LITHIUM EXTRACTION POTENTIAL OF HECTORITES FROM THE BIGADIÇ BORATE BASIN: MINERALOGICAL CHARACTERIZATION AND SELECTIVE CATION EXCHANGE EXPERIMENTS

Abstract

Although lithium is a common element worldwide, it is primarily concentrated in specific areas, including pegmatites, granites, and clays, as well as brine. Today, research in various countries is exploring experimental techniques for extracting Li from Li rich rocks and clays. The Bigadiç boron deposits form in a volcano-sedimentary environment in western Turkey, and their boron minerals interlayer with significant amounts of Li-rich hectorite. However, the clays' high Mg content presents a significant complication, increasing the cost of lithium processes and necessitating an intricate extraction process. In this study, a solution with high Li and low Mg content was obtained by a two-step extraction process from raw Bigadiç clays with high Li content. Raw hectorite samples NaCl, CaCl2 and FeCl3 cation sources were mixed by the mechanical mixing method to provide cation absorption on the clay surface. The targeted ion, Li, was transferred from the clay to the solution by preferential displacement using acid treatment. The findings produced through DLi =[Li(clay)]/[Li(aq)] (ppm/ppm) and logDLi= 1319/T(K) + 5.5 ([Li(aq)]) -0.0806 formulae were analyzed and interpreted. The investigation has demonstrated the viability of selective cation exchange procedures upon rich lithium clay reserves present in Bigadiç.

Keywords

• Bigadiç Borate Deposit
• Clay Minerals
• Hectorite
• Lithium Extraction
• Selective Cation Exchange

Ethical Statement

The author declares no known financial or personal relationships that could have influenced the work reported in this paper.

Thanks

The author thanks ETİMADEN and Engineer Yasin Yıldız for their hectorite mineral support, and Prof. Dr. Mustafa Topkafa for the provision of laboratory equipment.

References

1. D. C. Bradley, A. D. McCauley, and L. L. Stillings, "Mineral-deposit model for lithium-cesium-tantalum pegmatites," US Geological Survey, 2328-0328, 2017.
2. T. Bibienne, J.-F. Magnan, A. Rupp, and N. Laroche, "From mine to mind and mobiles: Society’s increasing dependence on lithium," Elements: An International Magazine of Mineralogy, Geochemistry, and Petrology, vol. 16, no. 4, pp. 265-270, 2020.
3. R. J. Bowell, L. Lagos, C. R. de los Hoyos, and J. Declercq, "Classification and characteristics of natural lithium resources," Elements, vol. 16, no. 4, pp. 259-264, 2020.
4. D. E. Garrett, Handbook of lithium and natural calcium chloride. Elsevier, 2004.
5. L. Wiklander and M. Elgabaly, "Relative uptake of adsorbed monovalent and divalent cations by excised barley roots as influenced by the exchange capacity," Soil Science, vol. 80, no. 2, pp. 91-94, 1955.
6. W. Kelley, "Soil properties in relation to exchangeable cations and kinds of exchange material," Soil Science, vol. 98, no. 6, pp. 408-412, 1964.
7. N. Kumari and C. Mohan, "Basics of clay minerals and their characteristic properties," Clay Clay Miner, vol. 24, pp. 1-29, 2021.
8. L. Delavernhe, M. Pilavtepe, and K. Emmerich, "Cation exchange capacity of natural and synthetic hectorite," Applied Clay Science, vol. 151, pp. 175-180, 2018.

9. J. Zhang, C. H. Zhou, S. Petit, and H. Zhang, "Hectorite: Synthesis, modification, assembly and applications," Applied Clay Science, vol. 177, pp. 114-138, 2019.
10. N. Hegyesi, R. T. Vad, and B. Pukánszky, "Determination of the specific surface area of layered silicates by methylene blue adsorption: The role of structure, pH and layer charge," Applied Clay Science, vol. 146, pp. 50-55, 2017.
11. A. Decarreau, N. Vigier, H. Pálková, S. Petit, P. Vieillard, and C. Fontaine, "Partitioning of lithium between smectite and solution: An experimental approach," Geochimica et Cosmochimica Acta, vol. 85, pp. 314-325, 2012.
12. P. Stoffynegli and F. T. Mackenzie, "Mass balance of dissolved lithium in the oceans," Geochimica et Cosmochimica Acta, vol. 48, no. 4, pp. 859-872, 1984.
13. A. Hamzaoui, A. M'nif, H. Hammi, and R. Rokbani, "Contribution to the lithium recovery from brine," Desalination, vol. 158, no. 1-3, pp. 221-224, 2003.
14. J. Velasco et al., "Foaming behaviour and cellular structure of LDPE/hectorite nanocomposites," Polymer, vol. 48, no. 7, pp. 2098-2108, 2007.
15. W. H. Awad et al., "Material properties of nanoclay PVC composites," Polymer, vol. 50, no. 8, pp. 1857-1867, 2009.
16. L. Yu and P. Cebe, "Crystal polymorphism in electrospun composite nanofibers of poly (vinylidene fluoride) with nanoclay," Polymer, vol. 50, no. 9, pp. 2133-2141, 2009.
17. L. M. Dykes, J. M. Torkelson, W. R. Burghardt, and R. Krishnamoorti, "Shear-induced orientation in polymer/clay dispersions via in situ X-ray scattering," Polymer, vol. 51, no. 21, pp. 4916-4927, 2010.
18. A. Walther and A. H. Muller, "Janus particles: synthesis, self-assembly, physical properties, and applications," Chemical reviews, vol. 113, no. 7, pp. 5194-5261, 2013.
19. H. Tan et al., "ASA-in-water emulsions stabilized by laponite nanoparticles modified with tetramethylammonium chloride," Chemical Engineering Science, vol. 116, pp. 682-693, 2014.
20. M. Stöter et al., "Controlled exfoliation of layered silicate heterostructures into bilayers and their conversion into giant Janus platelets," Angewandte Chemie, vol. 128, no. 26, pp. 7524-7528, 2016.
21. M. Daab et al., "Two-step delamination of highly charged, vermiculite-like layered silicates via ordered heterostructures," Langmuir, vol. 33, no. 19, pp. 4816-4822, 2017.
22. Z. Sun, H. Chen, T. B. Caldwell, and A. M. Thurston, "Selective extraction of lithium from clay minerals," ed: Google Patents, 2021.
23. B. Sawhney, "Sorption and fixation of microquantities of cesium by clay minerals: effect of saturating cations," Soil Science Society of America Journal, vol. 28, no. 2, pp. 183-186, 1964.
24. D. Carroll, "Ion exchange in clays and other minerals," Geological Society of America Bulletin, vol. 70, no. 6, pp. 749-779, 1959.
25. D. Eberl, "Clay mineral formation and transformation in rocks and soils," Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences, vol. 311, no. 1517, pp. 241-257, 1984.
26. B. B. Velde and A. Meunier, The origin of clay minerals in soils and weathered rocks. Springer Science & Business Media, 2008.
27. S. C. Aboudi Mana, M. M. Hanafiah, and A. J. K. Chowdhury, "Environmental characteristics of clay and clay-based minerals," GeoloGy, ecoloGy, and landscapes, vol. 1, no. 3, pp. 155-161, 2017.
28. F. Anouar, A. Elmchaouri, N. Taoufik, and Y. Rakhila, "Investigation of the ion exchange effect on surface properties and porous structure of clay: Application of ascorbic acid adsorption," Journal of Environmental Chemical Engineering, vol. 7, no. 5, p. 103404, 2019.
29. G. Ataman and O. Baysal, "Clay mineralogy of Turkish borate deposits," Chemical Geology, vol. 22, pp. 233-247, 1978.
30. C. Helvaci, "Stratigraphy, mineralogy, and genesis of the Bigadiç borate deposits, Western Turkey," Economic Geology, vol. 90, no. 5, pp. 1237-1260, 1995.
31. C. Helvaci, H. Mordogan, M. Çolak, and I. Gündogan, "Presence and distribution of lithium in borate deposits and some recent lake waters of west-central Turkey," International Geology Review, vol. 46, no. 2, pp. 177-190, 2004.
32. M. m. Çolak, C. Helvaci, and M. Maggetti, "Saponite from the Emet colemanite mines, Kutahya, Turkey," Clays and Clay Minerals, vol. 48, no. 4, pp. 409-423, 2000.
33. B. Ertan and Y. Erdoğan, "Emet-Espey bölgesindeki borlu killerde eser element tayini," Journal of Science and Technology of Dumlupınar University, no. 033, pp. 25-32, 2014.
34. W.-J. Lee et al., "Lithium extraction from smectitic clay occurring in lithium-bearing boron deposits in Turkey," Journal of the Mineralogical Society of Korea, vol. 29, no. 4, pp. 167-177, 2016.
35. A. Obut, İ. Ehsani, Z. Aktosun, A. Yörükoğlu, İ. Girgin, A. Temel and H. Deveci, "Leaching behaviour of lithium from a clay sample of Kırka borate deposit in sulfuric acid solutions," Journal of Boron, vol. 5, no. 4, pp. 170-175, 2020.
36. H. Şensöz, Z. E. Sayın, M. Savaş, and Y. Erdoğan, "Emet Bor Üretim Tesisleri Atıklarının Lityum İçeriğinin İncelenmesi," Afyon Kocatepe Üniversitesi Fen Ve Mühendislik Bilimleri Dergisi, vol. 21, no. 6, pp. 1460-1469, 2021.
37. H. Mordoğan, M. Akdağ, and C. Helvacı, "Lithium recover from low-grade lithium-bearing clays by H2SO4 and roast-water leach processes," Geosound (Yerbilimleri), vol. 24, pp. 141-150, 1994.
38. C. Helvacı and O. Alaca, "Geology and Mineralogy of the Bigadiç Borate Deposıts and Vicinity," Bulletin of the Mineral Research and Exploration, vol. 113, no. 113, pp. 31-63, 1991.
39. A. I. Okay, "Was the Late Triassic orogeny in Turkey caused by the collision of an oceanic plateau?," Geological Society, London, Special Publications, vol. 173, no. 1, pp. 25-41, 2000.
40. İ. Koçak and Ş. Koç, "Trace element contents of Bigadiç and Kestelek borate deposits," to Boron, p. 232, 2011.
41. İ. Koçak and Ş. Koç, "Major and trace element geochemistry of the Bigadiç Borate deposit, Balikesir, Turkiye," Geochemistry International, vol. 50, pp. 926-951, 2012.
42. Y. Y. Öztürk, A. Selin, and C. Helvacı, "Bor Minerallerinin Duraylı İzotop Jeokimyası: Bigadiç (Balıkesir) Borat Yatağından Bir Örnek," Yerbilimleri, vol. 35, no. 1, pp. 141-168, 2014.
43. Y. Dilek and Ş. Altunkaynak, "Geochemical and temporal evolution of Cenozoic magmatism in western Turkey: mantle response to collision, slab break-off, and lithospheric tearing in an orogenic belt," Geological Society, London, Special Publications, vol. 311, no. 1, pp. 213-233, 2009.
44. F. Gulmez, H. U. Ercan, N. Lom, G. Gocmengil, and E. Damci, "The inherited structure of the Gediz Graben (Aegean Extensional Province, Turkey): insights from the deep geothermal wells in the Alasehir sub-basin," International Journal Of Earth Sciences, 2023.
45. S. İşçi, "Kil/PVA ve organokil/PVA nanokompozitlerin sentezi ve karakterizasyonu," Fen Bilimleri Enstitüsü, 2007.
46. G. Brown, Crystal structures of clay minerals and their X-ray identification. The mineralogical society of Great Britain and Ireland, 1982.
47. D. M. Moore and R. C. Reynolds Jr, X-ray Diffraction and the Identification and Analysis of Clay Minerals. Oxford University Press (OUP), 1989.
48. S. Yamashita, H. Mukai, N. Tomioka, H. Kagi, and Y. Suzuki, "Iron-rich smectite formation in subseafloor basaltic lava in aged oceanic crust," Scientific Reports, vol. 9, no. 1, p. 11306, 2019.
49. S. Kadir, T. Külah, H. Erkoyun, C. Helvacı, M. Eren, and B. Demiral, "Mineralogy, geochemistry, and genesis of lithium-bearing argillaceous sediments associated with the Neogene Bigadiç borate deposits, Balıkesir, western Anatolia, Türkiye," Applied Clay Science, vol. 242, p. 107015, 2023.
50. M. D. Foster, "The importance of exchangeable magnesium and cation-exchange capacity in the study of montmorillonitic clays," American Mineralogist: Journal of Earth and Planetary Materials, vol. 36, no. 9-10, pp. 717-730, 1951.
51. J. Mering, "Smectites," in Soil Components: Vol. 2: Inorganic Components: Springer, 1975, pp. 97-119.
52. S. Petit, A. Decarreau, W. Gates, P. Andrieux, and O. Grauby, "Hydrothermal synthesis of dioctahedral smectites: The Al–Fe3+ chemical series. Part II: Crystal-chemistry," Applied Clay Science, vol. 104, pp. 96-105, 2015.
53. Y. Tardy, G. Krempp, and N. Trauth, "Le lithium dans les minéraux argileux des sédiments et des sols," Geochimica et Cosmochimica Acta, vol. 36, no. 4, pp. 397-412, 1972.
54. A. Decarreau, "Cristallogènese expérimentale des smectites magnésiennes: Hectorite, stévensite," Bulletin de minéralogie, vol. 103, no. 6, pp. 579-590, 1980.
55. H. C. Starkey, The role of clays in fixing lithium (no. 1278). US Government Printing Office, 1982.
56. C. S. Ross and S. B. Hendricks, Minerals of the montmorillonite group: Their origin and relation to soils and clays (no. 205). US Government Printing Office, 1945.
57. E. F. Brenner-Tourtelot and R. K. Glanzman, "Lithium-bearing rocks of the horse spring formation, Clark County, Nevada," in Lithium Needs and Resources: Elsevier, 1978, pp. 255-262.
58. H. J. Koo, B. Y. Lee, H. G. Cho, and S. M. Koh, "Study of Heat and Acid Treatment for Hectorite in Turkey Boron Deposit," Journal of the Mineralogical Society of Korea, vol. 29, no. 3, pp. 103-111, 2016.
59. A. Obut, Z. Aktosun, İ. Girgin, H. Deveci, and A. Yörükoğlu, "Characterization and treatment of clayey waste using a sulfuric acid roasting-water leaching process for the extraction of lithium," Physicochemical Problems of Mineral Processing, vol. 58, no. 4, 2022.
60. R. D. Shannon, "Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides," Acta crystallographica section A: crystal physics, diffraction, theoretical and general crystallography, vol. 32, no. 5, pp. 751-767, 1976.
61. K. Birdi, Handbook of surface and colloid chemistry. CRC press, 2008.
62. B. Tansel, "Significance of thermodynamic and physical characteristics on permeation of ions during membrane separation: Hydrated radius, hydration free energy and viscous effects," Separation and purification technology, vol. 86, pp. 119-126, 2012.
63. B. J. Teppen and D. M. Miller, "Hydration energy determines isovalent cation exchange selectivity by clay minerals," Soil Science Society of America Journal, vol. 70, no. 1, pp. 31-40, 2006.
64. M. W. Washabaugh and K. D. Collins, "The systematic characterization by aqueous column chromatography of solutes which affect protein stability," Journal of Biological Chemistry, vol. 261, no. 27, pp. 12477-12485, 1986.
65. J. Havel and E. Högfeldt, "Evaluation of water sorption equilibrium data on Dowex ion exchanger using WSLET-MINUIT program," Scripta Fac. Sci. Nat. Univ. Masaryk. Brun. Chem, vol. 25, pp. 73-84, 1995.
66. P. R. Bodart, L. Delmotte, S. Rigolet, J. Brendlé, and R. D. Gougeon, "7Li {19F} TEDOR NMR to observe the lithium migration in heated montmorillonite," Applied Clay Science, vol. 157, pp. 204-211, 2018.
67. T. Ebina, T. Iwasaki, And A. Chatterjee, "XPS and DFT study on the migration of lithium in montmorillonite," Clay science, vol. 10, no. 6, pp. 569-581, 1999.
68. U. Hofmann and R. Klemen, "Verlust der austauschfähigkeit von lithiumionen an bentonit durch erhitzung," Zeitschrift für anorganische Chemie, vol. 262, no. 1‐5, pp. 95-99, 1950.
69. R. Greene-Kelly, "A test for montmorillonite," Nature, vol. 170, no. 4339, pp. 1130-1131, 1952.
70. R. Tettenhorst, "Cation migration in montmorillonites," American Mineralogist: Journal of Earth and Planetary Materials, vol. 47, no. 5-6, pp. 769-773, 1962.
71. P. Komadel, J. Madejová, and J. Bujdák, "Preparation and properties of reduced-charge smectites—a review," Clays and Clay Minerals, vol. 53, pp. 313-334, 2005.
72. B. K. G. Theng, Formation and properties of clay-polymer complexes. Elsevier, 2012.
73. I. Tkáč, P. Komadel, and D. Müller, "Acid-treated montmorillonites—a study by 29Si and 27Al MAS NMR," Clay Minerals, vol. 29, no. 1, pp. 11-19, 1994.
74. C. Breen, J. Madejová, and P. Komadel, "Characterisation of moderately acid-treated, size-fractionated montmorillonites using IR and MAS NMR spectroscopy and thermal analysis," Journal of Materials Chemistry, vol. 5, no. 3, pp. 469-474, 1995.
75. B. R. Bickmore, D. Bosbach, M. F. Hochella Jr, L. Charlet, and E. Rufe, "In situ atomic force microscopy study of hectorite and nontronite dissolution: Implications for phyllosilicate edge surface structures and dissolution mechanisms," American Mineralogist, vol. 86, no. 4, pp. 411-423, 2001.
76. P. Komadel, "Acid activated clays: Materials in continuous demand," Applied Clay Science, vol. 131, pp. 84-99, 2016.
77. F. Franco, M. Pozo, J. A. Cecilia, M. Benitez-Guerrero, and M. Lorente, "Effectiveness of microwave assisted acid treatment on dioctahedral and trioctahedral smectites. The influence of octahedral composition," Applied Clay Science, vol. 120, pp. 70-80, 2016.
78. N. Vigier, A. Decarreau, R. Millot, J. Carignan, S. Petit, and C. France-Lanord, "Quantifying Li isotope fractionation during smectite formation and implications for the Li cycle," Geochimica et Cosmochimica Acta, vol. 72, no. 3, pp. 780-792, 2008.
79. Z. Zhao, X. Si, X. Liu, L. He, and X. Liang, "Li extraction from high Mg/Li ratio brine with LiFePO4/FePO4 as electrode materials," Hydrometallurgy, vol. 133, pp. 75-83, 2013.
80. G. t. Brown and G. Brindley, "X-ray diffraction procedures for clay mineral identification," 1980.