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Energies 2021, 14, 6805 38 of 72 Zante et al. [221] investigated the extraction of lithium from brines using the ionic liq- uid methyltrioctylammonium chloride (Aliquat-336) and the extractant DEHPA (Figure 18), dissolved in n-dodecane. These investigators targeted the extraction of lithium from pro- duced waters from oil and gas wells and selected these reagents due to their commercial availability and relatively lower costs [221]. Lithium extraction was optimized by varying mixing time, aqueous phase acidity, ionic liquid concentration in the solvent phase, and aqueous lithium concentration. Stripping was accomplished with 0.5 molar HCl. A two- stage approach was developed to recover lithium from synthetic brine. In the first stage, divalent metals are removed using five successive cycles of extraction with 1 M DEHPA dissolved in n-dodecane. The second step employed a 1 M mixture of Aliquat-336 and DEHPA to remove 83% of the dissolved lithium in one cycle. This result was reported to be superior to other methods using other extractant combinations [221]. Although ionic liquids show promise for use in the selective extraction of lithium from geothermal brines, their application may be problematic. [185]. Loss of the ionic liquids into the extracted solution is a common problem [63]. When using ionic liquids as synergistic extraction agents, it was established that diluent losses were less with more hydrophobic ionic liquids, but that more hydrophobic liquids did not engage in the cation- exchange process as efficiently [63,209]. The extraction systems containing TBP as the extractant with imidazole ionic liquids as co-extractants and diluents appeared to suffer less dissolution loss than solutions without TBP [63,215,220]. Physical properties (such as viscosity) and solubilities with water will limit the choice of ionic liquids that can be used [185]. The high cost of these solvents also suggests that ionic liquids are better suited to small volume applications for extraction of high value metals [185]. However, the prospect of concentrating metals from large volumes of dilute aqueous solution into small volumes of ionic liquids is promising and interest in lithium extraction using these materials is an active area of research [63,183,185,222]. 2.4.5. Modification of Solvent Extraction: Supported Liquid Membranes and Other Surfaces Supported liquid membranes (SLM) are a variant of multicomponent solvent sys- tems [223–225]. In SLM, a porous polymer support membrane holds a solution of the extractant mixture in its pores. SLM can be made with flat or hollow-fiber membranes. Modification of this idea include bulk liquid membranes, where a flat membrane sepa- rates a solvent phase from the aqueous phase, and emulsion liquid membranes, where surfactants are added to form emulsions that can be separated by a membrane [223]. Other modifications on solvent extraction include impregnation of resins or solid supports with extractants or extractant mixtures [68,202]. The SLM is formed by impregnating the pores of a thin, porous, polymeric membrane, such as those used in ultrafiltration, with an extractant in a diluent [223–225]. The stability of the liquid phase membrane is provided by capillary or surface forces between the support and the extractant mixture [223]. The impregnated membrane acts as a common interface between the feed and strip solutions, which are kept in compartments on the two sides of the membrane, thus aiding in selective transport of the diffusing species of interest through the membrane [223]. Ma and Chen [226] used the SLM technique to extract lithium from geothermal water. A mixture of extractants consisting of LIX 54 and TOPO were immobilized in a Celgard® 2500 membrane having 37–48% porosity. LIX 54, a mixture containing α-acetyl-m- dodecylacetophenone as a primary ingredient, is commonly used for extraction of copper from ammonia leaching solutions [226,227]. This SLM achieved 95% extraction of lithium in just 2 h; however, it exhibited stable performance for only up to 63 h before the flux dropped drastically [226]. The markedly decreased performance was attributed to the pressure difference over the membrane sheet, the solubility of the liquid membrane in the adjacent solutions, and emulsion of the liquid membrane into the aqueous solutions [80,226]. Using an SLM composed of LIX 54 and TOPO in kerosene, Bansal et al. [228] developed a mathe- matical transport model based on fundamental mass transfer and kinetics mechanisms thatPDF Image | Recovery of Lithium from Geothermal Brines
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