Hydrometallurgy 117–118 (2012) 64–70Contents lists available at SciVerse ScienceDirect Hydrometallurgy journal homepage: www.elsevier.com/locate/hydromet Recovery of lithium from Uyuni salar brine Jeon Woong An a, Dong Jun Kang a, Khuyen Thi Tran b, Myong Jun Kim b, Tuti Lim c, Tam Tran b,⁎ a Technology Research Institute, Korea Resources Corp, Seoul, South Korea b Department of Energy & Resources Engineering, Chonnam National University, Gwangju, South Korea c School of Life Sciences and Chemical Technology, Ngee-Ann Polytechnic, Singapore a r t i c l e i n f o a b s t r a c t Article history: A hydrometallurgical process was developed to recover lithium from a brine collected from Salar de Uyuni, Received 27 December 2011 Bolivia, which contains saturated levels of Na, Cl and sulphate, low Li (0.7–0.9 g/L Li) and high Mg (15– Received in revised form 4 February 2012 18 g/L Mg). Unlike other commercial salar brines currently being processed, the high levels of magnesium Accepted 8 February 2012 and sulphate in Uyuni brine would create difficulties during processing if conventional techniques were Available online 16 February 2012 used. A two-stage precipitation was therefore first adopted in the process using lime to remove Mg and sul- Keywords: phate as Mg(OH)2 and gypsum (CaSO4.2H2O). Boron (at 0.8 g/L in the raw brine), a valuable metal yet dele- Uyuni salar brine terious impurity in lithium products, could also be mostly recovered from the brine by adsorption at a pH High purity lithium carbonate lower than pH11.3 in this first stage. The residual Mg and Ca (including that added from lime) which were Removal of magnesium and sulphate subsequently precipitated as Ca–Mg oxalate could be roasted to make dolime (CaO ∙MgO) for re-use in the Calcium first stage of precipitation. Evaporation of the treated brine up to 30 folds would produce 20 g/L Li liquors. Boron The salt produced during evaporation was a mixture of NaCl and KCl, containing acceptable levels of sulphate, Mg, Ca, etc. The final precipitation of lithium at 80–90 °C produced a high purity (99.55%) and well crystalline lithium carbonate. © 2012 Elsevier B.V. All rights reserved. 1. Introduction Galaxy Resources in Western Australia (Galaxy Resources, 2011). The concentrate was sent to its lithium carbonate plant in Jiang Su, Lithium has found application in many industries, from the China to produce 17,000 tpa lithium carbonate of 99.9% grade. Other manufacturing of glass, ceramics, rubbers and pharmaceuticals to projects are also considered for the processing of wastes from China production of lithium-ion batteries. The global market share of lithi- clay operations (Siame and Pascoe, 2011; Sitando and Crouse, 2012) um used in batteries has grown significantly over the last few years and zinnwaldite wastes from tin–tungsten mines in Cinovec, the and has reached 23% in 2010 (USGS, 2011). The demand for lithium Czech Republic (Jandova et al., 2008, 2009, 2010). However, up till is forecast to increase by ~ 60% from 102,000 t to 162,000 t of lithium now lithium has been mostly produced from salar brines which con- carbonate equivalent in the next 5 years, with application in batteries tain 0.06–0.15% Li due to the low cost of production as shown in taking a large percentage (40,000 t) of this growth (Hykawy, 2010; Table 1 below for major operations around the world (Evans, 2008; Siame and Pascoe, 2011). Yaksic and Tilton (2009) completed an ex- Roskill, 2009). Brine production until 2013 by Chemetall, FMC and tensive survey and reported that the current resource of lithium in SQM is forecast to increase by an annual rate of 4–5% per year, where- continental/salar brines is approximately 52.3 million tonnes of lithi- as up to a growth rate of 35% per year is expected for the lithium car- um equivalent, mostly in Chile, Argentina and Bolivia, of which bonate production from China, due to the significant expansion of the 23.2 million tonnes is recoverable. On the other hand, lithium from lithium battery industry (Roskill, 2009). mineral resources accounts for 8.8 million tonnes, where large de- Salar de Uyuni in the highland of Bolivia, ranked as one of the rich- posits have been located in the USA, Russia and China. The reserves est in the world, has a lithium reserve estimated at 5.4 million tonnes, and recoverable resources of lithium were estimated by Evans (USGS, 2011). Apart from the fact that the Uyuni salar is located well (2008) as 29.79 million tonnes Li. above 3600 m altitude, the processing of this brine would present a Several commercial projects have been recently considered or de- challenge as it has a high Mg/Li ratio (16–22:1) while the Li content veloped to process lithium carbonate from lithium minerals. A mine only averages b0.08% Li compared to other geothermal or salar brines treating 1 million tonne spodumene ore per year to produce (Table 1). Apart from other by-products such as boric acid, potash, 131,000 tpa lithium concentrate (6% Li2O) was recently built by sylvite (KCl), sylvinite (KCl ∙NaCl) commonly recovered from salar brines, the value of Mg in the Uyuni brine is as high as for lithium if a chemical grade Mg oxide or hydroxide could be produced. ⁎ Corresponding author. Tel.: + 82 62 530 1726; fax: + 82 62 530 0462. The recovery of lithium from salar brine usually involves continu- E-mail address:
[email protected] (T. Tran). ous solar pond evaporation of the brine in several stages until its 0304-386X/$ – see front matter © 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2012.02.008 68 187. However the process yields very fine and poorly crystalline Mg(OH)2.61 41. covery of Mg is therefore necessary for the production of high purity lithium carbonate or lithium chloride.06 1.7 21.0026 0. Bolivia and the optimization of the ducing the lithium recovery from the process.3 . USA 5.4 0. USA 11.35 19. Attempts have been made to The precipitation of Mg and Ca salts was conducted at ambient promote the “ripening” of nano-sized primary crystals of Mg(OH)2 temperature (20–22 °C) using various reactors incorporating differ- to improve its settling and filterability by aging the precipitate in ent modes of stirring. 2011.2. An et al.01 0.09 15.9–10.09 1.84 0. USA 8.2 15.33 16.%) (wt.05 0. 1994. Roskill.29 16.061 Sua Pan.5% to 99.0306 5 Searles Lake.068–0.70 0.6H2O.17 0.5 0.2 After evaporation to 30 g/L Li 37. 2011). to treat the salar brine from Uyuni.40 0.26 0. / Hydrometallurgy 117–118 (2012) 64–70 65 Table 1 Compositions of various brines of commercial value around the world (Boryta et al.005 0. 1–4% Mg. LiCl.82 0.%) (wt. 2003).5–0.0057 0.9 14. 2. Argentina 9.02 0.65 30. B and K as by-products.76 0. whiteness. Products of 99.3 0. Hot plates or temperature-controlled water baths before lithium carbonate can be recovered.0054 0.4 0. 2002.30 0.0016 12.08 2. India 6 0. fur.W. oil ad.045 18.071 0.121 0. 2005).036 7.82 0.965 0.20 196.36 0.00–7. China 5. 2. 2011.26–0. In this study the chemical compositions of the brines were deter- sorption.65 0. B and sulphate are recovered. USA 3. The clean bishoffite (MgCl2. The Mg(OH)2–CaSO4∙2H2O mixture has all properties (BET area. Boron (B) should also be recov. the concentrated brine In salar brines containing Mg.4% Li (Atashi et al.6H2O) starts precipitating when the brine is con.0163 0. however.5% Li before plant operations can produce lithium carbonate of >99.96 0.%) (wt.14 Salar de Uyuni. Bolivia. This study therefore focuses on the development of a general process By then lithium carnallite.17 0.9 0.95 1. Alamdari et volumes of brine.019–0.26–3.019 0. Source Na K B Li Mg Ca Cl SO4 (wt. 2.007 0.3 4.003 0. were used in experiments where heating was required.6H2O) or can then be purified to remove other residual impurities. carnallite (KCl. 1995). brine is then subjected to carbonation to precipitate lithium carbon- centrated to ~ 4.6 13. A different ap. particle size.83 Bonneville.. solvent extraction or ion exchange to remove other impu.7 0.67 After oxalate precipitation 115.6 After lime precipitation 92.90 42–50 Salar de Atacama.04 0. Henrist et al.29 1.0057 14 Zabuye.9 b0.91 201.22 215.. Equipment used sulphate.MgCl2. ate using sodium carbonate.53–1. Approximately 15 m 3 of the salar brine from Salar de Uyuni was A new process scheme therefore needs to be developed for high sampled for the experimental testwork conducted at our laboratories Mg salar brines such as that found in Uyuni. (2008) could precipitate Mg(OH)2 of a larger particle size range can now be manufactured using brine evaporation. In the presence of 2.018–0. also precipitates thus re.97 0. adding seeds (5–40 μm) and adopting slow NaOH addition.70 203.24–0..00–15. the concentrated brine is processed to lithium carbonate or chloride.0012 3.53 0.%) Clayton Valley. rities (Boryta et al. Perkin-Elmer) or IC (ICS-2000. The structure of lithium carbonate product was determined ther refining of this mixture is required before Mg can be recovered as by X-ray diffraction analysis (Cu-tube60kv 50 Ma.0321 0.14 0. All chemicals Mg can be removed from sea water.. Mg(OH)2 using slaked dolomite (CaMgCO3) or lime (Ca(OH)2) (Carson and Simandl.72 0.3 b0.007 0.59 HombreMuerto. The conventional process used by most Wilkomirsky.5–1% boron (as borate).63 0. Experimental ered as apart from improving the process economics its removal from the concentrated brine is essential for the production of low B feed.42 3.. 2005).07–0.4 15.2 0.4 20.57 2. Brine before/after treatment Na K Ca Mg Li B Cl SO4 Raw Brine 1 105.00 1.. J. Boryta et al.. Philips).2H2O) is normally formed.039 0. 2009). 2011). process considered also has to recover Mg.0106 9. 1988.031 2.34 Salton Sea.045 7. The zeta a chemical grade product or as feedstock for Mg metal production.1.5% grade.002 7. Karidakis et al. Israel 3.026–0. purity Mg product.53 Taijinaier. 0.%) (wt.41 content reaches 6% Li. After Ca.34 17. in Korea.0018 0..44 52. Evans.157 0.80–16.7 3.61 Great Salt Lake. Experimental techniques tion stage required for its recovery from the highly viscous brine (Baird et al.69 0.1 0. 2010..8 2.09 0.5 22. either 2 L or 4 L) in solid form to avoid the dilution Table 2 Compositions (in g/L) of the Uyuni salar brine before and after treatment.30–2.5 b0. etc. 2008. China 7. precipitation of (5–60 μm) within 60 min from a sea bittern containing 30 g/L Mg by K and Mg. Materials stock required for advanced battery manufacturing or Li metal pro- duction (Boryta et al. Karidakis et al.3 13. bittern or process liquors as used in the study were of analytical grade.5 0. The potential of the Mg(OH)2 precipitate was measured using an instru- use of NaOH to precipitate Mg(OH)2 would no doubt produce a high ment from Otsuka Electronics (ELZ-Z2). Bolivia 7.76 After evaporation to 20 g/L Li 56.00 Dead Sea.%) (wt.20–20.80 0.3.%) (wt. Chile 9.77 16. retarding fillers (Hull et al.30 0.01–0. The solar evaporation reaches 5. The contain ~ 6% Li.05 0.%) (wt.5–6.4 0. 2011.04 0. Mg. The brine was analysed by ICP-AES and its composition is proach has to be implemented to remove Mg and B as by-products shown in Table 2.56 0.97 0. 1999).3 Raw Brine 2 95. Different precipitants were added (to known 24 h in non-stirring conditions (Turek and Gnot.94–2.. The separate re.MgCl2. gypsum (CaSO4.0489 0.70–8. USA 4.05 0. Dionex).) required to be used as fire mined by ICP-AES (Optima-5300DV.3 4.60 0. However.02 13.1 2.66 0.44 0. The brine by then will unit operations used to recover a high purity lithium carbonate.36 189.01 16.3 0.99% lithium carbonate al. creating difficulty during the solid/liquid separa. Results and discussion selectively precipitating Mg and Ca using different precipitants. B Removal Mg(OH)2 Re-processing L S CaSO4. Mg Removal L S Roasting of Ca-Mg oxalate CaO. 2008) was first used to predict the conditions for 3.5 g/L Li 80-90 oC solar evaporation 99. Flowsheet developed for the recovery of lithium as carbonate from Uyuni brine.1:1. For Na. A typ- ical example of the results obtained from Stabcal modelling is shown This study investigates conditions for. Mg.2H2O to recover Adsorbed B Mg(OH)2 and B Na2C2O4solid Ca.1. Each unit operation of this flowsheet was tested and the re- added to the reactor at 5 g/L would help the reaction to reach equilib. / Hydrometallurgy 117–118 (2012) 64–70 Ca(OH)2solid Brine Mg. 1.1:1) pH Fig.66 J.1:1 lime/Mg addition at a low pH range. 2 for the addition of lime to the raw brine at the Lime/Mg molar as by-products. whereas at 1:1 lime/Mg molar ratio the precipitation takes place at pH > 12. The use of ceramic balls (5 mm diameter) products. (b) impeller-type stirrer 20–60 g/L Li for the precipitation of lithium carbonate. (a) recovery of Mg. An et al. 1 outlines set at 200 rpm and (c) impeller plus ceramic balls for grinding the the major steps involved in the recovery of lithium and other by- precipitant added as solid. which hindered the mass balance calculation including sulphate which causes gypsum formation during proces- and the brine concentration afterwards. Li and B species at different pHs and lime additions of 1:1 lime/Mg molar ratio. Fig. rium quickly within 1 h.MgOrecycling Solar evaporation Purification Residual Ca. Brine evaporation 3. The precipitate suspension sing and (c) concentrating the brine by evaporation to achieve was based on either (a) magnetic bar stirrer. etc… 20 g/L Li Li Evaporation Carbonate treatment Na2CO3 Carbonation before recycling to solid 1.W. . B and to re- centrifuging. Using lime.55% Li2CO3 Fig. duce the levels of Ca and sulphate from the raw brine. of the original brine. Stabcal soft- ware (Huang. sults are presented and discussed as follows. Mg. Samples were taken during the precipitation to confirm the reaction has reached completion. (b) purification to remove deleterious impurities ratio of 1:1 and 0. Mg could be removed as Mg(OH)2 Concentration (g/L) Ca Mg Na (1:1) B Li Na (0. the precipitation of Na2- SO4∙10H2O was predicted at 0. Recovery of magnesium and boron tests were also conducted by continuous boiling and the concentrated liquors were separated from the precipitates by vacuum filtration or Different alternatives were evaluated to recover Mg. B and Ca in Fig. Stabcal modelling showing the stability of different Ca. 2. However even at additions of phosphate at PO4/Mg stoi.7 60 0. Stabcal however could not predict the Our preliminary studies based on precipitation tests and Stabcal Mg equilibrium conditions accurately as there was large variation of modelling showed Ca could be removed selectively in the first stage Mg concentration with respect to pH along the steep precipitation using phosphate.MgCO3 was formed in the neutral pH hour however showed lower precipitated Mg compared to stoichio- range. / Hydrometallurgy 117–118 (2012) 64–70 67 Fig. higher Mg concentration remaining in the Lime is the best precipitant that can be used for removing Mg from brine) indicating incomplete reaction of lime and Mg ions. as seen in Fig. 3.6 0. Zeta potential measurements at different pHs showing the point-of-zero-charge (diamonds: addition at 0. be reported later. whereas the precipitation of gypsum (CaSO4. Measured concentration profiles of Brine 2 after precipitation of Mg at different lime/Mg molar ratios. The precipitate formed (at 0.3 × mole ratio). . Mg. the double salt of CaCO3.6. 2) within chiometric ratios >2:1 the residual Mg concentration in the treated this range of pH. at different consecutive additions of Ca(OH)2 Fig.8 1 -20 7 8 9 10 11 12 13 Ca(OH)2/Mg2+ Ratio pH Fig.2H2O) and pH > 8. ther processed to separate Mg from the gypsum waste.2 0 0. As shown um concentrations of Ca. additions. although it has to be added in slight excess for complete Mg expected with lime neutralization as the formation of gypsum coating removal. At a lime addition of 0. negating the complete recovery of pure Mg products. Residual Mg after lime precipitation and almost ing the brine) were also tested. This second-stage precipitate can be converted to MgO ∙CaO itation of Ca/Mg carbonate.3 20 PZC 0. caustic (sodium hydroxide) and sodium oxalate. The results of this study will Several other precipitants (containing Na or Ca to avoid contaminat. 2) was also used to predict accurately the state within 1 h. Na.1× stoichiometry each time. later.4 0. including sodium carbonate. causing slight dips in both Na and SO4 concentra- brine was still very high (at ~4 g/L Mg). The precip. 3. Further processing of as soluble Li + ions over a wide range of pHs whereas solid this mixed product is required to recover high purity Mg and B by- (CaO)2∙ B2O3 and (CaO)3∙B2O3 could be formed at a pH > 12.4 0. The steady state concentrations measured after one itant. circles: at 0. place rapidly and residual Ca/Mg concentration could reach steady Stabcal modelling (Fig. phate would contaminate the liquor and cause further complications Na2SO4 re-dissolves. Continuous or dotted lines are those predicted by stoichiometric cal- culations (for Mg) or from Stabcal. oxalate. The precipitation of gypsum (CaSO4. As more lime is added.2 0. 5. releasing SO4 ions for the formation of the less in the following stages. phosphate and oxalate precipitates equilibrium concentrations of Na. The equilibri. at a pH > 8. ments in the brine as shown in Fig.5 40 Zeta Potential (mV) 0. and SO4 ions are therefore con. An et al. When sodium carbonate was used as precip.1:1 tate formed from NaOH addition was fine and non-crystalline (particle Ca(OH)2/Mg molar ratio. Removal of boron from Brine 1. gles: 0. sodium all soluble Ca can then be subsequently removed by adding sodium phosphate. K.6 Boron Concentration (g/L) 0. Li and Cl and other minor ele- could be recovered easily by filtration.6) is a mixture of gypsum and Mg(OH)2 which needs to be fur- Na2SO4 takes place over a range of pH from pH2 to 12.1 0 0 0. hydroxide and oxalate took (dolime) by roasting for re-use in the lime precipitation stage. effecting sizes b10 μm) and could not be easily separated from the viscous brine. metric predictions (i.e. However the Mg(OH)2 precipi. except pH which was measured throughout the test. This excessive use of phos.1 to pH8. tions as measured by chemical analysis. 4. This is the brine. this precipitate also contained boron which was recovered by trolled by these precipitates during lime addition. Sodium sulphate started precipitating also (Fig. the pH rises from pH7. All carbonate. Lithium is stable adsorption during the first-stage precipitation. products from the mixed precipitate.6.2 × mole ratio. Mg could also be removed as pure Mg3(PO4)2 salts line of Mg(OH)2. 2. phosphate. The predicted Mg equilibrium con- in the subsequent stage. These phosphates are valuable fertilizer centration therefore was stoichiometrically calculated from the lime products.2H2O) also reduces the sulphate to b1 g/L in the treated brine.W. J. soluble gypsum. the precipitation of Mg(OH)2. trian- (PZC) at pH11.3. The separation operation would not be as effective as in laboratory Stabcal modelling however could not predict the adsorption process studies. 80 3. 2) boron exists as filtration is ~ 80% and 60%. i. to 6% Li by solar evaporation. In practice. As shown in Fig. 5 (at 0. where large discrepancies exist between the The cumulative losses of major ions are shown in Fig. 4 the brine was concentrated by. Recovery of residual magnesium and calcium Li recovery (%) 60 The residual Mg and Ca. The operation was simulated in the lab- Stabcal predicts that sodium sulphate would re-precipitate at 1:1 oratory in several trials to concentrate the brine several folds from the lime/Mg molar ratio (as shown Fig. Fig.6 0.2 8 0.5 at a further addition of lime.2. The precipitate obtained is a mixed Ca–Mg oxalate 20 which can be converted to dolime (CaO∙MgO) by roasting for re-use in the first stage of lime precipitation. 0. 0 0 10 20 30 40 50 3. Above pH12. This was confirmed by the ing. KCl and other complex salts precipitated during range of pH8–11.5 0. it was confirmed that most of the salt The adsorption process was reproducible at different modes of lime addition as shown in Fig.3.2× or 0. The loss of lithium throughout the 50 g/L Li targets. until the 1:1 Ca(OH)2/Mg molar ratio was reached. the maximum recovery of Li from evaporation and pressure shown in the Stabcal stability diagrams (Fig. using pond solar HB4O7− or B(OH)4− cation within the range pH8–12. the surface of Mg(OH)2 is only lightly negatively charged.1:1 to 1:1 is mainly due to adsorption by brine recovered after evaporation and pressure filtration or centrifug- the Mg(OH)2-gypsum mixed precipitate. 7. The con- centrations of other ions after sodium oxalate treatment are also shown in Table 2. to achieve 20 g/L and this pH. Concentration of lithium by evaporation Achieved Li concentration (g/L) After Mg. could be removed using sodium oxalate (added at 1:1 sodium oxa- 40 late/[Ca + Mg] molar ratio to b50 ppm Ca and 170 ppm Mg).3 Mg Li 1.68 J.5 B 0. including added amounts from lime.3× lime/Mg stoichio. respectively. and therefore is evaporation the recovery is expected to be lower as the solid/liquid easily adsorbed onto Mg(OH)2 below the point-of-zero-charge. Δ(mol). causing incomplete recovery of boron at high pHs. (CaO)2B2O3 and (CaO)3B2O3 started precipitating as in. the adsorbed boron was released from co-precipitates with some loss of Mg measured. In this context the degree of evaporation was The recovery of boron during lime addition corresponding to the measured as the ratio between the initial volume and the volume of lime/Mg molar ratio of 0. As 30 g/L Li. the precipitation of NaCl pH increased steadily to pH ~ 11. with the zero-point-of-charge at pH11. After this. removal of Mg and Ca by lime and oxalate precipitation is minimal The pH rose steadily from pH8. After that (concentration factor: 5–20) KCl 1:1 stoichiometry. 20. would prevent complete dissolution of lime particles for the reaction. 7. initial volume of 4 L. / Hydrometallurgy 117–118 (2012) 64–70 120 220 Na 20 80 210 15 Cl 10 SO4 Concentration (g/L) 40 200 K 5 0 190 0 0 10 20 30 40 50 60 0 10 20 30 40 50 60 0 10 20 30 40 50 60 0.5 24 3 0. representing the number of folds measurement of zeta potential of the Mg(OH)2 precipitate.2 at further additions of lime (within 3% of the analytical analysis error) as indicated in Table 2. 6. as shown in Fig. Na and K Fig.3. . Concentration profile of concentrated brines after evaporation of Brine 1. possibly as Mg- the Mg(OH)2 back to the brine.7 32 4.4 16 0. An et al. 30. the pH Following conventional techniques. Heavy losses of Li due to evaporated shows the zeta potential Ezeta measured as 0–60 mV for the pH brine caught in NaCl. Li recovery after consecutive evaporation of Brine 1 to achieve 10. obtained after evaporation. 8. Typical compositions of the brine after lime treatment. the cumulative number of moles losses. lithium could be concentrated would rise to pH > 11. from the liquor dicated by Stabcal.5 at further additions of lime until is more predominant. 2). B and Ca were removed the brine contained Li.W. 3.3. 100 metric ratio). By mass balancing stoichiometry. Above evaporation were observed.e.6 to pH9. After this. added at 1:1 Ca(OH)2/Mg molar ratio are listed in Table 2. However with lime addition past 1:1 chloride salt or by adsorption on NaCl and/or KCl. The solution period when the concentration factor is b5.1 0 0 0 0 10 20 30 40 50 60 0 10 20 30 40 50 60 0 10 20 30 40 50 60 Concentration Factor Fig.1×. defined as Concentration Factor. 40 and in a chloride brine of low sulphate. In the first model prediction and boron concentration measured. 15 0. the recovery of lithium was measured for boron and sulphate at 20-fold evaporation con. 8.4 mole Li contained in 4 L of the original brine of ~0. Lithium carbonate precipitation A hydrometallurgical process was developed to recover lithium At 20 g/L Li concentration.1 Run 2 Run 2 Run 3 Run 3 0. a high purity product (99. For example at the concentration factor of 30. This loss increases at further evaporation of the Content (%) 0. A concentration ratio of 14 and 26 lithium carbonate). by division)..005 Run 5 Run 5 0.5 and 1. After washing precipitating.7 0.55%) and well crystalline lithium carbonate could then be produced from this process. 6) indicating sulphate salts started crystalline materials as confirmed by its XRD pattern.2 0. . An et al.05 0. Content (ppm) b 10 b 10 b10 b10 b 10 b 10 b 10 representing losses of ~ 20% (of ~0. Process. 0. The carbon. gyp- ation stage therefore is usually conducted at elevated temperature sum and adsorbed boron from the first stage of precipitation needs to be re-processed to produce high purity Mg and B products.8–8. 10 Acknowledgement 8 This work was supported by a grant from the Energy Efficiency & Resources of the Korea Institute of Energy Technology Evaluation and Planning (KETEP). Conclusions 3. Resid- 16 ual Mg and Ca can then be totally removed by sodium oxalate in the second stage of precipitation. 6 0 20 40 60 80 100 2010 T100100408).15 0.5 K Run 4 Cl Run 4 5 5 Run 5 Run 5 Run 5 Δ(Mol) 0 0 0 0 10 20 30 40 50 60 0 10 20 30 40 50 60 0 10 20 30 40 50 60 0.01 0.. Cl and sulphate. and saturated with Na. 2008.015 Run 2 0. / Hydrometallurgy 117–118 (2012) 64–70 69 25 2 25 20 20 1. could be recovered.5 15 Run 1 Run 1 15 Run 1 Run 2 1 Run 2 Run 2 10 Run 3 10 Run 3 Run 3 Na Run 4 0. highlighting the fact that no sulphate salt will precipitate bonate is between 1. B and sulphate from the brine at temperatures higher than ambient (Garrett.55%) product. Nourafkan. using lime first and then sodium oxalate. E.9 g/L Li cover the product can be performed using sodium carbonate precipi. Korea (no. the solubility of lithium carbonate decreases was employed to remove Mg. A two stage precipitation tant. Eng. At a higher concentration factor (>30) the loss of sul.1 mol. Chem. Δ(mol) (Cl −) = Δ(mol)(Na +) + Δ(mol) Composition of lithium carbonate (99.05 Run 4 0.7–0.1 mol/L Li). Under these conditions. 9.2 g/L up to this level of evaporation.e. M. 215–221. in the final stage is expected to be higher than 90% using a feed liquor firmed minimal losses of these two ions (within experimental error of 20 g/L Li. The product produced from this precipitation was a well- phate was also observed (Fig. 4.03 0. A. Lithium carbonate solubility at different temperatures. 9. Ca.02 Run 1 Run 1 0. Alamdari.04 brine. Ministry of Knowledge Economy.4. precipitation of lithium carbonate to re.W.02 Run 3 0.8 g/L Li (corresponding to 7. in hot water. Up to the concentration factor of 20 the loss of lithium and Component Ca Mg Na K Li B Sr boron is minimal.06 0.R.04 0. sium hydroxide precipitation from sea bittern. Esfandiari. As shown in Fig. Sulphate concentration shows a one-to-one linear relationship with the concentration factor up to in the range 80–90 °C. The composition of this product is shown in ducted in future commercial operations to produce concentrated Table 3. Temperature (oC) References Fig.03 Run 1 0. the lithium con. 2004).01 Mg Run 4 Li B Run 4 0...025 0. from the Uyuni salar brine containing 15–18 g/L Mg. where the maximum solubility of lithium car- 20 folds. Cumulative losses (as number of moles) of various ions after evaporation of Brine 1. Kinetics of magne- Data from Garrett (2004). J. (K +)). precipitated during the early stage of evaporation (at b20 folds) was a Table 3 mixture of NaCl and KCl (i. Further polishing 14 purification can be conducted to remove residual Ca and Mg before Li2CO3solubility (g/L) the treated brine was subjected to carbonation at 80–90 °C using so- 12 dium carbonate.06 18. The mixed Mg(OH)2. Component Fe Cu Al Ni Zn Cr Pb centration in the liquor was 20 g/L whereas Δ(mol)(Li +) is 0.04 b 0. N. Following a 30-fold evaporation the brine could be concentrated to achieve 20 g/L Li.55% lithium carbonate) Evaporative concentration up to 30-folds can therefore be con. A high purity (99. 47. Rahimpour.01 Run 5 0 0 0 0 10 20 30 40 50 60 0 10 20 30 40 50 60 0 10 20 30 40 50 60 Concentration Factor Fig. brines of ~20 g/L Li. Processing of zinnwaldite waste to obtain lithium Boryta. T. pp.1016/j. H. A. Miner. production. Kinetics of magnesium hydroxide precipitation from sea 105–114. doi:10. M. M. Polym. 2011. Hydrometallurgy 103. C. J. 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