Separation and Purification Technology 296 (2022) 121326

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Separation and Purification Technology

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Separation of cobalt and nickel via solvent extraction with Cyanex-272:

Batch experiments and comparison of mixer-settlers and an agitated
column as contactors for continuous counter-current extraction
Isadora R. Rodrigues , Clio Deferm , Koen Binnemans , Sofía Riaño *
KU Leuven, Department of Chemistry, Celestijnenlaan 200F, P.O. Box 2404, B-3001 Leuven, Belgium

A R T I C L E I N F O A B S T R A C T

Keywords: The separation of cobalt and nickel was carried out via solvent extraction using the commercial extractant bis
Acidic extractant (2,4,4-trimethylpentyl)phosphinic acid (Cyanex-272). Solvent extraction experiments were performed on a
Battery metals batch scale to optimize the extractant concentration, saponification degree, equilibration time, organic-to-
Contactors
aqueous phase ratio (O/A), and stripping conditions. High selectivity of cobalt over nickel was obtained at an
Counter-current solvent extraction
Diluents
extractant concentration as low as 0.2 M (or 20% v/v), with a saponification degree of 40% and a phase ratio O/
Stirred column A of 1/1. Furthermore, eleven diluents, covering different aliphatic– aromatic compositions were tested to
Transition metals evaluate their effect on the separation of cobalt and nickel. Cobalt extraction efficiencies were not significantly
impacted by the nature of the diluent. However, the co-extraction of nickel was approximatively 10% higher
when toluene was used as a diluent in comparison with the aliphatic diluent Shell GS270. The process was
validated in continuous mode using a battery of mixer-settlers and an agitated Kühni column. High recovery of
cobalt and negligible co-extraction of nickel were achieved in both cases. The specificities, advantages, and
challenges of the operation of both types of liquid-liquid extraction equipment were further discussed.

1. Introduction metals increases in the following order: D2EHPA (di-2-ethylhexyl

Cobalt and nickel are important for various metallurgical and
chemical applications, including cathode materials for lithium-ion bat­
teries [1–4]. Both are found together in nature and their purification by
hydrometallurgical methods is challenging due to their similar physi­
cochemical properties. Separation of cobalt from nickel is performed in
industry mainly via solvent extraction (SX) [5–8].
SX is a hydrometallurgical unit operation commonly used for the
concentration and separation of metals, where two immiscible phases
are brought into contact. The aqueous feed contains the metals of in­
terest, and the organic phase contains the extractant, a diluent and
sometimes a modifier. The separation of cobalt and nickel by SX can be
carried out with different types of extractants. The use of acidic
extractants such as dialkylphosphinic, dialkylthiophosphinic, dia­
lkylphosphoric and carboxylic acids has been well documented in the
literature [5,9–11]. Organophosphorus extractants show selectivity for
cobalt over nickel, whereas carboxylic acid extractants show the oppo­
site selectivity [12]. According to studies on the separation of cobalt and
nickel from sulfate solutions, the separation factor between the two
phosphoric acid) < PC88A (2-ethylhexyl phosphonic acid-mono-2-
ethylhexyl ester) < bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex-
272) [12–14]. Other extractants such as bis(2,4,4-trimethylpentyl)
dithiophosphinic acid (Cyanex-301), have also been demonstrated to
be effective for the separation of cobalt and nickel, but they require
stronger conditions for stripping [15,16]. Cobalt solutions with a purity
above 99% can easily be obtained via SX using Cyanex-272 from sulfate
leachates of cathode scrap of Li-ion batteries [10].
Acidic extractants, such as Cyanex-272, generally extract metals
through a cationic exchange mechanism:
2H2A2 + CoSO4 → CoA2⋅H2A2 + H2SO4 (1)
where A represents the conjugate base of the acidic extractant. The
metal cation dissolved in the aqueous phase is combined with the
deprotonated extractant and forms a stable complex soluble in the
organic phase. Since this is a pH-dependent mechanism, strict control of
the pH during the extraction is required [11]. One of the possible
methods to control the pH during extraction is by neutralization of the

* Corresponding author.
E-mail address: Sofia.Riano@kuleuven.be (S. Riaño).

https://doi.org/10.1016/j.seppur.2022.121326
Received 14 April 2022; Received in revised form 17 May 2022; Accepted 19 May 2022
Available online 29 May 2022
1383-5866/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
I.R. Rodrigues et al.
extractant, which is commonly called “saponification”. In saponifica­
tion, the extractant is partially converted into its sodium salt [17,18].
Cyanex-272 and its sodium salt (Na-Cyanex-272) are both miscible with
most commercial aliphatic and aromatic diluents [17]. The saponifica­
tion of the extractant is a simple method for pH control, but it usually
increases the solubility of the extractant in the aqueous phase.
The selection of the diluent is a key parameter in SX operations. The
diluent allows changing the concentration of the extractant in the
organic phase, lowers the density and viscosity of the organic phase, and
dissolves the complex that will be extracted [19,20]. Furthermore, the
diluent can also have an impact on the efficiency and selectivity of the
extraction [20–23]. Among other parameters, a good diluent must have
a high flash point, low volatility, low miscibility in the aqueous phase,
and should be environmentally friendly, non-toxic, chemically stable,
readily available, and affordable. Even though the selection of the
diluent is an important parameter, only few studies on the effect of the
diluent on SX can be found in the literature.
Small-scale SX investigations can be easily performed by a single
batch equilibrium contact of the aqueous and organic phases. However,
the ability to operate in continuous, multistage, counter-current mode is
an important aspect when considering industrial applications. This may
allow for higher percentages of extraction and separation factors while
processing large volumes. Counter-current operation is achieved by
repeating single-stage contacts, with the aqueous and organic phases
moving in opposite directions between the different stages. The three
main types of liquid–liquid extraction contactors are mixer-settlers,
columns, and centrifugal contactors [8,18,24–27]. Several examples of
large-scale SX operations have been reported for the separation of cobalt
and nickel, but in general, practical comparisons of different types of SX
equipment for a particular separation are hard to find in the literature.
Zhou et al. used an aqueous phase of cobalt and nickel sulfate and an
organic phase of 10% 2-ethylhexylphosphonic acid mono-2-ethylhexyl
ester in kerosene [28]. The experimental results showed that the
extraction rates of both cobalt and nickel were high, and that the
extraction rate of cobalt was generally higher than that of nickel. The
difference in extraction kinetics was used to optimize the separation and
the mixing times were kept short [29]. In another flowsheet, cobalt was
recovered with 99.5% efficiency from a calcium-saturated solution using
Cyanex-272. Nickel was extracted using Versatic Acid 10 and the re­
covery yield was 99% [30]. A continuous ionic liquid extraction process
in mixer-settlers using undiluted Cyphos IL 101 was also described for
the selective extraction of cobalt over nickel [31]. The performance of
this continuous extraction process was similar to the current industrial
processes, with the advantage of eliminating volatile compounds from
the extraction phase. Although there exist several reports on the large-
scale separation of cobalt and nickel using mixer-settlers, not much
can be found about other contactors. In one of the few reports, the
extraction and separation of cobalt and nickel in a pulsed sieve-plate
column was studied using 10% D2EHPA as the extractant. Mass trans­
fer coefficients were determined for the extraction, scrubbing, and
stripping steps [32].
In this paper, the separation of cobalt and nickel was optimized using
partially saponified Cyanex-272. The process (i.e. extraction and strip­
ping) was validated in mini-pilot mixer-settlers and in an agitated col­
umn. Advantages and disadvantages of both types of contactors are
described and discussed. To the best of our knowledge, this is the first
time that a comparison on the use of mixer-settlers and a column for
cobalt–nickel separation is reported.
2. Experimental
2.1. Chemicals
Cyanex-272 (bis(2,2,4-trimethylpentyl)phosphinic acid) was ob­
tained from Cytec Industries B.V. (Vlaardingen, Netherlands),
CoSO4⋅7H2O (99%) was purchased from Acros Organics (Geel,
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Separation and Purification Technology 296 (2022) 121326
Belgium), NaOH (98%), NiSO4⋅6H2O (99%), HNO3 (65 wt%), cobalt,
nickel, and scandium standard solution for ICP-OES (1000 ± 10 mg L-1)
were purchased from Chem-Lab (Zedelgem, Belgium). The solvents Shell
GS270, GS250, GS215, GS190, G70, D70, 2046, 2325, A150, were ob­
tained from Shell Global Solutions (Amsterdam, Netherlands). Toluene
(99%) and o-xylene (98%) were obtained from Sigma-Aldrich (Diegem,
Belgium). Milli-Q water (18.2 MΩ cm at 298.2 K) was used to prepare
the aqueous solutions. All chemicals were used as received, without any
further purification.
2.2. Instrumentation
Cobalt and nickel concentrations were measured using a Perki­
nElmer Optima 8300 ICP-OES equipped with a Scott crossflow nebu­
lizer. Samples were diluted with a 3 vol% HNO3 solution. Calibration
was performed using solutions containing 0.12, 2.5, 5, and 10 mg L− 1 of
the corresponding metals, scandium was added as internal standard (5
mg L− 1). Batch-scale extraction experiments were performed in 4 mL
vials and using a shaker (Thermo Scientific 2000). The aqueous and
organic phases were separated by centrifugation (Heraeus Megafuge
centrifuge 1.0). All pH measurements were performed using a pH meter
(S220 Seven Compact Mettler-Toledo).
2.3. Procedures
For the solvent extraction experiments, a synthetic aqueous feed was
prepared by dissolving CoSO4⋅7H2O and NiSO4⋅6H2O in water. The final
metal concentration was 1 g L-1 of cobalt and 1 g L-1 of nickel, and the pH
of the solution was 6.0. These concentrations were chosen to have a
simple system that allowed us to focus on the practical comparison be­
tween centrifugal contactors and mixer-settlers. It has to be noted that it
is extremely recommended to work with real solutions (i.e. more
concentrated, containing impurities) when the goal is to optimize a
solvent extraction process. The organic phases consisted of 0.2 M
Cyanex-272 in different diluents, except for the tests with variable
extractant concentrations. Prior to its use, the extractant Cyanex-272
was partially neutralized by dissolving NaOH directly in the organic
phase. In general, 40% of the Cyanex-272 was converted in the Na-
Cyanex-272 salt unless otherwise stated.
Batch experiments were carried out by contacting 2 mL of the
aqueous phase with 2 mL of the organic phase in closed 5 mL glass vials.
The vials were shaken at 25 ◦ C and 300 rpm for 30 min, unless otherwise
stated. Afterwards, samples were centrifuged at 3000 rpm to accelerate
phase separation. Samples of the aqueous phases were taken, diluted,
and measured with ICP-OES. The extraction of cobalt and nickel at
different concentrations of Cyanex-272 was studied, as well as their
extraction with variable degrees saponification of the extractant. Series
of extractions were carried out using 0.2 M of Cyanex-272 40% sapon­
ified in GS215, and samples were taken in different time intervals to
determine the loading profile as a function of time. Additionally, the
organic-to-aqueous phase ratio (O/A) was varied by keeping the total
volume of the phases fixed and changing the volumes of the organic and
aqueous phases accordingly. Batch extraction experiments were con­
ducted to simulate a counter-current multistage solvent extraction. Up
to 8 series of contacts were carried out, with each batch shaken for 5
min, and phase separation accelerated by centrifugation for 3 min.
Stripping of the loaded organic phase with H2SO4 was carried out using
the same procedure. The extraction percentage (%E) of a metal is calcu­
lated using Eq. (2):
Corg Vorg
%E = × 100 (2)
Corg Vorg + Caq Vaq
where corg and caq and Vorg and Vaq are metal concentrations and vol­
umes of the organic and aqueous phase at extraction equilibrium,
respectively. The percentage stripping (%S) is defined as the amount of
I.R. Rodrigues et al. Separation and Purification Technology 296 (2022) 121326

metal stripped from the organic phase to the total amount of metal in the
organic phase before stripping (Eq. (3)):
Caq .Vaq
%S = × 100 (3)
Corg Vorg + Caq Vaq

A battery of mixer-settlers (SX Kinetics, Canada) comprising 3

extraction and 3 stripping units was used to study the up-scaling of the
cobalt and nickel separation in counter-current mode. A mixer-settler
stage consisted of, (a) mixing chamber (270 mL), where the aqueous
and organic phases are mixed using a Caframo BDC250 stirrer, (b) the
settling chamber (1.050 L), where the phases were separated by density
difference. At the beginning of an experiment, each unit was filled by
adding first the aqueous phase and then the organic phase. Afterwards,
both aqueous and organic phases were pumped using a Masterflex L/S
Precision Variable-Speed Console Drive equipped with Easy-Load pump
heads. For the extraction experiments, the organic phase consisted of
0.2 M Cyanex-272 40% saponified in GS215, and a solution of 1 g L-1
cobalt and 1 g L-1 of nickel was used as the aqueous phase. A solution of
1.0 M H2SO4 was used to strip cobalt from the loaded organic phase. The
flowrates for the organic and aqueous phases during extraction and
Fig. 1. Effect of Cyanex-272 concentration on the extraction of cobalt and
stripping were 27 mL min− 1 and the mixing speed in the mixer chambers nickel from a sulfate solution of initial pH = 6. Experimental conditions: Cya­
was 1000 rpm. The organic-to-aqueous phase ratio (O/A) was 1/1 for nex-272 = 40% saponified in GS215; cobalt and nickel = 1 g L-1; phase ratio of
both the extraction and stripping, unless stated otherwise. Samples were O/A = 1/1; equilibration time: 30 min and equilibrium pH ~ 5 for all the
taken from the aqueous weir of each mixer-settler and diluted and extractions.
analyzed with ICP-OES. For comparison, the same separation was also
performed in an agitated extraction column type Kühni ECR 32 (Sulzer, metal loadings and in non-polar diluents, the acidic extractant tends to
Switzerland) made of borosilicate glass. The column consisted of 5 exist in its dimeric form, whereas at high metal loadings and in polar
sections with an inner diameter of 32 mm, the active volume was 0.9 L diluents it exists as a monomer [18,33]. The neutralization reaction can
when all the 5 column sections were used. The wetted internals (rotor be written as:
and stator) were made of PEEK and agitation in each stage was achieved
with a turbine agitator on top of the column. Two settlers were located at Na+ + 1/2 (HA)2 →NaA + H+ (4)
each end of the column. Both aqueous and organic phases were pumped
using a Masterflex L/S Precision Variable-Speed Console Drive equipped where HA represents the acidic extractant.
with Easy-Load pump heads. To ensure aqueous-continuous conditions, The degree of saponification was varied from 0 to 60%, whereas the
the column was quickly loaded by pumping the aqueous phase (90 mL concentration of the extractant kept constant at 0.2 M. A degree of
min− 1) from the upper inlet until the liquid was just below the upper saponification higher than 60% caused gel formation, and hence these
inlet, then the flow was reduced and set to 27 mL min− 1. The organic conditions were not further considered. The extraction of cobalt
phase was further pumped counter-currently from the bottom inlet at 27 increased with the increase in the degree of saponification. Almost all
mL min− 1 and when it reached the organic overflow in the top settler the the cobalt was extracted when the degree of saponification was 40% or
stirrer was started and set at 200 rpm. The interphase level was set in the higher, but some extent of nickel co-extraction was observed as well
middle of the top settler with the help of a siphon. Samples were taken (Fig. 2).
via the sampling points of each section of the column, diluted and
analyzed with ICP-OES.

3. Results and discussion

3.1. Optimization in batch

The separation of cobalt and nickel was studied via solvent extrac­
tion using Cyanex-272 as extractant diluted in Shell GTL GS215. The
first parameter investigated was the extractant concentration. Extrac­
tions were performed using an aqueous feed solution containing 1 g L-1
of cobalt and 1 g L-1 of nickel and pH = 6. For all tested extractant
concentrations, Cyanex-272 was partially converted to its sodium salt to
avoid large pH changes during extraction (40% degree of saponifica­
tion). The equilibrium pH was approximately 5 for all the extractions.
The extraction of cobalt increases from 16 to 97% with the extractant
concentration increasing from 0.015 to 0.2 M, whereas no co-extraction
of nickel is detected (Fig. 1).
Cyanex-272 is a cationic acidic extractant and releases protons as the
extraction proceeds. Therefore, it is expected that the pH of the aqueous
solution decreases during extraction. It is important to control the pH so Fig. 2. Effect of degree of saponification of the extractant Cyanex-272 on the
that the extraction of cobalt(II) can take place. One of the possible extraction of cobalt and nickel from a sulfate solution of initial pH = 6.
methods to maintain the equilibrium pH is the saponification of Cyanex- Experimental conditions: Cyanex-272 = 0.2 M in GS215; cobalt and nickel = 1
272. The sodium salt of the extractant was prepared by adding stoi­ g L-1; phase ratio of O/A = 1/1; equilibration time: 30 min. Equilibrium pH is
chiometric amount of sodium hydroxide to the organic phase. At low indicated at each point.

3
I.R. Rodrigues et al. Separation and Purification Technology 296 (2022) 121326

An extractant concentration of 0.2 M with a degree of saponification

of 40% was chosen as the condition to optimize the contact time. As it
can be seen in Fig. 3, the extraction of cobalt proceeded quickly, and
equilibrium was attained in less than 5 min. For nickel, some fluctua­
tions in the percentage extraction values were observed during the first
minute, but almost no nickel extraction was observed after 1 min.
Nevertheless, shaking for longer times, at the same extraction conditions
seems to have resulted in some co-extraction of nickel (Fig. 2). This is in
agreement with results by Zhou et al., where short contact times resulted
in less co-extraction of nickel [29] but further experiments would be
needed to corroborate that this is also our case.
By varying the organic-to-aqueous phase ratio (O/A = 1/11, 1/7, 1/
5, 1/3, 1/2, 1/1, 2/1, 3/1 and 5/1), a McCabe-Thiele diagram was
constructed for the cobalt extraction (Fig. 4). An O/A phase ratio of 1/
0.9 was selected to keep the nickel co-extraction negligible and work at
maximum loading conditions. Fig. 4 shows that for operating at O/A =
1/0.9, it is estimated that at least 3 extractions stages are required for
quantitative recovery of cobalt. For practical reasons an O/A phase ratio
of 1/1 was used in subsequent experiments.
The nature of the diluent can influence the selectivity of metals ions, Fig. 4. McCabe-Thiele diagram for the counter-current extraction of cobalt
playing an important role in the process of solvent extraction. Here, the using three extraction stages with phase ratio of O/A = 1/0.9. Experimental
separation of cobalt and nickel was evaluated for 11 different diluents. conditions: Cyanex-272 = 0.2 M 40% saponified in GS215; cobalt and nickel =
The diluents can be separated in 3 distinct groups: (1) fully aliphatic, (2) 1 g L-1; equilibration time: 30 min; and equilibrium pH ~ 5 for all the
mixed aliphatic–aromatic, and, (3) fully aromatic diluents. The first extractions.
group consisted of 6 aliphatic diluents: Shell GTL solvent GS270, Shell
GTL solvent GS250, Shell GTL solvent GS215, Shell GTL solvent GS190,
Shell GTL fluid G70, and ShellSol D70. The latest has a larger fraction of
cyclic aliphatic compounds in comparison to the GTL solvents. The
second group consisted of 2 mixed aliphatic–aromatic diluents: ShellSol
2046, and ShellSol 2325. The third group consisted of 3 aromatic dilu­
ents: ShellSol A150, o-xylene and toluene. The percentage extraction of
cobalt remained similar for the 3 groups of diluents tested, ranging be­
tween 95 and 98% (Fig. 5). These results show that different diluents can
replace each other without major changes in extraction behavior, which
was also reported by Singh et al. [34]. However, a significantly higher
nickel extraction efficiency was found with aromatic diluents, while the
lowest nickel extraction efficiency was observed for the aliphatic diluent
GS250. The increase in nickel extraction when using aromatic diluents
was previously reported by Preston et al. [28]. Moreover, in the group of
aliphatic diluents, the extraction efficiency of nickel decreased for
longer alkyl chains. Even though to a lesser degree, this trend was

Fig. 5. Effect of different diluents on the extraction of cobalt and nickel from a
sulfate solution of initial pH = 6. Experimental conditions: Cyanex-272 = 0.2 M
of 40% saponified indifferent diluents; cobalt and nickel = 1 g L-1; phase ratio of
O/A = 1/1; equilibration time: 30 min; and equilibrium pH ~ 5 for all the
extractions.

observed for the extraction of cobalt in the aliphatic group as well.

Fig. 3. Effect of the contact time on the percentage extraction of cobalt and
nickel from a sulfate solution of initial pH = 6. Experimental conditions: Cya­
nex-272 = 0.2 M 40% saponified in GS215; cobalt and nickel = 1 g L-1; phase
ratio of O/A = 1/1; and equilibrium pH ~ 5 for all the extractions.
Generally, the most often used aliphatic Shell diluent is the Shellsol D70.
Due to their similarity in flash point and viscosity, Shellsol D70 (78 ◦ C
and 2.0 mm2 s− 1) and Shell GS215 (85 ◦ C and 2.2 mm2 s− 1), and
considering the fact that GS215 presents a better selectivity for cobalt,
the aliphatic diluent Shell GS215 was selected for the up-scaling of this
study.
The next variable investigated was the stripping of cobalt from the
loaded organic phase. The effect of the sulfuric acid concentration on the
stripping efficiency was studied. Three concentrations were tested 0.5,
1.0 and 2.0 M of sulfuric acid. It can be seen from Fig. 6a that a stripping
percentage of 95% is obtained with 0.5 M of sulfuric acid. Fig. 6b shows
that the stripping is fast, and is completed in less than 1 min.

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I.R. Rodrigues et al.
Fig. 6. Effect of sulfuric acid concentration on the stripping of cobalt from the
loaded organic phase, cobalt = 0.9 g L-1 (a). Effect of the contact time on the
stripping of cobalt using 0.5 M of H2SO4 (b). Experimental conditions: Cyanex-
272 = 0.2 M, 40% saponified in GS215, phase ratio of O/A = 1/1; and variable
equilibration time.
3.2. Counter-current simulations
Before performing the counter-current experiments in the mixer-
settlers and the agitated column, a batch counter-current simulation
was carried out to detect possible problems that could arise in counter-
current extraction mode. Procedures to carry out the batch counter-
current simulation can be found in literature [35,36]. From the
McCabe-Thiele diagram (Fig. 4), three extraction stages were predicted
to be necessary for the full extraction of cobalt. As a precaution, an extra
stage was added in the counter-current tests. As it can be seen in Fig. 7a,
after four extraction stages cobalt was fully extracted, while nickel
remained in the raffinate. For this reason a scrubbing step was not
included in this study. Considering both extraction of cobalt and co-
extraction of nickel, three extraction stages and a O/A phase ratio of
1/1 were selected as optimal conditions for the up-scaling with mixer-
settlers. Fig. 7b shows the concentration profile of cobalt in the
aqueous phase during the three-stage counter-current simulation test,
which confirmed complete cobalt extraction. Fig. 7c shows the stripping
of the loaded organic phase that was obtained after the counter-current
stripping simulation experiments. It can be seen that only three stripping
stages are needed to recover cobalt quantitatively.
5
Separation and Purification Technology 296 (2022) 121326
Fig. 7. Percentage extraction of cobalt and nickel during a four-stage counter-
current extraction simulation (a), concentration profile of cobalt in the aqueous
phase during a three-stage counter-current extraction simulation (b) Experi­
mental conditions: Cyanex-272 = 0.2 M of 40% saponified; cobalt and nickel =
1 g L-1; phase ratio of O/A = 1/1; and equilibration time: 5 min.
3.3. Mixer-settler and agitated column tests
Based on the results obtained in the batch counter-current experi­
ments, a mixer-settler test was carried out using 3 stages for the
extraction at O/A ratio of 1/1. According to the stripping results (Fig. 6a
and 6b) 2 stages at O/A ratio of 1/1 should be enough but one extra
stage was added to be on the safe side. The flow rates were chosen as 27
mL min− 1 for each phase so that a retention time of 5 min could be
achieved in each mixer. To start the experiment, the mixers and the
settlers were half-filled with the aqueous phase and then the organic
phase was carefully poured on top. Both phases were then pumped, and
the stirring was started. Within minutes of operation, the system started
to develop a milky emulsion in all the settlers. Neither decreasing the
flow rates or reducing the stirring speed helped to break the emulsion.
The experiment was stopped when the emulsion started entering the
aqueous flow outlet in one of the settlers, the battery was emptied and
cleaned. In a second attempt, the pumps were started at a lower flow rate
(18 mL min− 1), but the same white emulsion was present again and
could not be broken. The battery had to be cleaned and re-started one
more time. It is important to note that during the batch experiments in
small scale (4 mL vials) this emulsion was never seen. When running
tests in a larger scale (i.e. in a beaker, mixing 100 mL of each phase and
I.R. Rodrigues et al. Separation and Purification Technology 296 (2022) 121326

using an overhead stirring) it was observed that the system tended to

emulsify when the organic phase was the continuous one. In other
words, when the aqueous phase was dispersed in the organic one by
either placing the impeller of the overhead stirrer in the organic phase or
by having a larger amount of organic phase with respect to the aqueous.
For these reasons, it was decided to re-start the battery using an O/A
ratio of 1/1.5 to ensure aqueous continuous conditions. The stirrers in
the mixer were also located in the aqueous phase. Based on the infor­
mation gathered from the batch experiments it was expected that using
an O/A ratio of 1/1.5 would not allow the complete extraction of cobalt
from the feed, but the goal of this experiment was to see if by ensuring
aqueous continuous conditions the formation of the emulsion could be
avoided. To keep such O/A ratio the flow rates were kept at 27 mL min− 1
for the aqueous phase and 18 mL min− 1 for the organic phase. The
operation of the mixer-settler at these conditions was smooth and
straightforward. No third phase, precipitation or emulsion was observed
in any of the chambers during the 4 h of operation. The loaded-organic
phase obtained during this 4 h of operation was then used to fill the
mixers and settlers of the stripping stages together with the stripping
solution. The extraction and the stripping sections were connected so
that loaded organic freshly produced in the extraction stages could flow
to the first stripping stage. The stripping was tested at O/A 1/1 and the
flow rates were kept at 18 mL min− 1 for the aqueous phase and 18 mL
min− 1 for the organic phase. No emulsion was formed, and no problems
were encountered when operating both the extraction and the stripping.
Fig. 8 shows the extraction and stripping stages at equilibrium at the end
of the experiment. In this figure it can be seen how the pink, charac­
teristic color of the feed, due to the presence of cobalt(II) sulfate, fades
away as the feed, which enters in the stage EX1, is contacted with the
organic phase in the different extraction stages. In EX3 it can be seen
how at equilibrium the aqueous phase has the characteristic blue-
greenish color of the nickel(II) sulfate solution. The loaded organic
phase that exits EX1 flows to the first stripping unit STP1 and the
stripping is so efficient that almost all cobalt is stripped in the first stage
and the intense blue color, characteristic of the loaded organic phase, is
almost completely gone. In STP3 the fresh stripping H2SO4 solution
enters, and it exits through STP1 fully loaded with cobalt.
Fig. 9a shows the concentration profile of cobalt and nickel in the
aqueous phase in each stage at equilibrium, using an O/A ratio of 1/1.5. Fig. 9. Concentration profile of cobalt and nickel during extraction in mixer-
settlers using O/A = 1/1.5 (a), concentration profile of cobalt in the organic
As expected, the concentration of cobalt in the aqueous phase decreased
phase during stripping in mixer-settlers with O/A = 1/1 (b).
as it was extracted to the organic phase, however it was not fully
extracted because the maximum loading capacity of the extractant was

Fig. 8. Recovery of cobalt from a nickel and cobalt sulfate feed using three stages of extraction and three stages of stripping in mixer-settlers. Picture taken at
chemical equilibrium. The organic phase circulates from left to right and the aqueous phase moves from right to left. Loaded organic phase from the extraction exits
from EX1 and enters STP1. Fresh stripping solution enters from the right in STP3 and exits in STP1. O/A = 1/1.5 for the extraction and O/A = 1/1 for the stripping
with H2SO4.

6
I.R. Rodrigues et al.
reached at these conditions. Nickel also behaved as expected and was
not co-extracted in any of the stages. Fig. 9b shows the concentration of
cobalt in the organic phase during stripping. As it can be seen, only 1
stage is enough to fully strip cobalt from the loaded organic phase. This
is consistent with the photograph shown in Fig. 8 where it can be seen
that in stage STP1 the organic phase is no longer blue whereas the
aqueous phase (i.e. the strip product solution) has the characteristic pink
color of cobalt(II) sulfate in solution.
Although the experiment was successful and it was possible to carry
out the extraction of cobalt without having problems or emulsion for­
mation, the system did not fully extract cobalt because the organic phase
reached its maximum loading. Either the concentration of extractant
had to be increased to reach 100% of extraction at O/A of 1/1.5 or a way
to operate the mixer-settler at O/A of 1/1 that tackled down the emul­
sion formation had to be found. Before running the mixer-settler at O/A
of 1/1, the system was tested in an agitated column. The aim of this
experiment was to compare and analyze the differences that exist when
operating two different types of solvent extraction equipment.
Currently, it is still very difficult to find in the literature concrete ex­
amples in which two or more contactors are compared for the same type
of extraction experiments. Most available information about the oper­
ation of columns and mixer-settlers in SX corresponds to textbook ex­
amples in which the practicalities and bottlenecks are usually not
covered. In general, agitated columns are preferred over mixer-settlers
in cases in which a larger number of stages are required to achieve the
separation and if there are floor area limitations but no height con­
straints. In a column, the continuous phase will be the phase that is used
to fill in the column which is also usually the phase that is being used in a
larger proportion. For comparison purposes, the same flows and the
same O/A ratios that were employed in the previous mixer-settler
experiment were also used for the experiment in the column.
Fig. 10 shows a picture of the column during the extraction using an
O/A ratio of 1/1.5 (27 mL min− 1 aqueous phase and 18 mL min− 1
organic phase) and a stirring speed of 150 rpm. The different sampling
Fig. 10. Extraction of cobalt in an agitated column (ECR32 Kühni-type).
Conditions: Cyanex-272 = 0.2 M of 40% saponified; cobalt and nickel = 1 g L-1;
phase ratio of O/A = 1/1.5; stirring speed = 150 rpm. Hn (n = 1, 2…) denotes
the sampling points of each one of the sections of the column.
7
Separation and Purification Technology 296 (2022) 121326
points are denoted as Hn (n = 1, 2…). The blue cobalt-loaded organic
phase can be seen in the top settler, whereas the blue-greenish raffinate
rich in nickel is present in the bottom settler. Fig. 11a shows the con­
centration profile of cobalt as a function of the height in the column once
chemical equilibrium was attained. The feed enters from the top of the
column, and it can be seen how the concentration of cobalt decreases as
the feed heads towards the bottom of the column. The concentration of
nickel remains constant through the column. No emulsification, flooding
or precipitation was observed during the 6 h that the column was
operated. As expected, cobalt was not fully extracted and part of it
remained in the raffinate because, as in the case of the previous exper­
iment in the mixer-settler, there was not enough extractant available
when operating in an O/A ratio of 1/1.5. After collecting enough loaded
organic phase to carry out the stripping, the column was emptied,
cleaned and filled with the stripping solution and then the loaded-
organic phase was dispersed in it. The results of the stripping at equi­
librium conditions can be seen in Fig. 11b. No problems were encoun­
tered during the operation of the stripping in the agitated column. As it
can be seen in Fig. 11b the stripping of cobalt proceeded smoothly and
all the cobalt could be stripped by using all the sections of the column. It
Fig. 11. Extraction of cobalt from a cobalt and nickel sulfate feed in an agitated
column; experimental conditions: Cyanex-272 = 0.2 M in GS215; cobalt and
nickel = 1 g L-1; phase ratio of O/A = 1/1.5, aqueous phase 27 mL min− 1,
organic phase: 18 mL min− 1 (a). Stripping of cobalt in an agitated column,
experimental conditions: H2SO4 0.5 M, O/A = 1/1, aqueous phase 18 mL
min− 1, organic phase: 18 mL min− 1(b).
I.R. Rodrigues et al. Separation and Purification Technology 296 (2022) 121326

is important to notice that this system is far from being optimized. When
working with an agitated column the flows and the stirring speed play a
key role because they influence the droplet size which at the same time is
related to flooding and back mixing. Further optimization should lead to
a system in which less sections of the column are required to carry out
the extraction and the stripping.
The results obtained from both contactors are consistent with each
other. Even though in both cases cobalt was almost fully extracted and
could be completely stripped, there are differences on the way the
agitated columns and mixer-settlers are operated in practice. Contrary to
a column which is a differential contactor, a mixer-settler is composed of
discrete stages. In each one of these discrete stages, not only the mixing
but also the separation of both phases takes place, which allows to
maintain the chemical and hydraulic equilibrium whenever the mixer-
settlers need to be shut down. The height of the interphase in each
one of these stages is regulated by a weir. In simple systems and in large
mixer-settlers, it is very straightforward to determine the height at
which the weir needs to be positioned so that a given height of the
interphase in the settler can be reached. In more complex systems in
which the density of the phases is changing dramatically between stages
the weirs would need to be readjusted from time to time until hydraulic
and chemical equilibrium is attained. This is not problematic at all in
systems in which a small number of mixer-settlers are being controlled.
In systems in which dozens of stages are required, this can become
cumbersome and difficult the work at a small pilot scale where opti­
mization is still needed. On the other hand, there is only one weir per
column, and this simplifies the work when operating systems in which a
larger amount of stages are required and there are not the resources for
automation nor the footprint for placing mixer-settlers. One of the
biggest advantages of working with the mixer-settlers is that it is very
easy to re-start them after shutting them down at the end of the workday
or in case problems arise. In a column, where no discrete stages exist, the
phases will disengage, and the equilibrium conditions will be lost once
the column is stopped. One would need to run the column for some time
before the equilibrium is reached again. Depending on the characteris­
tics of both phases this re-starting procedure can become challenging.
Furthermore, connecting mixer-settlers between each other is relatively
easy, the extraction and the stripping units are usually connected
without problems. In the case of agitated columns, more engineering
would be needed because any fluctuation in the operation in the first
column can significantly involve a perturbation in the second one. For
this particular system, there were no huge differences in what concerns
the operation of the extraction and stripping either in one equipment or
Fig. 12. Extraction of cobalt in an agitated column (ECR32 Kühni-type) at
the other as long as aqueous conditions could be met (i.e. O/A = 1/1.5).
equilibrium. The organic phase enters from the bottom and the feed from the
Finally, we wanted to test again the possibility to carry out the
top of the column. The top settler is rich in loaded organic phase containing the
extraction and the stripping at O/A = 1/1. Already from the first ex­ cobalt whereas the bottom settler contains the raffinate rich in nickel (a).
periments, it became clear that it was almost impossible to start the Profile concentration of cobalt and nickel as a function of the column height (b).
mixer-settlers under those conditions by using the standard typical start Conditions: Cyanex-272 = 0.2 M of 40% saponified; cobalt and nickel = 1 g L-1;
procedures. Therefore, the column was operated at O/A 1/1 and it was phase ratio of O/A = 1/1, stirring speed = 200 rpm; aqueous and organic flows
observed that it could be started without any problem and no emulsion = 28 and 27 mL min− 1.
was present at any time. The extraction and the stripping ran smoothly
and by increasing the flow rates and the stirring speed the efficiency exits from the top settler. The way the column is loaded, and the phase
could also be improved, to the point that only three sections of the continuity maintained by filling the column first with the aqueous
column were used instead of five. Even though for this experiment the phase, strengthened the idea that the system could be run at O/A = 1/1
stirring speed was kept at 200 rpm and the flows at 27 mL min− 1 for each in the mixer-settler if aqueous continuous conditions were ensured all
phase, the authors are convinced that there is room for further optimi­ the time. In fact, the emulsion in the mixer-settler only appeared when
zation and that probably the process can be even carried out in a shorter the phase continuity was lost, and this was due to small changes in the
column. However, further optimization experiments were not per­ flows when trying to reach hydraulic equilibrium. For example, at the
formed because they would have been too lengthy and consume too start-up when filling any of the mixers or the settlers with the aqueous
many chemicals. Fig. 12a shows a picture of the column at equilibrium phase, part of this aqueous phase goes to the aqueous weirs. One must be
when using O/A = 1/1. Fig. 12b shows the profile of concentrations in careful and add more aqueous phase so that one can ensure that there is
the different heights of the column for the aqueous phase during a small excess of aqueous phase. Moreover, working with a slightly
extraction at O/A = 1/1. As it can be seen, cobalt is fully extracted and higher flow of the aqueous phase is also recommended. When one is not
loaded into the organic phase whereas nickel remains in the raffinate. In careful during start-up and adds an excess of the organic phase on top of
Fig. 12a it can be seen how the blue-greenish raffinate rich in nickel the aqueous phase, the organic phase will become the continuous one.
leaves the column from the bottom and how the loaded organic phase

8
I.R. Rodrigues et al. Separation and Purification Technology 296 (2022) 121326

This, in the case of the present study, leads to an emulsion that is

extremely difficult to break. The only way to solve this is to fully stop the
extraction battery, empty and re-start it again, this situation is expensive
in terms of time and money. In conclusion, if aqueous continuous con­
ditions are required and it is desired to work at O/A = 1/1, one must
start-up the mixers and the settlers with a larger proportion of aqueous
phase. For example, O/A = 1/1.2, and run the aqueous phase with a
slightly larger flow than the one of the organic. It is also important to
slowly adjust the aqueous weirs so the system can have O/A = 1/1
conditions in the mixers and in the settlers. For these experiments, the
flows for the aqueous and the organic phases corresponded to 28 and 27
mL min− 1, respectively. Fig. 13a shows a picture of the extraction being
carried out in the mixer-settler at nearly O/A = 1/1 and Fig. 13b shows
the concentration profile of cobalt. It can be seen how in the same case as
in the column, cobalt could be fully extracted as it was expected ac­
cording to the batch counter-current experiments. In the end, the sep­
aration can be carried out in both types of equipment, but it was much
easier to keep aqueous continuous conditions in the column than in the
mixer-settlers. This could be due to two reasons, the first one is the way
the set-ups are filled up. Since the whole column is filled with aqueous
phase and then the organic phase is easily dispersed into it, it is easier to
maintain aqueous continuous conditions in a column. The second reason
is that in the mixer-settlers there are more weirs that need to be adjusted
and if the height of these is changed drastically, it can lead to much less
or much more aqueous phase in the next mixer. If less aqueous phase
enters the subsequent mixer and the mixer already contains a significant
amount of organic phase, the phase continuity will change, and an
emulsion will be formed. In some systems, this is not really critical
because the emulsion breaks easily, but in the system studied in this
work the emulsion was very stable. It must be realized that the geometry
and the design of the settler plays a key role on the separation of the
emulsion that is formed and that for extraction systems that tend to
emulsify it would be worth considering the use of settlers with a larger
area than the one used in this study [37].

4. Conclusions

This paper addresses the optimization of several variables for the

separation of cobalt and nickel via solvent extraction. The commercial
extractant Cyanex-272 partially converted to its sodium salt was
investigated for the removal of cobalt from a synthetic feed containing
equivalent amounts of cobalt and nickel. The performance of different
aliphatic, mixed aliphatic–aromatic, and aromatic diluents was studied.
The nature of the diluent had no significant impact on the extraction of
cobalt. However, the co-extraction of nickel was found to be approx­
imatively 10% lower in aliphatic diluents than in aromatic ones. The
separation process was up-scaled using mixer-settlers and an agitated
column. The two types of contactors were efficient for the separation
and recovery of cobalt from a cobalt and nickel sulfate feed. In both
cases, after some optimization, excellent separation was achieved and
cobalt could be recovered. The advantages and disadvantages of the
practicalities for the use of the contactors were discussed. Recommen­
dations on how to startup and operate the contactors when working with
systems that tend to emulsify were also given.
Fig. 13. Extraction of cobalt from a nickel and cobalt sulfate feed in mixer-
settlers at equilibrium. The organic phase circulates from left to right and the
aqueous phase moves from right to left (a). Profile concentration of cobalt and
nickel in the different stages of the mixer-settler (b). Conditions: Cyanex-272 =
0.2 M of 40% saponified; cobalt and nickel = 1 g L-1; phase ratio of O/A = 1/1,
aqueous phase 28 mL min− 1, organic phase: 27 mL min− 1.
relationships which may be considered as potential competing interests:
Sofia Riano reports financial support was provided by Horizon 2020.
Isadora R. Rodrigues reports financial support was provided by Horizon
2020. Clio Deferm reports financial support was provided by Horizon
2020. Koen Binnemans reports financial support was provided by Ho­
rizon 2020.
Acknowledgments

CRediT authorship contribution statement
Isadora R. Rodrigues: Investigation, Writing – original draft. Clio
Deferm: Conceptualization, Writing – review & editing. Koen Binne­
mans: Conceptualization, Supervision, Writing – review & editing,
Funding acquisition. Sofía Riaño: Conceptualization, Investigation,
Supervision, Writing – review & editing.
Declaration of Competing Interest
The authors declare the following financial interests/personal
The research leading to these results has received funding from the
European Union’s Horizon 2020 research and innovation program
under grant agreement no.776846 (NEMO). This publication reflects
only the author’s view, exempting the Community from any liability.
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