Kinetics of Leaching Lithium
Kinetics of Leaching Lithium
Kinetics of Leaching Lithium
Hui GUO1,2,3, Hai-zhao YU1, An-an ZHOU1, Meng-hua LÜ1, Qiao WANG1, Ge KUANG2, Hai-dong WANG1
1. School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China;
2. Institute of Chemical Technologies, College of Chemical Engineering, Fuzhou University, Fuzhou 350108, China;
3. Department of Chemical Engineering, University of Louisiana at Lafayette, Lafayette 70504, United States
Received 19 January 2018; accepted 24 October 2018
Abstract: An enhanced leaching of Li from α-spodumene was carried out using a mixture of hydrofluoric and sulfuric acid
(HF/H2SO4) as the medium. Based on the optimized leaching conditions, the leaching kinetics of Li was investigated in an
ore/HF/H2SO4 ratio of 1:3:2 g:mL:mL with leaching temperature ranging from 50 to 100 °C. The results indicate that the leaching
kinetics of Li fitted well with a model based on the shrinking core model. In addition, the leaching rate of Li was controlled by
chemical reactions and diffusion through the product layers. The apparent activation energy Ea was calculated to be 32.68 kJ/mol.
Solid films were formed because of the generation of insoluble products such as cryolithionite (Na3Li2Al2F12), cryolite (Na3AlF6),
calcium fluoride (CaF2), potassium cryolite (K2AlF5), aluminum fluoride (AlF3), and fluorosilicates (Na2SiF6 or KNaSiF6).
Furthermore, the effects of the ore/HF ratio and leaching temperature on the leaching behavior of Li, Al and Si were investigated.
The results indicate that the ore/HF ratio and leaching temperature could clearly affect the distribution of HF molecules on the
leaching of Li, Al and Si, which are important for the selective leaching of Li over Al and Si with this fluorine-based chemical
method.
Key words: α-spodumene; lithium extraction; leaching kinetics; hydrofluoric acid; fluorine-based chemical method
Foundation item: Project (51474237) supported by the National Natural Science Foundation of China
Corresponding author: Hai-dong WANG; Tel: +86-731-88879217; E-mail: [email protected]
DOI: 10.1016/S1003-6326(19)64950-2
408 Hui GUO, et al/Trans. Nonferrous Met. Soc. China 29(2019) 407−415
were also investigated for different ore/HF ratios continuously with 1:1 H2SO4 and deionized water. Once
(1:1−1:3 g/mL) and leaching temperatures (50−100 °C). the desired temperature was reached, the HF was
The kinetics investigation aims to reveal the mechanism immediately added while still stirring the solution for a
of α-spodumene involved in HF/H2SO4, which is certain leaching time. Then, water-leaching was
important for the selective leaching of Li over Al and Si subsequently performed to stop the reaction and obtain
with this fluorine-based chemical method. kinetics data for different leaching time. The obtained
lixivium and insoluble residues were analyzed separately
2 Experimental to reveal the leaching behavior and further determine the
leaching kinetics of lithium.
2.1 Materials and chemicals
The concentrate α-spodumene ore was sampled 2.3 Analytical methods
from Greenbushes, Australia, and contained 5 wt.% Li2O. L was introduced to determine the leaching
Analyses of other major elements were carried out by efficiency of lithium, which was calculated using Eq. (1).
X-ray fluorescence (XRF) and the results are listed in Similarly, leaching efficiencies of silicon and aluminum
Table 1. The ore sample was first ground and then sieved were also determined. In addition, the percentage of
with a particle size <75 µm to carry out the leaching insoluble residues (R) was introduced using Eq. (2) to
experiments. evaluate the generation of the insoluble solid phase:
Qm V
Table 1 Elemental analysis result of concentrate ore of L 100% (1)
106 more w
α-spodumene (wt.%)
Si Al Li O Na K Ca Fe mres
R 100% (2)
32.63 11.43 2.56 41.04 0.35 0.68 0.45 0.54 more
Fig. 2 Effect of different factors on leaching of lithium from α-spodumene using mixed acid HF/H2SO4: (a) Ratio of HF/ore;
(b) Leaching temperature; (c) Ratio of H2SO4/ore; (d) Leaching time
410 Hui GUO, et al/Trans. Nonferrous Met. Soc. China 29(2019) 407−415
molecules to attack Li—O, Al—O or Si—O. Then, the
incongruent leaching of Li and Al over Si takes place,
which is important for the selective leaching of Li and
subsequent purification of lixivium.
However, more Li could be converted into lixivium at Fig. 4 Effect of leaching temperature on leaching of Li, Al and
higher temperatures. The selective leaching of Li and Al Si (ore/HF/H2SO4 ratio 1:3:2 (g/mL/mL), stirred at 150 r/min):
over Si is enhanced at 100 °C compared to 75 °C, which (a) 100 °C; (b) 75 °C; (c) 50 °C
can be attributed to the increasing generation of K2SiF6
or Na2SiF6, resulting in a decrease in retention of Si in 3.3 Analysis of leaching under optimal conditions
liquid. 3.3.1 Leaching of lithium under optimal conditions
To briefly summarize, the ore/HF ratio and leaching To further understand the leaching behavior,
temperature clearly affect the leaching behavior of Li, Al leaching experiments under optimal conditions were
and Si because of the effects on the distribution of HF conducted at 100 °C in the ore/HF/H2SO4 ratio of
Hui GUO, et al/Trans. Nonferrous Met. Soc. China 29(2019) 407−415 411
1:3:2 (g/mL/mL) for different leaching time. The results
in Fig. 5 indicate that the leaching rate of lithium
increases with the leaching time; 96% of Li and <10% of
R are obtained.
Fig. 7 SEM−EDS images of residues under optimal conditions for different leaching times: (a, b, c) Ore sample; (d, e) 15 min;
(f, g, h) 30 min; (i) 180 min
Fig. 9 Protonation of bond lattices by introduced H+ (M represents Si, Al or other metal elements)
Fig. 12 Kinetics of lithium leaching from α-spodumene in HF/H2SO4: (a) Kinetics at different temperatures; (b) Particle size
distribution; (c) Fitting results of leaching kinetics data; (d) Arrhenius fitting results