Separation of lithium from brines

Erdoğan, Barış
Lithium is one of the valuable and promising metals having extensive potential use in long lasting rechargeable batteries in automotive and electronics industry. Regarding scarcity of world lithium reserves, the most efficient method must be utilized in lithium separation and purification process. The scope of this study is to increase the efficiency of lithium separation by liquid-liquid extraction and adsorption methods with various materials synthesized throughout the study. In liquid-liquid extraction method, N-alkyl formamides (hexyl formamide, octyl formamide, dibutyl formamide, dihexyl formamide) were synthesized and lithium separation performances were evaluated. Hexyl formamide was found to have a distribution coefficient of 0.14 for LiCl in dilute concentrations at 25 oC which is the largest value cited in the literature for a single solvent so far. In adsorption method, lithium manganese oxides (LiMnO) were synthesized with solid-solid and hydrothermal reaction procedures under different temperature and Li/Mn ratios. The performance of the adsorbent with the highest capacity value was characterized at different pH, lithium and foreign ion (Na, K, Mg) concentrations. It was found out that, LiMnO adsorbent has a capacity value of 22.8 mg Li/g adsorbent at pH:10.2 in dilute lithium chloride solutions with a very high selectivity towards foreign ions such as sodium, potassium and magnesium. In order to employ LiMnO adsorbents in an adsorption column, micron sized particles were impregnated into millimeter sized beads made of poly(styrene-maleic anhydride-glycidyl methacrylate) (PSMA) by precipitation method. PSMA has been utilized in bead formation process for the first time in this study and gave superior results compared to previous analogs in terms of its swelling and self-crosslinking ability. The column performance filled with PSMA-LiMnO beads were evaluated with artificial brine, concentrated brine taken from Çamaltı Salina (İzmir) and boron clay extract taken from Bigadiç. The lithium concentration in brines was increased from 0.43 ppm to 1675.6 ppm while reducing the foreign ion concentrations significantly in adsorption column. The post treatment of the column product with LiMnO resulted in a solution with 3200 ppm Li. That concentration is above the required minimum concentration for Li2CO3 production, which is the raw material for lithium battery industry. The adsorption method, utilizing new PSMA-LiMnO beads in a column was found as a promising candidate for practical use in conventional separation of lithium from brines.


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Citation Formats
B. Erdoğan, “Separation of lithium from brines,” Ph.D. - Doctoral Program, Middle East Technical University, 2015.