Hydrometallurgy 162 (2016) 7178

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Hydrometallurgy

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Lithium Extraction with a Synergistic System of Dioctyl Phthalate and

Tributyl Phosphate in Kerosene and FeCl3
Lianmin Ji a,b,c, Yuehua Hu a,, Lijuan Li b,c,, Dong Shi b,c, Jinfeng Li d, Feng Nie b,c, Fugen Song b,c,
Zhongmin Zeng b,c, Wei Sun a, Zhiqi Liu b,c
a
School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, Hunan, China
b
Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008, Qinghai, China
c
Key Laboratory of Comprehensive and Highly Efcient Utilization of Salt Lake Resources, Chinese Academy of Sciences
d
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 200032, Shanghai, China

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

Article history: Innovative applications of dioctyl phthalate (DOP) as a synergist for the extraction of lithium chloride from sat-
Received 10 October 2015 urated MgCl2 solutions were investigated using tributyl phosphate (TBP) as the extractant and FeCl3 as the co-
Received in revised form 17 February 2016 extractant. The effects of solvent concentration, HCl concentration, phase ratio, Fe/Li molar ratio, and other factors
Accepted 25 February 2016
on Li extraction were analyzed. The preliminary results demonstrated that a single-stage Li extraction efciency
Available online 2 March 2016
of N 90% was obtained with a low TBP concentration of 40% (V/V) and 20% (V/V) DOP without phase separation
Keywords:
problems. A Li extraction efciency of 99.5% was obtained via a three-stage simulation of countercurrent extrac-
Lithium chloride tion. A study on the mechanism revealed that TBP and DOP molecules associated with the Fe-Li complex through
dioctyl phthalate hydrogen bonding. Compared with the traditional TBPkerosene system, the proposed system prevented the for-
tributyl phosphate mation of the third phase and signicantly reduced the TBP concentration, resulting in less severe causticity to
solvent extraction the equipment and reduced aqueous loss of TBP during the extraction process.
synergist 2016 Elsevier B.V. All rights reserved.

1. Introduction
Lithium is considered an important metal for the energy industry
and is the lightest active metal, exhibiting wide industrial applications
in lithium batteries (Jung et al., 2012; Meshram et al., 2014; Zhu et al.,
2014) and AlLi alloys (Prasad et al., 2013). Li is also an essential raw
source of Li isotopes (Li6 and Li7) with extensive uses (Qin et al., 2011;
Lind et al., 2013; Hoshino, 2013; Ryu et al., 2014). Therefore, Li was
regarded as the metal of the future by Mahi et al. (1986). Most Li de-
posits naturally exist in brines, pegmatites, and sedimentary rocks. Peiro
et al. (2013) indicated that nearly 60% of the global Li production in
2011 was still obtained from brines. Among the various techniques of
producing Li, solvent extraction has been extensively developed to sep-
arate Li quantitatively from salt brines with a high Mg/Li ratio because of
the techniques high selectivity and easy accessibility.
The use of tributyl phosphate (TBP) as an extractant and (FeCl4)- as a
co-extractant was demonstrated as the most feasible method of recov-
ering Li ion from salt lake brines (Tong et al., 1987; Sun et al., 2011;
Foundation item: Project (U1407203) supported by Qaidam Salt Lake Chemical Joint
Scientic Research Funds; Project (KGZD-EW-604) supported by Chinese Academy of
Sciences; Project (2014-GX-C10) supported by QingHai Science & Technology
Department.
Corresponding author.
Correspondence to: Lianmin Ji, Qinghai Institute of Salt Lakes, Chinese Academy of
Sciences, Xining 810008, Qinghai, China
Zhou et al., 2012; Zhou et al., 2013). However, high concentrations of
TBP cause severe causticity to equipment and signicant loss in the
aqueous solution during extraction, which may result in considerable
reduction of extracted lithium. Tong et al. (1987) reported that a third
phase appeared when the TBP concentration was reduced to less than
75% (V/V). Sun et al. (2011) demonstrated that the third phase disap-
peared when the TBP concentration in these systems continuously in-
creased above 46% (V/V). A considerable portion of the TBP was used
as a synergist.
Using organic esters as modiers can effectively alleviate phase sep-
aration problems and simultaneously increase the selectivity of Cu/Fe
and the stability of oxime, the applications of which have become in-
creasingly advanced in the process of copper extraction (Kordosky,
2002; Lan, 2004; Kumar et al., 2013; Ochromowicz and Chmielewski,
2013). Esters have also been used as synergistic extractants in Li extrac-
tion. Gao et al. (2011) and Li et al. (2014) used the TBP-butyl-acetate
(BA)FeCl3 synergistic extraction system to extract Li. Polymer inclu-
sion membranes as base polymers combined with different plasticizers
and modiers (i.e., 2-nitrophenyloctylether (NPOE), dioctyl phthalate
(DOP), and 1-tetradecanol) have been evaluated for selective extraction
and recovery of numerous cations and anions (Almeida et al., 2012,
2015; Baba et al., 2015). In the majority of cases, the plasticizer sepa-
rates the polymer chains to reduce membrane rigidity, thereby improv-
ing the diffusion and solubility of the extracted species in the liquid-
phase membrane (Fontas et al., 2007; Pereira et al., 2009).

http://dx.doi.org/10.1016/j.hydromet.2016.02.018
0304-386X/ 2016 Elsevier B.V. All rights reserved.
72 L. Ji et al. / Hydrometallurgy 162 (2016) 7178

DOP, acetyl tributyl citrate (ATBC), and tri-n-butyl citrate (TBC) are
widely used plasticizers with low to negligible solubility. The present
study systematically investigated the extraction of Li from salt lake
brine by adding these ester plasticizers into the TBP-sulfonated
kerosene-FeCl3 traditional extraction system. The effects of several
factors on Li extraction with the TBP/DOPsulfonated keroseneFeCl3
extraction system were determined. An extraction mechanism was
proposed based on the slope analysis of extraction data and infrared
(IR) spectra.

2. Experimental

2.1. Reagents and instrumentation

Lithium chloride monohydrate (N97% purity; Sinopharm Chemical

Reagent Co., Shanghai, China), magnesium chloride hexahydrate
(N 98% purity; Tianjin Kemiou Chemical Reagent Co., Tianjin, China),
iron chloride hexahydrate (N 99% purity; Tianjin Baishi Chemical, Ltd.,
Tianjin, China), and hydrochloric acid (G.R.) were used. The ion concen-
trations in brine were as follows: Li+ (2.604 gL-1), Mg2+ (108.2 gL-1),
Na+ (2.20 gL-1), and K+ (0.486 gL-1). The plasticizers included dioctyl
phthalate (DOP) (N99% purity; Tianjin Yongda Chemical Reagent Co.,
Tianjin, China), acetyl tributyl citrate (ATBC) (98%; Klamar, Shanghai,
China), and tri-n-butyl citrate (TBC) (N 99% purity; Sinopharm Chemical
Reagent Co., Shanghai, China). TBP (N 98.5% purity; Tianjin Yongda
Chemical Reagent Co., Tianjin, China) and kerosene (260#; Beijing
Sinopec Chemical Reagent Co., Beijing, China) were also used.
The instruments used included the following: a strong shaker (SR-2
DW; TAITEC), a centrifuge (TDL-40B-W; Shanghai Anting Scientic
Instrument Factory), inductively coupled plasmaatomic emission
spectrometry (ICP-AES) (ICAP6500 DUO; America Thermo Scientic,
USA), and a Fourier Transform Infrared Spectroscopy (FTIR) spectro-
photometer (670; Thermo Nicolet Corporation, Madison, USA).
2.2. Extraction experiments
Li extraction was conducted by mixing different volumes of aqueous
and organic phases in a 25 mL funnel with a PTFE stopcock. The mixture
was mechanically shaken for 6 min to obtain equilibrium. Then, the or-
ganic phases were centrifuged. Approximately 5 mL of the organic
phases were stripped with 10 mL 6 molL1 HCl. The aliquots of the
Fig. 2. Effect of TBP/DOP ratio on Li extraction with an aqueous solution at an O/A ratio
of 2/1. The total volume concentration of TBP and DOP is 60%, initial [Li+]=1.861 g/L,
[Fe/Li]=1.3, CHCl =0.05 mol/L, CMgCl2 =4.8 mol/L, and t=6 min. Li extraction efciency
(), Li/Mg separation factor LiMg ().
aqueous phases were analyzed by ICPAES to determine the concentra-
tions of Li and Mg ions.
2.3. Analytical method
The hydrogen ion concentration in the aqueous phase was adjusted
with hydrochloric acid. The concentration of HCl in the aqueous phases
was determined using a 0.03 molL1 NaOH standard solution. The Li+
concentrations in the brine and the rafnate were analyzed by ICPAES
and were diluted 1000-fold and 250-fold, respectively. The concentra-
tions of Li+, Mg2+, Na+, K+, Ca2+, SO2-
4 and Fe
3+
in the organic phases
were also analyzed by ICPAES and diluted 50-fold.
3. Results and Discussion
3.1. Effect of various factors on single-stage Li extraction
3.1.1. Effect of solvent concentration
To determine the effect of solvent concentration on Li extraction ef-
ciency, experiments were conducted by changing the synergist (DOP,
ATBC, and TBC) and the extractant (TBP) at a volume ratio of 1:1
(synergist:extractant). The solvent volume concentration ranged from
30% to 80% (diluted in sulfonated kerosene). For example, a system
with 30% solvent contained 15% synergist and 15% TBP by volume. As
shown in Fig. 1, the extraction efciency of Li rapidly increased as the
solvent concentration increased. However, the magnitude of increase
was reduced at solvent concentrations greater than 60%. A third phase
was formed at a solvent concentration of 50% and was composed of
25% TBP and 25% synergist. Given the same solvent concentration, the
Li extraction efciencies with the following synergists were as follows
(in decreasing order): DOP N ATBC N TBC. The highest Li extraction

Table 1
Distribution coefcient of Li (DLi) at different TBP/DOP volume concentration
ratios.

TBP/DOP volume concentration ratio DLi

5/1 4.1
4/1 4.2
3/1 4.4
2/1 4.6
1/1 3.4
1/2 1.4
Fig. 1. Effect of synergist/TBP (1:1) concentration on Li extraction efciency with aqueous
1/3 0.6
solution at an O/A ratio of 2/1. The synergist is DOP, ATBC, or TBC. DOP +TBP (),
1/4 0.4
ATBC +TBP (), TBC+TBP (). Initial [Li+] = 1.861 g/L, [Fe/Li] = 1.3, CHCl =
1/5 0.3
0.05 mol/L, CMgCl2 = 4.8 mol/L, and t = 6 min.
 L. Ji et al. / Hydrometallurgy 162 (2016) 7178 73

Table 2
Effect of initial Fe(III) concentration on the extraction of Li, Mg, and Fe with DOP (0.5 mol/L), A/O=1:1. The Fe/Li molar ratio in the aqueous solution is 1.3.

[Fe3+]O 10-3 [Li+]O 10-3 [Mg2+]O 10-4

No. [Fe3+]aq, init (mol/L) DFe DLi DMg
(mol/L) (mol/L) (mol/L)

1 0.20 0.6790 0. 1730 0.9364 0.003408 0.001128 1.9510-5

2 0.40 1.596 0. 6300 1.864 0.004005 0.002053 3.8810-5
3 0.50 1.794 0. 718 1.972 0.003601 0.001870 4.1110-5
4 0.60 2.756 1.216 3.130 0.004614 0.002642 6.5210-5
5 0.80 3.767 1.870 3.912 0.004731 0.003048 8.1510-5
6 1.0 9.531 5.257 12.51 0.009623 0.006881 2.6110-4
7 1.7 8.124 6.586 5.949 0.004802 0.005061 1.2410-4
8 2.6 88.49 73.82 55.96 0.03523 0.03833 1.1710-3
9 3.3 159.0 141.7 86.03 0.05063 0.05911 1.8010-3
10 3.5 189.8 174.0 78.30 0.05734 0.06911 1.6310-3

efciency exhibited by the system with DOP was attributed to the con- only prevented the formation of the third phase but also improved the
jugation effect of benzene in DOP. This effect contributed to the ease of separation factor of Li over Mg.
incorporating the Li complex via hydrogen bonding and facilitated
C=O bonding to benzene, thereby increasing the solubility and extrac- 3.1.3. Effect of DOP on metals
tion efciency of the Li complex. Therefore, using DOP as a synergist re- The coordination of DOP with Li+, Mg2+, and FeCl-4 ions in the pres-
sulted in the most efcient Li extraction. ence of FeCl3 was evaluated. An organic phase was used, consisting of
20% DOP (0.50 mol/L) and 80% sulfonated kerosene, and an aqueous so-
lution composed of saturated magnesium chloride with HCl (0.05 mol/
3.1.2. Effect of TBP/DOP volume concentration ratio L) and Fe (0.2 to 1.0 mol/L at an Fe/Li molar ratio of 1.3) was used. The
The effect of the TBP/DOP ratio on Li extraction efciency was eval- solvent and the aqueous solution (O/A=1/1) were allowed to contact
uated by changing the TBP/DOP ratio (V/V) from 1/5 to 5/1 at a solvent for 10 min and then were set aside for 30 min. The two phases were
concentration of 60% TBP/DOP. As shown in Fig. 2, the Li extraction ef- then separated, and the loaded organic phase after centrifugation was
ciency sharply increased as the TBP/DOP ratio increased, corresponding stripped with 0.05 M HCl. Aliquots of the aqueous phase were analyzed
to an increase in the TBP volume concentration. The Li extraction by ICPAES to determine the Fe, Li, and Mg levels.
efciency reached the maximum value at a TBP/DOP ratio of 1/1. No im- The characteristics of the extraction reaction in this system are pre-
provement was observed at TBP/DOP ratios higher than 1/1. As shown sented as follows:
in Table 1, the distribution coefcient of Li (DLi) reached 4.6 at a TBP/
DOP ratio of 2/1. Kex
Fe3
aq 3C1 xDOPorg FeC13  xDOPorg 1
The Li/Mg separation factor initially increased and later decreased as
the TBP/DOP ratio (V/V) increased, reaching a maximum at a TBP/DOP Kex

ratio of 1/1. From the data, it is inferred that Li extraction reached equi- Li
aq FeCl4;aq mDOPorg LiFeCl4  mDOPorg 2
librium with TBP at the TBP/DOP ratio of 1/1. When the TBP/DOP ratio
continued to increase, excessive TBP led to extraction of Mg in the aque- Kex
Mg2
aq 2FeCl4;aq nDOPorg MgFeCl4 2  nDOPorg 3
ous solution because of the high Mg concentration. Thus, the Mg con-
centration increased in the loaded organic phase, and the Li/Mg
separation factor decreased. Therefore, appropriate DOP addition not

Fig. 3. Effect of TBP concentration on Li extraction with an aqueous solution at an O/A ratio Fig. 4. Effect of equilibrium extraction time on Li extraction efciency at different organic-
of 2/1. The volume concentration of DOP is 20%, initial [Li+]=2.046 g/L, [Fe/Li]=1.3, CHCl to-aqueous volume ratios. The volume concentrations of TBP and DOP are 40% and
=0.05 mol/L, CMgCl2 = 4.8 mol/L and t=6 min. Li extraction efciency (), Li/Mg 20%, respectively. Initial [Li+]= 2.18 g/L, [Fe/Li]=1.3, CMgCl2 = 4.8 mol/L. O/A = 2/1
separation factor LiMg (). (), O/A=1/1 ().
74 L. Ji et al. / Hydrometallurgy 162 (2016) 7178

Fig. 5. Effect of the aqueous phase CHCl on Li extraction with an aqueous solution at an O/A Fig. 7. Effect of organic-to-aqueous phase ratio on Li extraction. The volume
ratio of 2/1. The volume concentrations of TBP and DOP are 40% and 20%, respectively. concentrations of TBP and DOP are 40% and 20%, respectively. Initial [Fe/Li]=1.3, [Li+]=
Initial [Li+]=1.861 g/L, [Fe/Li]=1.3, CMgCl2 =4.8 mol/L, and t =6 min. Li extraction 1.861 g/L, CHCl =0.05 mol/L, CMgCl2 =4.8 mol/L and t=6 min. Li extraction efciency
efciency (), Li/Mg separation factor Li Mg (). (), Li/Mg separation factor Li
Mg ().

The distribution ratio, DM, and average equilibrium constant, DM

(M = Fe, Li, or Mg), for the above equilibrium reactions are given as sulfonated kerosene. The DOP concentration was maintained at 20%
follows: (V/V). The solvents and feed solution were mixed in a phase ratio of
2/1 at an initial HCl concentration of 0.05 mol/L. The results of single-
M e;org stage extraction experiments at different TBP concentrations are
DM 4
M e;aq shown in Fig. 3. The Li extraction increased with increasing TBP concen-
tration. At a TBP concentration of 40% (V/V), the Li extraction reached
X
10 86.3%. However, a further increase in TBP concentration resulted in
DM;i no signicant improvement in Li extraction. In these experiments,
DM i1
5 the Li/Mg separation factor rst increased and then decreased signi-
10 cantly with increasing TBP concentration. At a TBP concentration of
40% (V/V), the Li/Mg separation factor reached a maximum of 347.5. A
Table 2 shows that the average equilibrium constants D Fe , DLi , and third phase was observed at TBP concentrations less than 30% (V/V).
DMg for the reaction of DOP with Fe, Li, and Mg were 1.78 10-2, This was approximately 16 to 45% (V/V) less than threshold TBP
1.8910-2, and 5.2310-4, respectively. These ndings indicated weak concentration values of 46% (V/V) and 75% (V/V) reported in previous
extractions of Fe, Li, and Mg by DOP. studies (Tong et al., 1987; Sun et al., 2011).
Therefore, a TBP concentration of 40% (V/V) is suitable for the
3.1.4. Effect of TBP concentration quantitative extraction of Li and its separation from Mg.
To determine a suitable concentration for the TBP extractant, exper-
iments were conducted using different TBP concentrations in the organ-
ic phase. The TBP concentration ranged from 15% to 65% (V/V) in 3.1.5. Effect of equilibrium extraction time
To establish the equilibrium extraction time, Li extraction using 40%
(V/V) TBP and 20% (V/V) DOP was performed at different organic-to-
aqueous volume ratios. The initial concentration of Li ([Li]0) in the aque-
ous solution was 2.18 g/L. As shown in Fig. 4, the equilibrium extraction
efciencies of Li increased with an increasing organic-to-aqueous vol-
ume ratio, whereas the Li equilibrium extraction time decreased. After
1.0 min, the equilibrium extraction efciency of Li slightly changed
with increasing shaking time. Therefore, further extraction experiments
were performed at an extraction time of 6 min.

3.1.6. Effect of HCl concentration

Fig. 6. Effect of Fe/Li molar ratios on Li extraction with an aqueous solution at the O/A ratio
of 2/1. The volume concentrations of TBP and DOP are 40% and 20%, respectively. Initial
[Li+]=1.861 g/L, CHCl =0.05 mol/L, CMgCl2 = 4.8 mol/L, and t=6 min. Li extraction
efciency (), Li/Mg separation factor Li Mg ().
Optimization of the hydrochloric acid (HCl) concentration in aque-
ous solutions was necessary to prevent the hydrolysis of Fe3+. In this
study, the HCl concentration in aqueous solutions was varied from
0.02 M to 0.20 M. As shown in Fig. 5, the Li extraction efciency contin-
uously decreased as the HCl concentration in the aqueous solutions in-
creased. A possible cause of this result is that H+ can be more easily
extracted than Li+ in the HFeCl4 complexes, thereby increasing the
HCl concentration in aqueous solutions. This increase later inhibits the
extraction of Li+. Fig. 5 shows that the Li/Mg separation factor signi-
cantly increased with increasing HCl concentration in the aqueous solu-
tions, which considerably inhibited further extraction of Mg2+.
 L. Ji et al. / Hydrometallurgy 162 (2016) 7178
Fig. 8. a. Relationship between the initial Li concentration in aqueous solution and the Li concentration in organic solution. Li extracted in the organic phase (), Li theoretically
extracted from the aqueous phase (). b. Effect of initial Li concentration in aqueous solution on Li extraction at an O/A ratio of 2/1. The volumes of TBP and DOP are 40% and
20%, respectively. Initial [Fe/Li] = 1.3, CHCl = 0.05 M, CMgCl2 = 4.8 M, and t = 6 min. Li extraction efciency (), Li/Mg separation factor Li
3.1.7. Effect of the Fe/Li molar ratio
The effect of the Fe/Li molar ratio on the extraction behavior was in-
vestigated using 60% TBP/DOP (2/1, V/V). The results are shown in Fig. 6.
The extraction efciency of Li increased as the Fe/Li molar ratio and fer-
ric ion concentration increased. However, Li extraction only slightly im-
proved when the Fe/Li molar ratio exceeded 1.3. In addition, the Li/Mg
separation factor initially increased and rapidly decreased thereafter
with increasing Fe/Li molar ratio. A third phase in the extraction was
formed when the Fe/Li molar ratio exceeded 1.4. An Fe/Li ratio of 1.3 ob-
tained the optimal extraction efciency of 90% and a Li/Mg separation
factor of 524.
3.1.8. Effect of the phase ratio (O/A)
Fig. 7 shows that the Li extraction efciency signicantly increased
with increasing phase ratio (O/A) and reached a maximum of 90%
when the phase ratio (O/A) exceeded 1.5. However, a third phase was
formed when the phase ratio (O/A) was lower than 2. The Li/Mg separa-
tion factor quickly decreased when the phase ratio (O/A) was increased
from 2/1 to 10/1 because the relative concentration of TBP increased
with increasing phase ratio (O/A). The excessive TBP molecules promot-
ed the reaction of Mg2+ and FeCl-4. The Mg concentration in the organic
phase increased, thereby decreasing the Li/Mg separation factor.
Fig. 9. Effect of initial Cl- concentration in aqueous solution on Li and Fe extraction
efciency at an O/A ratio of 2/1. The volumes of TBP and DOP are 40% and 20%,
respectively. Initial [Fe/Li]=1.3, CHCl =0.05 mol/L, and t=6 min. Li extraction efciency
(), Fe extraction efciency ().
75
Mg ().
3.1.9. Effect of initial Li concentration
To determine the loading capacity of TBP/DOP for Li, experiments
were conducted using 40% TBP (1.47 M) and 20% DOP (0.50
M) organic phases. Aqueous solutions with Li concentrations ranging
from 0.49 g/L to 8.7 g/L (7.06 10 2 M to 1.25 M) at a phase ratio
(O/A) of 2/1 were also used. At these concentrations, more than 83%
of Li was extracted for initial Li concentrations ranging from 1.8 g/L to
3.5 g/L (Fig. 8a). Li loaded in the organic phase reached a maximum at
an initial Li concentration of 5.0 g/L (0.72 M) in the aqueous solutions,
corresponding to a 2:1 (TBP:Li) molar ratio in the organic phase.
Fig. 8b shows that the Li extraction efciency and the Li/Mg separation
factor signicantly increased for initial Li concentrations less than 2.7
g/L (0.39 M). The Li extraction efciency decreased at initial Li concen-
trations greater than 2.7 g/L (0.39 M), although the Li concentration in
the organic phase gradually increased (Fig. 8a). Meanwhile, a third
phase appeared at the interface during extraction. Therefore, at an ini-
tial Li concentration of 1.82.7 g/L (0.260.39 M) in the aqueous solu-
tion, the highest Li extraction efciency and highest Li/Mg separation
factor were obtained.
3.1.10. Effect of initial Cl concentration
The effect of the Cl concentration in aqueous solutions on Li extrac-
tion was examined using 40% TBP (1.47 M) and 20% DOP (0.50 M) at a
2:1 ratio, diluted in sulfonated kerosene, and with Cl concentrations
varying from 2.00 M to 9.68 M. This experiment evaluated the extent
of Li and Fe extraction at varying chloride ion concentrations in aqueous
solutions. As shown in Fig. 9, the extraction efciencies of Fe and Li
initially increased sharply with increasing chloride ion concentration.
At chloride concentrations greater than 6.0 M, Fe extraction efciency
reached a maximum of 100%. Li extraction efciency also gradually
increased. These increases suggested that the continuous increase in
chloride concentration contributed to the formation of the complexes
of FeCl
4 and LiFeCl4 with Cl and the extraction of electrically neutral
FeCl3 into the organic phase. Optimal extraction of Li can only be obtain-
ed with high or saturated Cl concentrations. Chen and Chen (1997)
obtained similar results.
3.2. Extraction distribution isotherm and counter-current simulation
To determine the number of stages required at a chosen volume
phase ratio, extraction isotherms were obtained with 40% (V/V) TBP
and 20% (V/V) DOP in sulfonated kerosene using salt lake brines. The or-
ganic phases were equilibrated with the feed solution containing 2.604
g/L Li and 0.05 mol/L HCl at different phase ratios (O/A = 1/2 to O/A =
20/1) for 10 min, while the total volume of the phases was kept
76 L. Ji et al. / Hydrometallurgy 162 (2016) 7178

Fig. 10. a. McCabeThiele diagram of the theoretical stages of extraction: [Li]aq is the concentration of Li+ in aqueous phase in equilibrium, and [Li]org is the Li+ concentration in organic
phase in equilibrium. b. Process owsheet for 3-stage countercurrent extraction of lithium from salt brines at an O/A ratio of 2/1. Initial [Fe/Li]=1.3, CHCl =0.05 mol/L, and t=10 min.

constant. The McCabeThiele plot (Fig. 10a) shows that the complete
extraction of Li is theoretically possible in three stages using an O/A
phase ratio of 2/1. To conrm the predictions from the extraction distri-
bution isotherm, a three-stage counter-current simulation experiment
was conducted under the predicted optimum conditions. The nal
rafnate containing 0.0136 g/L Li was obtained, corresponding to
99.5% extraction of the metal. Based on these results, a three-stage
counter-current extraction was suitable for this system.
The analysis of the rafnate and loaded organic phase is shown in
Fig. 10b. The Li extraction efciency exceeded 99.5%. The Li/Mg, Li/Na,
and Li/K separation factor ratios (Dm1/Dm2, m1 = Li and m2 = Mg,
Na, K, respectively) were 31458, 1259, and 16508, respectively. These
ndings indicated that in a three-stage countercurrent extraction, Li
was efciently separated from the other metals. In addition, the Li
extraction efciency exceeded 99.4%, which is attributed to the increase
in the solubility of Li complex molecules induced by DOP addition.

3.3. Effect of the phase ratio (O/A) on lithium stripping

The effect of the phase ratio (O/A) on the efciency of stripping lith-
ium from the lithium-loaded organic phase was examined. The phase
ratio (O/A) changed from 1/2 to 30/1, whereas a HCl concentration of
6 M and a contact time of 6 min were maintained. The efciency of
lithium stripping as a function of the phase ratio is shown in Fig. 11.
The efciency of lithium stripping linearly decreased from 97.98% to

Table 3
Fe(III) concentrations in the rafnate.

TBP concentration=1.469 mol/L DOP concentration=0.5049 mol/L

3+ -7
[DOP] [Fe ]10 [TBP] [Fe3+]10-7
(mol/L) (mol/L) in rafnate (mol/L) (mol/L) in rafnate

0.1262 125.3 0.5508 10943

0.2525 b1.432(b8 g/L) 0.7345 877
0.3787 b1.432(b8 g/L) 0.9181 520
0.5049 b1.432(b8 g/L) 1.102 511
0.6311 b1.432(b8 g/L) 1.285 426
0.7574 b1.432(b8 g/L)
1.010 b1.432(b8 g/L)
1.262 b1.432(b8 g/L)
Fig. 11. Effect of O/A phase ratio on efciency of lithium stripping from Li-loaded organic
1.515 71.62
phase. [HCl] = 6.0 mol/L and t = 6 min.
 L. Ji et al. / Hydrometallurgy 162 (2016) 7178 77

The distribution coefcient D is dened as the total molar concentra-

tion of lithium in the organic phase divided by that in the aqueous
phase (Zhou et al., 2012):
 
Li e;org LiFeCl4  mTBP  nDOP e;org
DLi     8
Li e;aq Li e;aq

Therefore, Eq. (7) can be simplied as follows:

DLi
K ex   9
FeCl4 e;aq  TBP m n
e;org  DOP e;org

and its log form is the following:

 
LogDLi LogK ex Log FeCl4 e;aq mLog TBP e;org nLogDOP e;org 10

Extraction experiments were conducted by varying the DOP volume

Fig. 12. Effect of extractant S concentration on Li extraction at a constant volume
concentration of 40% TBP (open symbols) or 20% DOP (lled symbols) in kerosene. S
denotes DOP () and TBP ().
45.42% as the phase ratio increased. Therefore, further stripping exper-
iments were performed at a phase ratio of 1/2.
3.4. Extraction mechanism
3.4.1. Slope analysis
Based on the extraction characteristics and mechanism analyses
(Zhou et al., 2011), the characteristics of the extraction reaction in this
system are presented as follows:
concentration at a constant TBP volume concentration of 40% and vary-
ing the TBP volume concentration at a constant DOP volume concentra-
tion of 20% in sulfonated kerosene. The Fe(III) concentrations in the
rafnates shown in Table 3 indicate that [FeCl-4] can be regarded as a
constant. The plots of LogDLi versus Log[DOP]e,org and Log[TBP]e, org are
shown in Fig. 12. The slopes of the linear ts of the plots of LogDLi versus
Log[DOP]e , org and LogDLi versus Log[TBP]e , org are close to 0.1 and 2,
respectively. This indicates that the values of m and n in Eq. (10) are
2 and 0.1, respectively. Thus, the complex formed in Eq. (6) is
(LiFeCl4 2TBP) 0.1DOPorg, and the extraction reaction can be expressed
as follows:
Kex
Liaq FeCl4;aq 2TBPorg 0:1DOPorg LiFeCl4  2TBP
 0:1DOPorg 11

kex
Li
aq FeCl4;aq mTBPorg nDOPorg LiFeCl4  mTBP  nDOPorg 6
3.4.2. Infrared spectroscopic analysis
The IR spectra of the TBP/DOP organic system consisting of 40% TBP
The apparent equilibrium constant Kex for the above equilibrium
and 20% DOP before and after extraction are shown in Fig. 13a and b, re-
reactions is given as follows:
spectively. The C= O absorption peaks after extraction showed a red
shift (Fig. 13b) from 1728 cm-1 to 1719 cm-1. The value was 9
LiFeCl4  mTBP  nDOP e;org
K ex     7 cm-1, indicating weak chemical bonding between DOP and the Fe and
Li e;aq  FeCl4 e;aq  TBP m n
e;org  DOP e;org Li metals. Moreover, the C=O absorption peaks for the loaded organic
phase became broader because of the formation of hydrogen bonds,
through which the DOP molecules formed adducts connected to metal
Li complexes.
As shown in Fig. 13, the characteristic absorption peaks for the P-O-C
and P = O functional groups on TBP were observed at 1030 and 1280
cm-1, respectively, before extraction (Bellamy, 1975). In addition, the
P= O of the P = O absorption peak for TBP after extraction showed a
red shift (Fig. 13b) from 1280 cm-1 to a lower wave number ranging
from 1250 cm-1 to 1260 cm-1. The value ranged from 20 cm-1 to
30 cm-1, which indicated the bonding of the P = O group on TBP
with metal complexes, thereby reducing its energy (Zhou et al., 2013).
The inset in Fig. 13 shows that H2O exhibited a weak absorption peak
at 1630 cm-1, accounting for the LiFeCl4 complex and the TBP molecules
coordinating with H2O through hydrogen bonding. According to the
slope analysis in Section 3.4 and the complex ratio, the complex formula
was determined as (LiFeCl4 2TBPnH2O)0.1DOP, which was consistent
with the conclusions of Ye (2011) and Zhou et al. (2013).

4. Conclusions

Fig. 13. IR spectra of the 40% TBP/20% DOP system. a. TBP/DOP before extraction; b. TBP/
DOP after extraction.
The 40% (V/V) TBP/20% (V/V) DOP extraction system with the opti-
mal synergist DOP obtained an increased Li distribution ratio (4.6) and
Li/Mg separation factor in a single-stage extraction. The same system
also yielded increased Li extraction efciencies (99.5%) for the three-
stage countercurrent simulation extraction. Compared with the
78 L. Ji et al. / Hydrometallurgy 162 (2016) 7178
traditional TBP-kerosene system (Sun et al., 2011), this system avoided
the formation of a third phase and signicantly decreased the TBP con-
centration, resulting in less severe causticity to the equipment and re-
duced loss of TBP in the aqueous phase during the extraction process.
DOP molecules acted as the synergist and the dispersant and were as-
sociated with LiFeCl4 complexes by hydrogen bonding, thereby reducing
the polarity of Li complex molecules and increasing the liquidity and sol-
ubility of these molecules. Therefore, this system effectively prevented
the third-phase formation caused by reduced TBP concentrations.
Acknowledgments
The authors appreciate the nancial support of the Qaidam Salt Lake
Chemical Joint Scientic Research Funds of China (No. U1407203), the
Key Deployment Project supported by the Chinese Academy of Sciences
(KGZD-EW-604), and Key Project supported by the QingHai Science and
Technology Department.
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