Hydrometallurgy 177 (2018) 49–56

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

Extraction of lithium from β-spodumene using sodium sulfate solution

⁎
Ge Kuanga, , Yu Liua, Huan Lia, Shengzhou Xinga, Fujie Lia, Hui Guoa,b
a
Institute of Chemical Engineering and Technology, Fuzhou University, Fuzhou 350108, China
b
School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China

AR TIC LE I NF O AB S TR ACT

Keywords: The anticipated increase in demand for lithium salt brings a growing concern over lithium shortage and en-
β-spodumene vironmental problems in the industry of extracting lithium from ores. A closed-loop process for the extraction of
Lithium
lithium from β-spodumene (β-LiAlSi2O6) by leaching with Na2SO4, the by-product of the lithium precipitation
Autoclave
process, was proposed. Two kinds of additives (CaO and NaOH) were employed to enhance extraction effect,
Additive
Sodium sulfate respectively. The lithium extraction efficiencies were recorded to be 93.30% with CaO addition and 90.70% with
Leaching NaOH addition, which have the more environmentally friendly and economically viable latent capacity in
comparison to the currently industrialized sulfuric acid method. By analysis of leaching residue, the extraction
mechanism was found to be high-chemoselective ion-exchange between Li+ in β-LiAlSi2O6 and Na+ in Na2SO4
solution.

1. Introduction Li2O·Al2O3·4SiO2) with the advantage of relatively high theoretical Li

Lithium, known as the lightest metal, has been widely used in bat-
teries, ceramics, glass, lubricants, aluminum smelting, and polymers
(Reichel et al., 2017; Swain, 2017). Particularly, the demand for li-
thium-ion batteries (LIBs) used in vehicles as power sources have ex-
perienced an explosive growth, with the global market share reached
39% in 2016 (Jaskula, 2017; Zou et al., 2013). The worldwide lithium
consumption for LIBs in vehicles is expected to increase by 20% per
year through 2020 (Jaskula, 2016b). The annual global consumption of
lithium, measured in tonnes of lithium carbonate equivalent, reached
170,000 t/year in 2015 and is forecasted to increase to 280,000 t/year
in 2020 (Jaskula, 2013, 2016a). Resulting from the increasing demand
for lithium, the price of lithium salt has experienced considerable in-
crease. In 2015 alone, the price of spot lithium carbonate has risen by
300% in China and 40–60% worldwide (Jaskula, 2017).
Currently, 50% of the lithium produced in the world comes from
lithium brines (contain 0.06–0.15% Li) (Friedman-Rudovsky, 2011;
Jaskula, 2015; Jandová et al., 2010). However, the lithium brines in the
world are located almost exclusively in South America (Grosjean et al.,
2012), which may lead to monopolies, and a lithium shortage may
emerge in a few decades (Kuang et al., 2015). The Li bearing minerals
are distributed more widely in the world, which will be used more ef-
fectively. For meeting the growing demand, lithium-bearing minerals,
including spodumene, lepidolite and zinnwaldite, have attracted much
attention in recent years (Barbosa et al., 2015; Kuang et al., 2015;
Speirs et al., 2014; Tarascon, 2010). The spodumene (LiAlSi2O6 or
content (up to 8.03% Li2O) and comparatively lower process costs has
become the preferred mineral for the extraction of lithium (Jaskula,
2016b; Qiu et al., 2016; Rosales et al., 2014).
In nature, spodumene exists in the α-phase form and usually as-
sociates with quartz and feldspar (Botto, 1985). In most extraction
methods, due to the α-phase is resistant to the attack of chemicals.
Spodumene is first subjected to a calcination step at 1000–1100 °C for
~1 h to convert spodumene to β-phase that is much more reactive and
less resistant to common chemicals (Ellestad and Leute, 1950; Meshram
et al., 2014). Table 1 presents the reported methods and their experi-
mental profiles for the extraction of lithium from β-spodumene. Cur-
rently, the industrial process for the extraction of lithium from spodu-
mene is sulfuric acid method, which is summarized in Fig. 1 (Meshram
et al., 2014; Rosales et al., 2016; Tian et al., 2011; Xiao et al., 1997). In
this method, sulfuric acid is used to roast β-spodumene at a temperature
around 250 °C according to Eq. (1). The roasted product is then leached
with dissolve the metal sulfates. In this process a significant amount of
CaCO3 is used to neutralize excess H2SO4 and adjust pH value for re-
moving impurities. Next, Na2CO3 is introduced to the concentrated
solution to precipitate Li2CO3 as represented by Eq. (2). However, the
sulfuric acid process is performed in rotary kiln, which is not easy with
temperature controlling and energy recovering, and additional pro-
cesses with heavy investments are also required for the disposal of
mother solution to recover residual lithium and unprofitable Na2SO4.
The recovery efficiency of lithium from β-spodumene in this method
conducted is reported to be around 90% (Zhu et al., 2008; Zhang and

⁎
Corresponding author.
E-mail address: kuangge1970@sina.com (G. Kuang).

https://doi.org/10.1016/j.hydromet.2018.02.015
Received 3 August 2017; Received in revised form 12 February 2018; Accepted 24 February 2018
Available online 26 February 2018
0304-386X/ © 2018 Published by Elsevier B.V.
G. Kuang et al. Hydrometallurgy 177 (2018) 49–56

Yan, 2015).

(Meshram et al., 2014; Tian et al., 2011; Xiao et al., 1997)

(Rosales et al., 2014; Rosales et al., 2016) (Barbosa et al., 2013)

β − Li2 O·Al2 O3 ·4SiO2 (s) + H2 SO4 (l) → H2 O·Al2 O3 ·4SiO2
(s) (1)
+ Li2 SO4 (s)
(2)
Li2 SO4 (aq) + Na2CO3 (l) → Li2 CO3 (s) + Na2SO4 (aq)

(Chen et al., 2011)

In recent years, some novel methods have been proposed as alter-
natives to the sulfuric acid method, which can be divided into chlor-
ination roasting method (Barbosa et al., 2015, 2013), hydrofluoric acid
method (Rosales et al., 2014, 2016) and sodium carbonate method
Ref.

(Chen et al., 2011). However, as shown in Table 1, there are still some
drawbacks related to these methods, such as the use of high toxic re-
agents (Rosales et al., 2014, 2016) and high energy consumption
First step: 94; second step:91

(Barbosa et al., 2015, 2013). According to Chen et al. (2011), the

% Li extraction

process of extracting lithium from spodumene included two steps after

decrepitation. In the first step, lithium was extracted as lithium car-
bonate in solid phase. Then, the solid phase went through the carbo-
nation process and converted to soluble carbonate. However, this two
90.2

steps leaching decreased the operability and made the leaching process
90 –
–

become more complex. Therefore, the total Li extraction efficiency was

only 88%, the recovery of Li by sodium carbonate autoclave process
Acid gas emission, high concentration reagents.

High leaching temperature, corrosion resistant equipment required.

was just around 70% because of lithium lossing.

High toxic reagent, not commercialized yet.

In this study, a novel process for the extraction of lithium from β-

Complex steps and high reagents cost.

spodumene using sodium sulfate solution with addition of CaO or

NaOH is proposed, which is expected to be more cost-effective, en-
vironmentally friendly and straightforward, and to be an alternative to
the current industrial process.

2. Materials

The β-spodumene used in this study was supplied by Shandong

Drawbacks

RuiFu Lithium Industry Co., Ltd., (Shandong, China) and is originally

from Talison Lithium Pty Ltd. operation (Greenbushes, Australia). The
conversion of α-spodumene to β-spodumene is carried out by calcining
2SO4 (1.4 times higher than theoretical usage) at 250 °C for 30 min.

at 1100 °C for 1 h in a rotary kiln by the supplier to make it transfer to

β-phase with the conversion rate of 97%. The X-ray diffraction (XRD,
PANalytical-X'Pert PRO) analysis of the spodumene before and after
calcination indicates that the ore was initially composed of α-spodu-
mene (α-LiAlSi2O6) and quartz (SiO2) (Fig. 2a) and the α-spodumene
Reported methods and their experimental profiles for the extraction of lithium from β-spodumene. Table 1

was converted into β-spodumene (β-LiAlSi2O6) after calcination

(Fig. 2b). The Scanning Electron Microscopy (SEM, Hitach-S4800)
shows that the spodumene after calcination was fluffier and contained
many smaller particles (Fig. 3). The chemical analysis of the β-spodu-
Main reagents/process

mene used in this study is given in Table 3. The particle size distribution
of the β-spodumene measured by laser diffraction particle size analyzer
(Mastersizer 2000, Malvern Instruments Co., Ltd) shows that the D90
particle size (particle diameter at the 90 vol% undersize point in the
distribution (Higgins et al., 2003) was 75.225 μm (Fig. 4).

3. Procedures and methods

Li2O % in ore

The leaching of β-spodumene was performed by placing β-spodu-

6.05

7.20

mene/Na2SO4 mixture in a 200 mL autoclave (KCF, Beijing Century

7.25

6.06
Roasting with 93% H

Senlong experimental apparatus Co., Ltd., Beijing, China) which is

made up of #316 stainless steel. An aqueous solution of 0.15 g Na2SO4/
Hydrofluoric acid method

mL of distilled water was used in these tests. CaO or NaOH (analytical

Sulfuric acid method (currently industrialized)

reagent) were introduced into the autoclave to enhance the leaching

efficiency. The extraction efficiencies of Li with the CaO or NaOH ad-
Sodium carbonate method

dition in each test were compared under the same leaching conditions.
The effects of different variables, including Na2SO4/ore mass ratio,
additive/ore mass ratio, leaching temperature, ore particle size,
leaching time and liquid to solid ratio (L/S ratio), on the extraction
efficiency of lithium were investigated. In order to gain the different ore
Methods

particle sizes, the ore was grinded by jet mill (MQP01, Weifang Alpa
Powder Technology & Equipment Co., Ltd., Shandong, China) with the
different feed rate in a few seconds. Among all the leaching
5
0
 Fig. 1. Flow chart of the current industrial process for the extraction of lithium from β-spodumene.

Fig. 2. XRD patterns of spodumene before (a) and after (b) calcination.
Fig. 4. Particle size distribution of the β-spodumene used in this study.
experiments, the stirring speed was fixed at 300 rpm. After leaching, the
autoclave was cooled to room temperature with cooling water for
30 min. The mixture was then taken out and filtrated. The lithium the lithium content, the residue was completely digested with 98%
content in the filtrate was measured by Atomic Absorption sulfuric acid and 40% hydrofluoric acid (Brumbaugh and Fanus, 1954)
Spectroscopy (AAS, AA-6880, Shimadzu Co., Ltd). The leaching re- and was then analyzed by AAS. The XRD and SEM analysis of residues
sidues obtained after filtration were dried at 120 °C for 2 h and were were performed so as to evaluate the structure and components.
then weighted by analytical balance (BS 224S, Sartotius). To measure

Fig. 3. SEM images of spodumene before (a) and after (b) calcination.
Fig. 5. Effects of various variables on the extraction efficiency of Li. (a) Na2SO4/Ore mass ratio; (b) Additive/Ore mass ratio; (c) temperature; (d) time; (e) L/S ratio; (f) Particle size (D90).
4. Results and discussion
4.1. Leaching of β-spodumene
4.1.1. Effect of Na2SO4/ore mass ratio
To study the effect of Na2SO4 addition on the Li extraction effi-
ciency, experiments with different Na2SO4/ore mass ratio (w/w) were
conducted with additive/ore mass ratio (w/w, mass ratio between the
addition of CaO or NaOH and ore) of 1:20, leaching temperature of
230 °C, D90 particle size of 75.225 μm, leaching time of 3 h and L/S ratio
of 7.5 mL/g. The results (Fig. 5a) show that the Li extraction efficiency
with addition of CaO was always around 12–17% higher than that with
NaOH. While, with the increase of the Na2SO4/ore mass ratio, the
variation range of Li efficiency with both CaO and NaOH added was
always less than 5%. When the Na2SO4/ore mass ratio increased to
9:20, the Li extraction efficiency with CaO and NaOH addition rose to
90.59% and 75.48%, respectively. However, further increase of the
ratio did not result in a clear change of the extraction efficiency. This
result was better than (Yan et al., 2012), which considered the
evaluated Na/Li mole ratio (2.4:1), resulting in lithium extraction ef-
ficiency of about 90%. Therefore, the optimum mass ratio of 9:20 (Na/
Li mole: 1.5:1) was chosen for the following experiments.
4.1.2. Effect of additive/ore mass ratio
To investigate the effect of additive/ore mass ratio on the Li ex-
traction efficiency, experiments were carried out with the mass ratio
ranging from 0:20 to 1:20. Other conditions were fixed as follows:
Na2SO4/ore mass ratio of 9:20, leaching temperature of 230 °C, D90
particle size of 75.225 μm, leaching time of 3 h and L/S ratio of 7.5 mL/
g. The results (Fig. 5b) show that the use of CaO and NaOH as additives
had significant influence on the extraction efficiency of Li. When the
additive/ore mass ratio increased from 0:20 (no CaO or NaOH added)
to 0.2:20, the extraction efficiency of Li rose by about 58% for both CaO
and NaOH addition. When the ratio reached 0.4:20, the Li extraction
efficiency peaked at 90.67% for CaO and 87.34% for NaOH. However,
with more CaO or NaOH added, there was no obvious change of Li
extraction efficiency for CaO addition (stable at around 90%), while
that for NaOH decreased to 75.48% at the ratio of 1:20. In order to
 Table 2
Results of the ore reacted with additions of CaO and NaOH at different temperature.
Na2SO4/ore mass ratio = 9:20; Additive/ore mass ratio = 0.4:20; Leaching time = 3
h; Liquid-solid ratio = 7.5 mL/g and D90 particle size = 75.225 μm.

° a
Additives Mass of Temperature/ C Mass of Residue rate Lithium
ore/g residue/ extraction
g efficiency

CaO 20.0538 150 20.6018 102.73% 21.31%

20.0112 170 20.5837 102.86% 29.12%
20.0287 190 21.9313 109.50% 55.33%
20.0667 210 23.0548 114.89% 89.52%
20.0033 230 22.9001 114.48% 90.67%
NaOH 20.0718 150 20.8640 103.95% 36.62%
20.0260 170 21.4458 107.09% 66.98%
20.0473 190 22.6998 113.23% 85.12%
20.0256 210 22.5528 112.62% 84.96%
20.0085 230 22.5919 112.91% 87.34%

a
Fig. 6. XRD analysis of leaching residue at NaOH/ore mass ratio of 1:20. Residue rate is the ratio between the weight of residue and ore mineral.

investigate the reasons for the significant reduction of Li extraction
efficiency when the mass ratio of NaOH/ore was over 0.4:20, the
leaching residue at the NaOH/ore mass ratio of 1:20 was tested by XRD.
As can be seen from the result (Fig. 6), the residue was mainly com-
posed of analcime (NaAlSi2O6·H2O), quartz (Si2O) and virgilite
(LixAlxSi3−xO6), which means that the excess NaOH addition led to the
loss of Li in residue in the form of virgilite. Thus, in the present result,
the additive/ore mass ratio of 0.4:20 seems to favour the lithium ex-
traction. To reduce the addition amount of the additives and achieve
the high extraction efficiency for both CaO and NaOH, the mass ratio of
0.4:20 was chosen for the following experiments.
4.1.3. Effect of leaching temperature
The effect of leaching temperature on the Li extraction efficiency
was investigated in the range of 150 to 230 °C. The other conditions
were as follows: Na2SO4/ore mass ratio of 9:20, additive/ore mass ratio
of 0.4:20, D90 particle size of 75.225 μm, leaching time of 3 h, L/S ratio
of 7.5 mL/g. The results were shown in Fig. 5c, which indicates the
temperature had considerable influence on the Li extraction. In the
experimented temperature range, the Li extraction efficiency jumped
from 21.31 to 90.67% for CaO addition and from 36.62 to 87.34% for
NaOH addition. There was no obvious difference between the figure for
NaOH and CaO after the temperature reached 190 and 210 °C, respec-
tively. Taking into account the energy consumption, 190 °C for NaOH
addition and 210 °C for CaO addition are recommended for the leaching
of β-spodumene. However, in order to make a comparison between
NaOH and CaO addition under the same conditions and at a high Li
extraction efficiency, 230 °C was chosen for the following experiments.
In order to clearly investigate the relationship between the weight
of residue and Li extraction efficiency, the detailed results of Fig. 5c are
presented in Table 2. For showing the increase rate of the weight of
residue in comparison to the ore materials, the term of residue rate %
(the ratio between the weight of residue and ore material) was in-
troduced in the table. As can be seen, with the leaching temperature
increasing, the residue rate had a positive correlation with Li extraction
efficiency. At the optimum leaching temperature of 230 °C, the residue
rate was 114.48% for CaO addition and 112.91% for NaOH addition,
and the Li extraction efficiency reached 90.67% and 87.34%, respec-
tively.
4.1.4. Effect of leaching time
The effect of leaching time was investigated in the range from 2 to
6 h under the following conditions: Na2SO4/ore mass ratio of 9:20,
additive/ore mass ratio of 0.4:20, leaching temperature of 230 °C, D90
particle size of 75.225 μm and L/S ratio of 7.5 mL/g. The results
(Fig. 5d) indicate that the leaching time (over 2 h) had relatively slight
influence on the extraction efficiency of Li and the figure for CaO was
always 3–8% higher than that for NaOH. It is noticeable that the Li
extraction efficiency with NaOH addition peaked at 87.34% at leaching
time of 3 h followed with a decreased of around 3% until leaching time
of 6 h. This result indicates that further leaching time is not favorable
for lithium extraction, 3 h seems to be more suitable.
4.1.5. Effect of L/S ratio
The effect of different L/S ratio was conducted at 230 °C for 3 h with
Na2SO4/ore mass ratio of 9:20, additive/ore mass ratio of 0.4:20 and
D90 particle size of 75.225 μm. The results are plotted in Fig. 5e. With
the L/S ratio increasing from 3 to 7.5 mL/g, it is evident that the Li
extraction efficiency for CaO was always 2–6% higher than that for
NaOH. When the ratio reached 5 mL/g, the extraction efficiency for
CaO addition increased to 89.89% and remained stable at the following
ratios (only 90.67% at 7.5 mL/g). Whereas, from 5 mL/g to 7.5 mL/g,
the Li extraction efficiency for NaOH addition was still increased ob-
viously and peaked at 87.34% at 7.5 mL/g. Since higher L/S ratio
means more energy consumption for concentration in the downstream
recovery process, the L/S ratio of 5 mL/g for CaO addition and 7.5 mL/g
for NaOH addition seem to be advisable. Nevertheless, it should be
concerned that a low L/S ratio (below 5 mL/g) for CaO addition inhibits
the mass transfer and leads to solid mixtures sticking on the inner
surface of the reactor, making them difficulty to be washed out, because
of the swelling of CaO. To facilitate the operation of experiment and
make a comparison between two additives under the same conditions,
L/S ratio of 7.5 mL/g was chosen for both CaO and NaOH addition.
4.1.6. Effect of ore particle size
Some experiments with different particle sizes of the ore were
conducted to investigate its effect on Li extraction efficiency at 230 °C
for 3 h with Na2SO4/ore mass ratio of 9:20, additive/ore mass ratio of
0.4:20 and L/S ratio of 7.5 mL/g. The particle diameter at the 90 vol%
undersize point in the distribution (D90) was the variable used to de-
scribe the particle size (Higgins et al., 2003). The results were plotted in
Fig. 5f. When the particle size of ore materials decreased from 164.145
to 39.233 μm, the extraction efficiencies of Li experienced sharp rise.
While, when the particle size continues decreasing, the Li extraction
efficiency dropped slightly and the gap between the figure for CaO and
NaOH narrowed. A reasonable explanation is that the decreasing par-
ticle size led to the higher surface energy of particles and hence made
them easily form agglomerations (Vieceli et al., 2017; Zhang et al.,
2010) that inhibited extraction reaction. Agglomeration phenomenon
was extraordinarily obvious at the condition of D90 particle size
8.642 μm, as shown in Fig. 7. Since the Li extraction efficiencies for
both CaO and NaOH addition peaked at 39.233 μm, further experiments
were conducted using ore materials screened at this size. At this particle
size, the extraction efficiencies of Li for CaO and NaOH additives were
 Fig. 7. SEM images of leaching residue with addition of (a) NaOH and (b) CaO, D90 = 8.642 μm.

Table 3
Compositions (wt%) of the ore and leaching residues. Na2SO4/ore mass ratio = 9:20, Additive/ore mass ratio = 0.4:20, T = 230 °C, t = 3 h, L/S ratio = 7.5 mL/g and D90
particle size = 39.233 μm.

Sample Component (wt%) Li extraction efficiency

Li2O K2O CaO SiO2 Al2O3 Na2O MgO Fe2O3

Ore 6.17 0.92 0.57 63.00 26.38 1.46 0.21 0.61 –

Residue from CaO addition 0.39 0.32 1.50 54.62 21.23 11.92 0.11 0.63 93.30%
Residue from NaOH addition 0.53 0.28 0.21 55.42 21.85 12.24 0.082 0.50 90.70%

93.30% and 90.70%, respectively, and the pressure of autoclave was 4.2. Analysis of leaching residue
recorded as 2.7 ± 0.1 MPa.
Table 3 presents the chemical analysis of leaching residue obtained To confirm the leaching effect with addition of CaO and NaOH,
from the experiment with the highest extraction efficiencies, i.e. leaching residue obtained from the experiments with the highest ex-
93.30% for CaO addition and 90.70% for NaOH addition. Under the traction efficiencies was tested by SEM (Fig. 8). As shown in Fig. 8a,
reaction conditions, the mass of leaching residue was around 23.0 g there are large amount of agglomerations of small particles wrapped
(CaO) or 22.7 g (NaOH). As can be seen from the table, the Li content in around the residue, which may lead to less contact between Na2SO4
residue had decreased from the original value of 6.17% to 0.39 and solution and ore materials resulting in low extraction efficiency. In
0.53% with addition of CaO and NaOH, respectively, and the Na con- contrast, the addition of CaO resulted in the surface of the residue
tent in residues was risen by over 10% for both additive of CaO and particles being smooth with little agglomeration (Fig. 8b). These ob-
NaOH. According to analyzing, the decreased Li content was equal to servations explain why Li extraction efficiency with NaOH additive was
the increased Na content in the number of mole. Besides, other com- lower than that with CaO additive in some leaching experiments.
ponents, including K2O, CaO (for NaOH addition), SiO2, Al2O3, MgO To investigate the mechanism of the extraction process, the leaching
and Fe2O3 were also decreased more or less, this might be because the residue was analyzed by XRD. The results (Fig. 9) indicate that the
total weight of residue was increased overtaking the weight of ore residues with additive of both CaO (Fig. 9a) and NaOH (Fig. 9b) were
material as indicated in Table 2. mainly composed of analcime (NaAlSi2O6·H2O), β-spodumene (β-
LiAlSi2O6) and quartz (SiO2). Comparing the mineral composition of
4.1.7. Reproducibility experiments
LiAlSi2O6) was converted to analcime and the quartz still remained in
To confirm the reliability of the leaching result, Three parallel tests
residue. The result indicates that the extraction process was based on an
were conducted under the following conditions: Na2SO4/additive (CaO
ion-exchange mechanism, where Li+ in β-spodumene (β-
or NaOH)/ore mass ratio of 9:0.4:20, leaching temperature of 230 °C, +
leaching time of 3 h, L/S ratio of 7.5 mL/g and D90 particle size of LiAlSi2O6) was replaced by Na and leached into solution. The
39.233 μm. The results are shown in Table 4. The standard deviation reaction can be represented as:
with the addition of CaO (0.49%) and NaOH (0.57%) were less than OH−
2β − LiAlSi2 O6 (s) + Na2SO4 (s) + 2H2 O (l) ⎯⎯⎯⎯⎯→ 2NaAlSi2 O6 ·H2 O
2%, which indicated that the results are reproducible under the eval- (s)
uated conditions. The Li extraction efficiency of three parallel tests are + Li2 SO4 (aq) (3)
not significantly different. This is favorable for further researching the
optimum process in our future work. From Eq. (3), the weight of solid residue is predicted to be greater
than the ore materials, which can account for the residue rate being
Table 4 over 100% and the positive correlation between Li extraction efficiency
Results of parallel experiments under the conditions of Na2SO4/additive (CaO or NaOH)/ and residue rate (indicated in Table 2). The ion-exchange based me-
ore mass ratio 9:0.4:20, leaching temperature 230 °C, leaching time 3 h, L/S ratio 7.5 mL/ chanism is similar to that previously reported for methods using sulfuric
g and D90 particle size 39.233 μm. acid (Xiao et al., 1997) and calcium chloride roasting (Barbosa et al.,
2015) to extract lithium from β-spodumene, where Li+ was replaced by
Additives Li extraction efficiency (%) from Average (%) Standard
parallel experiments deviation (%) H+ and Ca2+, respectively. However, this extraction process was built
on strong base transforming to weak base in the alkaline atmosphere.
# # #
1 2 3 The product analcime can be applied in environmental protection,
catalyst preparation and ceramic production, which has been widely
CaO 92.73 93.92 93.18 93.28 0.49
NaOH 91.10 90.50 89.70 90.43 0.57 researched before. Such as, modified Ni (II) loaded analcime electrode
was used to catalyze the electrooxidation of methanol (Azizi et al.,
G. Kuang et al. Hydrometallurgy 177 (2018) 49–56

Fig. 8. SEM images of leaching residue with additive of (a) NaOH and (b) CaO. Na2SO4/ore mass ratio = 9:20, Additive/ore mass ratio = 0.4:20, T = 230 °C, t = 3 h, L/S ratio = 7.5
mL/
g and D90 particle size = 39.233 μm.

Table 5
Chemical composition of the leaching solution. Na2SO4/ore mass ratio = 9:20, Additive/
ore mass ratio = 0.4:20, T = 230 °C, t = 3 h, L/S ratio = 7.5 mL/g and D90
particle size = 39.233 μm. The volume of liquor was 1 L, mass of ore was 40 g.

Leaching solution The concentration of components (mg/L)

Li2O Na2O CaO SiO2 Al2O3 K2O MgO Fe2O3

Solution from 2293 1860 54.88 126 0.064 91.62 0.15 0.0034
CaO addition
Solution from 2250 2359 3.28 223 0.038 124.13 0.20 0.0170
NaOH
addition

Fig. 10. Firstly, β-spodumene is leached in an autoclave with Na2SO4

Fig. 9. XRD analysis of leaching residue with additive of (a) NaOH and (b) CaO. Na2SO4/
ore mass ratio = 9:20, Additive/ore mass ratio = 0.4:20, T = 230 °C, t = 3 h,
L/S ratio = 7.5 mL/g and D90 particle size = 39.233 μm.
2014), modified zincon loaded analcime to sorb preconcentration of
palladium (Taher et al., 2007), the contained F−, NH4+ and Cd2+ in
the waste water were separated by synthesis analcime as absorbent or
ion-exchange material (Chen, 2015; Yuan et al., 2016; Gu et al., 2008;
Wang et al., 2003), and the analcime-bearing ore was as a raw for
ceramic industry (Shushkov et al., 2011). So the leaching residue could
be recycled for another stage not to be abandoned, under these po-
tential applications the process may be an optionally environment
friendly course for extracting Li from β-spodumene.
4.3. A suggested closed-loop process for the extraction and recovery of Li
from β-spodumene
Based on the preceding results, a closed-loop process for extracting
and recovering Li from β-spodumene can be proposed as outlined in
and associated CaO or NaOH additive. Through filtration, Li+ will re-
main in solution and Na+ will report to the residue. The filter liquor
and washing water were diluted with few distilled water to 1 L together.
Table 5 lists the chemical composition of the leaching solution obtained
from the experiment with the highest extraction efficiencies. Relatively
few impurities in the leaching solution contributed to simplify the
purification process, which was a comparatively mature process in the
lithium industry (Vieceli et al., 2018; Sitando and Crouse, 2012; Swain,
2017). Some impurities were removed by pH control with lime in
leaching liquor, whereafter, redundant Ca2+ was cleaned by adding
moderate Na2CO3. After purification and concentration, Li contained in
solution could be easily recovered by adding Na2CO3 to form Li2CO3
precipitate according to Eq. (2) (Meshram et al., 2014). This method for
precipitating Li has been well studied and is very common in most in-
dustrial cases (Meshram et al., 2014; Swain, 2017; Wilkomirsky, 1999;
Zhang et al., 1998). Finally, the mother solution mainly containing
Na2SO4 obtained after precipitation of Li can be reused to commence
the next cycle of autoclave leaching to achieve a closed-loop. Compared
with the previously reported methods (Table 1), the suggested process
is largely simplified, just involves common chemicals, and the leaching
residue can be the reused resource for glass ceramic industry and en-
vironmental protection field, which make it cost-effective, eco-friendly
and straightforward.

Fig. 10. Flow chart of the suggested closed-loop process for the extraction and recovery of Li from spodumene.
G. Kuang et al.
5. Conclusions
A closed-loop process of extracting and recovery Li from β-spodu-
mene by leaching with Na2SO4 in pressure leaching was proposed. The
effects of two kinds of additive (CaO and NaOH) on the extraction ef-
ficiency of Li were investigated and compared. Over 90% Li was at-
tained with this process. The highest Li extraction efficiencies, i.e.
93.30% for CaO addition and 90.70% for NaOH, were observed under
the following conditions: Na2SO4/additive (CaO or NaOH)/ore mass
ratio of 9:0.4:20, leaching temperature of 230 °C, leaching time of 3 h,
L/S ratio of 7.5 mL/g and particle size (D90) of 39.233 μm. It was found
that significant amount of agglomerations were generated around ore
particles when adding NaOH, which may account for its lower extrac-
tion efficiency in comparison to adding CaO. By analysis of leaching
residue, the extraction reaction was found to be based on ion-exchange
between Li+ and Na+, with β-spodumene (β-LiAlSi2O6) converted into
analcime (NaAlSi2O6·H2O). Finally, a closed-loop process based on the
results of this study for the extraction of Li from β-spodumene was
proposed. This work provided an environmentally friendly, possibly
cost-effective and comparatively straightforward way to extract lithium
from β-spodumene, which has the potential to be industrially devel-
oped.
Acknowledgements
The authors thank the financial support from the National Key
Technology R&D Program of China during the 12th Five-year Plan
Period (Grant No.2012BAB10B02).
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