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Separation and Purication Technology 98 (2012) 396401

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Separation and Purication Technology


journal homepage: www.elsevier.com/locate/seppur

A hydrometallurgical process for the separation of aluminum, cobalt, copper


and lithium in acidic sulfate media
Tasuma Suzuki a,, Tomonori Nakamura a, Yuta Inoue a, Masakazu Niinae a, Junji Shibata b
a
b

Department of Environmental Science and Engineering, Graduate School of Science and Engineering, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi 755-8611, Japan
Department of Chemical, Energy and Environmental Engineering, Kansai University, 3-3-5 Yamate, Suita, Osaka 564-8680, Japan

a r t i c l e

i n f o

Article history:
Received 23 March 2012
Received in revised form 24 June 2012
Accepted 26 June 2012
Available online 6 July 2012
Keywords:
Spent lithium-ion secondary batteries
Solvent extraction
Lithium
Cobalt

a b s t r a c t
Acid leach liquors from spent lithium-ion batteries that use lithium cobalt dioxide (LiCoO2) as a cathode
active material contain valuable metals such as cobalt and lithium, as well as common metals such as
aluminum and copper. The objective of this study was to develop a hydrometallurgical process that provides a degree of high selectivity between aluminum, cobalt, copper, and lithium from acidic sulfate
media.
The results from batch experiments showed that a selective hydroxide precipitation approach was not
suitable because a signicant amount of cobalt was coprecipitated with aluminum and/or copper hydroxides. In contrast, batch experiments and the subsequent data analysis indicated that the sequence of solvent extraction circuits using PC-88A, Acorga M5640, and tri-n-octylamine (TOA) extractants effectively
separates four metals of interest. In the rst circuit of the proposed process, copper was selectively
extracted by Acorga M5640 at pH 1.52.0. Aluminum, cobalt, and lithium remained in the aqueous phase.
In the second circuit, aluminum was selectively extracted by PC-88A at pH 2.53.0. For separation of the
remaining cobalt and lithium, Acorga M5640 provided higher cobalt selectivity (separation factor could
not be accurately obtained due to negligible lithium extraction) compared to PC-88A (bCo, 90%/Li = 350 at
pH 4.5) and PC-88A/TOA (bCo, 90%/Li = 1,170 at pH 5.4). However, the stripping efciency of cobalt from the
Acorga M5640 organic phase was found to be low (less than 10%). Therefore, the PC-88A/TOA mixed
extractant rather than Acorga M5640 is a suitable choice for the separation of cobalt and lithium.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Lithium-ion secondary batteries (LIBs) offer several advantages
over other secondary batteries (e.g., nickel metal-hydride batteries) including higher energy density and slower charge loss when
not in use. Because of these favorable characteristics, LIBs are currently widely used for portable electronic apparatuses, and keeps
substituting for other secondary batteries. In Japan, for instance,
according to the machinery statistics released by the Japanese Ministry of Economy, Trade and Industry (METI), LIBs share went from
28% in 2001 to 67% in 2010 market share of secondary batteries [1].
In addition, it is anticipated that their use for automotive and
renewable energy storage applications will further expands their
consumption in the near future. Hence, it is highly desirable to develop a recycling process capable of properly treating spent LIBs for
environmental protection and recovering valuable metals from
them for resource conservation.
At present, lithium cobalt dioxide (LiCoO2) is one of the most
widely adopted cathode active material, although other active
Corresponding author.
E-mail address: tsuzuki@yamaguchi-u.ac.jp (T. Suzuki).
1383-5866/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.seppur.2012.06.034

materials such as LiNiO2 and LiMn2O4 are expected to be used


more frequently in the future. Various recycling processes for spent
LIBs have been proposed in the literature [220], and the current
status was recently reviewed by Xu et al. [21]. Among the previously proposed processes, many of them [5,11,13,15,17,18] have
focused on the recovery of cobalt because of its high price, and
other metals (e.g., aluminum and copper used for cathode and anode support substrates, respectively) were simultaneously removed as hydroxides because each separation of these metals
was not considered to be economically viable. However, as noted
by several studies, including Provazi et al. [18], selective precipitation is not efcient for selective recovery of metals due to the
coprecipitation of more concentrated metals, which may result in
the loss of valuable metals. Solvent extraction is more efcient in
the separation of metals than selective precipitation.
The objective of this study was to develop a hydrometallurgical
process capable of effectively separating aluminum, cobalt, copper,
and lithium. These four metals are typically included in acid leach
liquors from spent LIBs employing LiCoO2 as a cathode active
material. To achieve this objective, selective precipitation and solvent extraction experiments were performed using articially prepared metal solutions to simulate H2SO4 leach liquors, and the

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T. Suzuki et al. / Separation and Purication Technology 98 (2012) 396401

performance of the processes based on these two separation technologies was evaluated in terms of metal recovery and metal selectivity. The proposed process in this study was then compared with
other processes from the literature to determine the advantages of
the proposed process.
It is important to clearly state the reason behind our choice of
H2SO4 to prepare articial acid leach liquors because the counter
anion of metals inuences the metal recovery and separation efciencies in selective precipitation and solvent extraction processes.
The acid leaching of LiCoO2 is usually performed with either H2SO4
[612,15,17,19,23,24], HCl [2,3,8,14] or HNO3 [4,5,8,20,25], often
combined with reducing agents such as H2SO3, NH2OH, and
H2O2. Among these inorganic acids, we assumed H2SO4 is used
for acid leaching based on the following reasons, and the articial
acid leach liquors were prepared using metal sulfate and H2SO4.
First, HCl is highly corrosive and attacks metal materials that are
commonly used in acid leaching facilities. Therefore, to avoid
devoting considerable attention to materials selection, HCl was excluded for the choice of acids. Second, although HNO3 is less corrosive compared to HCl due to its ability to form passive layers, it has
been reported that oxime-type extractants become degraded under prolonged contact time with HNO3 solutions [22]. For these
reasons, in our opinion, H2SO4 is the most appropriate inorganic
acid for acid leaching.

2. Experimental methods
2.1. Materials
All solutions were prepared with distilled deionized (DDI) water
with a resistivity greater than 18 MX cm1 (WA200, Yamato Scientic Co. Ltd., Japan). All chemical reagents (guaranteed reagent
grade) were purchased from Nacalai Tesque, Inc. (Kyoto, Japan)
or Wako Pure Chemical Industries, Ltd. (Osaka, Japan) and used
without further purication. Tri-n-octylamine (TOA, guaranteed
reagent grade) was purchased from Nacalai Tesque, Inc. PC-88A
(2-ethylhexyl 2-ethylhexylphosphonic acid, minimum purity is
95 wt.%) and Acorga M5640 (5-nonyl-2-hydroxy-benzaldoxime,
purity is 3060 wt.%) were kindly donated by Daihachi Chemical
Industry Co. Ltd. (Osaka, Japan) and Cytec Industries Inc. (Woodland Park, NJ, USA), respectively. Kerosene, used as a diluent for organic phases in solvent extraction experiments, was purchased
from Nacalai Tesque, Inc., and its main component was saturated
aliphatic hydrocarbons.

2.3. Solvent extraction experiment


Metal stock solutions containing 2.0  103 mol/L of aluminum,
cobalt, copper, and lithium were prepared from Al2(SO4)314
18H2O, CuSO45H2O, CoSO47H2O, and Li2SO4H2O, respectively.
Metal stock solutions also contained 0.2 mol/L of Na2SO4 as a back
electrolyte. 15 ml of the stock solution was transferred into a 50 ml
glass conical ask, and the pH of the solution was adjusted to the
predetermined pH by adding concentrated H2SO4 or NaOH solutions as required. The change in volume during pH adjustment
was negligible. After the pH adjustment, 15 ml of extractant diluted in kerosene was transferred into the conical ask and it
was immediately tightly sealed with a glass cap. The conical ask
was then shaken at 160 rpm using a horizontal shaker (NTS4000, Tokyo Rikakikai Co. Ltd., Japan) for 2 h at 25 C. The preliminary experiments veried that 2 h was sufcient time to reach the
extraction equilibrium between the phases under the experimental
conditions that were investigated in this study. After 2 h of extraction time, the nal pH and the metal concentration in the aqueous
phase were measured, and the metal concentration in the organic
phase was calculated from the difference between the metal concentration in the aqueous phase before and after extraction.
2.4. Analytical methods
The pH of the solution was measured using a pH meter (HM30G, DKK-TOA Corp., Japan) with a pH electrode (GST-5721C,
DKK-TOA Corp., Japan). The metal concentrations were quantied
by ame atomic absorption spectroscopy (AA-6200, Shimadzu
Corp., Japan).
3. Results and discussion
3.1. Chemical precipitation experiments
The results of selective precipitation experiments using singlemetal and multi-metal component systems are shown in Figs. 1
and 2, respectively. Figs. 1 and 2 also show the hydroxide precipitation curves that were prepared from calculations using MINEQL + Version 4.5, a chemical equilibrium modeling software
[26,27]. As shown in Fig. 1, for the single-metal system, nearly
100% of the aluminum and copper was precipitated at pH 7.0,
while cobalt and lithium remained in solution when the pH was
below 7.0. These precipitation trends were qualitatively well-represented by the hydroxide precipitation curves that were calculated using MINEQL+. However, for the multi-metal system

2.2. Chemical precipitation experiment

Al: MINEQL+
Cu: MINEQL+
Co, Li: MINEQL+
Al: Experiment
Cu: Experiment
Co: Experiment
Li: Experiment

80
Precipitation (%)

An aqueous solution containing 2.0  103 mol/L of target metal(s) and 0.2 mol/L of Na2SO4 as a back electrolyte was prepared
by dissolving Al2(SO4)31418H2O, CuSO45H2O, CoSO47H2O,
Li2SO4H2O, and Na2SO4 in DDI water. 15 ml of the aqueous
solution was transferred into a 50 ml glass conical ask, and the
pH of the solution was adjusted to the predetermined pH by
slowly adding concentrated H2SO4 or NaOH solutions as required.
The change in volume during pH adjustment was negligible.
Immediately after the pH adjustment, the ask was tightly sealed
with a glass cap and shaken at 160 rpm using a horizontal shaker
(NTS-4000, Tokyo Rikakikai Co. Ltd., Japan) for 2 h at 25 C.
After 2 h of reaction time, the suspension was ltered through a
0.2-lm mixed cellulose ester type membrane lter, and the nal
pH was measured. The ltrate was immediately acidied by
HNO3 to avoid additional metal precipitation and analyzed for
aqueous metal concentrations.

100

60
40
20
0
0

3
4
5
Equilibrium pH

Fig. 1. Hydroxide precipitation of aluminum, copper, cobalt, and lithium as a


function of the aqueous equilibrium pH. Experiments were performed using a
single-metal system. Hydroxide precipitation curves calculated using MINEQL+ are
also shown.

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T. Suzuki et al. / Separation and Purication Technology 98 (2012) 396401

100

100
Al: MINEQL+
Cu: MINEQL+
Co, Li: MINEQL+
Al: Experiment
Cu: Experiment
Co: Experiment
Li: Experiment

60

Al
Cu

80

Co

Extraction (%)

Precipitation (%)

80

40
20

Li

60
40
20

0
1

3
4
5
Equilibrium pH

Fig. 2. Hydroxide precipitation of aluminum, copper, cobalt, and lithium as a


function of equilibrium aqueous pH. Experiments were performed using a multimetal system. Hydroxide precipitation curves calculated using MINEQL+ are also
shown.

(Fig. 2), a signicant amount of cobalt was precipitated when the


pH was above 5.0, and approximately 50% of cobalt in the solution
was precipitated at pH 7.0, indicating that cobalt was coprecipitated with aluminum and/or copper hydroxides. Additionally, the
hydroxide precipitation curves for aluminum and copper were
adjacent, thus making selective aluminum precipitation more difcult. Therefore, it was concluded that a selective precipitation approach was not suitable for separation of any single metals of
interest.
3.2. Solvent extraction experiments with single or mixed extractants
The pH extraction isotherms of metals with 10 vol.% Acorga
M5640 and 10 vol.% PC-88A extractants are shown in Figs. 3 and
4, respectively. A mixed extractant containing 10 vol.% PC-88A
and 5 vol.% TOA was also used to improve the metal separation
efciency, and the obtained pH extraction isotherms are shown
in Fig. 5. The order of metal extraction with Acorga M5640
(Fig. 3) was found to be:

Cu > Co > Al; Li:


Conversely, the order of metal extraction with PC-88A (Fig. 4)
was different from that observed using Acorga M5640, and aluminum was the most effectively extracted among the four metals
investigated in this study:

Al > Cu > Co > Li:

3
4
5
Equilibrium pH

Fig. 4. Metal pH isotherms with 10 vol.% PC-88A in a kerosene diluent. Experiments


were performed using a single-metal system. Experimental conditions: metal
concentrations = 2.0  103 mol/L, A/O ratio = 1.0, 25 C.

100
Al
Cu

80

Co

Extraction (%)

Li

60
40
20
0
0

3
4
5
Equilibrium pH

Fig. 5. Metal pH isotherms with 10 vol.% PC-88A and 5 vol.% TOA in a kerosene
diluent. Experiments were performed using a single-metal system. Experimental
conditions: Metal concentrations = 2.0  103 mol/L, A/O ratio = 1.0, 25 C.

The pH extraction isotherms were shifted to the right (i.e.,


extraction efciency decreased at the given pH due to an antagonism effect) by adding 5 vol.% TOA as the second extractant
(Fig. 5). This antagonism effect was partially due to the electric
interaction between TOA and PC-88A molecules which decreases
the number of PC-88A molecules involving metal extraction. Electric repulsion of positively charged metal ions by TOA molecules at
the aqueous-organic interface also might be responsible for the decreased metal extraction efciencies. However, the order of metal
extraction remained the same.

100

3.3. Evaluation of metal separation efciency for PC-88A and PC-88A/


TOA

Al

80
Extraction (%)

Cu
Co

60

Li

40
20
0
0

3
4
5
Equilibrium pH

Fig. 3. Metal pH isotherms with 10 vol.% Acorga M5640 in a kerosene diluent.


Experiments were performed using a single-metal system. Experimental conditions: metal concentrations = 2.0  103 mol/L, A/O ratio = 1.0, 25 C.

As demonstrated in Fig. 3, oxime-type Acorga M5640 extractant


completely extracted copper within the pH range of 1.52.0 without
extracting the other three metals. Therefore, Acorga M5640 is the
appropriate choice for copper separation. The data in Fig. 3 also indicate that cobalt seems to be separated from aluminum and lithium
at pH > 6.0. However, it is important to note that aluminum hydroxide starts to precipitate above pH 4.0 as shown in Figs. 1 and 2. In fact,
there are no aluminum data points above equilibrium pH above 4.0
in Fig. 3 because the initial aqueous pH was controlled so that the nal equilibrium pH was not greater than 4.0. In other words, aluminum removal from the aqueous phase using PC-88A or PC-88A/TOA
at a pH below 4.0 is a required step prior to considering cobalt separation in a near neutral pH range.

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T. Suzuki et al. / Separation and Purication Technology 98 (2012) 396401

Contrary to Acorga M5640, in cases of PC-88A and PC-88A/TOA


extractants (Figs. 4 and 5), the pH extraction isotherms were more
adjacent to one another, thus making it difcult to evaluate the
separation efciency between the metals. Hence, the experimental
data shown in Figs. 4 and 5 were analyzed by slope analysis with
the nal objective of evaluating the separation efciency between
the metals.
The overall reaction representing the extraction of metal cations
with m positive valence (Mm+) by PC-88A may be expressed as
follows:

Mm
aq nHR2org MRm  2n  mHR org mHaq

where (HR)2 represents PC-88A molecules in dimeric form, n represents the number of the dimeric PC-88A molecules involved in the
extraction, and the subscripts aq and org represent the aqueous
and organic phases, respectively. Eq. (1) can be rearranged into Eq.
(3) by combining with the denition of the distribution coefcient D
(Eq. (2))

D MRm  2n  mHRorg =Mm


aq

log D mpH log K ex 2n  m logHR2org 

where Kex represents the concentration equilibrium constant of Eq.


(1). As shown by Eq. (3), a plot of log D versus pH results in a
straight line with a slope of m and y-intercept of log Kex + (2n
m)log [(HR)2 org]. The results of the extraction data analysis using
Eq. (3) are shown in Fig. 6. As shown in Fig. 6, the slopes of the obtained straight lines for both single PC-88A and PC-88A/TOA mixed
extractants were approximately 1.0, 2.0, and 3.0 for lithium, cobalt,
and aluminum, respectively, indicating that Li+, Co2+, and Al3+ were
the extracted species. The straight lines in Fig. 6 were then used to
calculate the separation factor b90% = DMe1, 90%/DMe2, which was dened by the ratio of the distribution coefcients between the metals
at the pH providing 90% Me1 extraction efciency (i.e., log DMe1,
90% = log (0.9/0.1) = 0.954). The obtained b90% values are summarized
in Table 1. TOA added as the second extractant showed a larger
antagonism effect for aluminum compared to cobalt, which resulted
in a decline in b90% for aluminum/cobalt from 2480 to 1550. How-

Al (PC-88A)

Table 1
Separation factor between the metals at the pH 90% of Me1 was extracted.
Me1/Me2

Extractant

Extraction pH

Al/Co

10 vol.% PC-88A
10 vol.% PC-88A
+ 5 vol.% TOA
10 vol.% PC-88A
10 vol.% PC-88A
+ 5 vol.% TOA
10 vol.% PC-88A
10 vol.% PC-88A
+ 5 vol.% TOA

2.8
3.8

2480
1550

2.8
3.8

17,400
51,300

4.5
5.4

350
1170

Al/Li

Co/Lia

Separation factor (b)

Quote from our previous study [28].

Table 2
Effect of H2SO4 concentration on metal stripping efciencies from loaded organic
phases.
Element

Extractant

Aqueous
equilibrium
pH for
loaded
extractants
preparationa

Stripping
H2SO4 conc.
(mol/L)

Stripping
efciency
(%)

Cu

10 vol.%
Acorga M5640

1.9

Al

10 vol.%
PC-88A

2.3

Co

10 vol.%
Acorga M5640

5.7

Co

10 vol.%
PC-88A + 5 vol.% TOA

5.7

1.0
2.0
3.0
1.0
2.0
3.0
1.0
2.0
3.0
1.0
2.0
3.0

80.1
94.6
98.7
92.7
100
100
4.5
3.9
8.8
91.9
98.8
98.9

a
The metal extraction efciencies at these pH values were nearly 100% as shown
in Figs. 35.

ever, b90% for aluminum/lithium and cobalt/lithium were improved


by TOA addition, indicating that lithium received the most signicant antagonism effect in the presence of TOA and cobalt received
the least.

Co (PC-88A)

3.4. Metal stripping efciency

Li (PC-88A)
Al (PC-88A/TOA)
Co (PC-88A/TOA)
Li (PC-88A/TOA)

2
2
3

log D

1
1
1

-1

1
1

-2
0

3
4
5
Equilibrium pH

Fig. 6. Relationship between the metal distribution coefcient (log D) and the
aqueous equilibrium pH for 10 vol.% PC-88A (solid) and 10 vol.% PC-88A/5 vol.%
TOA (open). Experimental conditions: Metal concentrations = 2.0  103 mol/L, A/O
ratio = 1.0, 25 C.

Additional batch experiments were performed to obtain information on the metal stripping efciency, which is also an essential
aspect to be considered in developing the solvent extraction process. For these experiments, organic phases containing extracted
metals were rst prepared by repeating the experiments represented by Figs. 35. The initial aqueous pH was adjusted so that
nearly 100% of the metals were extracted into the organic phases.
Then, 15 ml of the loaded organic phase were shaken for 2 h with
15 ml of H2SO4 solutions of various concentrations, and the metal
stripping efciency was obtained. The experimental results are
shown in Table 2. While more than 95% of metal stripping efciency was obtained in most cases, cobalt extracted with Acorga
M5640 was not easily stripped, even with the 3.0 mol/L H2SO4
solution. Unfortunately, it was beyond the scope of this study to
investigate the chemical reactions between extracted cobalt and
Acorga M5640 in kerosene, which is why the low cobalt stripping
efciency from Acorga M5640 organic phases was not fully elucidated. However, it has been well documented in the literature that
cobalt(II) is oxidized to cobalt(III) by hydroxyoxime-type extractants and stabilized in the organic phase. As a result, the recovery
of cobalt(II) by stripping is difcult [2931]. Therefore, although

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T. Suzuki et al. / Separation and Purication Technology 98 (2012) 396401

Fig. 7. A proposed solvent extraction process for the separation of aluminum,


copper, cobalt, and lithium from acidic sulfate media.

Acorga M5640 provided higher cobalt selectivity over lithium compared to PC-88A/TOA, PC-88A/TOA mixed extractant rather than
Acorga M5640 is an advisable choice for the separation of cobalt
and lithium.
3.5. A proposed hydrometallurgical process for separating Al, Co, Cu,
and Li
In the literature, chemical precipitation methods are often applied for valuable metal separation from acid leach liquors of spent
secondary batteries [3,5,11,13,15,17,18,32,33]. For instance, Dorella and Mansur [11] performed selective precipitation and solvent
extraction experiments aiming to develop a hydrometallurgical
process for the recovery of cobalt from spent LIBs. It is important
to note that they manually separated the anode and cathode before
the acid leaching step. Therefore, the metal components included
in the acid leach liquors were aluminum, cobalt, and lithium (copper used for the anode substrate was not included). According to
the separation process they proposed, aluminum was rst removed
by hydroxide precipitation, followed by solvent extraction with
Cyanex 272 to extract cobalt. However, a signicant amount (more
than 50%) of cobalt was coprecipitated with aluminum hydroxide
when the pH increased to 7.0 to precipitate nearly 100% of the aluminum. As a result, a high recovery of cobalt with high purity was
not feasible with this process. These ndings are qualitatively consistent with our results (Fig. 2). More recently, Provazi et al. [18]
comprehensively compared selective precipitation and solvent
extraction processes for the selective separation of metals contained in the main types of spent secondary batteries. Based on
their experimental results, they concluded that selective precipita-

tion was not efcient in the selective separation of metals due to


the coprecipitation of more concentrated metals, and solvent
extraction was more efcient in the separation of metals. Again,
our results from chemical precipitation experiments (Fig. 2) were
qualitatively consistent with these ndings from the literature;
therefore, it can be reasonably concluded that chemical precipitation approaches are not suitable for selective metal separation.
Along these lines, the solvent extraction process for the separation of aluminum, cobalt, copper, and lithium was constructed
based on the experimental results and the subsequent data analysis. The process ow is presented in Fig. 7. In the rst circuit of the
proposed process, copper is selectively extracted by Acorga M5640
within a pH range of 1.52.0. Aluminum, cobalt, and lithium remain in the aqueous phase. In the second circuit, aluminum is
selectively extracted by PC-88A within the pH range of 2.53.0. Finally, for the separation of the remaining cobalt and lithium, PC88A/TOA rather than Acorga M5640 was used due to its higher
stripping efciency, although Acorga M5640 provided higher cobalt selectivity.
The solvent extraction process constructed in this study has
four unique features. First, the optimum pH range for three extraction circuits increases in a stepwise manner, thus eliminating tedious back and forth pH adjustments. Second, the solvent
extraction process constructed in this study is capable of recovering not only cobalt and lithium, which are the primary focus of
recycling efforts, but also copper and aluminum. Especially for copper, it is anticipated that depletion and shortage will occur during
the 21st century, even though progress in mining technologies is
assumed [34,35]. Therefore, the capability of recovering high purity copper will bring large economic benets in the not-so-distant
future. Third, the solvent extraction process proposed in this study
provides high selectivity between cobalt and lithium (Table 3). The
comparison of the cobalt/lithium separating factors for the process
used in this study and those in the literature are somewhat difcult
and misleading because the metal separation efciency varies
depending on extraction conditions (e.g., organic phase diluent,
O/A ratio, temperature, metal concentrations, extractant concentration, counter anion of metals). Nonetheless, the comparison still
provides some ideas. As shown in Table 3, the PC-88A/TOA extractant provided higher cobalt selectivity compared to other extractants used in the literature. This is clearly a technical advantage
of the process proposed in this study over those in the literature.
Finally, all extractants used in the proposed process were already
qualied and well marketed in many countries. Therefore, the proposed process can be quickly implemented into the currently operating solvent extraction plants in many countries. However,
needless to say, further studies will be required to comprehensively demonstrate the effectiveness of the proposed process in
the real solvent extraction plants. Subjects for further studies
might include the inuence of metal concentration on metal separation efciencies, construction and use of a McCabeThiele dia-

Table 3
Comparison of cobalt/lithium separation factors between the processes used in this study and those in the literature. All studies were performed at ambient temperature, O/A
ratio = 1.0, using kerosene as a diluent and sulfate media.
References

This studya
This studya
Swain et al. [8]
Swain et al. [10]
Chen et al. [19]
a

Metal concentration (g/L)


Cobalt

Lithium

0.118
0.118
0.59
6.52
20

0.013
0.013
0.138
4.49
2.5

Extractant

10 vol.% PC-88A
10 vol.% PC-88A + 5 vol.% TOA
0.03 M Na-Cyanex 272 + 5 vol.% TBPc
0.75 M Cyanex 272 + 5 vol.% TBPc
25 wt.% PC-88A (known as P507 in China)

Co extraction% and the corresponding separation factorb


Co extraction (%)

Separation factor

90
90
85
100
80

350
1,170
60
380
55

Quoted from Table 1; 2.0  103 mol/L corresponds to 0.118 g/L and 0.014 g/L for cobalt and lithium, respectively.
Separation factors for our previous study were calculated using slope analysis. Conversely, separation factors reported in the literature were calculated directly from
experimental results.
c
TBP (tributyl phosphate) was added as a phase modier.
b

T. Suzuki et al. / Separation and Purication Technology 98 (2012) 396401

gram, and demonstration of the validity of the proposed process on


a continuous basis.
4. Conclusions

[10]

[11]

In an effort to develop a hydrometallurgical process capable of


effectively separating aluminum, cobalt, copper, and lithium in
acidic sulfate media, selective precipitation and solvent extraction
experiments were performed. The following conclusions can be
drawn:

[12]

(1) Aluminum could not be selectively precipitated because the


hydroxide precipitation curves for aluminum and copper
were adjacent. Additionally, a signicant amount of cobalt
was coprecipitated with aluminum and/or copper hydroxides. Therefore, selective precipitation approaches were concluded to be unsuitable for the separation of the metals of
interest.
(2) Aluminum, cobalt, copper, and lithium were effectively separated using the following sequence of solvent extraction
circuits: (i) copper extraction with Acorga M5640 within
the pH range of 1.52.0, (ii) aluminum extraction with PC88A within the pH range of 2.53.0, and (iii) cobalt extraction with PC-88A/TOA within the pH range of pH 5.56.0.
Additionally, high metal stripping efciencies (>98%) from
the organic phases were obtained using a 3.0 mol/L H2SO4
solution.

[15]

[13]
[14]

[16]

[17]

[18]

[19]

[20]

[21]

[22]

Acknowledgements
[23]

The authors gratefully acknowledge the nancial support of the


Japanese Ministry of the Environment, Grants-in-aid for scientic
research (K22067), and Arai Science and Technology Foundation
to conduct this study. The authors also gratefully acknowledge
Daihachi Chemical Industry Co. Ltd. and Cytec Industries Inc. for
the donation of PC-88A and Acorga M5640, respectively.
References
[1] http://www.meti.go.jp/english/statistics/index.html.
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