CISAK 2015 – Paper Number (Will be replaced with paper registration or alphabetical number if the manuscript is accepted)

Process for the Recovery of Lithium Ion from

Aqueous Solution and Seawater
Gregorius R. Harvianto1, and Chang-Sik Ju2
1
School of Chemical Engineering, Yeungnam University
Dae-dong 214-1, Gyeongsan 712-749, Rep. of Korea
2
Department of Chemical Engineering, Pukyong National University
Busan 608-739, Rep. of Korea
1,*grharvianto@ynu.ac.kr

2csju@pknu.ac.kr

Abstract. Lithium ion is predominantly used as raw material of lithium battery. Seawater is expected as abundant resources of lithium
ion. In the development of a lithium ion recovery process from seawater, a series of experimental research was conducted. In this
work, lithium ion was effectively extracted by TTA-TOPO in kerosene within 80 minutes. Extraction efficiency severely influenced
by stoichiometric parameters. Among the stoichiometric parameters, volume ratio [A/E] was the most influential parameter. In high
volume ratio, lithium ion widely spreads in larger medium. Thus, TTA has difficulty to collide and combine with lithium ion in
aqueous solution for the extraction. In order to make scale-up design for continuous operation, kinetic study including an order of
reaction, extraction rate constant, and activation energy were performed in this work. This study proposed the rate of solvent
extraction −𝑟𝐿𝑖 = 0.460512 mmol/min[𝐿𝑖]7.6385 , with the activation energy was 42.285 J/mmole. After extraction process, lithium
ion could be easily stripped from the extraction solution by using acidic solutions. Stripping efficiency decreased with a pH of acidic
solutions, and the kind of acid did not affect on the stripping efficiency. Even though magnesium ion was precipitated by NH4OH
prior to solvent extraction process, 64% of lithium ion could be extracted from seawater by this solvent extraction process.

Keywords: lithium; solvent extraction;recovery; kinetic study; seawater.

A. INTRODUCTION TTA is a chelating agent which includes one type of β-

Lithium ion is primarily used as raw material of lithium
battery. A high energy fuel with the high temperature and fast
combustion character is made from lithium compounds [1]. The
average concentrations of lithium in seawater is 0.17 mg/L and
the full amount of seawater is estimated to be 1.36 × 1021 L,
therefore the total amount of seawater could reach more than
231.2 billion tonnes [2]. Seawater can be applied directly or after
concentrated. And brine water has a lithium concentration of
approximately 10 ppm [3]. Concentrated seawater discharged
from the desalination facilities can be a great resource of metals
that can be recovered. In recent years, a number of desalination
facilities have been constructed. Therefore, the extractions of
metal ions from concentrated seawater become important
challenges that must be resolved.
The solvent extraction method widely used because the
relatively quantitative result can be obtained with its simple
procedure [4]. A combination of β-diketone and neutral ligand is
an effective extractant for lithium ion extraction. Many
researchers have studied metal extraction using various
extractants such as thenoyltrifluoroacetone (TTA) and
trioctylphospone oxide (TOPO) [4, 5].
diketone derivatives in which R1 and R2 were substituted with 2-
thenoyl and CF3. TTA is known to create a synergistic effect
with TOPO that can increase the extraction efficiencies of
metallic ions as a form of adduct or ion-pair [6]. In the
development of lithium extraction using TTA and TOPO, Kim et
al. reported Li(TTA).(TOPO)2 was more stable than
Li(TTA)(TOPO) for extracting lithium into m-xylene [4]. Lee et
al. reported kerosene was the best organic solvents when used 2
moles of TOPO [7].
Stripping is an important operation of unloading the solute
from the extraction solution by extracting the solute back into a
phase like feed. Stripping also recovers the extraction solution
for recycling back to the extraction cascade [8]. There were
many researchers reported stripping metal from extraction
solution. Weiwei et al. studied extraction and stripping of Yb
(III) from heptane-Cyanex ®923 by using HCl, HNO3, H2SO4
[9]. The same acidic solutions were also used to strip cadmium
[10] from many types of organic solution.
To the best of our knowledge, there was no any research on
lithium ion stripping and recycling extraction solution. Thus, in
this work, solvent extraction technique is used for extracting
lithium ion in aqueous solution by using the combination of the
TTA and TOPO in kerosene. The specific objectives of this
CISAK 2015 – Paper Number (Will be replaced with paper registration or alphabetical number if the manuscript is accepted)
study were: (i) to study the equilibrium and kinetic of solvent
extraction of lithium ion, and (ii) to study the stripping of
lithium ion after solvent extraction process. Lastly, the results
were applied to the seawater and concentrated seawater.
B. EXPERIMENTAL
1. Reagents and Instruments
All the reagents were analytical grade. The distilled water
was further purified by Milipore Milli-Q water system. Solvent
extraction apparatus was batch type and the same as our
previous work [11]. The aqueous solution of lithium ion was
prepared by diluting lithium standard solution of 1000 µg/ml
(Aldrich Co.). NH4OH (Junsei Co.) was used for pH adjustment
of the aqueous solutions. For extraction solution, TTA (Aldrich
Co.) as β-diketone and TOPO (Aldrich Co.) as a neutral ligand
were dissolved in Kerosene (Aldrich Co.). HCl (Junsei Co.),
H2SO4 (PFP Co.), and H3PO4 (Junsei Co.) were selected for
acidic solution. Flame Atomic Absorption Spectroscopy (AA-
7000, Shimadzu), an instrument for measuring the absorbance of
metallic ions, was used for determining the concentration of
lithium ion.
2. Experimental Procedure
a. Solvent extraction
TTA and TOPO were added in kerosene to make an
extraction solution. The resulting mixture of these extractants
and kerosene was used to extract lithium ion in aqueous solution
without any pretreatment. Batch solvent extraction was
performed in the extraction chamber to extract lithium ion from
aqueous solution. pH of aqueous solution was adjusted using
NH4OH at 10.6.
A necessary volume of aqueous and extraction solution were
stirred for various extraction times. After the extraction is
completed, the mixture was allowed in a separatory funnel to
settle for 1 hour and then the aqueous solution was separated
from the extraction solution. 10 ml of aqueous solution was
sampled for AA analysis. In case of extraction of lithium ion
from seawater, pretreatment to precipitate magnesium ion was
performed before solvent extraction, since the magnesium ion
significantly decrease the extraction efficiency of lithium ion
using TTA and TOPO [11]. NH4OH was added to increase the
pH of seawater to 11, and the precipitant was removed by using
membrane filtration.
b. Stripping of lithium ion from extraction solution
After extraction, lithium ion was stripped from the extraction
solution by acidic solution. pH of the acidic solution was
adjusted in the range 2 - 4. The same volume of extraction
solution and acidic solution were mixed for 1 hour at the
ambient temperature in the batch chamber. And two phases were
separated in a separatory funnel. 10 ml of acidic solution that
containing lithium ion was sampled for AA analysis.
C. RESULTS AND DISCUSSION
1. Equilibrium extraction time and effect of volume ratio
For the establishment of equilibrium extraction time, a
kinetic study on the solvent extraction of lithium ion using TTA
and TOPO was performed with different volume ratio. An initial
concentration of 10 ppm was used in this work, because brine
water has amount of the lithium in the range of 10 ppm [3].
100
80
Extraction Efficiency (%)
60
40
A/E : 1
20 A/E : 2.5
A/E : 5
A/E : 10
0
0 20 40 60 80 100 120 140 160 180
Extraction Time (minute)
Fig. 1. Time profiles of extraction efficiency of lithium ion with
different volume ratio. [Li]o : 10.00 ppm, [TTA] : 0.02 M,
[TOPO] : 0.04 M, pH : 10.60.
Fig. 1 shows the time profile of extraction efficiency of
lithium ion at different volume ratios. As shown in Fig. 1,
equilibrium extraction efficiencies decreased with volume ratio.
However, equilibrium extraction time increased by volume ratio.
From the result of Fig. 1, variation of equilibrium extraction
time with the volume ratio could be obtained. It also shows the
equilibrium extraction time increases with the volume ratio up to
5, and then reaches a constant value of 80 minutes. Therefore,
further extractions were preformed at the extraction time of 80
minutes.
The volume ratio of aqueous solution to extraction solution
[A/E] is an important factor in the scale up of solvent extraction
process. Fig. 1 also shows the effect of volume ratio on the
equilibrium extraction efficiency. Extraction efficiency
monotonously decreases with volume ratio. The difference in
extraction efficiency might be explained as follows. In case of
the higher volume ratio at the same molar ratio, that means
lower lithium ion concentration, lithium ion widely spreads in
larger medium. Thus, TTA has difficulty to collide and combine
with lithium ion in aqueous solution for the extraction.
2. Kinetic Study of Solvent Extraction of Lithium
In order to make scale-up design for continuous operation,
kinetic study, including an order of reaction, extraction rate
constant, and activation energy were executed in this work. The
CISAK 2015 – Paper Number (Will be replaced with paper registration or alphabetical number if the manuscript is accepted)
value of the rate constant and activation energy can be obtained
in a volume ratio of aqueous solution to extraction solution was
adjusted at 5:1. The suitable condition that previously reported
was used in this work. The rate of this solvent extraction is
represented by Eq. (1),
−𝑟𝐿𝑖 = 𝑘[𝐿𝑖]𝑎 [𝑇𝑇𝐴]𝑏 (1)
where k is the extraction rate constant, [Li] is the concentration
of lithium as a function of time, [TTA] b is the concentration of
TTA as a function of time, a and b as orders of reaction. In this
work, [TTA] b can be neglected because the constant TTA
concentration is maintained in the extraction solution during the
solvent extraction process.
0,2
0,0
-0,2
ln k
-0,4
-0,6
-0,8
-1,0
0,00310 0,00315 0,00320 0,00325 0,00330
1/T (K-1)
Fig. 2. Plot of ln k versus 1/T for solvent extraction of lithium
ion. [TTA] : 0.02 M, [TOPO] : 0.04 M, pH : 10.60, volume ratio
[A/E] : 5.
To study the order of this extraction (a), differential method
that provided by Hill [12] was used in this work. The order of
reaction (a) was 7.6385. Svante Arrhenius showed that the
relationship between temperature and the rate constant for a
reaction obeys the following equation [13]
𝐸𝑎
𝑘 = 𝑍 𝑒 −𝑅𝑇 (2)
In Eq. (2), k is the rate constant for the reaction, Z is a
proportionality constant that varies from one reaction to
another, Ea is the activation energy for the reaction, R is the ideal
gas constant in J/mole-K, and T is the temperature in K.
The Arrhenius equation can be used to determine the activation
energy for a reaction. By taking the natural logarithm of both
sides of the equation and rearrange this equation to fit the
equation for a straight line.
𝐸𝑎 1
𝑙𝑛 𝑘 = − [ ] + 𝑙𝑛 𝑍 (3)
𝑅 𝑇
According to Eq. (3), a plot of ln k versus 1/T should give a
straight line with a slope of -Ea/R, as shown in the Fig. 2. After
calculating by using those equations, this work proposed the rate
of solvent extraction −𝑟𝐿𝑖 = 0.460512 mmol/min[𝐿𝑖]7.6385 ,
with the activation energy was 42.285 J/mmole.
3. Stripping of Lithium Ion
Acidic solutions were used to strip lithium ion from
extraction solution after solvent extraction process. HCl, H 2SO4,
and H3PO4 had been chosen as acids because of their different
characteristics. That is, HCl, H2SO4, and H3PO4 are monoprotic,
diprotic and triprotic acid, respectively.
For examining the effect of pH and kind of acids on the
stripping efficiency, acidic solutions with a pH range of 2.0 - 4.0
were made of each acid. And for the preparation of extraction
solution to be stripped, lithium extraction was performed at a
volume ratio of 1.0 and initial lithium concentration of 1 ppm.
The concentration of TTA in extraction solution was 0.02 M.
100
80
Recovery (%)
60
40
HCl
20 H2SO4
H3PO4
0
1.5 2.0 2.5 3.0 3.5 4.0 4.5
pH
0,00335
Fig. 3. Effect of pH and acids on the stripping efficiency of
lithium ion from extraction solution.
As shown in Fig. 3, acidic solutions effectively stripped
lithium ion from extraction solution at low pH, and then the
stripping efficiency seriously decreased with pH. The stripping
efficiency up to pH 3.0 maintained more than 90%. However,
the kind of acids did not significantly affect on the stripping
efficiency. These phenomena could be expected by the
mechanism of synergistic bonding between lithium ion and
TTA-TOPO. TTA-TOPO has a good synergistic combination
with lithium ion in alkaline condition. However, that
combination easily break down in acidic condition.
4. Application to Seawater
For the application of solvent extraction process to seawater,
two types of seawater were examined. One was the concentrated
seawater from desalination process, and the other was seawater.
0.02 M TTA and 0.04 M TOPO in kerosene was used as
extraction solution. Time profiles of extraction efficiency at
different volume ratios were examined, and shown in Fig. 4.
As shown in Fig. 4, the equilibrium extraction efficiency
decreased and time to get equilibrium increased with volume
ratio. This general trend is similar to Fig. 4. However, the value
of the extraction efficiency is much lower than that from
aqueous solution. In case of concentrated seawater, the
efficiency is lower than that of seawater. The lower value might
be caused by the other cations in seawater.
Seawater contains various kinds of cation, and concentration
of these cations in the concentrated seawater is higher than
seawater. Even though magnesium ion was precipitated by
CISAK 2015 – Paper Number (Will be replaced with paper registration or alphabetical number if the manuscript is accepted)
pretreatment prior to extraction, the concentration of some
cation, such as as Na+, K+, and Ca2+, still remained at a high
level. These cations might decrease the extraction efficiency
dramatically. The effect of these ions on the extraction efficiency
of lithium ion was reported in our previous work [11].
Nevertheless, 64% of lithium ion could be extracted from
seawater by this solvent extraction process.
100
80
Extraction Efficiency (%)
60
40
20
0
0 20 40 60
Extraction Time (minute)
Fig. 4. Time profiles of lithium extraction efficiency from
seawater and concentrated seawater at different volume ratio.
[TTA] : 0.02 M, [TOPO] : 0.04 M, pH : 10.60.
D. CONCLUSIONS
For the development of a lithium ion recovery process from
seawater, a series of experimental researches were performed
and following results could be obtained.
1. Lithium ion in aqueous solution was effectively extracted by
TTA-TOPO in kerosene within 80 minutes. Extraction
efficiency severely influenced by stoichiometric parameters.
Among the stoichiometric parameters, volume ratio [A/E]
was the most influential parameter.
2. This work proposed the rate of solvent extraction −𝑟𝐿𝑖 =
0.460512 mmol/min[𝐿𝑖]7.6385 , with the activation energy
was 42.285 J/mmole.
3. After extraction, lithium ion could be easily stripped from
the extraction solution by acidic solutions. Stripping
efficiency decreased with a pH of acidic solutions and the
kind of acid did not affect on the stripping efficiency.
4. Even though magnesium ion was precipitated by NH4OH
prior to solvent extraction process, 64% of lithium ion could
be extracted from seawater by this solvent extraction
process.
REFERENCES
[1] B. Scrosati and J. Garche, “Lithium batteries : status,
prospects and future,” Journal of Power Sources, vol. 195,
pp. 2419-2430, 2010.
[2] J. C. Lee, “Current Status in The Recovery of Metal Value
from Seawater,” The Korean Society for Geosystem
Engineering, vol. 42(5), pp. 513-522, 2005.
A/E : 1 (SW) [3] I. L. Chang, Y. J. Lin, J. Y. Shiu and J. R. Lin, “Process for
A/E : 1 (CW)
A/E : 2.5 (SW) producing lithium concentrate from brine or seawater,”
A/E : 2.5 (CW) U.S. Patent 6764584, 2004.
A/E : 5 (SW)
A/E : 5 (CW)
[4] Y. S. Kim, G. I. Choi and J. M. Choi, “Chemical
A/E : 10 (SW) equilibrium and synergism for solvent extraction of trace
A/E : 10 (CW)
lithium with thenoyl- trifluoroacetone in the presence of
trioctylphosphine oxide,” Bull. Korean Chem. Soc., vol.
24(10), pp. 1495-1500, 2003.
[5] B. Bansal, X. D. Chen and M. M. Hossain, “Transport of
lithium through a supported liquid membrane of LIX54
and TOPO in kerosene,” Chemical Engineering and
Processing, vol. 44, pp. 1327–1336, 2005.
[6] Y. S. Kim, I. G. Choi, J. M Choi and C. W. Lee,
“Chemical equilibrium and synergism for solvent
extraction of trace lithium with thenoyl- trifluoroacetone in
the presence of trioctylphosphine oxide,” Bull. Korean
Chem. Soc., vol. 24(10), pp. 1495-1500, 2003.
[7] J. K. Lee, S. G. Jeong, S. J. Koo, S. Y. Kim and C. S. Ju,
80 100 “Solvent extraction of lithium ion in aqueous solution
using TTA and TOPO,” Korean Chem. Eng. Res., vol.
51(1), pp. 53-57, 2013.
[8] V. V. Brunt, Extraction in The Engineering Handbook
Second Edition, Dorf, R. C., Ed. Boca Raton, U.S: CRC
Press. 2004.
[9] W. Weiwei, W. Xianglan, M. Shulan, L. Hongfei and L.
Deqian, “Extraction and stripping of ytterbium (iii) from
H2SO4 Medium by cyanex 923,” Journal of Rare Earths,
vol. 24, pp. 685-689, 2006.
[10] M. Touati, M. Benna-Zayani, N. Kbir-Ariguib, M.
Trabelsi-Ayadi, A. Buch, J. L. Grossiord, D. Pareau and
M. Stambouli, “Extraction of cadmium (ii) from phosporic
acid media using the di (2-ethylhexyl) dithiophosporic acid
(D2EHDTPA) : Feasibility of a continuous extraction-
stripping process,” Hydrometallurgy, vol. 95, pp. 135-140,
2009.
[11] G. R. Harvianto, S. G. Jeong and C. S. Ju, “The effect of
dominant ions on solvent extraction of lithium ion from
aqueous solution,” Korean J. Chem Eng., vol. 31(5), pp.
828-833, 2014.
[12] Hill, C. G., An Introduction to Chemical Engineering
Kinetics & Reactor Design, New York, US: John Wiley
& Sons Inc., 1977.
[13] O. Levenspiel, Chemical Reaction Engineering, New
York, US: John Wiley & Sons Inc., 1999.