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Energies 2021, 14, 6805 29 of 72 hanced lithium sorption by the synthetic zeolite, but not the natural zeolite (clinoptilolite). The effect of PAA was attributed to dissociated carboxyl groups that then form polymer- metal complexes, increasing lithium-ion adsorption. However, treatment with PAA also increased sorption of sodium and divalent cations [119]. Wisniewska et al. demonstrated that the amount of adsorption on the surfaces of aluminosilicates depends on their struc- ture (specific surface area size and porosity). The maximum recovery of lithium from geothermal water using zeolites (at pH 5.5) was approximately 50%, resulting in a sorption capacity of approximately 4.5 mg lithium per g clinoptilolite [119]. Titanium(IV) antimonate has been proposed as a cation-exchange sorbent for extract- ing lithium from seawater and hydrothermal brines [167,168]. Abe and coworkers [167,168] showed that the presence of ions such as potassium, calcium and magnesium interfered with the adsorption of lithium ions. However, they found that the presence of silica had no effect on the adsorption of lithium from hydrothermal water [168]. Spinel-type lithium antimony manganese oxide has also been shown to be an effective variant of MnOx for the sorption of lithium [144]. Thorium arsenate has been proposed as an adsorbent for lithium [169]. Alberti and Massucci [169] prepared crystalline Th(HAsO4)2·H2O by prolonged refluxing of a solution of thorium nitrate in arsenic acid. The hydrogen ion of this compound was reported to be completely exchanged by lithium ion but not by larger ions such as sodium or potassium, thus facilitating the separation of lithium from other alkali metal ions. Sorbed lithium was recovered using acid and the sorbent could be regenerated and used more than once [169]. Ho et al. [170] prepared and characterized an adsorbent based on filling the macrop- ores of activated carbon with a tin oxide. Tin oxide, as well as hydrous tin oxide, had high selectivity for lithium and was used to separate lithium from the other alkali metals. They also tested a number of other hydrous oxides, including Al(III), Fe(III), Zr(IV), and Nb(V), but these metal oxides were not found to be effective for lithium adsorption [170]. In summary, investigations have been conducted using a wide variety of inorganic sorbents, including AlOH, MnOx, and TiOx sorbents, for direct extraction of lithium from solution [63,80,94]. Inorganic molecular sieve ion-exchange sorbents are considered promising for commercial application due to the perceived simplicity of the recovery of lithium from the sorbent and the potential of the sorbent to be reused over repeated cycles of lithium sorption and extraction [63,80,94]. MnOx and TiOx adsorbents are being actively commercialized and marketed for direct lithium extraction, but have not yet been proven for direct lithium extraction from geothermal brines [128,153,155–157]. AlOH sorbents have been tested for extraction of lithium from geothermal brines, and are being marketed for this purpose as part of a direct lithium extraction process (see Section 3, below). 2.4. Solvent Separations Solvent extraction is a well-established technology for the separation of metals from aqueous solutions. Solvent extraction is economically used in the mining industry for the extraction and concentration of metals, particularly valuable or semi-valuable metals, such as copper and uranium [171–177]. Solvent extraction is economical for the extraction of metals from aqueous solutions due to the simplicity of the equipment and operation; however, chemical costs may be significant [172–175,177,178]. Typical hydrometallurgy processes employing solvent extraction include initial beneficiation (e.g., ammonia or acid leaching) followed by organic phase extraction [172,177,179]. It has been shown that solvent extraction techniques may be used to separate lithium quantitatively and selectively from aqueous solutions [17,53,63,180–183]. Solvent extraction techniques investigated for lithium extraction from brines fall broadly into three potentially overlapping categories: (1) crown ethers, (2) multicomponent systems consisting of an extractant, a synergistic co-extractant, and a diluent, and (3) ionic liquids [17,63,181]. Metals extracted into an organic, non-polar phase are typically recovered by use of an aqueous stripping agent, commonly an acidic solution, such as hydrochloric acid.PDF Image | Recovery of Lithium from Geothermal Brines
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Product and Development Focus for Infinity Turbine
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