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Hydrometallurgy 117–118 (2012) 64–70

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Hydrometallurgy
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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: tamtran@jnu.ac.kr (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
J.W. An et al. / Hydrometallurgy 117–118 (2012) 64–70 65

Table 1
Compositions of various brines of commercial value around the world (Boryta et al., 2011; Evans, 2008; Roskill, 2009).

Source Na K B Li Mg Ca Cl SO4

(wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)

Clayton Valley, USA 4.69 0.4 0.005 0.0163 0.019 0.045 7.26 0.34
Salton Sea, USA 5.00–7.00 1.30–2.40 0.039 0.01–0.04 0.07–0.57 2.26–3.9 14.20–20.90 42–50
Salar de Atacama, Chile 9.1 2.36 0.04 0.157 0.965 0.045 18.95 1.59
HombreMuerto, Argentina 9.9–10.30 0.24–0.97 0.068–0.121 0.018–0.14 0.019–0.09 15.80–16.80 0.53–1.14
Salar de Uyuni, Bolivia 7.06 1.17 0.071 0.0321 0.65 0.0306 5
Searles Lake, USA 11.08 2.53 0.0054 0.0016 12.3 4.61
Great Salt Lake, USA 3.70–8.70 0.26–0.72 0.007 0.0018 0.5–0.97 0.026–0.036 7.00–15.60 0.94–2.00
Dead Sea, Israel 3.01 0.56 0.003 0.0012 3.09 1.29 16.1 0.061
Sua Pan, India 6 0.2 0.002 7.09 0.83
Bonneville, USA 8.3 0.5 0.007 0.0057 0.4 0.0057 14
Zabuye, China 7.29 1.66 0.0489 0.0026 0.0106 9.53
Taijinaier, China 5.63 0.44 0.031 2.02 0.02 13.42 3.41

content reaches 6% Li. Products of 99.5% to 99.99% lithium carbonate al. (2008) could precipitate Mg(OH)2 of a larger particle size range
can now be manufactured using brine evaporation, precipitation of (5–60 μm) within 60 min from a sea bittern containing 30 g/L Mg by
K and Mg, solvent extraction or ion exchange to remove other impu- adding seeds (5–40 μm) and adopting slow NaOH addition.
rities (Boryta et al., 2002, 2011). After Ca, Mg, B and sulphate are recovered, the concentrated brine
In salar brines containing Mg, carnallite (KCl.MgCl2.6H2O) or can then be purified to remove other residual impurities. The clean
bishoffite (MgCl2.6H2O) starts precipitating when the brine is con- brine is then subjected to carbonation to precipitate lithium carbon-
centrated to ~ 4.4% Li (Atashi et al., 2010; Boryta et al., 2011; ate using sodium carbonate. The conventional process used by most
Wilkomirsky, 1999). The solar evaporation reaches 5.5–6.5% Li before plant operations can produce lithium carbonate of >99.5% grade.
the concentrated brine is processed to lithium carbonate or chloride. This study therefore focuses on the development of a general process
By then lithium carnallite, LiCl.MgCl2.6H2O, also precipitates thus re- to treat the salar brine from Uyuni, Bolivia and the optimization of the
ducing the lithium recovery from the process. The brine by then will unit operations used to recover a high purity lithium carbonate. The
contain ~ 6% Li, 1–4% Mg, 0.5–1% boron (as borate). The separate re- process considered also has to recover Mg, B and K as by-products.
covery of Mg is therefore necessary for the production of high purity
lithium carbonate or lithium chloride. Boron (B) should also be recov- 2. Experimental
ered as apart from improving the process economics its removal from
the concentrated brine is essential for the production of low B feed- 2.1. Materials
stock required for advanced battery manufacturing or Li metal pro-
duction (Boryta et al., 2011). 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, Bolivia. A different ap- in Korea. 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. Hot plates or temperature-controlled water baths
before lithium carbonate can be recovered. were used in experiments where heating was required. All chemicals
Mg can be removed from sea water, bittern or process liquors as used in the study were of analytical grade.
Mg(OH)2 using slaked dolomite (CaMgCO3) or lime (Ca(OH)2)
(Carson and Simandl, 1994; Karidakis et al., 2005). In the presence of 2.2. Equipment used
sulphate, however, gypsum (CaSO4.2H2O) is normally formed. The
Mg(OH)2–CaSO4∙2H2O mixture has all properties (BET area, oil ad- In this study the chemical compositions of the brines were deter-
sorption, particle size, whiteness, etc.) required to be used as fire mined by ICP-AES (Optima-5300DV, Perkin-Elmer) or IC (ICS-2000,
retarding fillers (Hull et al., 2011; Karidakis et al., 2005). However, fur- Dionex). 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, Philips). The zeta
a chemical grade product or as feedstock for Mg metal production. 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).
purity Mg product. However the process yields very fine and poorly
crystalline Mg(OH)2, creating difficulty during the solid/liquid separa- 2.3. Experimental techniques
tion stage required for its recovery from the highly viscous brine
(Baird et al., 1988; Henrist et al., 2003). 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. Different precipitants were added (to known
24 h in non-stirring conditions (Turek and Gnot, 1995). Alamdari et volumes of brine, 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.

Brine before/after treatment Na K Ca Mg Li B Cl SO4

Raw Brine 1 105.4 15.7 3.33 16.7 0.84 0.70 203.7 21.3
Raw Brine 2 95.01 16.9 0.34 17.4 0.76 0.68 187.5 22.6
After lime precipitation 92.77 16.3 13.96 0.30 0.82 0.36 189.5 0.67
After oxalate precipitation 115.2 15.9 b0.05 0.17 0.82 0.20 196.3 0.76
After evaporation to 20 g/L Li 56.44 52.5 b0.05 0.35 19.8 2.91 201.4 20.2
After evaporation to 30 g/L Li 37.61 41.3 b0.05 0.65 30.3 4.22 215.6 13.3
66 J.W. An et al. / Hydrometallurgy 117–118 (2012) 64–70

Ca(OH)2solid

Brine Mg, B Removal


Mg(OH)2 Re-processing
L S CaSO4.2H2O to recover
Adsorbed B Mg(OH)2 and B
Na2C2O4solid Ca, Mg Removal

L S Roasting of Ca-Mg oxalate CaO.MgOrecycling

Solar evaporation

Purification Residual Ca, Mg, etc…


20 g/L Li
Li Evaporation
Carbonate treatment
Na2CO3 Carbonation before recycling to
solid 1.5 g/L Li
80-90 oC solar evaporation

99.55%
Li2CO3
Fig. 1. Flowsheet developed for the recovery of lithium as carbonate from Uyuni brine.

of the original brine, which hindered the mass balance calculation including sulphate which causes gypsum formation during proces-
and the brine concentration afterwards. The precipitate suspension sing and (c) concentrating the brine by evaporation to achieve
was based on either (a) magnetic bar stirrer, (b) impeller-type stirrer 20–60 g/L Li for the precipitation of lithium carbonate. Fig. 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. The use of ceramic balls (5 mm diameter) products. 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- sults are presented and discussed as follows.
rium quickly within 1 h. Samples were taken during the precipitation
to confirm the reaction has reached completion. Brine evaporation 3.1. 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 to re-
centrifuging. duce the levels of Ca and sulphate from the raw brine. Stabcal soft-
ware (Huang, 2008) was first used to predict the conditions for
3. Results and discussion selectively precipitating Mg and Ca using different precipitants. A typ-
ical example of the results obtained from Stabcal modelling is shown
This study investigates conditions for, (a) recovery of Mg, B and Ca in Fig. 2 for the addition of lime to the raw brine at the Lime/Mg molar
as by-products, (b) purification to remove deleterious impurities ratio of 1:1 and 0.1:1. Using lime, Mg could be removed as Mg(OH)2
Concentration (g/L)

Ca Mg Na (1:1)

B Li Na (0.1:1)

pH

Fig. 2. Stabcal modelling showing the stability of different Ca, Mg, Li and B species at different pHs and lime additions of 1:1 lime/Mg molar ratio. For Na, the precipitation of Na2-
SO4∙10H2O was predicted at 0.1:1 lime/Mg addition at a low pH range, whereas at 1:1 lime/Mg molar ratio the precipitation takes place at pH > 12.
J.W. An et al. / Hydrometallurgy 117–118 (2012) 64–70 67

Fig. 3. Measured concentration profiles of Brine 2 after precipitation of Mg at different lime/Mg molar ratios. Continuous or dotted lines are those predicted by stoichiometric cal-
culations (for Mg) or from Stabcal, except pH which was measured throughout the test.

at a pH > 8.6, whereas the precipitation of gypsum (CaSO4.2H2O) and pH > 8.6) 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. The equilibri- ther processed to separate Mg from the gypsum waste. As shown
um concentrations of Ca, Mg, Na, and SO4 ions are therefore con- later, this precipitate also contained boron which was recovered by
trolled by these precipitates during lime addition. Lithium is stable adsorption during the first-stage precipitation. 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. products from the mixed precipitate. The results of this study will
Several other precipitants (containing Na or Ca to avoid contaminat- be reported later. Residual Mg after lime precipitation and almost
ing the brine) were also tested, including sodium carbonate, sodium all soluble Ca can then be subsequently removed by adding sodium
phosphate, caustic (sodium hydroxide) and sodium oxalate. The precip- oxalate. This second-stage precipitate can be converted to MgO ∙CaO
itation of Ca/Mg carbonate, phosphate, hydroxide and oxalate took (dolime) by roasting for re-use in the lime precipitation stage.
place rapidly and residual Ca/Mg concentration could reach steady Stabcal modelling (Fig. 2) was also used to predict accurately the
state within 1 h. All carbonate, phosphate and oxalate precipitates equilibrium concentrations of Na, K, Li and Cl and other minor ele-
could be recovered easily by filtration. However the Mg(OH)2 precipi- ments in the brine as shown in Fig. 3. At a lime addition of 0.1:1
tate formed from NaOH addition was fine and non-crystalline (particle Ca(OH)2/Mg molar ratio, the pH rises from pH7.1 to pH8.6, effecting
sizes b10 μm) and could not be easily separated from the viscous brine. the precipitation of Mg(OH)2. 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. Mg could also be removed as pure Mg3(PO4)2 salts line of Mg(OH)2, as seen in Fig. 2. The predicted Mg equilibrium con-
in the subsequent stage. These phosphates are valuable fertilizer centration therefore was stoichiometrically calculated from the lime
products. However even at additions of phosphate at PO4/Mg stoi- additions. Sodium sulphate started precipitating also (Fig. 2) within
chiometric ratios >2:1 the residual Mg concentration in the treated this range of pH, causing slight dips in both Na and SO4 concentra-
brine was still very high (at ~4 g/L Mg). This excessive use of phos- tions as measured by chemical analysis. As more lime is added,
phate would contaminate the liquor and cause further complications Na2SO4 re-dissolves, releasing SO4 ions for the formation of the less
in the following stages. When sodium carbonate was used as precip- soluble gypsum. The steady state concentrations measured after one
itant, the double salt of CaCO3.MgCO3 was formed in the neutral pH hour however showed lower precipitated Mg compared to stoichio-
range, negating the complete recovery of pure Mg products. metric predictions (i.e. 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. This is
the brine, although it has to be added in slight excess for complete Mg expected with lime neutralization as the formation of gypsum coating
removal. The precipitation of gypsum (CaSO4.2H2O) also reduces the
sulphate to b1 g/L in the treated brine. The precipitate formed (at
0.7
60
0.6
Boron Concentration (g/L)

0.5
40
Zeta Potential (mV)

0.4

0.3
20

PZC 0.2

0 0.1

0
0 0.2 0.4 0.6 0.8 1
-20
7 8 9 10 11 12 13 Ca(OH)2/Mg2+ Ratio
pH
Fig. 5. Removal of boron from Brine 1, at different consecutive additions of Ca(OH)2
Fig. 4. Zeta potential measurements at different pHs showing the point-of-zero-charge (diamonds: addition at 0.1× stoichiometry each time, circles: at 0.2 × mole ratio, trian-
(PZC) at pH11.3. gles: 0.3 × mole ratio).
68 J.W. An et al. / 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
0.7 32 4.5
0.6
0.5 24
3
0.4
16
0.3
Mg Li 1.5 B
0.2
8
0.1
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. 6. Concentration profile of concentrated brines after evaporation of Brine 1.

would prevent complete dissolution of lime particles for the reaction. removal of Mg and Ca by lime and oxalate precipitation is minimal
The pH rose steadily from pH8.6 to pH9.2 at further additions of lime (within 3% of the analytical analysis error) as indicated in Table 2.
until the 1:1 Ca(OH)2/Mg molar ratio was reached. After this, the pH Following conventional techniques, lithium could be concentrated
would rise to pH > 11.5 at a further addition of lime. Above pH12, to 6% Li by solar evaporation. 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. 2). initial volume of 4 L. 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 0.1:1 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. This was confirmed by the ing, defined as Concentration Factor, representing the number of folds
measurement of zeta potential of the Mg(OH)2 precipitate. Fig. 4 the brine was concentrated by. Heavy losses of Li due to evaporated
shows the zeta potential Ezeta measured as 0–60 mV for the pH brine caught in NaCl, KCl and other complex salts precipitated during
range of pH8–11.3, with the zero-point-of-charge at pH11.3. Above evaporation were observed. As shown in Fig. 7, to achieve 20 g/L and
this pH, the surface of Mg(OH)2 is only lightly negatively charged. As 30 g/L Li, the maximum recovery of Li from evaporation and pressure
shown in the Stabcal stability diagrams (Fig. 2) boron exists as filtration is ~ 80% and 60%, respectively. In practice, using pond solar
HB4O7− or B(OH)4− cation within the range pH8–12, 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. The separation operation would not be as effective as in laboratory
Stabcal modelling however could not predict the adsorption process studies.
as shown in Fig. 3, where large discrepancies exist between the The cumulative losses of major ions are shown in Fig. 8. In the first
model prediction and boron concentration measured. The solution period when the concentration factor is b5, the precipitation of NaCl
pH increased steadily to pH ~ 11.5 at further additions of lime until is more predominant. After that (concentration factor: 5–20) KCl
1:1 stoichiometry. After this, the adsorbed boron was released from co-precipitates with some loss of Mg measured, possibly as Mg-
the Mg(OH)2 back to the brine. However with lime addition past 1:1 chloride salt or by adsorption on NaCl and/or KCl. By mass balancing
stoichiometry, (CaO)2B2O3 and (CaO)3B2O3 started precipitating as in- the cumulative number of moles losses, i.e. Δ(mol), from the liquor
dicated by Stabcal, causing incomplete recovery of boron at high pHs. obtained after evaporation, it was confirmed that most of the salt
The adsorption process was reproducible at different modes of lime
addition as shown in Fig. 5 (at 0.1×, 0.2× or 0.3× lime/Mg stoichio- 100
metric ratio). Typical compositions of the brine after lime treatment,
added at 1:1 Ca(OH)2/Mg molar ratio are listed in Table 2.
80

3.2. Recovery of residual magnesium and calcium


Li recovery (%)

60
The residual Mg and Ca, including added amounts from lime,
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). The con-
centrations of other ions after sodium oxalate treatment are also
shown in Table 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 10 20 30 40 50
3.3. Concentration of lithium by evaporation
Achieved Li concentration (g/L)

After Mg, B and Ca were removed the brine contained Li, Na and K Fig. 7. Li recovery after consecutive evaporation of Brine 1 to achieve 10, 20, 30, 40 and
in a chloride brine of low sulphate. The loss of lithium throughout the 50 g/L Li targets.
J.W. An et al. / Hydrometallurgy 117–118 (2012) 64–70 69

25 2 25

20 20
1.5
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 0.5 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
0.03 0.2 0.05
0.025 0.04
0.15
0.02
Run 1 Run 1 0.03 Run 1
0.015 Run 2 0.1 Run 2 Run 2
Run 3 Run 3 0.02 Run 3
0.01 Mg Run 4 Li B Run 4
0.05 Run 4
0.005 Run 5 Run 5 0.01 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. 8. Cumulative losses (as number of moles) of various ions after evaporation of Brine 1.

precipitated during the early stage of evaporation (at b20 folds) was a Table 3
mixture of NaCl and KCl (i.e. Δ(mol) (Cl −) = Δ(mol)(Na +) + Δ(mol) Composition of lithium carbonate (99.55%) product.

(K +)). Up to the concentration factor of 20 the loss of lithium and Component Ca Mg Na K Li B Sr


boron is minimal. This loss increases at further evaporation of the Content (%) 0.04 b 0.01 0.15 0.06 18.7 0.06 0.04
brine. For example at the concentration factor of 30, the lithium con- Component Fe Cu Al Ni Zn Cr Pb
centration in the liquor was 20 g/L whereas Δ(mol)(Li +) is 0.1 mol, Content (ppm) b 10 b 10 b10 b10 b 10 b 10 b 10
representing losses of ~ 20% (of ~0.4 mole Li contained in 4 L of the
original brine of ~0.1 mol/L Li). Sulphate concentration shows a
one-to-one linear relationship with the concentration factor up to in the range 80–90 °C, where the maximum solubility of lithium car-
20 folds, highlighting the fact that no sulphate salt will precipitate bonate is between 1.5 and 1.8 g/L Li (corresponding to 7.8–8.2 g/L
up to this level of evaporation. A concentration ratio of 14 and 26 lithium carbonate). Under these conditions, the recovery of lithium
was measured for boron and sulphate at 20-fold evaporation con- 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.
by division). At a higher concentration factor (>30) the loss of sul- The product produced from this precipitation was a well-
phate was also observed (Fig. 6) indicating sulphate salts started crystalline materials as confirmed by its XRD pattern. After washing
precipitating. in hot water, a high purity product (99.55% lithium carbonate)
Evaporative concentration up to 30-folds can therefore be con- could be recovered. The composition of this product is shown in
ducted in future commercial operations to produce concentrated Table 3.
brines of ~20 g/L Li.
4. Conclusions
3.4. Lithium carbonate precipitation
A hydrometallurgical process was developed to recover lithium
At 20 g/L Li concentration, precipitation of lithium carbonate to re- from the Uyuni salar brine containing 15–18 g/L Mg, 0.7–0.9 g/L Li
cover the product can be performed using sodium carbonate precipi- and saturated with Na, Cl and sulphate. A two stage precipitation
tant. As shown in Fig. 9, the solubility of lithium carbonate decreases was employed to remove Mg, Ca, B and sulphate from the brine
at temperatures higher than ambient (Garrett, 2004). The carbon- using lime first and then sodium oxalate. The mixed Mg(OH)2, 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. Resid-
16
ual Mg and Ca can then be totally removed by sodium oxalate in the
second stage of precipitation. Following a 30-fold evaporation the
brine could be concentrated to achieve 20 g/L Li. 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. A high purity (99.55%) and well crystalline lithium
carbonate could then be produced from this process.

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), Ministry of Knowledge Economy, Korea (no.
6
0 20 40 60 80 100
2010 T100100408).
Temperature (oC) References

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