Lithium Extraction from Hybrid Geothermal Power

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Stringfellow and Dobson boron in the form of calcium borate (CaB2O4·6H2O). Magnesium can also be removed from lithium brines by using oxalic acid precipitation (Meshram et al., 2014). Many other approaches for removing or controlling alkaline earth metals have been proposed as part of direct lithium extraction processes including nanofiltration and modified nanofiltration using chemical reagents (e.g., Li et al., 2017; Li and Binnemans, 2020; Renew and Hansen, 2017). Xu et al. (2021) concluded that a combination of techniques would be needed in order to achieve the high separation selectivity, stability, low cost, and environmentally friendly characteristics needed for successful lithium extraction (Xu et al., 2021). 4.3 Heavy Metals Numerous transition and post-transition metals co-occur with lithium in geothermal brines. Of particular concern are iron and the so- called heavy metals, which may occur in high concentration, may form scales or precipitates (e.g., iron), 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 could potentially benefit the economics of lithium recovery (Bakane, 2013; Millot et al., 2020). The US Department of the Interior, Bureau of Mines extensively investigated the potential for mineral recovery from Salton Sea geothermal brines (Blake, 1974; Berthold et al., 1975; Christopher et al., 1975; Crane, 1982; Maimoni, 1982; Schultze and Bauer, 1982a,b, 1984, 1985). One process that was developed involved the precipitation of mixed hydroxides of iron, zinc, manganese, and lead (Christopher et al., 1975; Maimoni, 1982). The hydroxide precipitation process was investigated and developed for a number of years, and included variations such as partial oxidation, but eventually the investigators concluded that the quality of the hydroxide precipitate was poor in terms of metal content and value and suggested that sulfide precipitation would be a better approach for metals recovery (Schultze and Bauer, 1982a). Subsequent studies by the Bureau of Mines investigated sulfide precipitation using real brines, but it was not apparent that sulfide precipitation was applied or tested at the pilot scale (Schultze and Bauer, 1985). CalEnergy Minerals operated a zinc metal manufacturing facility at its Elmore power plant in the Salton Sea KGRA (Clutter, 2000; Geothermal Resources Council, 2004; MidAmerican Energy Holding Co., 2003). The demonstration plant produced 41,000 lbs. of high- grade zinc using an ion-exchange process (Clutter, 2000). After recovery of the zinc from the ion-exchange resin, the zinc was placed in electrolytic cells and the zinc was deposited on cathodes as zinc metal and then recovered and melted into ingots (Clutter, 2000; EnergySource, 2012). The facility operated commercially for a number of years, but was the venture was ultimately abandoned (Bloomburg, 1999; Clutter, 2000; Geothermal Resources Council, 2004). Maimoni (1982) 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. Manganese and zinc have been identified as attractive targets for economic metals recovery (Bakane, 2013; Cetiner et al., 2015; Christopher et al., 1975; Harrison et al., 2014; Schultze and Bauer, 1985). MidAmerican Energy Holding Co. (2003) conducted laboratory-scale studies using solvent extraction for manganese pretreatment and recovery. Solvent-extracted manganese was converted to manganese dioxide by electrolytic oxidation, however co- extracted iron and calcium affected the value of the process (MidAmerican Energy Holding Co., 2003). 4.4 Metalloids & Other Elements High concentrations of silica occur in geothermal brines and geothermal power plants have silica control processes as part of their normal operations (Brown, 2011; MidAmerican Energy Holding Co., 2003; von Hirtz, 2016). 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 (MidAmerican Energy Holding Co., 2003; von Hirtz, 2016). It is recognized that silica is a major scale-forming chemical and will need to be managed as part of any geothermal lithium process (Bakane, 2013; Bourcier et al., 2005; Harrison, 2014; Harrison and Burba III, 2014; Harrison and Burba, 2017a, b, 2019; Rothbaum and Middendorf, 1986). In most cases considering geothermal lithium, silica control is presumed to be precipitation, but other processes such as ultrafiltration and electrocoagulation to remove silica have been proposed (Iwanaga et al., 2007; Bourcier et al., 2009; Sato et al., 2020). There is also some interest in creating a marketable product out of silica precipitated during geothermal power production and geothermal lithium production process (Bloomquist and Povarov, 2008; Harrison et al., 2014; MidAmerican Energy Holding Co., 2003). Boron is a commonly co-occurring metalloid that must be separated from lithium for most lithium applications (Bell, 2020; Belova, 2010; Bunani et al., 2017; Kesler et al., 2012; Recepoglu et al., 2018; Steinmetz, 2017; Tan et al., 2018; Wisniewska et al., 2018). Most boron removal processes involve precipitation, but solvent extraction is also applied (Brown et al., 1981; Perez et al., 2014). Precipitation treatment was used as part of a process train to produce to produce high purity lithium carbonate and chloride (Brown and Boryta, 1981, 1993; Brown et al., 1981). Other elements such as arsenic, phosphates and fluorides can interfere with lithium adsorption from geothermal brines or reduce the value of recovered lithium (Park et al., 2012; Recepoglu et al., 2018). Although these compounds have not been investigated extensively in the context of geothermal lithium, they have been considered in in the context of battery recycling (e.g., Asano et al., 2017; Park et al., 2012). Recycling companies use staged pH adjustment and solvent stripping to separate lithium from contaminants such as phosphorus and fluorine (Asano et al., 2017; Ishida and Asano, 2015). During chemical treatment of Salton Sea brines with acids or reducing agents to inhibit the formation of ferric silicate scales in well casings and brine pipelines, the deposition of silver-rich scales was observed (Gallup, 1992). 10

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