The Journal of Supercritical Fluids 128 (2017) 26–31

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The Journal of Supercritical Fluids

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

Improvement of recovery performance in the solvent extraction of Cu(II) MARK

using [bmim][Tf2N] and a β-diketone as extractant and its stripping with
supercritical carbon dioxide
⁎
Rossana Sepúlvedaa, , Jonathan Castilloa, Andrea Plazab,c, José Sánchezd, Alejandra Torrese,
Julio Romeroc
a
Department of Metallurgy Engineering, University of Atacama, Av. Copayapu 485, Copiapó, Chile
b
Centro de Estudios en Alimentos Procesados (CEAP), CONICYT-Regional, Gore Maule R09I2001, Casilla 1007, Talca, Chile
c
Laboratory of Membrane Separation Processes (LabProSeM), Department of Chemical Engineering, University of Santiago de Chile, Av. Libertador Bernardo O‘Higgins
3363, Estación Central, Chile
d
Institut Européen des Membranes (IEM), ENSCM, UM2, CNRS, Université de Montpellier 2, CC 047,Place Eugène Bataillon 34095, Montpellier, France
e
Food Packaging Laboratory, University of Santiago de Chile, Obispo Manuel Umaña 050, Estación Central Santiago, Chile

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

Keywords: This study deals with the improvement of the recovery performance in the solvent extraction of Cu(II) using the
Metal extraction ionic liquid [bmim][Tf2N] and the β-diketone 1,1,1-trifluoro-2,4-pentanedione (TFA) as extractant and its
Stripping stripping with supercritical carbon dioxide.
1-Butyl-3-methylimidazolium bis This work describes a modified procedure, which shows better L-L extraction percentages with a decreasing of
(trifluoromethylsulfonyl)imide
the concentration of TFA, the contacting time and the volumetric O/A ratio respect to the previously reported
Copper
tests. Thus, the extraction was implemented with a concentration of TFA in [bmim][Tf2N] equal to 60 mol m−3,
β-Diketone
Supercritical carbon dioxide a contacting time of 5 min and an O/A ratio equal to 1:7.
The stripping of the metal complex from the organic phase was achieved in semi-continuous mode with
scCO2. This configuration allowed obtaining a stripping percentage higher than the obtained with a previously
tested procedure in batch mode with a consumption of CO2 4.3 times lower than the observed one in previous
work.

1. Introduction conventional techniques, such as precipitation, adsorption and ion

In recent decades, our environment both urban and industrial has
had an accelerated growth, which involves the generation of a great
amount of wastes such as mining wastes, fertilizers, batteries, pesti-
cides, dyes, among others. Solutions containing heavy metals from
different sources are directly or indirectly discharged into the environ-
ment. Even at very low concentrations, these discharge streams strongly
affects environment and living beings. Elements with atomic weight
between 63.5 and 200.6 g mol−1 and specific gravity greater than 5 are
considered heavy metals. These elements are not biodegradable, tend to
accumulate in living organism, its contamination is more persistent
than the observed ones for organic pollutants such as pesticides or
petroleum derivative products. Furthermore, some of these elements
are carcinogenic [1–3]. Copper, zinc, nickel, mercury, cadmium, lead
and chromium are the most common heavy metals present in industrial
wastewaters. The treatment of these wastewaters can be achieved with
exchange. However, novel techniques that involve the use of ionic
liquids or supercritical fluids as extraction phases have been proposed
in literature in the last years [4–6].
Ionic liquids (ILs) are compounds with a wide variety of chemical
structures, gaining attention because of its unique and specific physi-
cochemical properties as tunable broad-spectrum solvents with extre-
mely low volatility and specific electrochemical characteristics, among
others. These remarkable properties can be explained by the special
chemical nature of ILs, which are completely formed by ions in liquid
phase. These species are in the most of cases composed by a relatively
large organic cation such as imidazolium, pyridinium, pyrrolidinium,
phosphonium or ammonium jointly with an anion, which may be
inorganic (e.g. Cl−, PF− −
6 or BF 4) or organic (e.g. trifluoroethanoate,
− − −
TFO , NTf2 , CH3COO ). This combination offers many possibilities
to develop task-specific solvents and reagents [7–13]. Thus, ILs have
been considered a new class of “green solvents”. The use of ionic liquids

⁎
Corresponding author at: Universidad de Atacama, Departamento de Ingeniería en Metalurgia, Av. Copayapu 485, Copiapó, Región de Atacama, Chile.
E-mail address: rossana.sepulveda@uda.cl (R. Sepúlveda).

http://dx.doi.org/10.1016/j.supflu.2017.05.003
Received 10 January 2017; Received in revised form 3 May 2017; Accepted 4 May 2017
Available online 04 May 2017
0896-8446/ © 2017 Elsevier B.V. All rights reserved.
R. Sepúlveda et al.
has covered areas such extraction and separation of compounds,
catalysis, lubricants, materials manufacture, analytical chemistry and
energy [14,15].
In this framework, this work is presented as the natural continuation
of our previous study on the copper(II) extraction [16]. In this
contribution, the extraction with and IL containing an extractant agent
is improved in terms of its operational parameters; meanwhile, the
respective stripping with supercritical carbon dioxide has been verified
as a feasible process coupled to the first extraction step.
1.1. Ionic liquids and supercritical fluids in the extraction of metal species
The specific extraction of copper from aqueous solutions has
motivated the development of a great variety of processes such as
liquid/liquid extraction, micro-encapsulation, membrane process, ad-
sorbent materials impregnation, among others. All these processes use
organic solvents (e.g. n-heptane, toluene and kerosene, etc), which are
volatile, toxic and flammable, as well as extractants mainly represented
by aldoximes and ketoximes, such as LIX® 984, LIX® 860, Acorga® P50,
LIX® 54 and esters (PC-88A) [17–23]. In this framework, one of the
main goals in the design of greener extraction or recovery processes
involves the decreasing in the requirement of organic solvents. Thus,
the use of hydrophobic ionic liquids (ILs) has been considered an
alternative in biphasic or solvent extraction (commonly called SX) of
different metal ions from aqueous solutions [16,24,25]. In this way, the
extraction of copper has been reported in literature using ammonium or
quaternary phosphonium-based ionic liquids for biphasic extraction;
meanwhile PF6-based ionic liquids have been used as solvents [26–28].
When ILs are used as solvents in SX processes little amounts of
extractants, which form hydrophobic metallic complex, are required.
A vast body of literature reports this type of extraction of copper as well
as the subsequent stripping from the organic phase [12,17–23,29–33].
Furthermore, academic studies report the use of pyrridinium, ammonia
and phosphonium-based ILs for copper recuperation. These ILs are
proposed as extractants and as solvents, which show high extraction
efficiencies and selectivities, achieving very high values of Cu(II)
recovery and other metal species such as Zn, Co and Pb [34–37].
On the other hand, the effort to develop green separation processes
involves other technologies, which share the conceptual condition of
reducing the requirement of organic solvents and its drawbacks. One of
these technologies is the supercritical fluid extraction, mainly focused
on the use of dense CO2 as alternative solvent. Supercritical carbon
dioxide (scCO2) is the most used supercritical fluid because of its special
properties, which confer it a hybrid character between gas and liquid
with good transport properties and high solvent capacity specially of
apolar organic molecules. Moreover, the solvent power of dense CO2
can be “tunable” as a function of density, its critical temperature is
Table 1
Name and structural formula of the hydrophobic ionic liquid and the β-diketone used in this work as diluent and extractant, respectively.
Name
1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
([bmim][Tf2N])
1,1,1-trifluoro-2,4-pentanedione (TFA)
The Journal of Supercritical Fluids 128 (2017) 26–31
relatively low (31 °C) and it is cheap, chemically inert, non-flammable
and non-toxic [15,38].
Conventional L/L extraction processes remove metal ions from
dilute aqueous solution to be transferred to an organic solution, the
extracted specie is concentrated in the organic phase and finally
retroextracted and concentrated in a second aqueous solution. The
extraction process coupling IL to scCO2 follows this same principle by
means of the extraction of the metal specie of interest from an aqueous
solution using a hydrophobic ionic liquid as solvent; meanwhile the
supercritical fluid is used as stripping phase to recover the complex
formed in the IL phase [15]. This metal extraction process can be
carried out with amounts of water, solvent and extractant lower than
are commonly used in conventional processes and reaching similar
extraction efficiency values.
There are some studies reported in literature on the extraction of
metal ions using supercritical fluids [39–43] and ILs coupled to super-
critical fluids [16,44,45]. In our previous contribution [16] we have
tested an extraction technique to recover Cu(II) from aqueous solutions
based on the use of an organic phase formed by an imidazolium-based
ionic liquid as solvent and a β-diketone (1,1,1-trifluoro-2,4-pentane-
dione, TFA) as extractant agent. The complex formed in the organic
phase, i.e. Cu(TFA)2 in [hmim][PF6], was retroextracted with super-
critical carbon dioxide and the organic phase was regenerated for reuse.
In those work [16], three different imidazolium-based ILs were tested as
solvents: [bmim][PF6], [hmim][PF6] and [bmim][Tf2N], obtaining the
best results with the last one after sequential loads of copper ions.
In this framework, the aim of this work involves the improvement of
the extraction and stripping of Cu(II) ions from an aqueous solution
using [bmim][Tf2N] as solvent containing a fluorated β-diketone as
extractant and dense carbon dioxide as stripping phase. This study is
focused on the effect of the concentration of extractant, phase contact
time, volumetric Organic/Aqueous (O/A) ratio and overall volume of
dense CO2 on the whole process efficiency.
2. Materials and methods
2.1. Materials and reagents
The ionic liquid used in this study was 1-butyl-3-methylimidazolium
bis(trifluoromethylsulfonyl)imide ([bmim][Tf2N]), which was supplied
by Sigma-Aldrich® with purity higher than 99% with synthesis grade,
the density and viscosity reported in literature are equal to 1.43 g cm−1
and 52 cp at 20 °C, respectively [46]. The chosen extractant was the β-
diketone 1,1,1-trifluoro-2,4-pentanedione, commonly referred to as
TFA, supplied by Sigma-Aldrich®, and used without further purification.
Table 1, shows the chemical structures of the ionic liquid and
extractant.
Structural formula
Cation
Anion
R1 = CF3; R2 = CH3
27
R. Sepúlveda et al.
Fig. 1. Extraction percentage of copper from aqueous solution as a function of the initial
concentration of TFA in the IL phase. Initial concentration of Cu2+ = 250 mg L−1;
volumetric O/A rate 1:1, initial pH = 5.3 ± 0.2, SO42− = 0.1 M.
On the other hand, copper sulphate pentahydrate (CuSO4 × 5H2O),
copper chloride (II) dihydrate (CuCl2 × 2H2O) and sulphuric acid
(H2SO4) were supplied by Biopack® and anhydrous sodium sulphate
(Na2SO4) in analytical grade was supplied by Merck®. Carbon dioxide
99.9% was purchased from Linde®.
Aqueous solutions containing Cu(II) ions were prepared from
dilution of CuSO4 × 5H2O, CuCl2 × 2H2O and H2SO4 in deionized
water. Furthermore, anhydrous Na2SO4 was added to these solutions in
order to enhance the phase separation before the L-L extraction step. pH
of these solutions was measured before and after extraction tests using a
pHmeter.
After L-L extraction test ionic liquid phase samples were collected
and analysed by atomic absorption spectroscopy. These samples were
previously dissolved in analytical grade ethanol supplied by Biopack®.
2.2. Analyses
The concentration of copper in aqueous and organic phases was
quantified by Atomic Absorption Spectroscopy (AAS) (GBC Scientific
Equipment Model AA, equipped with a mono-element Photron lamp of
4 mA). The concentration of Cu(II) ions was measured in the aqueous
phase before and after L-L extraction tests. Meanwhile, the quantifica-
tion of concentration of copper was carried out on the ionic liquid phase
samples after the L-L extraction tests and the L-scCO2 stripping test.
2.3. Liquid-liquid extraction and L-scCO2 stripping tests
The removal of copper from the aqueous solutions has been carried
out by means of the same procedure reported in our previous work
[16]. Thus, L-L extraction tests were achieved by contacting 3 mL of
aqueous solution with 3 mL of organic phase formed by [bmim][Tf2N]
and TFA for 45 min in order to reach the equilibrium conditions.
Na2SO4 was added to the aqueous solution (0.1 mol L−1 of SO42−) in
order to facilitate the phase separation, which was achieved by
centrifugation [16]. After phase separation the final values of pH and
the concentration of Cu(II) in the aqueous phase were measured with a
pH-meter and by AAS, respectively.
From the results previously reported in literature [16], it has been
verified that the extraction of Cu(II) from an aqueous phase using
[bmim][Tf2N] as diluent and TFA as extractant is governed by the
following reaction, which describes the cation exchange with formation
of a neutral complex Cu(TFA)2:
2+
Cuaq +
+ 2TFAIL ⇔ CuTFA2IL + 2Haq
The Journal of Supercritical Fluids 128 (2017) 26–31
The initial concentration of Cu(II) ions in the aqueous solution was
250 mg L−1; meanwhile, the initial concentration of TFA in [bmim]
[Tf2N] was ranged from 7.83 to 310 mol m−3 in order to find the
minimal concentration quantity of extractant for a feasible extraction.
Moreover, contact times were varied from 5 to 90 min and O/A ratio
was ranged from 1:1 to 1:10.
After the L-L extraction step, the aqueous and organic phases were
separated by centrifugation and the concentration of copper in both
phases was quantified.
The extraction performance has been quantified through the
extraction percentage (%E) and the total extracted mass of copper for
each extraction step (EMtotal), which are defined by Eqs. (2) and (3),
respectively:
⎛ Amount of extracted metal ⎞
%E = ⎜ ⎟ × 100
⎝ Initial amount of metal in the aqueous solution ⎠ (2)
n
EMtotal = ∑ Mass extracted in step i
i =1 (3)
On the other hand, specific L-L extraction experiments were carried
out in order to prepare IL phases loaded with Cu(II) ions. Thus, these
organic solutions were used in stripping tests. The IL phase loaded with
copper was placed in a 100 mL high-pressure extraction vessel and
contacted with supercritical carbon dioxide at 18 MPa and 40 °C with
sequential discharges and recharges of dense CO2 every 20 min main-
taining pressure and temperature. After contact time the cell was
depressurized, the IL phase was recovered and its sample diluted in
ethanol was analysed by AAS. The experimental systems of extraction
and stripping used in this study preserve the same configuration of the
reported one in our previous work [16].
3. Results and discussion
3.1. Effect of the concentration of extractant on the L-L extraction
performance
One of the main parameters in the SX process is the concentration of
extractant, since the chemical nature of this extraction process depends
on the concentration of this reagent. Fig. 1 shows the extraction
percentage of copper obtained from L-L extraction as function of the
initial concentration of the extractant, i.e. TFA, when the volumetric O/
A rate was 1.0 and the initial pH and concentration of sulphate in the
aqueous solution was equal to 5.3 and 0.1 M, respectively. The
experimental results reported in Fig. 1 are as expected, since the
increasing of the extractant concentration involves an increasing of
the extraction percentage of copper. Nevertheless, these results show
that it is not necessary a significant increase of the extractant
concentration to reach a large improvement in the extraction capacity.
Thus, in the range between 60 and 310 mol m−3 of TFA in [bmim]
[Tf2N] the extraction percentages are varying from 79% to 88%. This
response could be explained by a maximum load of complexes in the LI
phase, which would be independent of the excess of extractant present
in the L-L system. In this way, the initial concentration chosen for the
improved extraction tests is equal to 60 mol m−3.
3.2. Effect of the stirring time on the extraction efficiency
The other parameter that has to be optimized to assess the scale up
and design of this type of extraction process is the operating time.
Previous work [16] reported L-L extraction experiments during 45 min,
assuming this time as the necessary to reach equilibrium. However,
there is no detailed studies about the influence of the operating time on
the extraction performance with ILs containing β-diketones as organic
(1) phase. Thus, this work considered additional L-L extraction test at
different contacting times varying from 5 to 90 min. All these test were
28
R. Sepúlveda et al.
Table 2
Extraction percentage of copper from aqueous solution at different operating times.
Contacting time (minutes) Extraction percentages (%)
5 87.35 ± 1.30
10 86.53 ± 1.30
20 87.35 ± 1.30
40 88.98 ± 1.30
90 88.16 ± 1.30
Extraction conditions: Initial concentration of Cu2+ = 250 mg L−1; initial concentra-
tion of TFA = 310 mol m−3; volumetric O/A ratio 1:1 (3 mL each); initial
pH = 5.3 ± 0.2, SO42− = 0.1 M.
carried out at the same O/A ratio and stirring conditions.
Table 2 shows the extraction percentages obtained for experimental
runs with different contacting times. It is possible to observe that there
is no significant difference between the obtained extraction percen-
tages. Thus, the equilibrium seems to be reached very fast and 5 min
can be considered the best contacting time to obtain close to 88% of the
extraction under the operational conditions of this study.
Experiments reported in Table 2 consider a constant pH value,
which was maintained unchanged using a buffer solution controlling
the chemical equilibrium of the complex formation without influence of
the proton production.
3.3. O/A ratio
Once the best or most economical concentration of extractant and
contacting time were found to improve the L-L extraction process, the
volumetric O/A ratio was modified in order to assess its effect on the L-
L extraction performance. In this way, a set of extraction tests was
carried out using an initial concentration of extractant in [bmim][Tf2N]
equal to 60 mol m−3, using a buffer solution with a pH = 5.3 ± 0.2
and a concentration of SO42− equal to 0.1 M. Fig. 2 shows the results
obtained related to the extracted amount of extracted copper in mg as a
function of different volumetric O/A ratios, which vary in volumes of
1:1, 1:3; 1:7 and 1:10. The values reported in Fig. 2 involves extraction
with a constant volume of IL equal to 3 mL.
From these results it is possible to see an optimal value of O/A equal
to 1:7. It could be expected that a higher O/A ratio involves higher
extraction percentage. However, in this case a higher volume of
aqueous phase contains an amount of copper, which is larger than
the amount of extractant available in the IL phase according to the
stoichiometry of Eq. (1).
On the other hand, the value of extraction percentage obtained in
Fig. 2. Phases ratio effect IL/aqueous on extracted mass per liter of copper, initial
concentration of Cu2+ = 250 mg L−1, concentration of TFA = 60 mol m−3, buffer solu-
tion = 5.3 ± 0.2, SO42− = 0.1 M.
29
The Journal of Supercritical Fluids 128 (2017) 26–31
Table 3
Best operating condition for extraction of copper from an aqueous solution containing
250 mg L−1 of Cu(II) using [bmim][Tf2N] containing TFA as organic extraction phase.
Condition Value Unit
Concentration of TFA in [bmim][Tf2N] 60 mol m−3
Stirring time 5 minutes
Initial pH value 5.3 ± 0.2 (buffered) –
Volumetric O/A phase ratio 7:1 –
these experimental runs for an O/A ratio equal to 1:1 is higher than the
obtained one in the experiments reported in Fig. 1 when the initial
concentration of TFA in the IL is equal to 60 mol m−3. This fact proves
again that the use of a buffered aqueous solution reduces the effect of
the equilibrium pH on the extraction performance.
From these results, we can suggest the L-L extraction operating with
a volumetric O/A ratio equal to 7:1 when the concentration of TFA is
equal to mol m−3 and the aqueous solution is buffered at pH = 5.3.
Table 3 summarizes the values of operational parameters found in
this work to obtain the best extraction percentages and amounts of
extracted copper from an aqueous solution with 250 mg L-1 of Cu(II) at
25 °C.
3.4. Optimization of the L-scCO2 stripping step
The final step of this study involved the improvement of the
stripping performance using dense carbon dioxide to recover the metal
complex formed in the IL phase. Processes coupling ILs with super-
critical fluids, specially with scCO2, represent a synergic partnership of
two different and complementary green solvents, which involves
multistep operations without cross contamination because of the
negligible solubilisation of ILs in dense gases.
In this work, the stripping of copper as Cu(TFA)2 from the IL using a
stripping with supercritical carbon dioxide was carried out at the same
conditions reported in our previous contribution [16]. IL phase samples
(3 mL) loaded with copper as metal complex were collected and the
metal specie was retroextracted with scCO2 at a pressure and tempera-
ture of 18 MPa and 40 °C, respectively. However, in this work the
stripping configuration has been modified in order to pressurize the
same 100 mL high-pressure vessel used in the previous study [16], but
decreasing the total contacting time from 4 h to 1 or 2 h. Thus, the
stripping procedure involves between three and six partial depressur-
ization and recharge steps of fresh CO2 every 20 min, keeping the
pressure constant and equal to 18 MPa during the whole procedure time
of 1 or 2 h, respectively. Each depressurization step involved a release
of 250 mL (NTP) of CO2 from the high-pressure vessel using a
micrometric valve. Additional stripping tests carried out during 4 h
were not reported in this work because no improvement was observed
when its results were compared with experiments developed during 2 h.
The results of the original methodology and the modified one are
reported in Table 4, which reports the total amount of recovered metal
complex, the required overall mass of CO2, the recovered complex/used
CO2 ratio and the stripping percentage as a function of the initial
amount of copper loaded in the IL phase.
From the results reported in Table 4, it can be seen the great
improvement in terms of amount of metal complex recovered with the
modified stripping procedure. Thus, the mass of recovered metal
complex was increased in more than 9 times in this work; meanwhile,
the consumption of CO2 increased from 0.082 to 0.178 kg with this
modified procedure. This increasing in the overall amount of CO2
required by this new procedure does not represent a restriction because
the mass of recovered complex per mass of CO2 increases 4.3 times in
this work, obtaining a global stripping percentage of 48.36%. The
performance of this stripping technique could be even more improved
in a future study with a continuous phase contactor device in order to
R. Sepúlveda et al.
Table 4
Results of stripping procedures for copper recovery obtained for batch mode [16] and for the modified method proposed in this work.
Condition Initial amount of Cu(TFA)2 in Recovered
LI, mg Cu(TFA)2, mg
Stripping in batch mode 0.636 0.237
(18 MPa, 40 °C, 4 h) [16]
Stripping with depressurization and recharge 4.470 2.162
steps
(18 MPa, 40 °C, 4 h)
(this work)
optimize fluid dynamic conditions as well as to increase the superficial
contact area between the phases.
4. Conclusions
This work describes a significant improvement in the performance
of extraction and recovery of copper from aqueous solutions using L-L
extraction with an ionic liquid as organic diluent coupled to the use of
supercritical carbon dioxide as stripping phase. Thus, this study reports
better extraction percentages than previous results [16], decreasing the
concentration of the extractant agent (TFA), the contacting time and the
volumetric O/A ratio in 5, 9 and 7 times, respectively.
Furthermore, the stripping step to recover the metal complex, Cu
(TFA)2, from the IL phase obtained from L-L extraction tests, was
achieved by using a semi-continuous procedure with a scCO2 stream.
This stripping process allows obtaining a stripping percentage higher
than the obtained one with a previously tested procedure in batch mode
under the same pressure, temperature and overall time. In this case, the
consumption of carbon dioxide was reduced in 4.3 times to obtain the
same amount of recovered copper.
This study aims to improve the operating conditions to remove
Cu+2 from an aqueous solution in a solvent-free process. The config-
uration based on a L-L extraction step followed by a L-scCO2 stripping
step was chosen to compare its performance with well-known hydro-
metallurgical processes. However, conventional processes are certainly
easier and cheaper to the recovery of copper with the current
technology. In this way, the studied case can be considered as a model
system to propose the direct obtaining of metal beta-diketonates, which
can be used as precursors for inorganic materials prepared by sol-gel
method [47], chemical vapor deposition (CVD) [48] or atomic layer
deposition (ALD) [49].
The reported results show a real improvement in the process yield
decreasing the requirements of ionic liquid, extractant and dense CO2.
Future research should be focused on the selectivity of this extraction-
stripping procedure and its application to obtain metal beta-diketonates
from other metal species.
Acknowledgments
This study has been supported by the Research Projec DIUDA 22274
from the University of Atacama and the Project FONDECYT 1140208
from CONICYT Chile. The Laboratory of Membrane Separation
Processes, LabProSeM, is supported by the Project RC-130006, CILIS,
granted by Fondo de Innovación para la Competitividad, del Ministerio
de Economía, Fomento y Turismo, Chile.
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