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Lithium Extraction from Hybrid Geothermal Power

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Lithium Extraction from Hybrid Geothermal Power ( lithium-extraction-from-hybrid-geothermal-power )

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Stringfellow and Dobson 3.4.4 Modification on solvent extraction: Supported liquid membranes and other surfaces Supported liquid membranes (SLM) are a variant of multicomponent solvent systems (Misra and Gill, 1996; Parhi, 2013; Parhi and Sarangi, 2008). In SLM, a porous polymer support membrane holds a solution of the extractant mixture in its pores. SLM can be made with flat or hollow fiber membranes. Modification of this idea include a bulk liquid membrane, where a flat membrane separates a solvent phase from the aqueous phase and an emulsion liquid membrane, where surfactants are added to form emulsions that can be separated by a membrane (Misra and Gill, 1996). Other modifications on solvent extraction include impregnation of resins or solid supports with extractants or extractant mixtures (Guo et al., 2013; Nishihama et al., 2011). Stability of SLM is a key issue for the application of these solvent membrane systems (Song et al., 2014; Swain, 2016; Zante et al., 2020a). For example, Ma and Chen (2000) reported the extraction of lithium from geothermal water with the SLM technique using a mixture of extractants, including TOPO, immobilized in a porous membrane. This SLM showed 95% extraction of lithium ions in just 2 hours; however, it exhibited stable performance for only up to 72 hours before the flux dropped drastically (Ma and Chen, 2000). Membranes have been observed to lose capacity quickly (Paredes and de San Miguel, 2020; Zante et al., 2020a). Some systems appear to be more stable than other systems and several investigators concluded that SLM is suitable for the extraction of lithium from brines (Song et al., 2014; Zante et al., 2020a). 3.5 Membrane Separations Technology Research on membrane separations for direct lithium extraction is predominantly focused on filtration membranes that allow permeation of the lithium ion and reject other ions (Zhang et al., 2020b). Rejection of other ions (i.e., not allowing them to pass the membrane) occurs via size exclusion, membrane surface charge, or other chemical and physical properties (Zhang et al., 2020b). In the context of lithium recovery from brines, membranes are predominately used to pretreat brines for the removal of divalent cations, metals, and other interfering substances before the process of concentrating, precipitating or otherwise extracting lithium (Li et al., 2019b; Liu et al., 2019; Zhang et al., 2020b). Membranes that are designed to retain lithium are typically not rejecting lithium, per se, but rather are adsorbing lithium preferentially and allowing other ions to pass (e.g., Lu et al., 2018). Polymer membranes that adsorb lithium are discussed under adsorbents. Reverse osmosis (RO) could potentially be applied to pretreatment of geothermal brines; however, the application would be for water removal to concentrate brines before precipitation, sorption, or other concentration steps (e.g., Somrani et al., 2013; Wang et al., 2020a). RO is not selective for lithium or other specific ions and serves the same function as evaporation or distillation in lithium processing (i.e., water removal). It is not apparent that RO will ever be economical to apply to treatment of geothermal brines. Nanofiltration has been investigated extensively for the separation of lithium from magnesium and other interfering divalent cations (Bi et al., 2014; Li et al., 2017; Somrani et al., 2013; Sun et al., 2015; Tian et al., 2010; Wang et al., 2020a; Wen et al., 2006; Yang et al., 2011; Zhang et al., 2020b; Zhongwei and Xuheng, 2015). Since commercially available nanofiltration membranes have been used for the separation of divalent cations from lithium, it is likely that nanofiltration will be incorporated into some process for the commercial separation of lithium from geothermal brines (e.g., Eramet, 2020b; Featherstone et al., 2019; PurLucid Treatment Solutions Inc., 2020; Renew and Hansen, 2017; Wang et al., 2020a). 3.6 Electrochemical Separation Electrodialysis is a membrane separation process that uses an electric field to aid the movement of ions across a semipermeable membrane. Electrodialysis is separate from the process of electrowinning, which is a metal extraction process that, to our knowledge, is not applied to lithium (Duyvesteyn, 1992; Duyvesteyn and Sabacky, 1995; McKinley and Ghahreman, 2018). Electrodialysis for lithium extraction is dependent on the use of a lithium-selective membrane and has process components, such as anodes and cathodes, which are similar or analogous to technology in lithium-ion batteries (Ball and Boateng, 1987; Yang and Hou, 2012; Zhang et al., 2020b). Electrodialysis for lithium extraction can be used with SLM and potentially other modifications of solvent extraction technology (e.g., Hoshino, 2013; Liu et al., 2020). Electrodialysis for lithium extraction can include the coating or construction of anodes or cathodes with metal oxides or other molecular sieve or lithium-sorbent materials, which also has parallels with battery applications (Ammundsen and Paulsen, 2001; Liu et al., 2015b; Liu et al., 2014; Xu et al., 2012; Zhongwei and Xuheng, 2015; Zhu et al., 2018). In systems for the separation and recovery of lithium, electrical potential is applied to improve selectivity or process kinetics in combination with membrane and sorbent technology discussed above. Ball and Boateng (1987) used electrodialysis with lithium-selective membranes and lime precipitation to separate lithium from magnesium and other multivalent cations. Itoh et al. (1999) proposed an electrodialysis method using a lithium- t would allow the selective passage of lithium. Chang et al. (2004) proposed combining adsorption and electrodialysis to enrich lithium ions in brine from a level of several ppm to about 1.5% in a process that uses electrodialysis as a post-extraction concentration step. Zhongwei and Xuheng (2015) proposed using electrodialysis to separate lithium from manganese using an anion-exchange membrane and a cathode coated with an ion sieve in the brine chamber. Ion sieves were made of iron phosphate, manganese oxide, or various ratios of lithium, iron, manganese, and phosphate (Zhongwei and Xuheng, 2015). Mroczek et al. (2015) applied electrodialysis to geothermal brines from the Wairakei (NZ) geothermal power station. The geothermal fluid was first desilicated using electrocoagulation with aluminum electrodes and then lithium was extracted with electrodialysis. The influence that the voltage, current, fluid temperature, and acidification had on lithium extraction was measured in a laboratory electrodialysis unit (Mroczek et al., 2015). Acid dosing was found to be essential to the electrodialysis process due to the alkalinity of the desilicated geothermal brine. The greatest extraction rates were obtained at a pH of about 2-4, and the highest extraction rate achieved 8

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