Hydrometallurgy 121124 (2012) 5459

Contents lists available at SciVerse ScienceDirect

Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

A novel process for extracting lithium from lepidolite

Qunxuan Yan, Xinhai Li , Zhoulan Yin, Zhixing Wang, Huajun Guo, Wenjie Peng, Qiyang Hu
School of Metallurgy Science and Engineering, Central South University, Changsha, Hunan Province, 410083, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A novel technique was developed to extract lithium from lepidolite.
Received 6 February 2012 The lepidolite was pre-roasted at a high temperature with water steam atmosphere for deuorination. Then
Received in revised form 27 March 2012 the deuorinated lepidolite was leached in a limemilk autoclave. Various parameters including the deuori-
Accepted 9 April 2012
nation percentage of lepidolite, milling time, temperature, time, lime-to-deuorinated lepidolite ratio, and
Available online 17 April 2012
liquid-to-solid ratio in the leaching process were optimized. The lithium extraction efciency can reach
Keywords:
98.9% under the optimal conditions. The purity of the lithium carbonate obtained can be up to 99.9%.
Lepidolite 2012 Elsevier B.V. All rights reserved.
Lithium
Deuorination
Limemilk
Autoclave

1. Introduction
Lithium is the lightest known metal and has been widely utilized for
many commercial lithium products due to its fascinating electrochemical
reactivity as well as other unique properties. Lithium compounds
and minerals have attracted much attention for their applications in ce-
ramics, glass, aluminum, lubrication industries, and pharmaceuticals
(Ebensperger et al., 2005). Its journey as the metal of the future truly
began in the late 90s when it became greatly popular in portable elec-
tronic devices (Ferro and Pipoli, 2010). Reports indicates that the global
consumed amount of lithium related products for batteries has been in-
creasing by more than 20% per year during the past several years
(Jaskula, 2008; Wang et al., 2011).
Most lithium products are currently produced from brine sources.
Compared with brines, lithium extraction from spodumene, lepido-
lite, and other solid lithium minerals is not costly effective (Helvaci,
2003). Nevertheless, the tremendous growth in the demand for lithi-
um batteries to power hybrid and fully electric automobiles over the
coming century has raised great concerns about the future availability
of lithium (Bradbury, 2008; Legers, 2008; Tahil, 2007). For that rea-
son, the current production levels should be further improved to
meet the increasing demand for lithium and lithium salts. The solid
lithium minerals could be considered as sub-economic resources if
the price of lithium continues to rise. Various methods have been de-
veloped to produce lithium from lithium ores (Brandt and Haus,
2010; Bykbur et al., 2006; Chen et al., 2011; Jandov et al., 2010;
Robinson, 1961; Victor, 1953; Walter, 1935). The most important
processes for the extraction of lithium from lepidolite are the sulfuric
acid and the lime methods (Distin and Phillips, 1982). However, the
extraction of lithium by sulfate acid method uses high concentration
acid and the purication procedure is complex. The lime process
uses limestone and requires a large amount of energy. The drawbacks
of the above mentioned processes limit their further applications.
In order to overcome these drawbacks, an autoclave method for
the production of lithium carbonate from lepidolite has been pro-
posed as an alternative. But the temperature in the autoclave is nor-
mally more than 200 C ( The absolute saturated vapor pressure of
water at 200 C is 15.549 bar). The severe operating conditions neces-
sitate heavy-duty equipments to withstand high temperature and
pressure (Xu and Wang, 1993). Therefore, it is desirable to lower
the temperature and pressure of the autoclave process.
To solve these problems, a novel technique was developed to
extract lithium from lepidolite in this paper. The lepidolite was pre-
roasted at 860 C for 30 min with water steam atmosphere for
deuorination. Then the deuorinated ore was leached in a lime
milk autoclave where the leaching temperature is only 150 C (The
absolute saturated vapor pressure of water at 150 C is 4.760 bar).
During the process, the temperature and pressure are very low and
the reagent used is just lime. The related research is seldom studied
in literatures and the results of the present work could provide a sim-
ple and effective way for the extraction of lithium from lepidolite.
2. Experimental
2.1. Materials

Corresponding author. Tel.: + 86 731 88836633. The lepidolite in this study was provided by Jiangxi Province
E-mail address: yanqunxuan@163.com (Q. Yan). (China). The lepidolite was rst crushed in a jaw crusher, then ground

0304-386X/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2012.04.006
 Q. Yan et al. / Hydrometallurgy 121124 (2012) 5459 55

Table 2
Effect of reaction temperature and time on deuorination percentage.

Temperature (C) Time (min) F (%) Deuorination

percentage (%)

840 10 4.2 4.2

20 3.3 24.0
30 3.1 27.5
40 2.8 35.6
860 10 4.0 6.7
15 3.6 16.4
20 3.2 27.0
25 2.8 35.1
30 2.5 42.3
35 2.3 47.3
40 1.9 56.4
50 1.5 65.1
880 10 3.9 10.4
20 2.8 35.8
30 1.8 57.7
40 1.0 77.6

Fig. 1. XRD pattern of the ore.

3. Results and discussion

in a ball mill and screened to 100% b150 m. The X-ray powder diffrac-
tion pattern (XRD) of the ore is shown in Fig. 1 which indicates that the
3.1. Deuorination
raw material was primarily lepidolite (K(Li, Al)3(Si, Al)4O10(F,OH)2),
albite (Na(AlSi3O8)), and quartz(SiO2). The chemical analysis of the
Deuorination percentage of lepidolite is shown in Table 2. It
ore is given in Table 1.
shows that deuorination percentage increases with the increase of
the reaction temperature and time. The deuorination percentage is
35.6, 56.4 and 77.6% at 840, 860 and 880 C respectively when the
2.2. Equipment and procedure
duration of deuorination is 40 min. Although the deuorination per-
centage at 880 C is higher than that at 860 C, part of the deuori-
Lepidolite was heated in an electric tube furnace with water steam
nated ore will turn to vitreous clinker at 880 C. Therefore, the
atmosphere for deuorination. The deuorination temperature is
suitable deuorination temperature is 860 C.
from 840 to 880 C and the duration of deuorination is from 10 to
The XRD patterns of the deuorinated lepidolite at 860 C for
40 min. The leaching experimental was carried out in a 1-l stainless
different time are shown in Fig. 2. When the deuorination time
steel autoclave (GCF, Dalian Automatically-controlled Reactor Co.,
is 10 min, the main components of the sample are lepidolite
Ltd). Temperature was controlled within 1 C by a temperature
(K(Li,Al)3(Si,Al)4O10(F,OH)2), albite (Na(AlSi3O8)), and quartz(SiO2).
controller with both an electrical heating mantle and a water-
After the deuorination time is increased to 20 min, the diffraction
cooling stream. Agitation was maintained by a magnetically driven
peaks of lepidolite become weaker, and the main phases are aluminum
stainless steel twin-impeller.
silicate (LiAl(SiO3)2) and leucite (KAlSi2O6). As the deuorination time
The deuorinated lepidolite (DL) was then ground by a vertical
increases from 30 to 40 min, the diffraction peaks of lepidolite almost
planetary ball mill at a rotation speed of 160 rpm. The milling cell
disappear and the main phases are aluminum silicate (LiAl(SiO3)2)
was a 500 ml stainless steel vessel lled with steel balls of 5 mm.
and leucite (KAlSi2O6). The structure of the original mineral is
The ball to ore mass ratio was 10:1.
destroyed and transformed to aluminum silicate (LiAl(SiO3)2) and
The limemilk and DL was charged in the autoclave which was
leucite (KAlSi2O6) during the deuorination process.
then sealed and heated at 5 C/min to the targeted temperature for
The mechanism of deuorination was as follows: H2O will be
leaching. At the end of the experiment, the autoclave was cooled by
absorbed onto the lepidolite surface at high temperature when the
water-cooling stream, and the slurry in the reactor was discharged.
Lithium was analyzed by atomic absorption (AAS, TAS-990, Beijing
Purkinje General Instrument Co., Ltd) in all the experiments. Comput-
erized X-ray diffraction equipment (XRD, Rint-2000, Rigaku Co., Ltd)
was used to identify the components of the raw ore, DL, and the
leached residue. The specic surface area of the ores was determined
by BrunauerEmmettTeller nitrogenhelium absorption method
(BET,V-Sorb 2800P, Gold APP Instruments Co., Ltd) while the particle
size of the ore was determined using particle-size analyzer(Mastersizer
2000, Malvern Instruments Co., Ltd). The uorine contents in the
samples were determined by uorine ion selective electrode.
In order to evaluate the experimental error, each experiment was
replicated and the result was the mean value of three experiments.

Table 1
Chemical composition of the ore (wt.%).

Li Na Fe Mn K Ca F SiO2 Al2O3 Rb Cs

1.40 1.28 0.12 0.24 5.29 0.15 4.33 50.96 27.53 0.71 0.11
Fig. 2. XRD patterns of deuorinated ore.
56 Q. Yan et al. / Hydrometallurgy 121124 (2012) 5459

Fig. 3. Particle size distribution of the DL at different milling time. Fig. 4. Effect of milling time on the lithium extraction efciency.

water steam contacts with the heated lepidolite. H2O may decompose particle size and the increase of the specic surface area. However,
into H + and OH where H + will combine with F - to form HF and OH - further increase of the milling time seems to have little inuence on
will combine with SiOSi bond to form SiOH group. The SiOH the extraction efciency. Therefore, the milling time was chosen as
group will react with nearby OH - to form new phases such as H2O, 100 min in further experiments.
leucite or aluminum silicates (Xu and Wang, 1994). These are also
conrmed by XRD patterns of DL.
3.2.2. Effect of deuorination percentage of lepidolite
3.2. Autoclave process The effect of deuorination percentage of lepidolite on the lithium
extraction efciency was studied. The deuorination experiments
To nd the optimal condition for the limemilk leaching of DL in were carried out at 860 C for different time and the deuorination
autoclave, the effect of different variables on the lithium extraction percentage of lepidolite is shown in Table 2. The experimental condi-
efciency was evaluated. tions of the autoclave leaching were as follows: lime-to-DL ratio 1, L/S
4, stirring speed 400 rpm, reaction temperature 150 C, and the reac-
tion time 60 min. The leaching results are shown in Fig. 5. It shows
3.2.1. Effect of the milling time
that the lithium extraction efciency of the undeuorinated ore is
The effect of milling time on the lithium extraction efciency of DL
7.9%. With the increase of the deuorination percentage, the lithium
was studied from 0 to 120 min. The experimental conditions of the
extraction efciency increases signicantly. The lithium extraction ef-
autoclave leaching were as follows: lime-to-DL ratio 1, liquid-to-
ciency is 98.9% when the deuorination percentage of lepidolite is
solid ratio 4 (L/S, L represents water and S represents lime and DL),
42.3%. However, further increase of the deuorination percentage of
stirring speed 400 rpm, reaction temperature 150 C and reaction
lepidolite does not result in an obvious increase of the lithium extrac-
time 60 min. The particle size distribution of the DL is shown in
tion efciency. When the deuorination temperature is 860 C and
Fig. 3. The cumulative distribution (D90, D50, and D10 refer to the par-
the deuorination time is 30 min, the deuorination percentage of
ticle sizes when the total cumulative distributions are 90%, 50%, and
lepidolite is 42.3% from Table 2.
10%, respectively) and the specic surface area are shown in
The deuorination process will be performed at 860 C for 30 min
Table 3. Fig.3 and Table 3 illustrate that the particle size decreases
in the following experiments.
rapidly and the specic surface area increases with the increase of
the milling time. The leaching results are shown in Fig. 4. It shows
that the extraction efciency depends strongly on the milling time.
When the milling time is less than 5 min, the extraction efciency is
relatively low. The lithium extraction efciency is raised signicantly
when the milling time is increased from 5 to 20 min. It reaches up to
98.9% when the milling time is 100 min due to the decrease of the

Table 3
Effect of milling time on cumulative volume and BET.

Milling time Particle size (m) BET

(min) (m2g 1)
D10 D50 D90

0 27.48 106.24 341.86 0.28

5 2.24 19.15 56.09 0.79
10 1.41 9.55 31.22 1.46
20 1.16 7.05 26.95 1.88
40 1.00 4.54 19.58 3.10
60 0.95 4.37 20.77 3.56
80 0.94 4.05 19.32 3.80
100 0.83 3.98 18.60 4.22
120 0.78 3.52 18.28 4.95
Fig. 5. Effect of the deuorination percentage on the lithium extraction efciency.
 Q. Yan et al. / Hydrometallurgy 121124 (2012) 5459
Fig. 6. Effect of the leaching temperature on lithium extraction efciency.
3.2.3. Effect of leaching temperature
In order to investigate the effect of leaching temperature on the
lithium extraction, a series of leaching experiments were performed
from 130 to 170 C. Conditions of the autoclave leaching were as fol-
lows: lime-to-DL ratio 1, L/S 4, stirring speed 400 rpm, and reaction
time 60 min. The experimental results are shown in Fig. 6. It illus-
trates that the reaction temperature has an obvious effect on the
leaching process. The extraction efciency increases signicantly
when the leaching temperature is increased from 130 to 150 C. The
extraction efciency is 98.9% when the reaction temperature is
150 C. However, further increase of the temperature does not result
in a clear increase of the extraction efciency.
3.2.4. Effect of leaching time
To study the effect of leaching time on the lithium extraction, ex-
periments were conducted on conditions of lime-to-DL ratio 1, L/S 4,
temperature 150 C, and stirring speed of 400 rpm. The results are
plotted in Fig. 7, which shows that the leaching time has a remarkable
effect on the lithium extraction. As time increases from 20 to 60 min,
the lithium extraction efciency raises from 62.3% to 98.9%. As the
leaching time increases to 90 min, the extraction efciency remains
almost constant.
3.2.5. Effect of lime-to-DL ratio
The effect of lime-to-DL mass ratio on lithium extraction efciency
was investigated from 0.8 to 1.2. Conditions of the autoclave leaching
Fig. 7. Effect of leaching time on lithium extraction efciency.
57
Fig. 8. Effect of lime-to-DL ratio on lithium extraction efciency.
were as follows: leaching time 60 min, L/S 4, temperature 150 C, and
stirring speed of 400 rpm. The results are presented in Fig. 8, which
shows that the lithium extraction efciency increases from 83.7% to
98.9% as the lime-to-DL ratio raises from 0.8 to 1. However, the ex-
traction efciency decreases when the lime-to-DL ratio is further in-
creased because lithium will be adsorbed by more leaching residues.
3.2.6. Effect of liquid-to-solid ratio
The liquid-to-solid ratio on the lithium extraction efciency was
investigated from 3 to 5. Experimental conditions of the autoclave
leaching were as follows: lime-to-DL 1, leaching time 60 min, tem-
perature 150 C, and stirring speed 400 rpm. The results are plotted
in Fig. 9, which shows that the liquid-to-solid ratio has a slight effect
on the extraction efciency. When the liquid-to-solid ratio is over 4:1,
the lithium extraction efciency will remain constant. Liquid-to-solid
ratio of 4:1 is considered to be optimal for both the economic and
efcient reasons.
3.2.7. Effect of agitation
To study the effect of stirring speed on the lithium extraction ef-
ciency, experiments were conducted on conditions of lime-to-DL
ratio 1, L/S 4, leaching time 60 min and temperature 150 C. The ex-
perimental results are shown in Fig. 10. It illustrates that the stirring
speed has an obvious effect on the leaching process. When the
Fig. 9. Effect of liquid-to-solid ratio on lithium extraction efciency.
58 Q. Yan et al. / Hydrometallurgy 121124 (2012) 5459

Table 6
Content of the major impurities in LiOH (wt.%).

Na K Rb Cs Ca Si Al

0.001 1.27 0.12 0.06 0.001 0.01 0.001

Table 7
The chemical composition of Li2CO3.

Sample Purity of Content of the major impurities (wt.%)

Li2CO3 (wt.%)
K Ca Si Rb Na, SO4, Cl, Cs, Al

1# 98.8 0.65 0.01 0.01 0.02 b0.001

2# 99.9 0.04 0.005 0.005 b0.001 b0.001

Fig. 10. Effect of strirring speed on lithium extraction efciency.
stirring speed is over 400 rpm, the lithium extraction efciency will
remain constant. 400 rpm is considered as the optimum stirring
speed.
3.2.8. The composition of the leaching solution
Table 4 lists the chemical composition of the leaching solution
under the optimum conditions: milling time 100 min, leaching time
60 min, liquid-to-solid ratio 4, temperature 150 C, and stirring
speed 400 rpm. The concentration of the main elements Li, K, Rb
and Cs is 1743, 3798, 645 and 112 mgL 1, respectively. Potassium,
rubidium and cesium are very important by-products during the ex-
traction process. Their extraction efciencies in the current research
are 57.5%, 72.7%, and 81.7%, respectively, which will be further inves-
tigated in our future work.
3.3. Crystallization of LiOH and Li2CO3
Na2CO3 of 2% stoichiometric excess was added into the leaching
solution to remove extra lime (Botten, 1965). Table 5 lists the solubil-
ities of alkali metal hydroxides in 100 g of water at 20 C. It indicates
that LiOH will crystallize thermodynamically easier by evaporation of
water compared with other alkali metal hydroxides.
When 97.5% (mass fraction) of the solution was evaporated, 85%
of lithium was crystallized as LiOHH2O, and part of lithium was pre-
cipitated as Li2CO3. Table 6 lists the content of major impurities in
LiOH. The rest of the lithium in mother liquor could be selectively
extracted using CO2 according to reaction (1).
Table 7 (1#) shows the analysis of the Li2CO3 with the main impu-
rity being K. The mother liquor after Li2CO3 crystallization was suit-
able for the recovery of K, Rb, and Cs.
The crystallized LiOH was dissolved again with distilled water to
obtain LiOH solution of 1.2 molL 1. The insoluble residue (Li2CO3)
was then ltered. For carbonation reaction, carbon dioxide was
sparged into the solution (250 ml) at a ow rate of 0.5 L/min for
120 min to ensure that almost all the lithium carbonate in the solu-
tion was converted to lithium bicarbonate and the impurities (Si,
Al) were precipitated in residue (Jandov et al., 2010). The ltrate
was heated at 90 C for 1 h to eliminate CO2 and then ltered to ob-
tain lithium carbonate crystals. The lithium carbonate crystals were
dried at 120 C for 10 h to obtain Li2CO3 product with a purity of
99.9%. The chemical composition of Li2CO3 is listed in Table 7 (2#).
3.4. Characterization of the residue
Fig. 11 shows the XRD pattern of the leaching residue. The leaching
experiment was performed at 150 C for 60 min. Fig. 11 shows that
there are katoite (Ca2.9Al1.97Si0.64O2.56(OH)9.44), anorthite (CaAl2Si2O8),
albite (Na(AlSi3O8)) and calcium hydroxide Ca(OH)2 in the residue.
Their contents were rened by Rietveld analysis of the X-ray powder
diffraction. It indicates that the composition of the leaching residue
are Ca(OH)2 10.8 0.3 (wt.%), Ca2.9Al1.97Si0.64O2.56(OH)9.44 9.3 0.6
(wt.%), CaAl2Si2O8 75.4 3 (wt.%), and Na(AlSi3O8) 4.4 0.2 (wt.%).
4. Conclusions
An improved method including deuorination followed by lime
milk leaching was employed to extract lithium from lepidolite. The

2LiOH CO2 Li2 CO3 H2 O 1

The water-washed lithium carbonate product contained more
than 98% of Li2CO3.

Table 4
Chemical composition of the leaching solution.

Leaching The concentration of component (mgL 1)

solution
Metal ions

Fe Na Ca Si Mn Li Al K Rb Cs

0 12.0 353.0 11.9 0 1743.8 18.7 3798.8 645.5 112.3

Table 5
Solubilities of alkali metal hydroxides in 100 g of water at 20 C (Speight, 2005).

LiOH NaOH KOH RbOH CsOH

12.8 g 109 g 112 g 180 g

Fig. 11. XRD pattern of the leaching residue.
 Q. Yan et al. / Hydrometallurgy 121124 (2012) 5459
results indicate that the deuorination percentage of lepidolite, mill-
ing time, lime-to-DL ratio, leaching temperature and time will affect
the lithium extraction. The optimum operating parameters with a
lithium extraction efciency of 98.9% were established as follows:
deuorination temperature 860 C, deuorination time 30 min (the
deuorination percentage of lepidolite is 42.3%), milling time
100 min, leaching temperature 150 C, leaching time 60 min, lime-
to-DL ratio 1, and liquid-to-solid ratio 4:1. The purity of the lithium
carbonate product was up to 99.9%. The results of the current work
could provide a simple and effective way to extract lithium from
lepidolite.
References
Botten, R., Paul, Delgrannge, J.P., Vesinet, L., Steinmetz, A., 1965. Method of recovering
lithium from lepidolite. Saint, Gobain, US Patent 3189407.
Bradbury, D., 2008. What is going to power our cars? The Guardian. July 31. Available
at bwww.guardian.co.uk/technology/2008/jul/31/motoring.energy> (accessed on
August 10, 2008).
Brandt, F., Haus, R., 2010. New concepts for lithium minerals processing. Miner. Eng. 23
(8), 659661.
Bykbur, A., MaraslIoglu, D., Bilici, M.S.U., Kksal, G., 2006. Extraction of lithium from
boron clays by using natural and waste materials and statistical modelling to
achieve cost reduction. Miner. Eng. 19 (5), 515517.
Chen, Y., Tian, Q., Chen, B., Shi, X., Liao, T., 2011. Preparation of lithium carbonate from
spodumene by a sodium carbonate autoclave process. Hydrometallurgy 109 (12),
4346.
59
Distin, P.A., Phillips, C.V., 1982. The acid extraction of lithium from the granites of South
West England. Hydrometallurgy 9 (1), 114.
Ebensperger, A., Maxwell, P., Moscoso, C., 2005. The lithium industry: its recent evolu-
tion and future prospects. Resour. Policy 30 (3), 218231.
Ferro, Ral, Pipoli, Renzo, 2010. The future of lithium. Mining intelligence series. Avail-
able at http://www.salareslithium.com/i/pdf/Media/Lithium_2010_BNA.pdf.
Helvaci, C., 2003. Presence and distribution of lithium in Borate Deposits and some
recent lake waters of West-Central Turkey. Int. Geol. Rev. 45 (2), 114.
Jandov, J., Dvork, P., Vu, H.N., 2010. Processing of zinnwaldite waste to obtain Li2CO3.
Hydrometallurgy 103 (14), 1218.
Jaskula, B.W., 2008. Lithium, Minerals Yearbook2007. U.S. Geological Survey,
pp. 44.144.8. Available at bhttp://minerals.usgs.gov/minerals/pubs/commodity/
lithium/myb1-2007-lithi.pdf> (accessed on 12.5.2009).
Legers, L., 2008. The trouble with lithium 2. Under the Microscope. Meridian Interna-
tional Research, Martainville, France. Available at bhttp://www.evworld.com/
library/WTahil_Lithium_Microscope.pdf> (accessed on May 29, 2008).
Robinson, G.P., 1961. Recovery of lithium from ore. US Patent 2983576.
Speight, J.G., 2005. Lange's Handbook of Chemistry, 16th Edition. McGraw-Hill.
Tahil, W., 2007. The Trouble with Lithium: Implications of the Future PHEV Production
for Lithium Demand. Meridian International Research, Martainville, France.
Available at bhttp://www.meridian-int-res.com/Projects/Lithium_Problem_2.pdf>
(accessed on August10, 2008).
Victor, K.A., 1953. Method of recovering lithium compounds from lithium minerals. US
Patent 2793933.
Walter, R., Bichowsky, Francis R., 1935. Method of recovering lithium from its ores. US
Patent 2020854.
Wang, H., et al., 2011. Electrochemical property of NH4V3O80.2H2O akes prepared
by surfactant assisted hydrothermal method. J. Power Sources 196 (2), 788792.
Xu, S.M., Wang, X.X., 1993. Study on pressure leaching process for the calcine of lepid-
olite by ammonium chloride. Rare Met. Cem. Carbides (115), 2226.
Xu, S.M., Wang, X.X., 1994. A study on the roasting process of Yichun lepidolite. Min.
Metall. Eng. China 14 (1), 5658.