Hydrometallurgy 177 (2018) 109–115

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

Recovery of lithium from a synthetic solution using spodumene leach T

residue
⁎ ⁎
Guofei Han, Donglei Gu, Guo Lin, Qun Cui , Haiyan Wang
College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, China

A R T I C LE I N FO A B S T R A C T

Keywords: There exist active adsorption sites in the spodumene leach residue (SLR), the solid waste of spodumene after
Spodumene leach residue high-temperature roasting and leaching. It is potential for SLR to selectively adsorb Li+ from brine because of the
Lithium adsorption performance “memory effect”. Lithium ion adsorption isotherm and adsorption rate of SLR were studied. Effects of adsorption
Adsorption mechanism temperature and initial pH of solution on lithium adsorption performance were investigated. Physicochemical
Ion exchange
properties of SLR before and after adsorption were characterized via powder X-ray diffraction (XRD), X-ray
fluorescence (XRF) and scanning electron microscopy (SEM). Adsorption mechanism of SLR for lithium ion in the
liquid solution was discussed. Results show that the major component of SLR is aluminosilicate (HAlSi2O6),
whose theoretical lithium adsorption uptake of HAlSi2O6 is 37 mg/g. Lithium adsorption behavior of SLR could
be well described by the pseudo-second-order kinetic model and Langmuir isotherm, indicating adsorption
process conforms to a monolayer chemical adsorption, that is a H+-Li+ exchange process. Adsorption capacity
and adsorption rate of SLR could be effectively enhanced with the increase of adsorption temperature, initial Li+
concentration and pH value. Lithium uptake of SLR in Li+ solution (C0 = 500 mg/L, pH = 12.95, at 90 °C for
36 h) reached 25.40 mg/g, which was 68.65% of its theoretical uptake. SLR exhibits an excellent adsorption
stability, whose uptake remains above 17 mg/g in 100 mg/L Li+ solution after 5 cycles.

1. Introduction 2003; Bauman and Burba, 2013), titanium lithium ionic sieves
(Moazeni et al., 2015; Shi et al., 2013; Tang et al., 2015; Zhang et al.,
Lithium and its compounds have been widely used in batteries, 2016; Wang et al., 2016) and manganese lithium ionic sieves (Hunter,
ceramics and glass, lubricating greases, pharmaceuticals and other in- 1981; Xiao et al., 2013; Yang et al., 2000; Chitrakar et al., 2000, 2001;
dustries (Zhang et al., 2011; Sun et al., 2014; Key et al., 2012; Goriparti Shi et al., 2011; Zhang et al., 2009). Aluminum salt adsorbents
et al., 2014). According to the existing forms of lithium resources, li- (Bauman and Burba, 2013) showed a high and stable selectivity for Li+
thium is mainly extracted from ores like spodumene and aqueous re- with lithium uptake of merely 2–3 mg/g. Chitrakar et al. (2014) syn-
source such as sea and brine. However, ore sources are scarce and non- thesized nanoscale H2TiO3 by solid-phase reaction and its lithium ad-
renewable, which limits further development. The lithium resource of sorption capacity reached 32 mg/g. Tang et al. (2015) and Zhang et al.
salt lake brine is abundant. Recovery methods of lithium from brines or (2016) used different raw materials to synthesize H2TiO3. Wang et al.
seawater such as evaporative crystallization (Kim, 2008), co-pre- (2016) prepared lithium-enriched β-Li2TiO3 with the maximum lithium
cipitation (Hamzaoui et al., 2008; Um and Hirato, 2014), solvent ex- uptake of 76.7 mg/g in LiOH solution. Although the maximum Li+
traction (Zhou et al., 2011; Shi et al., 2015; Bukowsky et al., 1992) have adsorption uptake of H2TiO3 adsorbent from the lithium-enriched so-
been widely reported. However, these methods require long-period lution reached 76.7 mg/g, the high cost of synthesis and dissolution loss
operation, excessive reagents and intensive labor. Adsorption using li- of titanium ion still poses an obstacle. Chitrakar et al. (2001) synthe-
thium-ion sieve adsorbents is a significantly promising method for a sized Li1.6Mn1.6O4 by a hydrothermal reaction and its Li+ adsorption
further industrial application because it is not only highly selective but capacity reached 52 mg/g. Xiao et al. (2013) and Shi et al. (2011)
also cost-effective. synthesized spinel-structured hydrogen manganese oxides, whose sa-
In recent years, increasingly more studies on the adsorbents for li- turated adsorption capacity was up to 42 mg/g. Zhang et al. (2009)
thium extraction from brine have been reported. Researchers were synthesized 1-D MnO2 whose maximum lithium adsorption capacity
mainly concentrated on aluminum salt adsorbents (Rjabtsev et al., reached 46.34 mg/g in LiOH solution (C0 = 35 mg/L). Whereas,

⁎
Corresponding authors.
E-mail addresses: cuiqun@njtech.edu.cn (Q. Cui), haiyanwang@njtech.edu.cn (H. Wang).

https://doi.org/10.1016/j.hydromet.2018.01.004
Received 2 April 2017; Received in revised form 13 December 2017; Accepted 10 January 2018
0304-386X/ © 2018 Elsevier B.V. All rights reserved.
G. Han et al. Hydrometallurgy 177 (2018) 109–115

dismutation reaction during pickling may result in lattice distortion and 2.3. Cycle performance of SLR
dissolution of manganese, which undermines its cycle performance.
Most of residue is derived from leaching ores. For example, 8–10 The cycle performance of SLR was tested in Li+ solution
tons of lithium residue will be produced during leaching the spodumene (C0 = 100 mg/L, pH = 12.95, at 90 °C for 36 h). After each adsorption
ore using sulfuric acid to obtain 1 ton of lithium carbonate (Meshram cycle, SLR was regenerated in 0.5 mol/L HCl solution at 70 °C for 60 h.
et al., 2014). Currently, spodumene leach residue (SLR) was mainly The elution solution was collected for Li+ analysis by ICP. The re-
used as cement clinker, concrete, raw materials of ceramic glazed tiles generated SLR was subsequently washed with deionized water and
and activated clays (Beushausen et al., 2012; Tan et al., 2015), whose dried at 60 °C. Dried sample could be applied in fresh Li+ solution for
comprehensive utilization rate is merely about 10%. A large amount of next adsorption cycle.
SLR is exposed outside, which poses a severe threat to environment.
Therefore, it is extremely essential to efficiently deal with SLR. In our 2.4. Chemical analysis methods
previous studies (Chen et al., 2012; Hu et al., 2013; Wang et al., 2015;
Lin et al., 2015), high value-added zeolites (A/X) have been successfully The concentration of Li+ in the solutions was measured by an in-
synthesized with SLR, which could be applied to the fields of adsorp- ductively coupled plasma optical emission spectrometry (ICP-OES)
tion, catalysis and detergent additives, considering that SLR contains (Optima DV7000, PerkinElmer, USA). Operating parameters were as
high contents of silicon and aluminum. follows: Argon with purity of 99.999%, as the plasma source, was
With active adsorption sites, in our current work, SLR was used as purchased from Tianze Gas Corporation (Nanjing, China). Ar outputs
an adsorbent to extract Li+ from lithium solution, which would ad- for plasma, nebulizer and auxiliary gas were 15 L/min, 0.8 L/min and
vance its comprehensive utilization and turn it into an effective re- 0.2 L/min, respectively, with a RF power of 1300 W. The flow rate of
source. sample solutions was 1.5 mL/min. The Li+ concentration of the stan-
dard solution is 10 mg/L. And the detection limitation of Li+ was
2. Experimental section 0.01 mg/L.

2.1. Materials and reagents 2.5. Characterization methods of SLR

SLR was from Haimen General Lithium Co., Ltd. (China). Lithium Chemical composition of SLR was determined by X-ray fluorescence
hydroxide monohydrate (LiOH, AR, 97 wt%) and hydrochloric acid spectrometer (XRF, ARL ADVANTXP). The crystalline phases of SLR
(HCl, AR, 36.0–38.0 wt%) were obtained from Shanghai Lingfeng before and after adsorption were performed by X-ray diffractor meter
Chemical Reagent Co., Ltd. (China). Lithium chloride monohydrate (XRD, SmartLab, Rigaku) using Cu Kα radiation with a scanning rate of
(LiCl, AR, 97 wt%) was purchased from Guangdong Guanghua 20°/min in a 2θ ranges from 10° to 80°, a tube current of 40 mA and a
Technology Co., Ltd. (China). Deionized water was made in author's tube voltage of 100 kV. Morphology analysis of SLR was performed
laboratory. using a field emission scanning electron microscope (SEM, S-4800,
Hitachi). Each sample was coated with 5 nm, followed by spraying gold
2.2. Lithium adsorption measurement of SLR for 90 s.

Lithium solutions with various initial pH values and concentrations 3. Results and discussion
were prepared by LiOH and LiCl. The pH values of solutions were
measured precisely using a pH meter. Lithium adsorption property was 3.1. Compositions and adsorption mechanism of SLR
investigated by stirring 0.50 g of SLR in 0.1 L synthetic lithium solution
at a constant temperature for a period of time. SLR after adsorption was 3.1.1. XRF analysis compositions of SLR
isolated by filtration, washed with deionized water, and finally dried at The raw material used in this study was the solid waste of spodu-
60 °C for 6 h. Filtrates were collected and then diluted to the appro- mene ore after sulfuric acid roasting and leaching to produce lithium
priate concentrations for determination. The Li+ concentration of so- carbonate. It was mainly composed of SLR, delithiated spodumene
lutions before and after lithium adsorption experiments was measured (HAlSi2O6), along with few impurities including quartz. Considering
by inductively coupled plasma (ICP). The lithium uptakes of SLR at density difference, SLR could be obtained by flotation removal and
equilibrium and at time t were calculated by the following Eq. (1) and other treatment process. The chemical compositions of SLR are listed in
(2), respectively: Table 1.
As is shown in Table 1, SLR (HAlSi2O6) is mainly composed of SiO2
(C0 − Ce ) × V and Al2O3. Total content of SiO2 and Al2O3 is 97.91% with few other
Qe =
m (1) impurities. Therefore, the structure and adsorption mechanism of SLR
can been analyzed without taking other impurities into consideration.
(C0 − Ct ) × V
Qt = According to the formation of SLR, the theoretical lithium adsorption
m (2)
uptake could reach 37 mg/g.
Where Qe is adsorption uptake per gram of SLR at equilibrium, mg/
g; Qt is adsorption uptake per gram of SLR at time t, mg/g; C0 is the 3.1.2. Crystal structure analysis of β-spodumene and SLR
initial lithium ion concentration in the solution, mg/L; Ce and Ct are Lithium ions of β-spodumene are replaced by hydrogen ions of
lithium ion concentration in the solution at equilibrium and at time t, sulfuric acid in the acid leaching process to obtain soluble lithium
respectively, mg/L; V is the solution volume, L; and m is the mass of sulfate and insoluble residue. During the Li+-H+ ion exchange process,
lithium slag, g. there are no changes in the crystal structure(Chen et al., 2012) of β-

Table 1
Chemical compositions of SLR.

Chemical component SiO2 Al2O3 Fe2O3 SO3 CaO K2O MgO Na2O P2O5 Others

Mass fraction/% 70.67 27.24 0.52 0.45 0.29 0.22 0.16 0.13 0.12 < 0.1

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G. Han et al. Hydrometallurgy 177 (2018) 109–115

Fig. 1. Crystal structure diagrams of β-spodumene and SLR.

spodumene. Based on the compositions of β-spodumene and SLR, the

crystalline structure models were established by using Materials Studio
6.0 and shown in Fig. 1.
As can be seen in Fig. 1(a), β-spodumene (He et al., 2014) is mainly
composed of AleO and SieO bonds by analyzing molecular config-
uration. [SiO4] tetrahedron is formed by Si with coordination numbers
of four and O atoms and then the [SiO4] tetrahedral chain is formed by
covalent O. Analogously, [AlO6] octahedron consists of Al with the
coordination numbers of six and O atoms and then [AlO6] octahedron
chain is obtained in covalent form. [SiO4] tetrahedral and [AlO6] oc-
tahedron are connected by O atoms to form Al-O-Si bonds. Li atoms
coordinate with 4 O atoms. Therefore, β-spodumene with tetragonal
prismatic crystal structure is formed.
Considering the similar structure with SiO2, β-spodumene (β-
Li2O·Al2O3·4SiO2) could be regarded as SiO2, whose Si atoms are partly
replaced by Al atoms. Li atoms exist in the structure with the quantity
equivalent to Al atoms for a charge balance. There are so many gaps
resulting in many channels that Li+ in the structure can move along
within these channels. Due to the presence of these ion channels, β-
Fig. 2. Lithium ion adsorption isotherm of SLR.
spodumene has the ability of cation exchange. Therefore, unit cell
structure of obtained SLR could conform to β-spodumene. As is shown
in Fig. 1(b), after replacing Li atoms, H atoms coordinate with 4 O

Fig. 3. (a) Freundlich and (b) Langmuir plots of SLR for Li+ adsorption.

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Fig. 4. Lithium adsorption rate curves of SLR at different adsorption temperature.

Table 2
Two different adsorption kinetic models of SLR for adsorption lithium ions.

T(°C) Qe(mg/g) Pseudo-first-order Pseudo-second-order

2
k1(/h) Qe1(mg/g) R k2(g/(mg·h)) Qe2(mg/g) R2

30 4.34 0.0411 11.22 0.8756 0.00241 6.41 0.9808

40 6.36 0.0406 14.21 0.8988 0.00235 8.67 0.9907
50 8.22 0.0437 17.69 0.9102 0.00275 10.37 0.9961
60 9.62 0.045 13.99 0.9588 0.00511 10.94 0.9990
70 13.30 0.1392 23.43 0.9705 0.00906 15.70 0.9988
80 15.52 0.2088 85.32 0.8959 0.00831 18.21 0.9975
90 17.80 0.1308 13.11 0.9491 0.0204 19.01 0.9910

Fig. 5. Effect of initial pH on adsorption uptake of SLR.

Fig. 6. Lithium equilibrium uptake of SLR at different temperatures.

atoms in unit cell structure of SLR.

from SLR and entering the bulk solution, (Eq. (6) and (7)).
+ +
Lisolution → Lisurface (3)
3.1.3. Adsorption mechanism of SLR for lithium ion in the Li+ solution
+ +
According to the formation mechanism and the crystalline structure Lisurface → Liinside (4)
model of SLR, there are active adsorption centers for H+-Li+ ion ex-
+ +
change in SLR that have a specific memory effect and selectivity for Liinside + HAlSi2 O6 → LiAlSi2 O6 + Hinside (5)
lithium ion. As is shown Fig. 1(c), Li+ in the solution can been adsorbed + +
Hinside → Hsurface (6)
by SLR to exchange some H atoms, which makes SLR structure partly
transform to β-spodumene. According to the above analysis and the +
Hsurface +
→ Hsolution (7)
literatures (Moazeni et al., 2015; Bavykin and Walsh, 2007), adsorption
mechanism and process are proposed as follows: (1) Diffusion of Li+
from the bulk solution to the surface of SLR (Eq. (3)). (2) Li+ trans- 3.2. Lithium ion equilibrium adsorption performance of SLR
ferring from surface to the ion exchange positions (Eq. (4)). (3) Ion
exchange reaction between H+ and Li+ (Eq. (5)). (4) H+ moving away According to the proposed lithium extraction mechanism of SLR,

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uptake (37 mg/g). The adsorption uptake almost remains stable with
the further increase of initial concentration. The increase of lithium
concentration can not only enhance contact opportunities between SLR
and Li+ in the solution, but also advance adsorption driving force. As a
result, Li+ in the solution can exchange continuously with H+ in the
SLR.
The experimental data was fitted with Freundlich (Eq. (8)) and
Langmuir (Eq. (9)) isotherms, where Qe and Qm are the equilibrium
adsorption uptake and the maximum adsorption uptake of SLR for li-
thium ions, respectively, mg/g; Ce is the equilibrium concentration of
lithium ions, mg/L; KF, n and KL are the constants of Freundlich and
Langmuir equation, respectively, which are related to adsorption force
and uptake of adsorbents. KF, n and KL can be calculated from the slope
and intercept of linear fitting, respectively.
1
InQe = × InCe + InKF
n (8)

Ce C 1 1
= e + ×
Qe Qm Qm KL (9)
Fig. 3 shows that correlation coefficient (R2) of Langmuir isotherm
reaches 0.9987, which is much greater than that of Freundlich iso-
therm. The maximum lithium adsorption uptake calculated by Lang-
muir isotherm is nearly consistent with the experimental data (26.18 vs
25.40 mg/g), indicating that the Langmuir isotherm is more suitable to
fit adsorption isotherm of SLR. It could be included that SLR has
homogeneous adsorption sites and adsorption process for lithium ions
conforms to a monolayer chemical adsorption (Chitrakar et al., 2014).
Fig. 7. XRD patterns of SLR before and after adsorption lithium ions.
3.2.2. Lithium ion adsorption rate curves of SLR and model fitting
0.5 g of SLR was dispersed in 0.1 L of the solutions (pH = 12.89) at
various temperatures (T = 30, 40, 50, 60, 70, 80 and 90 °C), respec-
tively. The results are presented in Fig. 4.
It is depicted that the equilibrium adsorption time is extremely
shortened with temperature increasing. As adsorption temperature in-
creases from 30 to 90 °C, the equilibrium adsorption time reduces from
120 h to 30 h. At the fixed temperature, adsorption time extension can
obviously increase adsorption uptake of SLR before equilibriums.
To illustrate adsorption process of SLR, the pseudo-first-order ki-
netic model (Eq. (10)) and pseudo-second-order kinetic model (Eq.
(11)) were used to fit the adsorption uptake data (Xiao et al., 2015;
Lawagon et al., 2016), where Qe and Qt are the equilibrium adsorption
uptake and adsorption uptake at time t, respectively, mg/g; k1 is the
rate constant of pseudo-first-order model,/h; k2 is the rate constant of
pseudo-second-order model, g/(mg h). Obtained parameters of the two
models are listed in Table 2.
In (Qe1 − Qt ) = InQe1 − K1 × t (10)
t 1 t
= +
+
Qt K2 × Qe22 Qe2 (11)
Fig. 8. XRD patterns of SLR before and after adsorption Li ion at different adsorption
temperature. From Table 2, the adsorption process of SLR could be well described
by the pseudo-second-order kinetic model, considering that Qe2 value is
lithium ion adsorption isotherm and adsorption rate were investigated relatively closer to the experimental data (Qe). The obtained correlation
to explain its adsorption process. coefficients are higher than 0.99. The adsorption rate constants k2 of
SLR at different adsorption temperature can be calculated according to
the intercept and slope. The values of k2 increases with the rise of ad-
3.2.1. Lithium ion adsorption isotherm of SLR and model fitting sorption temperature. It might be explained that lithium adsorption
Li+ solutions (pH = 12.95) with various initial lithium concentra- process of SLR is a chemical adsorption (ion-exchange) process, which
tions (~ 100, 200, 300, 400, 500 and 600 mg/L) were prepared by LiOH is an endothermic reaction.
and LiCl. 0.5 g of SLR was dispersed in 0.1 L of the solutions at 90 °C for
36 h. The result is shown in Fig. 2. 3.3. Adsorption properties of SLR for lithium ions
As is displayed in Fig.2, with initial lithium concentration increasing
from 100 mg/L to 400 mg/L, adsorption uptake of SLR increases from It is found that adsorption temperature and initial pH values of the
17.68 mg/g to 24.94 mg/g. And the equilibrium adsorption uptake of solution plays significant roles to lithium adsorption of SLR. Therefore,
SLR reaches 25.40 mg/g when the initial lithium concentration is in the following experiment, these conditions were investigated to
500 mg/L in the solution,which is 68.65% of its theoretical adsorption analyze adsorption performance of SLR.

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Fig. 9. SEM images of SLR before and after adsorption lithium ion.

Fig. 10. (a) lithium adsorption capacity and (b) Al3 + and Si4 + loss rate of SLR during five adsorption-desorption cycle experiments.

3.3.1. Effect of the initial pH values on adsorption uptake of SLR 3.4. Characterization analysis of SLR before and after adsorption lithium
Initial lithium concentration of the solution, adsorption temperature ions
and time are 100 mg/L, 90 °C and 36 h, respectively. 0.5 g of SLR was
submerged in 0.1 L of the solutions with various pH values. The results 3.4.1. XRD
are presented in Fig. 5. (T = 90 °C, C0 = 100 mg/L)
As is displayed, adsorption uptake of SLR merely increases from As is illustrated in Fig. 7, XRD pattern of SLR is identical to that of
0.28 mg/g to 1.58 mg/g when initial pH value advances from 6.97 to monoclinic HAlSi2O6 (JCPDS No. 79-1982), namely H2O·Al2O3·4SiO2,
9.04. With initial pH value further increasing from 10.94 to 12.89, without other apparent impurities after pretreatment. After lithium
adsorption uptake of SLR increases remarkably from 5.92 mg/g to adsorption at 90 °C, the principal crystalline phase of HAlSi2O6 converts
17.68 mg/g. Based on Eq. (5), under more alkaline conditions, released to spodumene LiAlSi2O6 (JCPDS No. 76-0921). The crystal structural
H+ during Li+–H+ ion exchange can be neutralized by OH- in the so- change of SLR after adsorption would be discussed in Fig. 8.
lution, which promotes lithium adsorption. And pH value after ad- Fig. 8 shows the change of characteristic peaks due to the insertion
sorption decreases because OH- in the solution is consumed. However, of lithium ions, which is reflected that adsorption uptake gets improved
Li+ ions could not be completely exchanged during the adsorption with the increase of temperature. Especially, when the temperature is
process because of existing mass transfer resistance and declining pH higher than 50 °C, the characteristic diffraction peaks of the spodumene
value in the solution, which inhibits the ion exchange progress. (LiAlSi2O6) are more obvious. It is clearly presented that after adsorp-
tion, the diffraction peaks at 2θ = 24.2°, 25.7° and 26.8° shifts to 22.7°,
25.5° and 26.6°, respectively, considering characteristic diffraction
3.3.2. Effect of temperature on adsorption uptake of SLR peaks of spodumene and the peaks become stronger. It could be ex-
To evaluate the effect of temperature on adsorption capacity of SLR, plained that releasing of H+ and insertion of Li+ into SLR results in
0.5 g of SLR was dispersed in 0.1 L of the solutions (pH = 12.89) at expansion of crystal space. SLR is basically consistent with the structure
various temperature (T = 30, 40, 50, 60, 70, 80 and 90 °C), respec- of LiAlSi2O6, which means SLR has good adsorption properties and
tively. The results are shown in Fig. 6. stability.
It is presented in Fig. 6, higher temperature can effectively improve
the lithium uptake and adsorption rate of SLR. As the temperature in- 3.4.2. SEM
creases from 30 to 60 °C, the equilibrium uptake of SLR rises to Fig. 9 shows SEM images of SLR (a) and Li+-reinserted sample (b).
9.62 mg/g, with adsorption uptake increased by nearly 122%. Equili- SLR exhibits a strip shape and there is no change in the surface mor-
brium uptake of SLR is promoted to 17.68 mg/g with the temperature phology before and after lithium adsorption, which could also prove its
further increasing to 90 °C. It is showed that temperature has a positive structure is stable.
effect on adsorption, which reveals adsorption process or the H+-Li+
exchange reaction is an endothermic reaction.
3.5. Cycle performance of SLR

The application stability of the SLR could been investigated by

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