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Energies 2021, 14, 6805 51 of 72 geothermal lithium applications. For example, Sonu et al. [288] used solvent extraction to recover valuable metals such as cobalt, nickel, manganese, and lithium from acid leachate of secondary battery-related wastes. Powdered battery waste was leached using sulfuric or hydrochloric acid, with or without hydrogen peroxide to produce a solution containing lithium, manganese, cobalt, and nickel. Manganese was recovered using D2EHPA as an extracting agent, cobalt was recovered after manganese by extraction with Cyanex 272, and nickel was then recovered using neodecanoic acid [288]. A solution containing only lithium was obtained after the nickel extraction step and it was proposed that lithium would be recovered in a form of Li2CO3 by addition of sodium carbonate [288]. Sol- vent extraction to separate metals from lithium brines is a common approach in battery recycling [201,209,210,212,288–291]. 3.3.4. Metalloids and Other Elements Silica High concentrations of silica occur in hot geothermal brines (Tables 2 and 12) and geothermal power plants have silica control processes as part of their normal opera- tions [76,77,287]. Typical approaches to silica control include precipitation of silica as crystalline or amorphous silica at the head of the power plant or acidification to keep the silica in solution [77,287]. It is recognized that silica is a major scale-forming chemical and will need to be managed as part of any geothermal lithium process [129,277,284,292–296]. In most cases considering geothermal lithium, silica control is presumed to be precipitation, but electrocoagulation to remove silica has been proposed [297]. Silica removal by sorption and precipitation prior to direct lithium extraction was investigated in the laboratory by Simbol, Inc. as part of a US Department of Energy (DOE) funded study [129,130]. The sorbent used to remove silica from test solutions was not named in the reports, but may have been activated alumina [129,130,162]. Versions of the sorbent were tested for sorption of silica from laboratory solutions and was regenerated by alkaline extraction with sodium hydroxide and a regeneration treatment with acid [130]. In some experiments, the silica could not be stripped off the sorbent and in many cases the amount of chemical required for stripping and regeneration was high enough that it was concluded there was no practical way to regenerate the sorbent or recover the silica once it was adsorbed [129,130]. There is also some interest in creating a marketable product out of silica precip- itated during geothermal power production and geothermal lithium production pro- cess [130,287,298]. Harrison and coworkers investigated the conversion of ion-silicate solids to a more valuable product [129,130]. A process to produce iron phosphate, which is used in the production of lithium-ion battery cathodes and pesticides, was developed [129,130]. The iron-silicate filter cake was washed with water to remove sodium chloride and other soluble salts, then the filter cake was dissolved in hydrochloric acid or sulfuric acid to pro- duce ferric chloride or ferric phosphate [130]. The soluble ferric solution was then reacted with phosphoric acid and neutralized with caustic soda to precipitate iron phosphate that was reported to meet cathode powder purity specifications [130]. It was recognized that the process may not be economical [129,130]. Boron Boron is a commonly co-occurring metalloid that must be separated from lithium for most lithium applications (Tables 2 and 12) [59,117,119,299–303]. Most boron removal processes involve precipitation. Brown et al. [61] treated a 3% lithium chloride solar- concentrated brine with lime and calcium chloride to convert boron to calcium borate hydrate. The calcium borate hydrate was separated by precipitation, along with magnesium hydroxide and calcium sulfate dehydrate, which are formed in the same process [61]. Precipitation treatment is used as part of process trains to produce high-purity lithium carbonate and chloride [55,61,304].PDF Image | Recovery of Lithium from Geothermal Brines
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