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198 P. Meshram et al. / Hydrometallurgy 150 (2014) 192–208 Table 7 Adsorption process for lithium extraction with product synthesized from seawater, brines and bitterns. Source/Raw material Seawater Seawater (Li 0.17 mg/L) Seawater (Li 0.15 mg/L) Artificial seawater (Li 0.2 mg/L, 8.01 pH) Seawater (1 mmol/L Li) Brine (Salars de Uyuni, Bolivia) Seawater (Li 0.192 mg/L) Salt lake bitterns Egyptian bitterns (19.5, 5.5, 8.8 mg/L) Brine (Salar de Hombre Muerto, Argentina) Adsorbent used H1.6Mn1.6O4 Spinel type Mn-oxide λ-MnO2 (granulated) Ion-sieve type Mn-oxide spinels: HMg0.5Mn1.5O4(I) HZn0.5Mn1.5O4 (II) HMn2O4 LimMgxMnIIIyMnIVzO4 (0bx≤0.5) Surface deposition on corrosion product of Al Hydrated alumina: LiOH=2Mratio Al(OH)3 Hydrated alumina Conditions Adsorbent: 200 mg, sea water: 50 L, 4 weeks; desorption by 0.5 M HCl, 1 day 30 °C, 15 days 150 days Adsorption at 0.4 M HCl, 5 days 60 °C, 24 h 24 h, pH 6.5 30 °C, 10 days pH 5.8 30 °C, pH 9 LiCl solution— 1% Li (20 times conc.) by solar evaporation. Adsorption/Remarks Max. uptake: 40 mg Li/g adsorbent b 90% Li, Li uptake: 10.6 mg/g adsorbent Recovery—264 g LiCl in 791 g dried precipitated salt (816 m3 seawater) Adsorption: 88% Li by adsorbent I and 89% Li by adsorbent II. Equil. sorption: 30.3 mg/g (I) and 33.1 mg/g (II). Loading capacity: 1.53 mmol/g sorbent Adsorption capacity: 23–25 mg/g adsorbent 34% Li Adsorption:0.6–0.9 mg/g sorbent Adsorption capacity: 123 mg/g adsorbent Adsorbed Li eluted by acid and precipitated by sodium carbonate Product – LiCl LiCl LiCl Li salt Li2CO3 – – LiAlO2 Li2CO3 References Chitrakar et al. (2001) Umeno et al. (2002) Yoshizuka et al. (2006) Chung et al. (2004, 2008) Wajima et al. (2012) Chitrakar et al. (2013) Takeuchi (1980) Dong et al. (2007) Hawash et al. (2010) Clarke (2013) Mg(OH)2. A general flowsheet of Li2CO3 production from brine water is shown in Fig. 1. The basic approaches for the separation of mineral products (K, Mg, Na, Ca, Li) from the seawater comprises of flotation (using anionic col- lectors), sorption, ion exchange, solvent extraction etc. as described by Koyanaka and Yasuda (1977). The existing evaporation process for lith- ium recovery from brine lakes is time consuming and suffers from low recovery efficiency. Besides, tremendous burden is posed on the envi- ronment due to waste generation and substantial water consumption. 3.2.1. Adsorption process Various types of adsorbents have been used for selective lithium recovery from seawater and brines. In the adsorption method certain inorganic ion-exchangers such as the spinel-type manganese oxide show extremely high selectivity for lithium from seawater (Kitajou et al., 2003; Ooi et al., 1989, 1991; Umeno et al., 2002; Yoshizuka et al., 2002, 2006). Such materials exhibit high adsorption capacities in alkaline Table 8 Precipitation and other processes for lithium extraction from seawater and brines. medium (pH of seawater being ~8) for Li+ in the presence of alkali and alkaline earth ions. For instance Kitajou et al. (2003) reported the separa- tion of Li+ from a large amount of Na+ by the spinel-type λ-MnO2 whereby Li+ was concentrated 400 times leaving most Na+ in the sea- water. Extraction/separation of lithium from brines and such resources is summarized in Table 7. The manganese oxide (H1.6Mn1.6O4) prepared from the precursor, Li1.6Mn1.6O4 by hydrothermal and reflux methods, showed the maxi- mum uptake of 40 mg Li/g of adsorbent from the seawater, the highest among the inorganic adsorbents (Chitrakar et al., 2001). The very fine size (nano-size range) of the synthesized manganese oxide was found to be responsible for its high adsorption capacity towards lithium as compared to other adsorbents. Adsorption of lithium from seawater by a spinel type λ-MnO2 produced low purity (~33%) Li+ ions contaminat- ed with Na+ (Yoshizuka et al., 2006). Chung et al. (2004) synthesized nano-manganese oxide (Li1.33Mn1.67O4) through a gel process. The ion sieve-type adsorbent containing magnesium after acid treatment was Source/Raw material Synthetic solution, Geothermal water (Li = 10 mg/L) Synthetic solution (2.5 M LiCl, 0.3 M CaCl2 and 0.15 M MgCl2) Seawater (0.12–0.16 mg/L Li) Seawater (0.18–0.20 mg/L Li) Uyuni Salar brine, Bolivia, 15–18 g/L Mg, 0.7–0.9 g/L Li Brine from Salar de Hombre Muerto, Argentina Brine (high Mg/Li ratio) Process Precipitation Precipitation followed by IX using Poly BD® R45HTLO (MC50), Lewatit® (TP 207), Dowex®(Y80) Integrated ion-exchange method Two stage precipitation Two stage precipitation with lime & Na-oxalate Precipitation (2.5 g/L LiCl from solar pond) with lime and Na2SO4 Electrochemical Conditions pH 12.5 for [Al]: 50–1000 mg/L Precipitation with 1.8 M Na2CO3 at 80 °C. IX—50 °C, 30 min 1st stage: sorption on λ-MnO2, 150 days (264 g LiCl in 816 m3 seawater); 2nd stage: Sep. of Mg(II), Ca(II), Sr(II) and Mn(II) with SK110 resin (pH 9) 1st stage pH : 11.5–12.5; 2nd stage: Na2CO3 at 100 °C 1st stage pH: 11.3, 2nd stage: sodium oxalate, 80–90 °C Separation of Mg as hydroxide and Ca as sulfate Electrolyte: 0.5 M NaCl, 10 h Recovery (%)/Remarks 70% Li Good usable volume cap. of resin TP207: 56.4 g/L 56% yield Recovery of pure lithium carbonate Precipitation as Li2CO3 LiCl salt feed for Li extr. in a chemical plant ~94% Li; Li sorption: 28.65 mg/g LiFePO4 Product (% purity) – Li salt solution Li2CO3 (N99.9) Li2CO3 (99.4) LiCO3 (99.55) LiCl – References Yoshinaga et al. (1986) Bukowsky et al. (1991) Nishihama et al. (2011), Onishi et al. (2010) Um and Hirato (2012) An et al. (2012), Tran et al. (2013) Clarke (2013) Zhao et al. (2013)PDF Image | Extraction of lithium from primary and secondary sources
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