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Energies 2021, 14, 6805 50 of 72 When using a three-stage batch counter-current extraction process, Li and Ninnemans found that the HPMBP and Cyanex 923 mixture removed 100% magnesium with only 0.6% co-extraction of lithium [283]. Li et al. [182] used a composite nanofiltration (NF) membrane with a positively charged polyetherimide skin layer to separate magnesium ion from lithium in simulated brine. The NF membrane was treated with EDTA to modify the positively charged PA-B NF membrane in order to improve the permeation selectivity of lithium against magnesium. Renew and Hansen [143] used nanofiltration to separate divalent from monovalent cations, followed by membrane distillation to concentrate the lithium in the brine, and the Mn-oxide sorbent to recover the lithium from the brine. 3.3.3. Iron and Base Metals Numerous transition and post-transition metals co-occur with lithium in geothermal brines (Tables 2 and 12). Of particular concern are iron and the so-called base metals, which may occur in high concentration, may form scales or precipitates (e.g., iron, manganese), and may be toxic (e.g., lead). Management of metals, especially as precipitate solids, can be expensive, especially if they contain toxic or regulated elements. Alternatively, recovery of valuable metals in a purity or composition that is saleable could potentially benefit the economics of lithium recovery [48,284]. Maimoni [31] reviewed prior investigations that examined lithium extraction from Salton Sea geothermal brines and proposed that recovery of valuable metals could be achieved with precipitation and cementation reactions. Christopher et al. [275] investigated the recovery of iron, manganese, zinc, and lead from Salton Sea geothermal brines. They recovered iron as a magnetic oxide product containing 68% Fe. Manganese, zinc, and lead were recovered as a mixed oxide product containing 47% Mn, 18% Zn, and 2.8% Pb [275]. Manganese and zinc have been identified as attractive targets for economic metals recovery [130,275,284–286]. Laboratory studies were also conducted to examine zinc and manganese extraction and recovery from both synthetic and Salton Sea geothermal brines [129,130]. Manganese and zinc were recovered by precipitation as hydroxides at pH 8 to 9 with a removal efficiency of approximately 95% [130]. Sulfuric acid was used to dissolve the precipitate solids to produce a manganese and zinc sulfate solution. Zinc was separated from the manganese by solvent extraction, but the solvent was not identified [129,130]. The resulting zinc sulfate was purified by cementation with zinc dust and converted to zinc metal by electrowinning [129,130]. The manganese sulfate from geothermal brines was not purified further, but it was shown with synthetic solutions that manganese oxide (MnO2) could also be produced by electrowinning [129,130]. The process was considered economical and was apparently incorporated into pilot testing [129,130,270]. MidAmerican Energy Holding Co. [287] conducted laboratory-scale studies to deter- mine the best technique for removal of the manganese from the spent brine produced from energy and mineral extraction plants they operated in the Salton Sea KGRA. They deter- mined that solvent extraction was the best approach for manganese removal. They used an aliphatic-hydrocarbon solvent trade named Orfom SX-11 in mixture with di-(2-ethy\hexyl) phosphoric acid and Aliquat-336. Prior to use, the organic phase was equilibrated with aqueous NaOH so that the extractant solution contained the ion-pair, QL, where Q is the quaternary amine and L is the organic phosphate [287]. When this solvent was mixed with the aqueous brine, the ligand (L) complexed manganese and transferred it to the organic phase [287]. The metal was stripped from the organic phase with aqueous HCl. The final product, manganese dioxide, was produced by electrolytic oxidation [287]. This solvent process separates manganese from all of the significant constituents of the brine except iron and calcium. These metals in high concentrations interfere in the electrolytic production of manganese oxide, so additional studies were conducted on their removal [287]. Metals recovery is a key part of lithium battery recycling operations and there may be applications for technology and processes developed for lithium battery recycling inPDF Image | Recovery of Lithium from Geothermal Brines
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Product and Development Focus for Infinity Turbine
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