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194 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208 Table 2 Geographical availability for various Resources Pegmatites Spodumene Lepidolite Zabuyelite Petalite Amblygonite Eucryptite Sedimentary rocks Smectite (hectorite) Lacustrine evaporites Brine Continental Geothermal Oil field Sea water Secondary resource Spent LIBs lithium resources and their lithium contents. Li content % (w/w) 1.9–3.3 1.53–3.6 17–18.75 1.6–2.1 3.5–4.2% 2.34 0.27–0.7 1.8% lithium oxide Location of the largest amount Australia Zimbabwe China Zimbabwe Canada, Brazil, Surinam Zimbabwe Hector, California. and Nevada, US Jadar Valley, Serbia Chile Bolivia United States United States Chile, Argentina, China and Tibet b 2700 mg/L (with ~532 mg/L b 400 mg/L (with Mn b 700 mg/L (with Br) 0.18 mg/L 2–7% References Industrial Minerals and Rocks (2006), Legers (2008), Clarke (2013), AMRA (2013) Industrial Minerals and Rocks (2006) Evans (2008,2009), Legers (2008), Clarke (2013), Mohr et al. (2012) Shuva and Kurny (2013) plant. Lithium carbonate is mostly produced from both ores and brines and the production figures are often expressed as lithium carbonate equivalent (LCE). Other chemicals such as lithium chloride and hydrox- ide are also produced in varying amounts. In India small pocket deposits mostly comprising of lepidolite in pegmatites of mica fields are located. The maximum lithium content (lepidolite with 2–6% Li2O) is found in Jharkhand followed by that of Chhattisgarh (2.56% Li2O) and Rajasthan (2.25% Li2O as pegmatites in Udaipur, Bhilwara, Jodhpur and Ajmer, and zinnwaldite in Dagana). Others include spodumene in Raichur, Karnataka (Banerjee et al., 1994), amblygonite in granitic rocks of Paddar (Kashmir) and lepidolite at Dhir-Bil (Goalpara), Assam. Lithium bearing bauxite has also been identi- fied in the Salal area, Jammu (Brown and Dey, 1955; Krishnaswamy, 1979; Roonwal et al., 2005). 2.2. Secondary resources — lithium ion batteries Out of the various secondary resources, spent LIBs are the most prom- inent secondary source of lithium and other metals. To recycle these materials, it is desired to understand the construction/composition of the cells in brief and how they transform during their use. Lithium ion battery is a term generally used for a battery which has lithium metal, lithium alloy or material adsorbing lithium ions for its negative active material. LIB uses carbon as an anode and lithium ions exist in the carbon material; there is no metallic lithium at any state of charge during normal usage. Depending on their technical construction and properties batteries are categorized as either primary or secondary. From the legislative view point batteries are also categorized as portable (household) and vehicle or industrial batteries. Primary cells are con- structed with metallic lithium. The metallic lithium in a non- rechargeable primary lithium battery is a combustible alkali metal that self-ignites at 178 °C, and when exposed to water/seawater reacts exo- thermically and releases hydrogen. Primary batteries are single-use as irreversible discharge reactions occur in the cells and after use they are disposed off. Secondary battery cells have a chemistry that allows re- versing the discharge reaction and are rechargeable. LIBs are of the re- chargeable secondary type. The functional parts of LIBs are the cathode, anode, electrolyte and separator, which are housed in a protective metal casing. The chemical reaction in the cell expressed below shows the forms in which lithium and cobalt can be present in the spent LIBs. LiCoyOz þ 6C→LixC6 þ Li1−xCoyOz: ð1Þ K, B) and Zn) – known hectorite deposit with 0.7% Li is in Hector, California. Flint clays and other high-alumina clays contain b0.01 to 0.5% Li. Jadarite is a newly discovered lithium-boron containing mineral found in Serbia (Mohr et al., 2012). These minerals are often concentrated to around 2%–4% Li for use in the ceramics and glass industry (Garrett, 2004). Seawater contains about 0.1–0.2 mg/L Li (Bach and Wasson, 1981). Total amount of metallic lithium in seawater (globally) is estimated to be ~230 Gt. Brine sources include lithium found in salt water deposits — lakes, salars, oilfield brines, and geothermal brines. Oilfield brines are underground brine reservoirs that are located with oil. Geothermal brines are underground brines naturally heated, e.g., in the Salton Sea California. Brines containing lithium make up 66% of the world's lithium resources; pegmatites make up 26% and sedimentary rocks make up 8% (Gruber, 2010; Kesler et al., 2012). Almost 70% of the global lithium deposits are concentrated in South America's ABC (Argentina, Bolivia and Chile) region. Table 2 details the geographical availability of various resources of lithium vis-a-vis lithium content and their locations. The lithium concentrations in the salars of Chile, Argentina, and Bolivia are in the range 0.04–0.16%. According to Yaksic and Tilton (2009) the resource of lithium is estimated to be 64 Mt. Chile has the world's largest resource of brine (7.5 Mt, 1500– 2700 mg/L Li) containing lithium, followed by Bolivia (resource: 9.0 Mt with 532 mg/L Li) and Argentina (resource: 2.6 Mt, 400–700 mg/L Li) and these three countries account for almost 80% of the world's brine reserves (Mohr et al., 2012). Estimates of lithium resources are published extensively (Clarke and Harben, 2009; Gruber et al., 2011; Ono, 2009; Evans, 2010a, 2010b; USGS, 1980, 1986, 2005, 2009, 2010, 2011, 2012, 2013). Lithium rock production began with lithium minerals (1899) in the USA (Garrett, 2004). Since the first lithium production from brines at Searles Lake, USA in 1936, brines are exploited largely in South America and China. The largest producer of lithium in the world is Chile where lithium is extracted from salar brine at the Atacama Salt Flat. Lithium production from brines is also at salt lakes in Tibet and Qinghai in China, besides at Nevada in the United States. Several newer installations (by 2013) are on various stages of exploration/operation for brine source which are: one more in China, six in Argentina, three in Chile and one in Bolivia (Clarke, 2013). Currently 8% of lithium is obtained from salt lake brines and sea by sedimentation. Significant quantities of lithium com- pounds and ore concentrates are also produced in Australia, Canada, Portugal, Russia and Zimbabwe. Currently, Australia produces lithium concentrate from spodumene at the mines in Mt Catlin, Western Australia. The 160,000 t/annum concentrate produced in Western Australia is processed to 16,000 t/annum lithium carbonate in its ChinesePDF Image | Extraction of lithium from primary and secondary sources
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