan, P. Négrel, Geothermal waters from the Taupo volcanic zone, New Zealand: Li, B and Sr isotopes characterization, Appl Geochem, 27 (2012) 677–688.
  • Z. Qin, L. He, J. Duo, M. Li, Y. Li, Q. Du, G. Zhang, G. Wu, G. Liu, Origin and evolution of Li-rich geothermal waters from the Kawu geothermal system, Himalayas: based on hydrochemistry and HO, Li isotopes, Int Geol Rev 66 (2024) 1519–1534.
  • B. Sanjuan, B. Gourcerol, R. Millot, D. Rettenmaier, E. Jeandel, A. Rombaut, Lithium-rich geothermal brines in Europe: An up-date about geochemical characteristics and implications for potential Li resources, Geothermics 101 (2022) 102385.
  • J. Li, X. Wang, C. Ruan, G. Sagoe, J. Li, Enrichment mechanisms of lithium for the geothermal springs in the southern Tibet, China, J Hydrol (Amst) 612 (2022) 128022.
  • A. Gökgöz, G. Tarcan, Mineral equilibria and geothermometry of the Dalaman–Köyceğiz thermal springs, southern Turkey, Appl Geochem, 21 (2006) 253–268.
  • A. Vengosh, C. Helvacı, İ.H. Karamanderesi, Geochemical constraints for the origin of thermal waters from western Turkey, Appl Geochem, 17 (2002) 163–183.
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  • E.H. Temizel, F. Gültekin, A.F. Ersoy, R.K. Gülbay, Multi-isotopic (O, H, C, S, Sr, B, Li) characterization of waters in a low-enthalpy geothermal system in Havza (Samsun), Turkey, Geothermics 97 (2021) 102240.
  • S. S. Rangarajan, S.P. Sunddararaj, A.V. V Sudhakar, C.K. Shiva, U. Subramaniam, E.R. Collins, T. Senjyu, Lithium-ion batteries—The crux of electric vehicles with opportunities and challenges, Clean Technol, 4 (2022) 908–930.
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  • S. Sahu, A. Mohanty, N. Devi, Application of various extractants for liquid-liquid extraction of lithium, Mater Today Proc 76 (2023) 190–193.
  • J. Zhu, A. Asadi, D. Kang, J.C.-Y. Jung, P.-Y.A. Chuang, P.-C. Sui, Bipolar membranes electrodialysis of lithium sulfate solutions from hydrometallurgical recycling of spent lithium-ion batteries, Sep Purif Technol 354 (2025) 128715.
  • X. Chen, X. Ruan, S.E. Kentish, G.K. Li, T. Xu, G.Q. Chen, Production of lithium hydroxide by electrodialysis with bipolar membranes, Sep Purif Technol 274 (2021) 119026.
  • B. Swain, Separation and purification of lithium by solvent extraction and supported liquid membrane, analysis of their mechanism: a review, J Chem Technol Biotechnol, 91 (2016) 2549–2562.
  • M.R. Mojid, K.J. Lee, J. You, A review on advances in direct lithium extraction from continental brines: Ion-sieve adsorption and electrochemical methods for varied Mg/Li ratios, Sustain Mater Technol, (2024) e00923.
  • S. Ye, C. Yang, Y. Sun, C. Guo, J. Wang, Y. Chen, C. Zhong, T. Qiu, Application and Mechanism of Lithium-ion Sieves in the Recovery of Lithium-Containing Wastewater: a Review, Water Air Soil Pollut 235 (2024) 272.
  • S. Chen, Z. Chen, Z. Wei, J. Hu, Y. Guo, T. Deng, Titanium-based ion sieve with enhanced post-separation ability for high performance lithium recovery from geothermal water, Chem Eng J, 410 (2021) 128320.
  • X. Xu, Y. Chen, P. Wan, K. Gasem, K. Wang, T. He, H. Adidharma, M. Fan, Extraction of lithium with functionalized lithium ion-sieves, Prog Mater Sci 84 (2016) 276–313.
  • Y. Orooji, Z. Nezafat, M. Nasrollahzadeh, N. Shafiei, M. Afsari, K. Pakzad, A. Razmjou, Recent advances in nanomaterial development for lithium ion-sieving technologies, Desalination 529 (2022) 115624.
  • J. Xiao, X. Nie, S. Sun, X. Song, P. Li, J. Yu, Lithium ion adsorption–desorption properties on spinel Li4Mn5O12 and pH-dependent ion-exchange model, Adv Powder Technol, 26 (2015) 589–594.
  • J.-L. Xiao, S.-Y. Sun, J. Wang, P. Li, J.-G. Yu, Synthesis and adsorption properties of Li1. 6Mn1. 6O4 spinel, Ind Eng Chem Res 52 (2013) 11967–11973.
  • Q.-H. Zhang, S. Sun, S. Li, H. Jiang, J.-G. Yu, Adsorption of lithium ions on novel nanocrystal MnO2, Chem Eng Sci 62 (2007) 4869–4874.
  • Y.K. Recepoğlu, N. Kabay, İ. Yılmaz-Ipek, M. Arda, K. Yoshizuka, S. Nishihama, M. Yüksel, Equilibrium and Kinetic Studies on Lithium Adsorption from Geothermal Water by λ-MnO2, Solvent Extr Ion Exch, 35 (2017) 221–231.
  • Y.K. Recepoğlu, N. Kabay, K. Yoshizuka, S. Nishihama, İ. Yılmaz-Ipek, M. Arda, M. Yüksel, Effect of Operational Conditions on Separation of Lithium from Geothermal Water by λ-MnO2 Using Ion Exchange–Membrane Filtration Hybrid Process, Solvent Extr Ion Exch, 36 (2018) 499–512.
  • Y.K. Recepoğlu, N. Kabay, İ. Yılmaz-Ipek, M. Arda, M. Yüksel, K. Yoshizuka, S. Nishihama, Elimination of boron and lithium coexisting in geothermal water by adsorption-membrane filtration hybrid process, Sep Sci Technol, (Philadelphia) 53 (2018) 856–862.
  • G.M. Nisola, L.A. Limjuco, E.L. Vivas, C.P. Lawagon, M.J. Park, H.K. Shon, N. Mittal, I.W. Nah, H. Kim, W.-J. Chung, Macroporous flexible polyvinyl alcohol lithium adsorbent foam composite prepared via surfactant blending and cryo-desiccation, Chem Eng J, 280 (2015) 536–548.
  • S. Wei, Y. Wei, T. Chen, C. Liu, Y. Tang, Porous lithium ion sieves nanofibers: General synthesis strategy and highly selective recovery of lithium from brine water, Chem Eng J, 379 (2020) 122407.
  • G. Zhang, C. Hai, Y. Zhou, J. Zhang, Y. Liu, J. Zeng, Y. Shen, X. Li, Y. Sun, Z. Wu, Synthesis and performance estimation of a granulated PVC/PAN-lithium ion-sieve for Li+ recovery from brine, Sep Purif Technol 305 (2023) 122431.
  • J.-L. Xiao, S.-Y. Sun, X. Song, P. Li, J.-G. Yu, Lithium ion recovery from brine using granulated polyacrylamide–MnO2 ion-sieve, Chem Eng J, 279 (2015) 659–666.
  • I.A. Udoetok, A.H. Karoyo, E.E. Ubuo, E.D. Asuquo, Granulation of Lithium-Ion Sieves Using Biopolymers: A Review, Polymers (Basel) 16 (2024) 1520.
  • Y.K. Recepoğlu, B. Arabacı, A. Kahvecioğlu, A. Yüksel, Granulation of hydrometallurgically synthesized spinel lithium manganese oxide using cross-linked chitosan for lithium adsorption from water, J Chromatogr A (2024) 464712.
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  • I. Langmuir, The constitution and fundamental properties of solids and liquids. Part I. Solids., J Am Chem Soc 38 (1916) 2221–2295.
  • H. Freundlich, Über die adsorption in lösungen, Z Phys Chem, 57 (1907) 385–470.
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There are 56 citations in total.

Details

Primary Language English
Subjects Separation Science
Journal Section Research Articles
Authors

Yaşar Kemal Recepoğlu 0000-0001-6646-0358

Aslı Yüksel Özşen 0000-0002-9273-2078

Project Number 2022IYTE-2-0009
Publication Date May 31, 2025
Submission Date January 30, 2025
Acceptance Date March 23, 2025
Published in Issue Year 2025 Volume: 7 Issue: 2

Cite

APA Recepoğlu, Y. K., & Yüksel Özşen, A. (2025). Hydrometallurgy of lithium: Selective separation from geothermal brines using chitosan-lithium ion sieve composite. Turkish Journal of Analytical Chemistry, 7(2), 140-153. https://doi.org/10.51435/turkjac.1629713
AMA Recepoğlu YK, Yüksel Özşen A. Hydrometallurgy of lithium: Selective separation from geothermal brines using chitosan-lithium ion sieve composite. TurkJAC. May 2025;7(2):140-153. doi:10.51435/turkjac.1629713
Chicago Recepoğlu, Yaşar Kemal, and Aslı Yüksel Özşen. “Hydrometallurgy of Lithium: Selective Separation from Geothermal Brines Using Chitosan-Lithium Ion Sieve Composite”. Turkish Journal of Analytical Chemistry 7, no. 2 (May 2025): 140-53. https://doi.org/10.51435/turkjac.1629713.
EndNote Recepoğlu YK, Yüksel Özşen A (May 1, 2025) Hydrometallurgy of lithium: Selective separation from geothermal brines using chitosan-lithium ion sieve composite. Turkish Journal of Analytical Chemistry 7 2 140–153.
IEEE Y. K. Recepoğlu and A. Yüksel Özşen, “Hydrometallurgy of lithium: Selective separation from geothermal brines using chitosan-lithium ion sieve composite”, TurkJAC, vol. 7, no. 2, pp. 140–153, 2025, doi: 10.51435/turkjac.1629713.
ISNAD Recepoğlu, Yaşar Kemal - Yüksel Özşen, Aslı. “Hydrometallurgy of Lithium: Selective Separation from Geothermal Brines Using Chitosan-Lithium Ion Sieve Composite”. Turkish Journal of Analytical Chemistry 7/2 (May2025), 140-153. https://doi.org/10.51435/turkjac.1629713.
JAMA Recepoğlu YK, Yüksel Özşen A. Hydrometallurgy of lithium: Selective separation from geothermal brines using chitosan-lithium ion sieve composite. TurkJAC. 2025;7:140–153.
MLA Recepoğlu, Yaşar Kemal and Aslı Yüksel Özşen. “Hydrometallurgy of Lithium: Selective Separation from Geothermal Brines Using Chitosan-Lithium Ion Sieve Composite”. Turkish Journal of Analytical Chemistry, vol. 7, no. 2, 2025, pp. 140-53, doi:10.51435/turkjac.1629713.
Vancouver Recepoğlu YK, Yüksel Özşen A. Hydrometallurgy of lithium: Selective separation from geothermal brines using chitosan-lithium ion sieve composite. TurkJAC. 2025;7(2):140-53.
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