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Energies 2021, 14, 6805 40 of 72 2.4.6. Modification of Solvent Extraction: Supercritical Carbon Dioxide Crown ethers have been used with supercritical carbon dioxide (CO2) as a dilu- ent [187,189,190]. Supercritical CO2 is viewed as an attractive solvent because it allows extraction to be conducted at elevated temperature and pressure, thus reducing potential scaling problems that occur with geothermal brines [189,190]. The crown ethers methylene- 14-crown-4 (M14C4) and fluorinated 14-crown-4 (F14C4) (Figure 20) were investigated extensivly for use with supercritical CO2, with and without the synergistic extractant Energies 2021, 14, x FOR PEER REVIEWdi(2-ethylhexyl) phosphoric acid (HDEHP) (Figure 20) [187,189,190]. In additio4n2, oRf 7u4t- tinger et al. [187] experimented with tetraethylammonium perfluoro-1-octanesulfonate (TPFOS), based on its solubility in supercritical CO2. Figure 20. Crown ether and organophosphate extractants used with supercritical carbon diox- Figure 20. Crown ether and organophosphate extractants used with supercritical carbon dioxide as ide as the solvent ((A). methylene-14-crown-4 (M14C4), (B). fluorinated 14-crown-4 (F14C4), the solvent ((A). methylene-14-crown-4 (M14C4), (B). fluorinated 14-crown-4 (F14C4), (C). HDEHP (C). HDEHP [189,190]. Reprinted (adapted) with permission from Pálsdóttir, A. et al. Characteriza- [189,190]. Reprinted (adapted) with permission from Pálsdóttir, A. et al. Characterization of 14- tion of 14-Crown-4 Ethers for the Extraction of Lithium from Natural Brines: Synthesis, Solubility Crown-4 Ethers for the Extraction of Lithium from Natural Brines: Synthesis, Solubility Measurements in Supercritical Carbon Dioxide, and Thermodynamic Modeling. Ind. Eng. Chem. Measurements in Supercritical Carbon Dioxide, and Thermodynamic Modeling. Ind. Eng. Chem. RRees.s.2022012,16,060,7,9792266––77993344..CCopopyyrirgighhtt20220121AAmmereirciacnanCChhememiciacallSSoociceiteyty.. Pálsdóttir et al. [190] measured the solubility of crown ethers in supercritical CO Pálsdóttir et al. [190] measured the solubility of crown ethers in supercritical CO2 and2 and found that M14C4 was more soluble than F14C4 at 60 ◦C and 205 bar, but that both found that M14C4 was more soluble than F14C4 at 60 °C and 205 bar, but that both crown crown ethers had order of magnitude higher solubilities than other crown ethers. These ethers had order of magnitude higher solubilities than other crown ethers. These extractants were tested for lithium extraction from a synthetic geothermal brine with some extractants were tested for lithium extraction from a synthetic geothermal brine with some success [189,190]. Ruttinger et al. [187] tested the extraction efficiency of supercritical success [189,190]. Ruttinger et al. [187] tested the extraction efficiency of supercritical carbon dioxide, cation exchangers, and 14-crown-4 ethers against a solution of 100 ppm carbon dioxide, cation exchangers, and 14-crown-4 ethers against a solution of 100 ppm lithium and 2300 ppm sodium, with a 50-fold excess of exchanger relative to the lithium con- lithium and 2300 ppm sodium, with a 50-fold excess of exchanger relative to the lithium centration. For cation exchangers, they used both TPFOS and HDEHP. Molecular dynamics concentration. For cation exchangers, they used both TPFOS and HDEHP. Molecular modeling was used to understand the mechanism of binding between lithium and combi- dynamics modeling was used to understand the mechanism of binding between lithium nations of 14-crown-4 ethers and cation exchangers [187]. Ruttinger et al. [187] reported and combinations of 14-crown-4 ethers and cation exchangers [187]. Ruttinger et al. [187] good agreement between supercritical carbon dioxide extraction experiments conducted at reported good agreement between supercritical carbon dioxide extraction experiments 60 ◦C and 250 bar and corresponding computational predictions. Differences in the binding conducted at 60 °C and 250 bar and corresponding computational predictions. Differences free energies of sodium and lithium to crown ethers determine the extraction selectivity in the binding free energies of sodium and lithium to crown ethers determine the and fluorine groups had a positive influence on optimizing extraction efficiency. F14C4 extraction selectivity and fluorine groups had a positive influence on optimizing with TPFOS was determined to be a selective and efficient extraction system [187,189,190]. extraction efficiency. F14C4 with TPFOS was determined to be a selective and efficient Chemical characteristics that were considered important for design of effective lithium extraction system [187,189,190]. Chemical characteristics that were considered important extractants were (1) a fluorinated tail, (2) a sulfonic acid group, and (3) a proton as the for design of effective lithium extractants were (1) a fluorinated tail, (2) a sulfonic acid cation that participates in the ion-exchange process [190]. The hypothesis that the addition group, and (3) a proton as the cation that participates in the ion-exchange process [190]. of fluorinated groups to the crown ether or cation exchanger increases the binding free The hypothesis that the addition of fluorinated groups to the crown ether or cation energy and, consequently, the extraction efficiency of the system was supported by results exchanger increases the binding free energy and, consequently, the extraction efficiency of the molecular dynamics modeling simulations and the experiments [187]. of the system was supported by results of the molecular dynamics modeling simulations In summary, it can be concluded that ketone, beta-diketone and organophosphorus and the experiments [187]. compounds have not been shown to be sufficiently selective for lithium to be practical for In summary, it can be concluded that ketone, beta-diketone and organophosphorus application to geothermal waters. However, these compounds are useful in pretreatment compounds have not been shown to be sufficiently selective for lithium to be practical for of lithium brines and leachates before lithium recovery, particularly for the removal of application to geothermal waters. However, these compounds are useful in pretreatment divalent cations and interfering or valuable metals. Solvent extraction steps are also likely of lithium brines and leachates before lithium recovery, particularly for the removal of to be important components of commercial geothermal lithium extraction processes. Other divalent cations and interfering or valuable metals. Solvent extraction steps are also likely to be important components of commercial geothermal lithium extraction processes. Other solvents, such as crown ethers and cyclic siloxanes, have been shown to have selective reactivity with lithium and appear promising in the laboratory, but are still in the early phases of development (i.e., are low TRL).PDF Image | Recovery of Lithium from Geothermal Brines
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