Hydrometallurgy 134–135 (2013) 54–61

Contents lists available at SciVerse ScienceDirect

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

Factors affecting the extraction of lithium from lepidolite

Van Tri Luong a, Dong Jun Kang b, Jeon Woong An b, Myong Jun Kim a, Tam Tran a,⁎
a
Department of Energy & Resources Engineering, Chonnam National University, Gwangju, Republic of Korea
b
Technology Research Institute, Korea Resources Corp., Seoul, Republic of Korea

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

Article history: Key factors controlling the extraction of lithium from a lepidolite concentrate (2.55% Li) using a two-stage pro-
Received 9 September 2012 cess based on roasting with Na2SO4 and water leaching were determined in this study. HSC software was used to
Received in revised form 14 January 2013 predict lepidolite decomposition characteristics and products yielded from roasting. From this simulation
Accepted 14 January 2013
roasting was conducted at 850–1000 °C with different sodium sulphate additions (set at sodium sulphate-
Available online 31 January 2013
lithium molar ratios of 1:1 to 3:1) in 0.5–2 h to yield several calcines for leaching. Stabcal modelling was applied
Keywords:
to investigate the stability of various Li species formed during water leaching. From the simulation it was iden-
Lithium tified that LiKSO4, as one of the main Li-containing products formed in the calcine, has a low solubility and there-
Lepidolite fore controls the release of Li into water during leaching. The low solubility of LiKSO4 at 25 °C indicated by Stabcal
Processing was confirmed during leaching at different water–calcine mass ratios from 5:1 to 15:1. Leaching under these
Stabcal conditions only yields liquors containing b1.0 g/L Li, corresponding to Li extractions of 45–48%. The Li extraction
HSC modelling was significantly improved at 85 °C, yielding liquors containing 1–3 g/L Li, corresponding to extractions of
47–90%, with lower extractions of Li achieved at higher Li concentrations. At best, 90.4% of lithium was extracted
(at water–calcine mass ratio 15:1, 85 °C and 3 h) using calcines roasted at 1000 °C for 0.5 h (using Na2SO4 — Li
molar ratio of 2:1).
© 2013 Elsevier B.V. All rights reserved.

1. Introduction
Lithium has found application in many industries, from the
manufacturing of glass, ceramics, rubbers, pharmaceuticals to pro-
duction of batteries. The global market share of lithium used in batte-
ries has grown significantly over the last few years and has reached
23% in 2010 (USGS, 2011). The demand of lithium is forecast to in-
crease by ~ 60% from 102,000 tonnes to 162,000 tonnes of lithium
carbonate equivalent in the next 5 years, with application in batteries
taking a large percentage (~ 40,000 tonnes) of this growth (Hykawy,
2010; Siame and Pascoe, 2011). Yaksic and Tilton (2009) completed
an extensive survey and reported that lithium from mineral resources
accounts for 8.8 million tonnes, with large ore deposits located in the
USA, China, Australia and Russia.
Up to now, lithium has been mostly produced from salar brines
which contain 0.06–0.15% Li due to the low cost of production. How-
ever, several potential ore deposits are being considered or have been
recently developed to produce lithium carbonate from lithium min-
erals such as spodumene (by Galaxy Resources Ltd. WA, Australia),
from china clay (by Goonvean Ltd., Cornwall, UK) (Siame and
Pascoe, 2011) and zinnwaldite wastes from tin–tungsten mines in
Cinovec, the Czech Republic (Jandová et al., 2010). These minerals
contain Li, of which composition varies from 2.5 to 6% Li2O as
⁎ Corresponding author. Tel.: +82 62 530 1726; fax: +82 62 530 0462.
E-mail address: tamtran@jnu.ac.kr (T. Tran).
tabulated in Table 1. The recovery of Li from e-wastes has also been
recently reported (Jandová et al., 2012).
Spodumene (formula LiAl2SiO4) is the purest form of Li minerals
containing Si and Al whereas petalite (LiAlSi4O10) has a higher Si con-
tent. Lepidolite K(Li,Al)3(Si,Al)4O10(F,OH)2 contains Al in the same
lattice with Li and F as well as valuable metals worth recovering
such as Rb and Cs. Zinnwaldite is the impure form of lepidolite having
higher Fe oxide content (of up to 11.5% Fe mainly as FeO) and MnO
(3.2%) (Paukov et al., 2010).
The processing of lithium minerals involves first upgrading the
ground ores by beneficiation techniques such as flotation and wet
magnetic separation (Siame and Pascoe, 2011), optical sorting
(Brand and Haus, 2010) or heavy media separation as practised by
Galaxy Resources Ltd. in its plants constructed in Australia and
China (2011). Subsequent concentrates containing 4–6% Li2O can
then be subjected to a two stage (roasting and water leaching) treat-
ment to extract lithium into the solution and recover the metal values
as lithium carbonate or lithium chloride. Commercial lithium carbon-
ate (battery grade) products require purity of > 99.5% implying that
major impurities normally leached together with Li such as Fe, Ca,
Mg, K and Na need to be removed during processing.
Earlier work by Crocker et al. (1987) from the US Bureau of Mines
showed that >85% lithium could be recovered from montmorillonite-
type clays from Nevada (containing 0.3–0.6% Li) by different processes
based on roasting the ore with KCl–CaSO4 or CaCO3–CaSO4, followed
by water leaching and precipitation of 99% pure lithium carbonate
using potassium or sodium carbonate.

0304-386X/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.hydromet.2013.01.015
 V.T. Luong et al. / Hydrometallurgy 134–135 (2013) 54–61
Table 1
Most common Li minerals and typical compositions (%) (Garrett, 2004; Paukov et al., 2010).
Minerals Li2O Na2O K2O
Lepidolite 4.19 0.56 8.55
Spodumene 6 0.55 0.48
Petalite 4.73 0.17 0.02
Zinnwaldite 2-5 0.19 10.1
Galaxy Resources Ltd. (2011) chose the two-stage process based
on decrepitation (at 1070–1090 °C) and sulphation roast using
sulphuric acid (at 250 °C), followed by water leaching at 90 °C to pro-
duce acidic lithium sulphate liquors from spodumene. Other impuri-
ties such as Ca, Mg, Al and Fe are then removed by precipitation at
pH 12 using caustic soda. Lithium carbonate is finally precipitated at
90 °C by sodium carbonate for the production of 17,000 tpa (consid-
ered as the second largest in the world) in its plant in China which
came on line in late 2011. The concentrate feed to this processing
plant (137,000 tpa containing 6% Li2O) has been produced since late
2010 in Australia from the original spodumene ore containing
1.05–3% Li2O (mined from Mt Catlin and Greenbushes mines, West-
ern Australia). Chen et al. (2011) tested a similar scheme to treat an
α-spodumene ore containing 2.81% Li by first roasting at 1050 °C
for 30 min to convert the feed to β-form. This was followed by
autoclave leaching at 20–30% pulp density, 150–250 °C using a
sodium carbonate liquor (Na:Li ratio of 1:5) to extract > 90% Li into
the solution. Carbon dioxide was then pumped into the liquor for
2 h to complete the precipitation of lithium carbonate while
cooling. The proposed process removed the evaporation stage
mostly required for precipitating lithium carbonate and yielded a
product of 99.6% purity.
The recovery of lithium from a zinnwaldite waste produced from a
dressing plant treating a Sn–W ore (originally mined in Cínovec area
in the Czech Republic) was first reported by Jandová et al. (2008,
2009). The concentrate (1.4% Li) was recovered from zinnwaldite
wastes (0.21% Li) using dry magnetic and grain size separations. The
process used to extract Li involves sintering of the concentrate with
CaSO4 and Ca(OH)2, from which the double salt LiKSO4 was produced,
as identified by X-Ray Diffraction (XRD). The following treatment
steps include subsequent leaching of the sinters in water, solution pu-
rification and finally precipitation of Li2CO3 using potassium carbon-
ate. Up to 96% lithium was extracted in less than 1 h when sinters
prepared at 950 °C was leached at 90 °C using a water-to-solid ratio
of 10:1, yielding leach liquors reaching ~ 0.7 g/L Li. The lithium car-
bonate produced contained almost 99% Li.
Roasting of the zinnwaldite material in calcium carbonate seems
to maximise the Rb recovery as reported by Jandová et al. (2010). In
this later study, 99.5% purity lithium carbonate was recovered from
the carbonated leach liquor by multistage evaporation or solvent ex-
traction and precipitation using potassium carbonate. The improve-
ments made from previous studies include: (i) higher recovery of Li
and Rb after roasting using calcium carbonate and (ii) using solvent
extraction to complete separation of Li from Rb and other impurities
such as Ca, Al, Na and K.
Siame and Pascoe (2011) developed conditions for the recovery of
Li and Rb from a zinnwaldite waste rejected by a china clay produc-
tion plant. Using flotation, 98.6% of Li and 85.2% of Rb, respectively
could be recovered from a waste feed containing 0.87% Li2O and
0.38% Rb2O. Roasting of the zinnwaldite concentrate (containing
2.07% Li2O or 0.96% Li) with calcium sulphate (gypsum) at a 2:1
weight ratio to 1050 °C will produce a calcine which was identified
by X-Ray Diffraction to contain the main lithium-containing species
as LiKSO4 and other silicates formed from Ca, Al and F. The same re-
sults were obtained using zinnwaldite/sodium sulphate mixes of 2:1
weight ratios roasted at 850 °C, from which step lithium was
55
Rb2O Cs2O SiO2 Al2O3 F
3.39 0.25 52.3 28.8 5.88
None None 63.6 28.7 None
None None 77.7 17.1 Low
0.45 0.03 42.8 21.7 6.11
liberated, together with Na and K to also form mainly water-soluble
Li2KNa(SO4)2.
Sitando and Crouse (2012) processed an ore concentrate
containing 4.2% Li2O (of 57% petalite, 3% spodumene and 10% lepido-
lite and the rest as Na–Al silicates) by first roasting with concentrated
sulphuric acid at 300 °C, followed by water leaching at 50 °C for
60 min. Using a 1:7.5 solid/liquid ratio during leaching, lithium li-
quors of ~ 5 g/L Li was realised, which had to be evaporated to
>11.8 g/L for precipitating lithium carbonate at 90 °C. Without the
purification stage included in the treatment, a product of lower
grade than commercial norm (purity 99.2%) was yielded.
A sulphation roasting using Na2SO4 followed by water leaching
process was developed by Yan et al. (2012a) to extract lithium from
a lepidolite ore concentrate containing 2% Li and 4.46% F. A lithium
extraction of 91.6% was achieved using calcines produced from the
concentrate, Na2SO4, K2SO4 and CaO (mixed at the weight ratio of
1:0.5:0.1:0.1), roasted at 850 °C for 0.5 h. In another study (Yan et
al., 2012b), the ore was mixed with Na2SO4 and CaCl2 with the weight
ratio of 1:0.5:0.3 and then roasted at 880 °C for 0.5 h. In both cases,
the calcines obtained from roasting were leached by water at room
temperature for 30 min. Over 90% lithium was recovered using
these processes. In their latter study, Yan et al. (2012c) used a novel
technique to recover lithium from lepidolite ore containing 1.4% Li
and 4.33% F. During the process, the ore was firstly pre-treated with
steam at 860 °C for 30 min in an autoclave for defluorination. The
pre-treated ore was then milled and leached in an autoclave using
lime milk as the leachant. A lithium extraction of 98.9% was obtained
at 150 °C, leaching time of 1 h using a liquid to solid ratio of 4:1 in
which the solid is a mixture of the defluorinated lepidolite and lime
at 1:1 ratio.
These studies indicate that mica-type minerals containing lithium
have to be first roasted either in calcium carbonate/sulphate, or sodium/
potassium sulphate or sulphuric acid to convert lithium to a soluble sul-
phate form before leaching in water. Sulphation using sodium sulphate
seems to be the critical step for this scheme of treatment as it lowers
the calcination temperature to 850–1000 °C. In other fields, sulphation
roasting has also been used to treat Mo–Ni carbonaceous or Ni lateritic
ores to recover Mo and Ni metal values (Guo et al., 2009; Wang and
Wang, 2010). However, several critical issues related to potential libera-
tion of SO2 or F2 gases have not yet been addressed in most recent studies.
In an earlier work by Crocker et al. (1987), it was shown that roasting a
clay containing 1.5–2% F using CaSO4 would produce 0.1–0.2% fluorine
and 0.1% SO2 gases which need to be treated. Even when fluoride is
reported to the waste/residues or leach liquors during processing, it is
necessary to determine its stability before disposal.
This study therefore aims to optimise the conditions for recover-
ing lithium from a lepidolite ore collected from the BOAM mine
(Gyeongsangbuk-do, Korea) using sulphation roasting and water
leaching and to determine factors affecting its extraction. Specific at-
tention is given to the reactions that potentially liberate SO2 or fluo-
rine gases and/or produce any fluoride-containing residues after
leaching. To achieve these, thermodynamic modelling using HSC
and Stabcal programmes (Huang, 2005; Outotec, 2011) was carried
out to predict different reactions encountered during processing in
parallel to tests conducted over ranges of temperature, time and re-
agents used during roasting and leaching.
56 V.T. Luong et al. / Hydrometallurgy 134–135 (2013) 54–61
Fig. 1. XRD pattern of the lepidolite concentrate (2.55% Li).
2. Experimental
2.1. Materials
The lepidolite concentrate (2.55% Li or 5.49% Li2O), which was pro-
duced from a beneficiation of the lepidolite ore, was used as the feed
material for this study. The XRD pattern of the concentrate in Fig. 1
shows that it contains mainly lepidolite phase (KLi2Al1.128Si3.868O11FH)
and a minor amount of albite (NaAlSi3O8). The chemical composition of
the concentrate measured by X-Ray Fluorescence (with Li determined
by ICP-MS after digestion) is shown in Table 2.
2.2. Equipment and chemicals
In this study the chemical composition of the concentrate, calcines
and residues after leaching was analysed by X-Ray Fluorescence, XRF
(Rigaku ZSX Primus II) whereas their structure was determined by
X-Ray Diffraction (XRD) analysis (Cu-tube60kv 50 Ma, Phillips). The
elemental concentrations of leach liquors were measured by ICP-MS
(Agilent A5500). Chamber furnaces, temperature-controlled water
baths and hot plates were used in experiments. All chemicals used
in the study were of analytical grade.
2.3. Experimental techniques
To extract Li from lepidolite, the concentrate was first mixed with
Na2SO4 at different molar ratios of Na2SO4 to Li and then roasted at a
selected temperature for a range of durations from 0.5 h to 2 h. Mix-
tures of lepidolite and Na2SO4 were poured into ceramic crucibles,
then placed in a pre-heated furnace at 850 °C, 900 °C or 1000 °C.
After roasting, calcines were cooled to ambient temperature
(22–25 °C) and finely ground by a disc mill for 15 min. Ground sam-
ples were then subjected to water leaching. Leaching tests were car-
ried out at different temperatures using a water bath or a hot plate.
A selected mass of the calcine powder was introduced into a known
amount of water contained in a glass bottle, which was then im-
mersed in a water bath and shaken for leaching at 150 cycles/min.
Tests were conducted at different water–calcine mass ratios (varying
from 2:1 to 18:1) and the leaching temperature of 25 °C or 85 °C for
3 h. Preliminary tests showed that leaching has already reached a
steady state after 2 h.
Table 2
Composition (%) of the lepidolite concentrate by XRF and ICP-MS.
SiO2 Al2O3 Fe2O3 P2O5 Na2O
54.42 23.14 0.1 0.18 0.53
Fig. 2. XRD patterns of the concentrate, calcine (roasting at 1000 °C, Na2SO4–Li molar
ratio of 2:1 for 0.5 h) and residues — leaching for 3 h at 85 °C using water–calcine
mass ratio of 10:1 (residue 1), 15:1 (residue 2).
3. Results and discussion
Typical leaching tests at different conditions using a calcine pro-
duced from roasting the concentrate with Na2SO4 (at the Na2SO4–Li
molar ratio of 2:1) at 1000 °C for 0.5 h yielded residues having XRD
patterns shown in Fig. 2. The detailed discussion of this figure will
be provided in subsequent sections. There is an indication that the
calcine produced was not well-crystallined compared to the lepido-
lite concentrate feed. In cases where roasting was conducted at a
high temperature or for a longer duration, the formation of a glass
was clearly noted when the calcine was cooled to ambient tempera-
ture. This was confirmed by the non-crystalline pattern of the calcines
and residues shown in Fig. 2. A ~ 80% Li extraction was produced in a
leaching test carried out at 85 °C using the water–calcine mass ratio
of 10:1 whereas a Li extraction of ~ 90% was achieved at 15:1 ratio.
All leaching tests reached equilibrium after 2 h leaching as seen in
Fig. 3.
3.1. Thermodynamic modelling using HSC
A simulation of the roasting process using HSC software (Outotec,
2011) was undertaken to investigate the effect of input contents of
lepidolite, Na2SO4 and temperature on roasting products. As shown
in the HSC model (Fig. 4b), lepidolite completely breaks down at
~ 850 °C–900 °C. The reaction of lepidolite and sodium sulphate
forms Li-containing products including LiF, NaLiSO4 and LiKSO4,
Li2O·SiO2, Li2O·2SiO2 and minor amounts of silicates as LiAlO2, LiAlSiO4.
Of these only the well-crystallined LiKSO4 and Li2NaK(SO4)2 were
detected on the XRD pattern products as well as the residual Na2SO4.
These products were also identified by Siame and Pascoe (2011) and
Jandová et al. (2009, 2010) in their studies on zinnwaldite. After
K2O MgO CaO MnO Rb2O Cs2O Li F
11.22 0.18 1.34 0.23 1.56 0.75 2.55 3.69
 V.T. Luong et al. / Hydrometallurgy 134–135 (2013) 54–61 57

100

80
Lithium extraction (%)

60

40

Calcine - water mass ratio

20
5-1 10-1
0
0 1 2 3
Time (h)
Fig. 3. Effect of leaching time (at 85 °C) on Li extraction from calcine roasted using
Na2SO4–Li molar ratio of 2:1, at 1000 °C for 0.5 h.
leaching at the water–calcine mass ratio of 10:1, Li2NaK(SO4)2 was not
detected in the XRD profile of residue 1 whereas some remaining
peaks of LiKSO4 are still present. This indicates that the incomplete
dissolution LiKSO4 at 10:1 water–calcine ratio would cause a lower
Li extraction (~80%). However, when the water–calcine ratio of 15:1
was used a ~90% Li extraction was achieved, confirming that LiKSO4
plays an important role in determining the extraction of Li.
15-1
Fig. 5. TG-DTA profile of the lepidolite concentrate and Na2SO4 mixture (Na2SO4–Li
molar ratio of 2:1).
The TG-DTA profile of Na2SO4 — concentrate mixture (Na2SO4–Li
molar ratio of 2:1) in Fig. 5 shows the first small weight loss at
about 260 °C and the second at 784 °C. The first peak possibly corre-
sponds to a phase transition of Na2SO4 to rhombic Na2SO4 as shown
by the HSC model (Fig. 4). The second peak as indicated by HSC is
caused by a phase change of some LiF solid to LiF and Li2F2 gases. At
the end of roasting (1000 °C), the TG curve shows a minor weight
loss of ~ 1%. HSC modelling also predicts ~ 0.8% drop in weight of the
concentrate mixture at 1000 °C due to the liberation of gaseous com-
pounds such as LiF, Li2F2, F2, and SO2. A weight loss of 1.2–1.4% was
measured in experiments using the same Na2SO4 to Li molar ratio.
3.2. Role of LiF and LiKSO4 in controlling Li extraction

Jandová et al. (2009) reported the results of their study based on

roasting of zinnwaldite with CaSO4 and/or Ca(OH)2. The slightly insolu-
ble phase LiKSO4 was identified by them at roasting temperatures of
950 and 975 °C, which also results in a slight dependence of Li recovery
on temperature (range of difference: 10%) in the range 20–90 °C (Fig. 5,
Jandová et al., 2009). The use of Ca salts during lepidolite roasting in
passivating the fluoride (F) by forming CaF or Ca4Si2O7F2 (as observed
by Yan et al., 2012a,b,c) could prevent the formation of the slightly in-
soluble LiF. In this study, as only Na2SO4 was used during lepidolite
roasting, it is expected (Fig. 6) that both LiKSO4 and LiF were formed.
To investigate the stability and leachability of various Li species
(as indicated by HSC modelling) in water, Stabcal models were de-
rived to evaluate the equilibria of different Li species in water at
25 °C. The maximum concentrations at 100% extraction of all ele-
ments (calculated from mass balance) if all calcine were dissolved
were used for the simulation (Table 4). As indicated in Fig. 6, LiKSO4
is only sparingly soluble (thus hard to be leached completely) over
a wide range of pHs from 0 to 14 implying a low recovery of Li in
leaching using water. In cases where the concentration of K is low
(at lower K extraction %) LiF precipitate could also be formed. The
equilibrium controlling the Li dissolution therefore is represented as:

þ þ 2− −
LiF þ LiKSO4 ¼ Li þ K þ SO4 þ F : ð1Þ

In the presence of high F −, K + or SO42− the equilibrium is shifted

to the left hand side of the reaction represented by Eq. (1) above,
thus reducing the extraction of Li from the calcine during water
leaching. This could be the conditions created from lepidolite roasting
using only Na2SO4. On the other hand when F − and K + concentra-
tions are minimised, possibly by adding Ca salts during roasting, the
conditions seem to favour toward the right hand side of Eq. (1).
Thus it is now understandable why leaching of calcines produced
from lepidolite roasting using only Na2SO4 had to be conducted
with high water dilution, thus producing dilute Li liquors (Table 5).
Fig. 4. HSC model for roasting lepidolite and Na2SO4 mixture (Na2SO4–Li molar ratio of Real experimental results (at 25 °C) determined thereafter matched
2:1). the simulation predictions and similar trends of Li concentrations
58 V.T. Luong et al. / Hydrometallurgy 134–135 (2013) 54–61

Fig. 6. Stabcal simulation of leaching at water–calcine mass ratio of 15:1, therein (a), (b), (c) and (d), showing the dissolution of Li at 25%, 50%, 75% and 100% K extraction, respec-
tively. Calcine from roast using Na2SO4–Li molar ratio of 2:1 at 1000 °C for 0.5 h. Input Stabcal data (in g/L) except for K are maximum concentrations of components if all are
dissolved from calcine including sodium sulphate (Table 4).

measured in real tests and as predicted from Stabcal are clearly
shown in Fig. 7.
There was a marked improvement in Li extraction yielded from
tests conducted at 85 °C compared to those at 25 °C. At room temper-
ature, the leaching of calcines at water–calcine ratios in the range
5:1–15:1 yielded liquors of b1.0 g/L Li, corresponding to Li extrac-
tions of 45–48%. In contrast, the Li extraction rose sharply from 47%
to 90%, when the water–calcine ratio was increased from 2:1 to
15:1 ratio. This indicates that leaching at room temperature would
not yield concentrated liquors having high Li extractions due to the
low solubility of LiKSO4 and LiF as predicted by Stabcal. As shown in
Table 5, Jandová et al. (2009, 2010) produced liquors of 0.4–0.7 g/L
Li, which required dilute water leaching (water–calcine ratio of
10:1) to achieve a Li extraction > 90% of the Li from their zinnwaldite
calcines. The same was experienced by Siame and Pascoe (2011).
These studies rely on leaching at 85–90 °C, water–calcine ratio of
>10:1 to extract > 90% Li from the calcines. It is also worth noted
that the feed materials used in these studies contain 0.96–1.4% Li,
lower than for this study (2.55% Li). Only when a 10% lepidolite–
57% petalite mix containing 4.3% Li2O (or 2% Li) was used by
Sitando and Crouse (2012) that liquors of ~ 5 g/L Li were realised,
after leaching at 7.5:1 water–calcine ratio at 50 °C. Petalite minerals
do not contain K compared to lepidolite or spodumene which has
8–10% K2O in their composition. Thus no or low K is expected to
exist in the calcines or leach liquors produced by Sitando and
Crouse (2012) negating the possibility of LiKSO4 formation during
roasting or its precipitation while leaching. This favourable condition
would not hinder Li extraction compared to those experienced in

Table 3
Major chemical components (g/L) in leach liquors and extractions (%) from tests using water to calcine mass ratio of 15:1 at 25 °C and 85 °C. The calcine produced using Na2SO4 to
Li molar ratio of 2:1 at 1000 °C for 0.5 h.

Leaching temperature Component Li Na K Mg Ca Mn Rb Cs F

25 °C g/L 0.39 2.28 1.1 0.002 0.01 0.03 0.1 0.03 0.95
Extraction, % 47 19.9 36.4 6 3.3 49.3 20.7 12.9 79.2
85 °C g/L 0.75 6.36 0.69 0.003 0.0003 0.02 0.12 0.05 1.14
Extraction, % 90.4 55.4 22.9 9.8 0.1 33 27.3 23.5 94.8
 V.T. Luong et al. / Hydrometallurgy 134–135 (2013) 54–61 59

Table 4 100
Concentrations (g/L) used in Stabcal speciation simulation, of all components identified
in the leach liquors at maximum 100% extraction, assuming also that all Na2SO4 would 3

Concentration of Li (g/L)
(a)

Lithium extraction (%)

dissolve. 80
Water/calcine Li Na K Mg Ca Mn Rb Cs SO4 F
mass ratio 60
15:1 0.83 11.3 3.03 0.04 0.31 0.06 0.46 0.23 23.1 1.20
(c) 2

studies using zinnwaldite or lepidolite (8–10% K) or having their cor-
responding leach liquors (5–20 g/L K).
Results from the above and this study however are different from
those reported by Yan et al. (2012a,b), who achieved over 90% Li extrac-
tion after leaching at room temperature for 0.5 h, using less water.
These authors conduct experiments with sodium sulphate as base
runs (of which results are compatible to others as shown in Table 5
and later in Fig. 10). However in one study (Yan et al., 2012b) the
leach liquors reported reached 8.53 g/L Li, 68 g/L Na and 20 g/L K, with-
out specifying the conditions for the roasting for this end condition on
how much CaCl2 and/or K2SO4 was added to achieve this and whether
these special additives did improve the leaching characteristics. In an-
other study Yan et al. (2012a) reported leach liquors of 4.39 g/L Li,
8.51 g/L K and 22.2 g/L Na at >90% Li yielded from water leaching of
calcines produced from lepidolite concentrates mixed with sodium sul-
phate and CaO/K2SO4. They demonstrated that the Li extraction was in-
dependent of the water–calcine ratio used (from 1:1 to 5:1). It is noted
that the XRD patterns of calcines produced under different roasting con-
ditions in Yan et al's studies (2012a,b) did not show any well-crystalline
salts containing Li such as LiKSO4 or Li2NaK(SO4)2. Perhaps the different
complex mixes using extra additives such as CaO or CaCl2 and K2SO4
apart from Na2SO4 prevented the formation of such salts.
In this study, leaching at 85 °C using the water–calcine ratio of
15:1 yielded a leach liquor containing ~ 0.75 g/L Li (at ~ 90.4% extrac-
tion). The major chemical components of the sample are shown in
Table 3. Approximately 1–2 g/L F was also produced in the leach li-
quors, probably from LiF as predicted by HSC simulation, representing
80–95% extraction of fluoride. This soluble fluoride needs to be treat-
ed and removed from the liquor, possibly by lime, which also
removes sulphate. A lime precipitation step to remove fluoride and
sulphate to prevent the formation of LiF and LiKSO4 is required before
concentrating the Li in leach. The sulphate purification by lime pre-
cipitation and subsequent lithium carbonate production have been
demonstrated earlier by An et al. (2012). Other major impurities
such as Na and K should not interfere with the lithium carbonate re-
covery process as either sodium or potassium carbonate is commonly
used to precipitate Li from concentrated liquors containing ~ 20 g/L Li.
40
(d)
(b) 1
20
(e)
0 0
0 5 10 15 20
Water - calcine mass ratio
Fig. 7. Effect of water–calcine mass ratio on Li extraction (leaching for 3 h) and concen-
tration in leach liquors. (a) and (b): extraction and concentration at 85 °C, respective-
ly; (c) and (d) extraction and concentration at 25 °C, respectively; (e): concentration
predicted by Stabcal — calcine from roast using Na2SO4–Li molar ratio of 2:1 at
1000 °C for 0.5 h.
3.3. Effect of roasting temperature and duration
Since HSC modelling shows that the reaction of lepidolite with
Na2SO4 is completed at about 850 °C, a range of roasting tempera-
tures from 850 °C to 1000 °C was chosen for testing. Fig. 8 indicates
that the Li extraction increases with temperature. The best roasting
temperature is 1000 °C, resulting in the highest Li extraction from le-
pidolite compared to those achieved at 850 °C and 900 °C. More glass
formation was observed at a higher temperature in this range.
In addition, roasting time also affects the recovery of lithium
(Fig. 9). As observed when the calcines roasted at long durations
(> 1 h) or temperatures > 1000 °C were cooled down, the formation
of glassy sodium silicates was detected (which was also confirmed
by the poor-crystallinity of the calcines and leach residues using
XRD). As seen in Fig. 9, the duration of 0.5 h is adequate for the
roasting of lepidolite concentrate mixes at 1000 °C.
3.4. Effect of Na2SO4–Li molar ratio
To recover Li from lepidolite, Na2SO4 was used as the additive in
order to remove Li from the silicate structure and convert it to species
that can be leached into water. Fig. 10 shows that Li extraction
reaches the maximum (~ 90%) at the Na2SO4–Li molar ratio of 2:1.
However, an excessive use of Na2SO4 could reduce the Li extraction

Table 5
Comparison of conditions and results of different studies.

This study Siame and Yan et al. Yan et al. Jandová et al. Jandová Sitando and
Pascoe (2011) (2012a) (2012b) (2009) et al. (2010) Crouse (2012)

Mineral tested Lepidolite Zinnwaldite Lepidolite Lepidolite Zinnwaldite Zinnwaldite Petalite/lepidolite

Li % 2.55 0.96 2.00 2.00 1.4 1.21 1.9
K% 9.31 7.94 6.50 6.50 6.62 10.97 0.37
F% 3.69 3.36 4.46 4.46 Unreported Unreported 0.01
Optimum roast temperature (°C) 1000 850 850 880 950 825 1100 (1st stage)
Roasting time (h) 0.5 1 0.5 0.5 1 1 2
Additives Na2SO4 Na2SO4 Na2SO4 with/without Na2SO4, CaCl2 CaSO4, CaCO3 H2SO4 (300 °C, 2nd stage)
K2SO4, CaO Ca(OH)2
Best leaching temperature, °C 85 85 Room temperature Room temperature 90 90–95 50
Leaching time, h 0.5 0.5 0.5 0.5 0.1 0.5 1
Water–calcine mass ratio 2–18:1 10:1 2.5:1 0.8:1 10:1 5:1 7.5:1
Maximum Li extraction, % ~90 >90 ~90 ~90 96 ~90 97.3
Liquor Li concentration, g/L 1–3 Expected to be ~1 4.39 8.53 0.69 0.4 5.7
conditions not specified conditions not specified
60
100
80
Lithium extraction (%)
60
40
20
0 0
800 850
Temperature (oC)
Fig. 8. Effect of roasting temperature on Li extraction (Na2SO4–Li molar ratio of 2:1,
0.5 h) — leaching at water to calcine mass ratio of 15:1 at 85 °C for 3 h.
instead. The preferential formation of sodium silicate glass at higher
additions of sodium sulphate could encapsulate the soluble Li min-
erals and prevent them from solubilising into water during leaching.
As results from other studies are scattered and presented differently,
they are reviewed and tabulated in Table 5 for a better comparison.
Plotted in Fig. 10 are also results from studies by Siame and Pascoe
(2011) and Yan et al. (2012a,b), showing the effect of roasting at dif-
ferent Na2SO4–Li molar ratios. It seems that lepidolite having higher
Li content (2.55% Li in this study) requires a higher temperature for
maximising the Li extraction.
4. Conclusions
Using HSC simulation to identify conditions for decomposing le-
pidolite by roasting with sodium sulphate, we conducted experi-
ments at 850–1000 °C to produce calcines using different sodium
suphate to Li molar ratios from 1:1 to 3:1 at different roasting dura-
tions from 0.5 to 2 h. One of the major products identified by HSC
and confirmed by XRD, LiKSO4, has low solubility and thus controls
the leachability of Li into water. Stabcal modelling also predicts that
the equilibrium concentration of Li imparted by this double salt is
b1 g/L at 25 °C. The extraction of Li at an ambient temperature is gen-
erally b45% and a higher temperature (85 °C) therefore is required to
extract 50–90% Li, depending on the amount of water used for
leaching. As the water–calcine ratio was increased from 2:1 to 18:1,
100
Lithium extraction (%)
80
60
40
20
0 Jandová, J., Dvořák, T., Kondás, T., Harlák, H., 2012. Recovery of lithium from waste ma-
0.0 0.5
Fig. 9. Effect of roasting time on Li extraction (Na2SO4–Li molar ratio of 2:1, 1000 °C) —
leaching at water to calcine mass ratio of 15:1 at 85 °C for 3 h.
V.T. Luong et al. / Hydrometallurgy 134–135 (2013) 54–61
100
Lithium extraction (%)
80
(a)
60
(b)
40
(c)
20 (d)
0
1 2 3
900 950 1000 1050
Na2SO4/Li molar ratio
Fig. 10. Effect of Na2SO4–Li molar ratio on Li extraction — (a) this study — at 1000 °C;
(b) this study — at 850 °C, (c) results from Yan et al. (2012a), (d) results from Siame
and Pascoe (2011).
more diluted Li liquors were formed (concentration dropping from
3 to 1 g/L Li). However recoveries of Li could be increased to 90% as
a result of more lithium solubilising at higher water–calcine ratios.
At best, ~ 90.4% lithium extraction was achieved during leaching
using the water–calcine mass ratio of 15:1, at 85 °C for 3 h. The best
calcine was produced by roasting at 1000 °C for 0.5 h using the
Na2SO4–Li molar ratio of 2:1.
Acknowledgement
This work was supported by a grant from the Energy Efficiency &
Resources Department of the Korea Institute of Energy Technology
Evaluation and Planning (KETEP), Ministry of Knowledge Economy,
Korea (Grant No. 2010-T100100408).
References
An, J.W., Kang, D.J., Tran, K.T., Kim, M.J., Lim, T., Tran, T., 2012. Recovery of lithium from
Uyuni salar brine. Hydrometallurgy 117–118, 64–70.
Brand, F., Haus, R., 2010. New concepts for lithium minerals processing. Miner. Eng. 23,
659–661.
Chen, Y., Tian, Q.Q., Chen, B.Z., Shi, X.C., Liao, T., 2011. Preparation of lithium carbonate
from spodumene by a sodium carbonate autoclave process. Hydrometallurgy 109,
43–45.
Crocker, L., Lien, R.H., et al., 1987. Lithium and its recovery from low-grade Nevada clays.
Bulletin, 691. US Bureau of Mines, Department of Interior (Accessed on 2 October
2011, http://digicoll.manoa.hawaii.edu/techreports/PDF/USBM-691.pdf).
Galaxy Resources Ltd. Accessed on 2 November 2011 http://www.galaxyresources.
com.au/documents/GXY03LithiumCarbonateTestworkResults.pdf (http://www.
galaxyresources.com.au/project_jiangsu.shtml http://metalsplace.com/news/articles/
33315/galaxy-resources-ups-lithium-ore-reserves-by-23/).
Garrett, D.E., 2004. Lithium. Handbook of Lithium and Natural Calcium Chloride.
Elsevier Ltd., pp. 1–236 (Part 1).
Guo, X.Y., Li, D., Park, K.H., Tian, Q.H., Wu, Z., 2009. Leaching behavior of metals from a
limonitic Ni laterite using a sulphation roasting–leaching process. Hydrometallur-
gy 99, 144–150.
HSC Chemistry Software, Version 7.1. Outotec.
Huang, H.H., 2005. Stabcal Software. available from Montana Tech University of Mon-
tana, USA.
Hykawy, J., 2010. Looking at lithium: discussing market demand for lithium in elec-
tronics. Mater. World-Ceram. Lithium 18 (5), 34–35.
Jandová, J., Vu, H.N., Bĕlková, T., Dvořák, T., 2008. Lithium extraction from zinnwaldite
wastes using gypsum method. Acta Metall. Slovaca 14 (1), 101–105.
Jandová, J., Vu, H.N., Belková, T., Dvořák, T., Kondás, J., 2009. Obtaining Li2CO3 from
zinnwaldite wastes. Ceramics-Silikáty 53 (2), 108–112.
Jandová, J., Dvořák, P., Vu, H.N., 2010. Processing of zinnwaldite waste to obtain lithium
carbonate. Hydrometallurgy 103, 12–18.
1.0 1.5 2.0 2.5 terials. Ceramics-Silikáty 56 (1), 50–54.
Paukov, E.I., Kovalevskaya, Y.A., Kiseleva, I.A., Shuriga, T.N., 2010. A low-temperature heat
Time (h) capacity study of natural lithium micas — heat capacity of zinnwaldite. J. Therm. Anal.
Calorim. 99, 709–712.
Siame, E., Pascoe, D., 2011. Extraction of lithium from micaceous waste from china clay
production. Miner. Eng. 24, 1595–1602.
 V.T. Luong et al. / Hydrometallurgy 134–135 (2013) 54–61
Sitando, O., Crouse, P.L., 2012. Processing of a Zimbabwean petalite to obtain lithium
carbonate. Int. J. Miner. Process. 102–103, 45–50.
USGS - US Geological Survey, 2011. Mineral Commodity Summaries — Lithium. USGS,
Virginia, pp. 94–95 (January, ISBN 978–1–4113–3083–2).
Wang, M.Y., Wang, X.W., 2010. Extraction of Mo and Ni from carbonaceous shale by ox-
idative roasting, sulphation roasting and water leaching. Hydrometallurgy 102,
50–54.
Yaksic, A., Tilton, J.E., 2009. Using the cumulative availability curve to assess the threat
of mineral depletion: the case of lithium. Resour. Policy 34, 185–194.
61
Yan, Q., Li, X., Wang, Z., Wu, X., Guo, H., Hu, Q., Peng, W., 2012a. Extraction of lithium
from lepidolite by sulphation roasting and water leaching. J. Int. Miner. Process.
110–111, 1–5.
Yan, Q., Li, X., Wang, Z., Wu, X., Guo, H., Hu, Q., Peng, W., Wang, J., 2012b. Extraction of
valuable metals from lepidolite. Hydrometallurgy 117–118, 116–118.
Yan, Q., Li, X., Yin, Z., Wang, Z., Guo, H., Peng, W., Hu, Q., 2012c. A novel process for
extracting lithium from lepidolite. Hydrometallurgy 121–124, 54–59.