Journal of Sustainable Metallurgy (2021) 7:1368–1378

https://doi.org/10.1007/s40831-021-00430-7

RESEARCH ARTICLE

Extraction of Lithium from Magnesium‑Rich Solution Using Tri‑n‑butyl

Phosphate and Sodium Hexafluorophosphate
Wanji Zhou1,2 · Zheng Li3 · Shiai Xu1,2

Received: 4 December 2020 / Accepted: 16 August 2021 / Published online: 27 August 2021
© The Minerals, Metals & Materials Society 2021

Abstract 
Ionic liquids (ILs) such as 1-butyl-3-methylimidazolium hexafluorophosphate (­ [C4mim][PF6]) are considered suitable co-
extraction reagents of tri-n-butyl phosphate (TBP) for selective extraction of lithium from magnesium-rich salt lake brine.
However, ILs are very expensive and the loss of cations can cause the contamination of the aqueous solution. The cor-
responding inorganic salts of ILs such as sodium hexafluorophosphate (­ NaPF6) should play the same role as ILs in the
extraction of L­ i+ by TBP, and importantly, they are cheaper and more environmentally friendly. In this study, the effects of
­NaPF6 concentration, phase ratio, initial pH of the aqueous phase, temperature, and ­MgCl2 concentration on the extraction
of lithium were investigated. It was found that N ­ aPF6 was as good as [­ C4mim][PF6] in the extraction of L­ i+ from Mg-rich
solution by TBP, and their extraction mechanisms are also the same, which is certified by comparing the Fourier transform
infrared spectroscopy (FT-IR) and slope analysis. Hydrochloric acid (HCl) is more effective than sodium carbonate ­(Na2CO3)
in the stripping of L­ i+, but N
­ a2CO3 can avoid the regeneration of the organic phase and increase the reusability of both TBP/
[C4mim][PF6] and TBP/NaPF6 systems.

The contributing editor for this article was Grace Ofori-Sarpong.

* Shiai Xu
saxu@ecust.edu.cn
1
School of Materials Science and Engineering, East China
University of Science and Technology, Shanghai 200237,
China
2
School of Chemical Engineering, Qinghai University,
Xining 810016, China
3
Department of Chemistry, KU Leuven, 3001 Heverlee,
Belgium

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Journal of Sustainable Metallurgy (2021) 7:1368–1378 1369

Graphical Abstract
In TBP/NaPF6 system, the schematic of Li extraction/stripping from brine with high Mg/Li ratios using (a) HCl as stripping
agent and (b) ­Na2CO3 as stripping agent

Keywords  Lithium extraction · Tri-n-butyl phosphate · Sodium hexafluorophosphate · Stripping · Salt lake brine

Introduction in batteries [1–5]. In recent years, the consumption of Li

in lithium-ion batteries (LIBs) has increased significantly
Lithium (Li) is an energy metal with important applications with extensive use of LIBs in portable devices and electric

13

1370
vehicles. It is estimated that full-electric vehicles powered
by LIBs will account for 20% of all vehicles in 2050, result-
ing in an increase in global Li demand by 27 times compared
with that in 2012 [6, 7]. Pegmatite and brine are the two
main sources of Li. The global exploitable Li resources are
estimated to be 31.1 Mt, 70% of which are present in salt
lake brine [8]. Li is mainly extracted from brine [9, 10], and
its concentration in seawater is too low (~ 0.2 ppm) to be
exploited [11]. In China, the Li concentration varies from
0.10 to 6.70 g/L in salt lakes [12]. However, magnesium
(Mg) is also present in salt lake brine and the Mg/Li ratio is
a key factor affecting the recovery potential of Li from brine.
The extraction process of Li from the brine with low Mg/
Li ratios (< 8) consists of brine concentration by evapora-
tion, removal of Mg by Ca(OH)2, removal of Ca by N ­ a2CO3/
Li2CO3, and precipitation of ­Li2CO3 by N ­ a2CO3 [13, 14].
This may pose a serious environmental problem because of
high consumption of precipitation reagents, generation of
large amounts of waste, and high consumption of water for
washing the precipitate. In addition, the recovery efficiency
is low due to loss of Li during precipitation.
Recovery of Li from brine with high Mg/Li ratios (> 8) is
technically challenging, and only some processes are oper-
ated on an industrial scale. Given the increasing demand for
Li, it is necessary to develop more environmentally friendly
techniques for the recovery of Li from brine. Solvent extrac-
tion is a promising technique for the extraction of Li from
Mg-rich brine because of the reusability of extractants, fast
kinetics and simple requirement of equipment. Tri-n-bu-
tyl phosphate (TBP) in combination with F ­ eCl3 has been
extensively used for separating Li and Mg [15–21] due to
high separation factor, low cost, and large scale availability
of TBP. Zhou et al. [15] found that L ­ i+ formed a complex
[Li‧(TBP)x(H2O)4-x] [FeCl4] with TBP, ­H2O and ­FeCl4−,
+ −
in which ­FeCl4− worked as a counter anion. However, two
problems remain to be solved, which greatly limit its indus-
trial application. One is the formation of the third phase due
to hydrolysis of ­FeCl3 or the poor solubility of the complexes
in the organic phase, while the other one is the difficulty in
stripping of Li. Thus, ­FeCl3 needs to be replaced with a more
efficient co-extraction reagent.
Ionic liquids (ILs) have many excellent characteristics,
such as good solubility, high stability, and negligible vapor
pressure [22, 23]. More importantly, ILs can greatly improve
the extraction efficiency of metal ions without causing seri-
ous environmental pollution. Although ILs have been used
as extractants or solvents for the extraction of multivalent
metal ions, it remains unclear whether they could be used for
the extraction of ­Li+. ILs act as the co-extraction reagents of
TBP in the extraction of L ­ i+ as they have hydrophilic cations
and anions of P ­ F6 , ­NTf2−, and P
−
­ W12O403− [24–27]. The
anions of these ILs have good hydrophobicity and a stereo-
symmetric structure similar to that of ­FeCl4− [27], and thus,
13
Journal of Sustainable Metallurgy (2021) 7:1368–1378
they should play the same roles as F ­ eCl4−. The use of ILs
such as 1-butyl-3-methylimidazolium hexafluorophosphate
­([C4mim][PF6]) as co-extraction reagents can avoid the prob-
lems caused by ­FeCl3 [25]. However, the synthesis process
of ILs is complex and the cost is high, thus, making them
unsuitable for industrial applications. And ion exchange
involved in the extraction of ILs can lead to the loss of cati-
ons in ILs. N­ aClO4 and NaB(Phen)4 that have good hydro-
phobicity and stereo-symmetric anions could also extract
Li with TBP [28, 29]. However, ­NaClO4 as a co-extraction
reagent has low extraction for Li, and NaB(Phen)4 reacts
with ­K+ in brine to form a precipitate. These studies imply
that the counter anion can work in the form of an inorganic
salt instead of ILs, which can avoid the contamination of the
aqueous phase by ILs cations. Besides, inorganic salts are
cheaper than the corresponding ILs.
To our knowledge, there is no report about the use of
sodium hexafluorophosphate (­ NaPF6) as a co-extraction rea-
gent for extracting Li from Mg-rich solution. This study uses
TBP as the extractant and ­NaPF6 as the carrier of the counter
anion to extract Li from Mg-rich solution. In previous stud-
ies, HCl often acts as a stripping agent, while NaOH acts as
a regeneration agent. However, HCl may cause hydrolysis
of ­PF6−, resulting in the formation of HF [27]. ­Na2CO3 can
be a potential stripping reagent because L ­ i2CO3 precipitates
in the aqueous solution. The results show that N ­ a2CO3 as a
stripping agent is beneficial to the recycling of the organic
phase. In this study, the extraction efficiency and mechanism
of Li from Mg-rich brine by TBP/[C4mim][PF6] and TBP/
NaPF6 systems are compared. A new stripping method using
­Na2CO3 is proposed, and the reusability of the two extraction
systems is also discussed.
Experimental
Materials and Instruments
TBP (98.5%) was purchased from Meryer Technologies
(Shanghai, China); N­ aPF6 (98%) was purchased from Siyan
Chemistry (Shanghai, China); ­[C4mim][PF6] (99%) was pur-
chased from Adamas Chemical Reagent (Shanghai, China);
LiCl (99%), ­MgCl2 (99.5%), NaOH (97%), ­Na2CO3 (99.5%),
dichloromethane ­(CH2Cl2, 99.5%), and Eriochrome black
T (analytical grade) were purchased from Aikeda Reagent
(Chengdu, China); Ethylenediaminetetraacetic acid diso-
dium salt (99%) was purchased from Tianjin Kemiou Chemi-
cal Reagent (Tianjin, China); HCl (37%) was purchased from
Sinopharm Chemical Reagent (Shanghai, China). Deion-
ized water prepared by a deionization machine (Basic-Q15,
Hitech Instruments, Shanghai) was used to prepare aqueous
solutions.
Journal of Sustainable Metallurgy (2021) 7:1368–1378 1371

A pH meter (FE28, METTLER TOLEDO) was used to caq × Vaq

monitor the pH of the aqueous solutions. A table shaker
(THZ-92A, Yuejin Medical Instruments, Shanghai, China)
was used to mix the samples. Li and Na concentrations were
determined by atomic absorption spectroscopy (AA-6880,
Shimadzu). The functional groups of organic phase were
characterized by Fourier transform infrared spectroscopy
(FT-IR, Thermo Fisher 6700, USA) from 500 to 4000 ­cm−1.
%S = × 100%, (3)
corg × Vorg + caq × Vaq
where corg and caq are the concentrations of the organic and
aqueous phases at extraction or stripping equilibrium, and
Vorg and Vaq are the volumes of the organic and aqueous
phases at extraction or stripping equilibrium, respectively.

Experimental Methods Results and Discussion

Aqueous solutions with varying concentrations of
LiCl, ­M gCl 2 , and N­ aPF 6 were prepared with deion-
ized water. The TBP/NaPF 6 system contained 10  mL
of ­MgCl 2 + LiCl + ­NaPF 6 aqueous solution and 10  mL
of TBP, and TBP was diluted in C ­ H2Cl2 for slope analy-
sis [25], while the TBP/[C4mim][PF6] system contained
10 mL of M ­ gCl2 + LiCl aqueous solution and 10 mL of
TBP + ­[C4mim][PF6]. In both systems, the two immisci-
ble phases were contacted in a 100 mL cylindrical bottle
and shaken for 15 min in a shaking incubator. After that,
the mixture was allowed to stand still for 15 min for phase
separation. In order to study the effect of phase ratio, 10 mL
of aqueous solution was also used and the volume of the
organic phase was changed according to the phase ratio. In
the stripping test, the loaded organic phase was contacted
with the stripping solution and shaken for 15 min and then
allowed to stand still for 15 min. To investigate the effect
of phase ratio on the stripping, 10 mL of organic phase was
used and the volume of the aqueous solution was changed
according to the phase ratio. To increase the stripping effi-
ciencies of Li and Mg using N ­ a2CO3 as stripping agent,
multi-stage stripping experiment was conducted, using
fresh ­Na2CO3 solution in each stage. After phase separa-
tion for both extraction and stripping, the aqueous solution
was collected with a syringe and diluted to an appropriate
concentration. Li and Na concentrations were determined by
atomic absorption spectroscopy, and Mg concentration was
determined by titration with EDTA using eriochrome black
T as indicator. The metal concentration in the organic phase
was calculated by mass balance.
Comparison of TBP/[C4mim][PF6] and TBP/NaPF6
Extraction Systems
The extraction efficiencies of Li and Mg using ­NaPF6 and
­[C4mim][PF6] as the co-extraction reagents are compared
at the same concentration of ­PF6−. Figure 1 shows that the
extraction efficiency of Mg is almost the same for the two
extraction systems, while that of Li is slightly higher for
­[C4mim][PF6] system, which can be attributed to the pres-
ence of ­Na+ in TBP/NaPF6 system. Although TBP/[C4mim]
[PF6] system has a slightly higher extraction efficiency for
Li, the use of TBP/NaPF6 system avoids the contamination
of the aqueous phase caused by [­ C4mim]+ of [­ C4mim][PF6].
The Effect of ­NaPF6 Concentration
Figure 2 shows that the extraction efficiency of Li increases
rapidly from 35.0% at 0.05  mol/L ­NaPF 6 to 67.7% at
0.2 mol/L ­NaPF6, after which it remains nearly constant.
However, the extraction efficiency of Mg increases slightly
with increasing ­NaPF6 concentration. Thus, the optimal
90 + 2+
Li Mg 84.7
78.9
75
60
%E

45

The distribution ratio D, extraction efficiency %E,

30
and stripping efficiency %S are defined in Eqs. (1–3),
respectively:
15
corg 5.1 5.3
D=
caq
, (1) 0
NaPF6 [C4mim][PF6]
Co-extraction reagent
corg × Vorg
%E = × 100%, (2) Fig. 1  Comparison of N­ aPF6 and [­C4mim][PF6] as co-extraction rea-
corg × Vorg + caq × Vaq
gents for the extraction of Li and Mg (The aqueous phase contained
0.1  mol/L ­Li+, 1.0  mol/L M
­ g2+, and 0.2  mol/L ­NaPF6, the organic
phase contained TBP, 0.2 mol/L ­[C4mim][PF6], O/A = 2/1, T = 303 K,
pH 7.0)

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1372 Journal of Sustainable Metallurgy (2021) 7:1368–1378

80 that the extraction efficiency of Li reaches 78.9% at an O/A

ratio of 2 and further increasing the O/A ratio results in no
further increase in the extraction efficiency. Therefore, the
60
optimal O/A ratio is determined to be 2.
+
Li

40
Mg
2+

+
The Effect of Initial pH of the Aqueous Phase
%E

Na

The pH of the aqueous phase was adjusted in the range of

20 1.0–7.0 using HCl and NaOH, and precipitation of Mg(OH)2
may occur at pH higher than 7.0. Figure 4 shows that the
extraction efficiency of Li increases with increasing pH from
0 1.0 to 7.0, which is attributed to the stronger reaction compe-
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
tition between H ­ + and metal ions at lower pH. Considering
[NaPF6], mol/L
the extraction efficiency of Li, pH 7.0 is used for further
studies.
Fig. 2  The effect of ­NaPF6 concentration on the extraction of Li,
Na and Mg (The aqueous phase contained 0.1 mol/L ­Li+, 1.0 mol/L
The Effect of Temperature
­Mg2+, and 0.05–0.3  mol/L N ­ aPF6, the organic phase was TBP,
O/A = 1/1, T = 303 K, pH 7.0)
The effect of temperature on the extraction of Li and Mg
was investigated in a temperature range of 303–333 K. Fig-
­NaPF6 concentration for extraction of Li is determined to be ure 5 shows that the extraction efficiency of Li decreases
0.2 mol/L. The extraction efficiency of Na is slightly higher with increasing temperature. Therefore, 303 K is used for
than that of Mg. The ­Na+ of N
­ aPF6 may have a greater effect further extraction studies.
on Li extraction than [­ C4min]+, which results in the lower
extraction efficiency of Li in the TBP/NaPF6 system com- Extraction Isotherm
pared to the TBP/[C4mim][PF6] system.
The extraction isotherm in solvent extraction provides
The Effect of Phase Ratio important information about the maximum loading capac-
­ i+ as a function of
ity of the extractant. The loading of L
The effect of phase ratio should be equivalent to that of TBP LiCl concentration was investigated at an initial N ­ aPF6
amount because only TBP is in the organic phase. Figure 3 concentration of 0.2 mol/L. Figure 6 shows the relation-
shows that the extraction efficiency of Li increases with ship of the equilibrium concentrations of ­L i + between
increasing O/A ratio due to the increasing amount of TBP,
while that of Mg remains largely unchanged. It is observed
80

70
80
60
+
Li
2+
+
Li 50 Mg
60 Mg
2+

40
%E

30
%E

40

20
20
10

0
0 1 2 3 4 5 6 7
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
pH
O/A
Fig. 4  The effect of initial pH of the aqueous phase on the extraction
Fig. 3  The effect of phase ratio on the extraction of Li and Mg of Li and Mg (The aqueous phase contained 0.1 mol/L ­Li+, 1.0 mol/L
(The aqueous phase contained 0.1  mol/L ­Li+, 1.0  mol/L ­Mg2+, and ­Mg2+, and 0.2 mol/L N ­ aPF6, the organic phase was TBP, T = 303 K,
0.2 mol/L ­NaPF6, the organic phase was TBP, T = 303 K, pH 7.0) O/A = 2/1)

13
Journal of Sustainable Metallurgy (2021) 7:1368–1378 1373

80 The Effect of ­MgCl2 Concentration

70
A high ­MgCl2 concentration is beneficial to the extraction of
60
+
Li due to the salting-out effect [30]. In this study, the effect
Li
2+
of ­MgCl2 concentration on the separation of Li and Mg was
50 Mg
investigated at a constant LiCl concentration of 0.1 mol/L.
40 Figure 7 shows that increasing the ­MgCl2 concentration
%E

results in a decrease in the extraction efficiency of Mg but

30
an increase in the extraction efficiency of Li because of the
20 competition between the two metals for TBP. This finding
is consistent with an earlier study [30]. Thus, it is concluded
10
that TBP/NaPF6 system is suitable for extracting Li from
0 Mg-rich solution.
300 305 310 315 320 325 330 335
T, K Effect of HCl Concentration and Phase Ratio
on the Stripping
Fig. 5  The effect of temperature on the extraction of Li and Mg
(The aqueous phase contained 0.1  mol/L ­Li+, 1.0  mol/L ­Mg2+, and In order to examine the effect of HCl concentration on the
0.2 mol/L ­NaPF6, the organic phase was TBP, pH 7.0, O/A = 2/1)
stripping, 0.27 g/L Li and 0.64 g/L Mg were loaded to TBP
after extraction, which was then stripped by water and HCl
0.20 solutions with an A/O ratio of 1. Figure 8 shows that 15.2%
of Li and 35.5% of Mg can be stripped by water. The strip-
ping efficiency increases with the increase of HCl concentra-
0.15
Li
+ tion and reaches 89.6% for Li and 95.7% for Mg at 1.0 mol/L
HCl, respectively. However, further increasing HCl concen-
tration to 2.0 mol/L makes no contribution to the stripping
], mol/L

0.10
of Li or Mg. Considering that high HCl concentration can
cause equipment corrosion, 1.0 mol/L is used for further
org
+
[Li

study.
0.05
The effect of A/O ratio on the stripping efficiencies of Li
and Mg was also investigated using 1.0 mol/L HCl as the
0.00 stripping agent. Figure 9 shows that increasing the A/O ratio
0.0 0.5 1.0 1.5 2.0 ­ i+ and ­Mg2+.
can increase the stripping efficiencies of both L
+
[Li aq], mol/L

Fig. 6  Extraction isotherm of ­Li+ from LiCl solutions (The aque-

80
ous phase contained various concentrations of LiCl, and 0.2  mol/L
­NaPF6, the organic phase was TBP, pH 7.0, O/A = 1/1, T = 303 K)
60 +
Li
2+
Mg
aqueous and organic phases. The concentration of ­Li+ in
%E

the organic phase is 0.198 mol/L when the concentration 40

of ­Li+ in the aqueous phase is 1.202 mol/L, and further

increase in ­Li+ concentration in the aqueous phase results 20
in almost no change in the equilibrium concentration of
­Li+ in the organic phase. The loading of ­Li+ is limited not
0
only by TBP concentration but also by ­NaPF6 concentra- 0 1 2 3 4
tion. Therefore, the maximum loading of ­Li+ in the organic
[MgCl2], mol/L
phase is about 0.2 mol/L.

Fig. 7  The effect of ­
MgCl2 concentration on the extraction of Li
and Mg (The aqueous phase contained 0.1  mol/L ­Li+, 0.5–4  mol/L
­Mg2+, and 0.2 mol/L N­ aPF6, organic the phase was TBP, O/A = 1/1,
T = 303 K, pH 7.0)

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1374 Journal of Sustainable Metallurgy (2021) 7:1368–1378

100
90

80
+
+ 75 Li
Li 2+
2+ Mg
60 Mg

%S
60
%S

40

45
20

30
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
0.0 0.5 1.0 1.5 2.0 2.5
[Na2CO3], mol/L
[HCl], mol/L

Fig. 8  The effect of HCl concentration on the stripping of Li and Mg Fig. 10  The effect of ­Na2CO3 concentration on the stripping of Li and
(A/O = 1/1) Mg (A/O = 1/1)

100 92

90
95
Li
+
88
2+
Mg
86
90
%S

%S

84
+
Li
82 Mg
2+
85

80

80 78
0 1 2 3 4 5 6 7 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
A/O A/O

Fig. 9  The effect of A/O ratio on the stripping of Li and Mg Fig. 11  The effect of A/O ratio on the stripping of Li and Mg
(1.0 mol/L HCl as stripping agent) (2.5 mol/L ­Na2CO3 as stripping agent)

­ i+ and ­Mg2+ are 95.4% and

The stripping efficiencies of L Table 1  The stripping efficiencies of Li and Mg in multi-stage strip-
98.7% at an A/O ratio of 4, respectively, and no significant ping processes at the conditions of 2.5 mol/L ­Na2CO3 at an O/A ratio
of 2.5
increase is observed at A/O ratios higher than 4. Thus, the
optimum A/O ratio for the stripping of Li and Mg is 4. Stripping One-stage (%) Two-stage (%) Three-stage (%)
efficiency
Effect of ­Na2CO3 Concentration and Phase Ratio Li 85.7 92.8 95.1
on the Stripping Mg 89.8 96.5 98.3

Stripping with HCl may cause hydrolysis of P ­ F6−, resulting

in the formation of HF [27]. In this study, ­Na2CO3 was used
as a stripping reagent because L­ i2CO3 would precipitate in
aqueous solutions. Figure 10 shows that the stripping effi-
ciencies of Li and Mg gradually increase with increasing
­Na2CO3 concentration from 0.5 to 2.5 mol/L, and remain
constant with further increase of ­Na2CO3 concentration to
3.5 mol/L. The maximum stripping efficiencies of Li and Mg
are approximately 82.8% and 87.7% at 2.5 mol/L ­Na2CO3,
respectively. Thus, the optimal ­Na2CO3 concentration is
2.5 mol/L for Li and Mg stripping.
The effect of A/O ratio on the stripping efficiencies of Li
and Mg was investigated at a constant ­Na2CO3 concentration
of 2.5 mol/L. Figure 11 shows that the stripping efficien-
cies of Li and Mg increase with increasing A/O ratio and
reach a maximum of approximately 85.7% and 89.8% at an
A/O ratio of 2.5, after which they remain almost unchanged.

13
Journal of Sustainable Metallurgy (2021) 7:1368–1378 1375

Thus, the optimal A/O ratio is determined to be 2.5. Com- 1.2

pared with that of HCl, the use of N ­ a2CO3 as the stripping y=2.18048x+0.13775
agent results in lower stripping efficiencies of Li and Mg. 1.1 2
R =0.99155
In order to increase the stripping efficiencies of Li and Mg, 1.0
a multi-stage stripping experiment was carried out. Table 1

LogDLi -Log[PF6 ]
-
shows that the stripping efficiencies of Li and Mg reach 0.9

95.1% and 98.3% respectively after the three-stage strip- 0.8

+
ping processes.
0.7

Extraction Mechanism of TBP/[C4mim][PF6] and TBP/ 0.6

NaPF6 Systems
0.5

In order to better understand the role of hexafluorophos- 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50

phate anion, FT-IR spectroscopy was performed to char- Log[TBP]

acterize TBP and the organic phase after extraction using

TBP/[C4mim][PF6] and TBP/NaPF6 systems. The peak at Fig. 13  Linear relationship between ­ (LogDLi+–Log[PF6−]) and
+
Log[TBP] in L ­ i extraction (The initial aqueous phase contained
1282 ­cm−1 is assigned to the P=O stretching vibration [31].
0.1  mol/L ­Li+, 1.0  mol/L M­ g2+, and 0.2  mol/L ­NaPF6, the organic
Figure 12 shows that the peaks at 2962 ­cm−1, 2892 ­cm−1, and phase was TBP and C ­ H2Cl2, O/A = 2/1, T = 303 K, pH 7.0)
1028 ­cm−1 belong to − ­CH3 asymmetric stretching vibration,
C–H symmetrical stretching vibration, and P–O–C asym-
metric stretching vibration, respectively [26]. The peak cor- TBP/FeCl3 and TBP/ILs systems, the extraction mechanism
responding to P=O stretching vibration of TBP shifts from is described as follows:
1282 to 1258 ­cm−1 after extraction, indicating the interac-
tion between P=O and ­Li+. The bands at 820–860 ­cm−1 and PF−6 + nTBP + Li+ → Li(TBP)n ⋅ PF6 (4)
550–565 ­cm−1 are attributed to the characteristic peaks of
The plot of (LogDLi+–Log[PF6−]) versus Log[TBP] gives a
hexafluorophosphate, and the peaks at 827 and 557 ­cm−1 are
straight line with a slope close to 2, indicating that two TBP
assigned to the characteristic peaks of hexafluorophosphate
molecules are included in the complex, and the complex is
[32]. The characteristic peaks of the organic phase after
determined to be Li(TBP)2·PF6. The mechanism is the same
extraction are the same for TBP/[C4mim][PF6] and TBP/
as that of imidazolium ILs containing ­PF6− [25]. Therefore,
NaPF6 systems, revealing that the same extraction complex
­PF6− containing ILs are not essential in the extraction of Li
is formed.
with TBP, but P ­ F6− in the form of ILs or inorganic salts is
To determine the TBP amount in the extraction complex,
required. However, some of ­PF6− would remain in the aque-
the plot of (LogDLi+–Log[PF6−]) versus LogCTBP is shown
ous phase and cause some potential environmental problems.
in Fig. 13. According to the extraction mechanism of Li by
In the future, we will explore more environmentally benign
chemicals for the extraction of Li from brine.

Reusability of TBP/[C4mim][PF6] and TBP/NaPF6

(a) Systems
2892 1282 1028
2962
The following extraction reaction occurs in the TBP/
Transmittance, %

[C4mim][PF6] system:
(b)
827 557
1258
[C4 mim][PF6 ] + 2TBP + Li+ → Li(TBP)2 ⋅ PF6 + [C4 mim]+
(5)
(c) [C4min]+ of ­[C4mim][PF6] in the organic phase exchanges
827 557 with ­Li+ in the aqueous phase, leading to the contamina-
1258
tion of the aqueous phase. Based on the extraction mecha-
4000 3500 3000 2500 2000 1500 1000 500 nism, Li(TBP)2·PF6 is formed after extraction in both TBP/
Wavenumbers, cm
-1 [C4mim][PF6] and TBP/NaPF6 systems. In both systems,
when HCl is used as the stripping agent, the stripping,
Fig. 12  FT-IR spectra of a TBP, b TBP/[C4mim][PF6] and c TBP/ regeneration, and next extraction process are depicted in
NaPF6 systems after extraction Eqs. (6, 7 and 8), respectively, while when N
­ a2CO3 is used

13

1376 Journal of Sustainable Metallurgy (2021) 7:1368–1378

as the stripping agent, the stripping and next extraction pro- H(TBP)2 ⋅ PF6 + Na+ + OH− → Na(TBP)2 ⋅ PF6 + H2 O
cesses are depicted in Eqs. (8 and 9), respectively. In TBP/ (7)
NaPF6 system, the extraction cycle is schematically shown
(8)
+ +
in Fig. 14. Na(TBP)2 ⋅ PF6 + Li → Li(TBP)2 ⋅ PF6 + Na

Li(TBP)2 ⋅ PF6 + H+ → H(TBP)2 ⋅ PF6 + Li+ (6) 2Li(TBP)2 ⋅ PF6 + 2Na+ + CO2− → 2Na(TBP)2 ⋅ PF6 + Li2 CO3
3
(9)

Fig. 14  The schematic of Li extraction/stripping cycle from solution with high Mg/Li ratios using a HCl as stripping agent and b ­Na2CO3 as
stripping agent

13
Journal of Sustainable Metallurgy (2021) 7:1368–1378 1377

(a) 90 formation of HF and consequently a decrease in the amount

NaPF6 [C4mim][PF6]
of ­PF6− in the organic phase. However, as shown in Fig. 15b,
75 the extraction efficiency of Li remains almost constant using
­Na2CO3 as the stripping agent, suggesting that ­Na2CO3 can
60 improve the stability of the extraction system.

45
%E

Conclusions
30

In this study, N ­ F6−-containing

­ aPF6 is used as a substitute to P
15
ILs for extraction of Li from Mg-rich solution in order to
0
avoid the contamination of the aqueous phase caused by the
1 2 3 4 5 6 7 cations in ILs. Under the optimal conditions, the extraction
Regeneration times efficiency of Li is 78.9% for ­NaPF6/TBP system. N ­ aPF6 is
as good as [­ C4mim][PF6] in the extraction of L ­ i+ from Mg-
(b) 90
rich solution by TBP. The same complex Li(TBP)2PF6 is
NaPF6 [C4mim][PF6]
75
formed in the loaded organic phase after Li extraction for
both ­NaPF6/TBP and [­ C4mim][PF6]/TBP systems. HCl is
60 more efficient in stripping of the loaded organic phase com-
pared to ­Na2CO3, while regeneration of the organic phase is
45 not needed using ­Na2CO3 as the stripping agent. Stripping
%E

by ­Na2CO3 results in no changes in the extractability of the

30 organic phase, but stripping by HCl results in a decrease in
the reusability.
15
Acknowledgements  This research is financially supported by the
0 National Natural Science Foundation of China (Grant No. 52063025)
1 2 3 4 5 6 7 and the Foundation from Qinghai Science and Technology Department
Regeneration times (Grant No. 2020-HZ-808).

Fig. 15  Effect of regeneration times of the organic phase on the Declarations 

­ i+ using a HCl and b ­Na2CO3 as the strip-
extraction efficiency of L
ping agent (In the extraction, the aqueous phase contained 0.1 mol/L
­Li+, 1.0  mol/L M­ g2+, 0.2  mol/L N
­ aPF6, and the organic phase was
TBP, 0.2 mol/L ­[C4mim][PF6], O/A = 2/1, T = 303 K, and pH 7.0. In
the stripping, the aqueous phase was 1.0 mol/L HCl at an O/A ratio of
4, and 2.5 mol/L N ­ a2CO3 at an O/A ratio of 2.5 in three-stage strip-
ping processes)
The same complex Li(TBP)2·PF6 is formed for the two
extraction systems. The loaded Li can be stripped by HCl or
­Na2CO3 as discussed above. As the extraction efficiency of
­H+ is higher than that of ­Li+, the organic phase after strip-
ping by HCl is regenerated by base (e.g., NaOH) for the next
extraction cycle. However, regeneration of the organic phase
is not needed using N­ a2CO3 as the stripping agent, which
makes the process much simpler.
Seven extraction/stripping cycles were carried out to
study the stability and reusability of the two extraction sys-
tems. Figure 15a shows that the extraction efficiency of Li
decreases with the increase of extraction/stripping cycle
using HCl as the stripping agent for both TBP/[C4mim][PF6]
and TBP/NaPF6 systems. The reason is that HCl can cause
hydrolysis of ­PF6− in the stripping process, resulting in the
Conflict of interest  On behalf of all authors, the corresponding author
states that there is no conflict of interest.
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