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PROCEEDINGS, 43rd Workshop on Geothermal Reservoir Engineering Stanford University, Stanford, California, February 12-14, 2018 SGP-TR-213 Selective Recovery of Lithium from Brines Susanna Ventura, Srinivas Bhamidi and Marc Hornbostel Chemistry and Materials Laboratory, SRI International, 333 Ravenswood Avenue, Menlo Park CA 94025 susanna.ventura@sri.com Keywords: lithium, brine, sorbent, selectivity ABSTRACT Expansion of geothermal energy production over the entire U.S. will involve exploitation of low-to-medium temperature thermal waters. Creating value streams from the recovery of metals, such as lithium, will encourage geothermal expansion. We describe a lithium solid- phase extraction process based on a new, highly selective, low-cost, and reusable nanocomposite sorbent comprised of lithium ion sieve nanoparticles and a lithium-imprinted polymer. The sorbent is processed in the form of beads and tested in flow-through columns. When the brine contacts the sorbent, Li ions are selectively captured and concentrated in the sorbent. The sorbent was tested in a packed bed flow-through column for its ability to extract lithium in the presence of high concentrations of alkali and alkaline earth metals. The kinetics of lithium uptake were found to be fast with lithium capacity up to 16.2 mg Li/g sorbent. High selectivity for Li uptake in synthetic brines with high concentrations of Na+, K+, and Mg2+, and Ca2+ ions was determined. 1. INTRODUCTION Expansion of geothermal energy production in California will greatly benefit from the creation of a value stream produced by the recovery of critical metals from geothermal fluids. The efficient separation of metals, such as lithium, from geothermal brines promises to make the production of geothermal power economically favorable, even from low-temperature geothermal fluids. Revenue will be produced from the sale of the marketable metals, and the scaling and re-injection issues associated with high-solid-content brines will be minimized. Lithium is a high-value metal used in the production of lithium rechargeable batteries, and it is found in low but significant concentrations in geothermal waters (i.e., a few hundred ppm). Because of the very large volume of brine processed in a geothermal power plant (>6000 gal per min), even low-lithium brines represent a valuable resource. To support the rapid market growth of lithium rechargeable batteries, there is a strong demand for new lithium recovery methods. Extraction of Li from brines is currently the dominant method of Li production because of the higher cost efficiency of extraction compared to processing of mineral deposits. High-grade Li compounds are mostly processed from salar brines in Argentina, Chile, and Bolivia due to low operation costs. However, Li separation from salar brines is typically slow (i.e., a few months), since it is based on solar evaporation of the brines in ponds and requires multiple purification steps. Solvent extraction processes and solid-phase extraction processes are currently being evaluated for lithium recovery from brines (Neupane and Wendt, 2017). Geothermal brines present unique opportunities and challenges for mineral recovery and therefore require development of new low-cost extraction processes. Our proposed approach addresses selective recovery of lithium from brines that are rich in dissolved solids and relatively low in lithium and promises to enable the economic recovery of lithium from geothermal brines. 2. APPROACH Low-cost recovery of lithium from brines demands the use of selective high-capacity reusable sorbents. We have prepared a new hybrid sorbent consisting of nanostructured manganese oxide (HMO) embedded within a Li-imprinted polymer in the form of porous beads that has demonstrated selective lithium extraction in a continuous solid-phase extraction process. 2.1 Hydrous Manganese Oxide Ion Sieve Inorganic sorbents, such as aluminum hydroxide, manganese oxide, or titanium oxide are relatively inexpensive, stable over a high temperature range, and have shown promising properties for the selective adsorption of lithium. Hydrous manganese oxide (HMO) such as Li1.35Mn 1.61O4, is of great interest because of its high lithium capacity (up to 62 mg/g depending on pH) and selectivity for the removal of lithium in the presence of very large concentrations of Na, K, Ca, Mg and other metal ions (e.g., Zandevakili et al., 2014; Sun et al., 2014; Chitrakar et al., 2001; Shi et al., 2011). The HMO Li ion sieves are prepared with a two-step method. First, spinel-type lithium manganese oxide, such as Li1.35Mn 1.61O4 or others (i.e., Li4Mn5O12, Li1.6Mn1.6O4, or LiMn2O4), is prepared using the Li+ template ion. Next, Li+ is extracted by treatment with an acidic aqueous solution such as HCl (aq) to obtain HMO. The Li ions are replaced by H+ and the correspondent HMO is formed. The HMO retains the framework of the parent compound and is characterized by pore structures and vacant sites in the spinel phase that are uniquely suited for the insertion and de-insertion of lithium ions (Shi et al, 2011). The mechanism for the Li ion sieve adsorption of Li+ can therefore be explained by an ion-exchange process as follows: 1PDF Image | Selective Recovery of Lithium from Brines
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