Research Article

Received: 30 May 2013

Revised: 13 August 2013

Accepted: 14 August 2013

(wileyonlinelibrary.com) DOI 10.1002/jctb.4330

Copper removal from aqueous solutions by

means of ionic liquids containing a -diketone
and the recovery of metal complexes by
supercritical uid extraction
Rossana Seplveda,a Julio Romeroa* and Jos Snchezb
Abstract
BACKGROUND: This work is focused on the removal of Cu(II) ions from aqueous solutions by means of dierent hydrophobic
imidazolium-based ionic liquids containing 1,1,1-triuoro-2,4-pentanedione (TFA) as extractant and the subsequent extraction
of the metal complexes formed in the IL by means of supercritical uid extraction.
RESULTS: Solutions containing between 250 and 500 mg L-1 of Cu(II) ions were contacted with [bmim][PF6 ], [hmim][PF6 ] and
[bmim][Tf2 N] containing TFA. After liquidliquid extraction, both phases were analysed, verifying the formation of neutral
complex Cu(TFA)2 as the predominant extraction mechanism in [bmim][PF6 ] and [bmim][Tf2 N]. Meanwhile, the extraction of
Cu(II) in [bmim][PF6 ] was strongly inuenced by the direct interaction between the metal ion and the IL. ILs used in LL
extractions were regenerated using supercritical CO2 at 18 MPa and 40 C. [bmim][Tf2 N] showed the highest accumulative
extraction percentage ( 80%) after sequential loads of Cu(II) ions.
CONCLUSION: From these tests, [bmim][Tf2 N] was the solvent that showed the best performance in terms of accumulative
extraction and recycling capacity in sequential extraction cycles mediated by regeneration with supercritical CO2 . This study
demonstrates that this process could be considered an alternative separation technique for metal ions using green solvents,
and with extractant requirements lower than in conventional solvent extraction operations.
2014 Society of Chemical Industry
Keywords: metal extraction; ionic liquids; copper; -diketone; supercritical uids

INTRODUCTION

J Chem Technol Biotechnol 2014; 89: 899908

Some chemical aspects related to the extraction mechanisms of

metal ions in ILs and supercritical uids are still unknown.11,12 The
comparative analysis of well-known systems such as the extraction
of Cu(II), Ni(II) and Zn(II) could be the basis to understand and
propose more complex applications.13 15
In this work, three dierent imidazolium-based ionic liquids are used to extract Cu2+ from aqueous solutions, using
1,1,1-triuoro-2,4-pentanedione (TFA) as extractant agent. In this
way, the extraction performance and mechanism could be established and subsequently the IL with the best extraction capacity
was used in regeneration steps with supercritical CO2 .

Correspondence to: Julio Romero, Universidad de Santiago de Chile (USACH),

Departamento de Ingeniera Qumic, Av. Lib. Bdo. OHiggins 3363, Estacin
Central, Santiago Chile. E-mail: julio.romero@usach.cl

a Laboratory of Membrane Separation Processes (LabProSeM), Department of

Chemical Engineering, University of Santiago de Chile
b Institut Europen des Membranes, UMR 5635, Universit de Montpellier 2,
Montpellier, France

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899

Conventional treatments used to remove metal ions from aqueous solutions require the addition of large amounts of organic solvents, which can be highly polluting.1,2 Therefore, much research
has been devoted to the identication of alternative solvents
that are environmentally friendly. Among these unconventional
solvents, ionic liquids emerge as a versatile option with very
tunable properties because of the diversity of their chemical
structure.
The low volatility of the ionic liquids is a key property that makes
them good candidates for use as green solvents. However, this
characteristic also causes problems for the separation and recovery of the product.3 Other disadvantages of ionic liquids are their
toxicity, chemical and thermal instability (e.g. PF6 anion hydrolyzing), its slow degradability, high production costs and the diculty
of purication.4 6 In this way, the design of intensied processes
combining ILs with other green technologies such as supercritical uids could overcome this disadvantage. Several authors7 10
report studies about the combined use of ionic liquids and supercritical uids. Thus, solutes dissolved in ILs can be separated by
means of stripping with a dense gas phase. This conguration
avoids concerns related to cross-contamination and generation of
secondary wastes. Extractions combining the use of ionic liquids

and supercritical uids have been applied for soil remediation,10

the removal of metal ions and decontamination of radioactive
species.7 9

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EXTRACTION PROCESSES COUPLING IONIC

LIQUIDS AND SUPERCRITICAL FLUIDS

900

The advantages of using supercritical carbon dioxide as extraction

medium include low cost, non-toxic nature, recoverability and
facility for separation from the products. Supercritical uids (SCFs)
have been adapted for product recovery from RTILs and uid
extraction (SFE) is shown to be a viable technology with additional benets of environmental sustainability and pure product
recovery.16 Among the SCFs, an inexpensive and readily available
one, SC CO2 has become a partner of ILs and both environmentally
benign solvents are utilized together in several applications.3 The
volatile and non-polar SC CO2 forms dierent two-phase systems
with nonvolatile and polar ILs. The product recovery process with
these systems is based on the principle that SC CO2 is soluble in
ILs, but ILs are not soluble in SC CO2 .17 Since most of the organic
compounds are soluble in SC CO2 , with the high solubility of
SC CO2 in ILs, these products are transferred from the ILs to the
supercritical phase.
Keskin and coworkers3,10 reported a detailed review of the
major applications for ILs coupled to supercritical uids, including a summary of physico-chemical properties of ionic liquids
and its interaction with supercritical carbon dioxide. This review
shows the potential applications for solvent replacement, purication of gases, homogeneous and heterogeneous catalysis and
biological reaction media. Several studies found that nonvolatile
organic compounds can be extracted from RTILs by using SC CO2 .
Blanchard and coworkers18 showed that CO2 can be used to extract
naphthalene from an IL. They synthesized and used [bmim][PF6 ] as
IL. Naphthalene was readily soluble in the ionic liquid and in CO2 .
The IL was not detectable in the extract, indicating that the solubility is less than 10-5 mole fraction. Furthermore, the dissolution
of SC CO2 in [bmim][PF6 ] was completely reversible and pure IL
remained after extraction of naphthalene.
Liu and coworkers19 reported phase equilibrium data for the
separation of high boiling point organics from [bmim][PF6 ] and
[bmim][CF3 SO3 ] by supercritical uids. They propose the use of
C3 H8 as a good alternative to CO2 in some cases.
Moreover, the extraction of Cu(II), uranium and lanthanides by
adding -diketone and tributylphosphate (TBP) from ionic liquids
using supercritical carbon dioxide has been studied obtaining high
extraction eciency values.7 9,20 Furthermore, SC CO2 was also
used for the extraction of other organic compounds (aromatics:
benzoic acid, benzene, chlorobenzene, among other; aliphatics:
hexane, chlorohexane 1,4-butanediol, among others) from IL.16,21
Supercritical carbon dioxide (SC CO2 ) has been used to remove
metal ions from aqueous solutions by the formation of complex
between Cu(II) and a complex agent, due to its high solubility
in supercritical CO2 , allowing high extraction eciencies in the
stripping process.12,22 26 The literature contains a series of studies
focused on analysing the properties of the complexes formed
between copper(II) ion and extractants type -diketone12,27 29 or
Cu(II)-benzoyl acetone complexes extracted by SC CO2 .30 Other
works report specic points on the extraction of metals, such as the
solubility of the complexes in supercritical carbon dioxide.22,23,26
However, this information is available only for some systems.
The supercritical uid extraction of metal ions from aqueous
solutions could represent an expensive process, especially if the
volume of solutions to be treated is large. Furthermore, the complex formation could be explained by dierent mechanisms, which
could be dicult to identify due to the pH modication of aqueous solution in the presence of pressurized CO2 .12 In this way, the
coupling with IL could improve this separation process, since the

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R Seplveda, J Romero, J Snchez

aqueous-IL contact can be done at low pressure and optimized in
terms of the required volumes of IL. Thus, metal complexes formed
in the IL phase can be removed with supercritical carbon dioxide in
a more compact process system, which allows implementing the
recycling of both solvents.
Studied system
The system studied in this work considers in a rst step the
liquidliquid extraction of Cu2+ from aqueous solutions using
three dierent imidazolium-based ILs, which contained TFA as
extractant agent. As a second step, the removal of metal complexes formed in the IL phase was achieved by using supercritical
carbon dioxide as stripping phase. The main goal of this study is
the identication of the IL with highest potential to replace the
organic solvent used in a typical extraction process, identifying the
predominant extraction mechanism (cation exchange, solvation,
keto-enol tautomerism, etc.) and therefore the suitable extraction
conditions.
The rst set of experiments involved liquidliquid extractions.
Aqueous CuSO4 solutions were contacted with three dierent
imidazolium-based IL containing 1,1,1-triuoro-2,4-pentanedione
(TFA). The ionic liquids selected for these experiments were
1-butyl-3-methylimidazolium hexauorophosphate, [bmim]
[PF6 ], 1-hexyl-3-methylimidazolium hexauorophosphate, [hmim]
[PF6 ], and 1-butyl-3-methylimidazolium bis(triuoromethylsulfonyl)imide, [bmim][Tf2 N]. These ILs were chosen based on a
wide characterization of its properties and previous experiences
reported in the literature about their solvent capacities.3 TFA
shows a low solubility in water and it can form neutral metal
complexes, which are soluble in dense CO2 . Then TFA was chosen
as extractant considering its high extraction capacity of copper
ions from aqueous solutions when it is dissolved in supercritical
carbon dioxide.12

MATERIALS AND METHODS

Materials and reagents
The ionic liquids 1-butyl-3-methylimidazolium hexauorophosphate, [bmim][PF6 ], 1-hexyl-3-methylimidazolium hexauorophosphate, [hmim][PF6 ], and 1-butyl-3-methylimidazolium
bis(triuoromethylsulfonyl)imide, [bmim][Tf2 N], were supplied by
Sigma-Aldrich with purities higher than 99% for synthesis grade.
The -diketone used as extractant was 1,1,1-triuoro-2,4-pentanedione (TFA) and it was supplied by Sigma-Aldrich without
further purication.
For the preparation of aqueous solutions we used copper sulphate pentahydrate (CuSO4 5H2 O), copper chloride(II) dihydrate
(CuCl2 2H2 O) and sulphuric acid (H2 SO4 ) (Biopack) and anhydrous sodium sulphate (Na2 SO4 ), (Merck). All these compounds
were of analytical grade. The solutions were prepared in distilled
water.
The purity of CO2 used for the supercritical extraction tests was
99.9%.
For atomic absorption spectroscopy analysis of ionic liquid samples containing Cu-TFA complexes were dissolved in analytical
grade ethanol (Biopack).
Analyses
After the liquidliquid extraction experiments, aqueous solutions
were separated and analysed by means of atomic absorption spectroscopy (AAS) (GBC Scientic Equipment Model AA, equipped

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J Chem Technol Biotechnol 2014; 89: 899908

Copper ions removal by ionic liquids coupled to supercritical uid extraction

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Figure 1. Outline of extraction and regeneration experiments implemented in this work.

with a mono-element Photron lamp of 4 mA). Simultaneously, the

nal concentration of Cu(II) in the IL phase was measured with the
same AAS method, but these samples were dissolved in ethanol.
The same analyses were carried out in the IL phases after being previously separated and diluted in ethanol. pH of aqueous solutions
was measured with a pHmeter.

following equations:
(
)
Amount of extracted metal
%E =
Initial amount of the metal in the aqueous solution
100

(1)

J Chem Technol Biotechnol 2014; 89: 899908

(Mass extracted in step i)

(2)

i=1

In a second set of experiments, several sequential extractions

were done using to the same procedure described above, but
recycling the same initial volume of IL, which was regenerated
with supercritical carbon dioxide to remove the Cu(II) complexes
formed in the previous extraction. In these sequential extractions,
fresh TFA was added in the reused IL in order to maintain the
original concentration of TFA (310 mol m-3 ), taking into account the
assumption that all the not reacted TFA is removed in the contact
with supercritical CO2 .
Determination of extraction mechanism
During the extraction experiments, the initial and nal pH values of aqueous solution were monitored to verify the copper
removal mechanism. In the removal of copper ions by solvent
extraction with IL and beta-diketones, the expected mechanism is a cation exchange. However, if this is the mechanism,
which can be veried in conventional organic solvents, it must
be proved in ILs, since dierent complexation modes have been
observed.31 33 Indeed Cu(II)-TFA complex formation in ILs may
generate three type of neutral or ionic species (n molecules
of copper react with m molecules of TFA): Cu(TFA)n with n = 2;
Cu(TFA)n (2-n)+ with n < 2; and Cu(TFA)n (n-2)- with n > 2, where Cu(II)
complexes with m molecules of TFA release n protons. Previous
reports in the literature31 33 described the extraction of Cu(II)

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901

Liquidliquid extraction experiments

Extraction of Cu(II) ions from aqueous solutions using ILs was done
using the conguration described in Fig. 1. For experiments we
used aqueous solutions with Cu(II) ion concentrations between
250 and 500 mg L-1 . Meanwhile, the concentration of TFA solutions
in ILs used for extraction was 310 mol m-3 . This concentration was
chosen in order to compare the extraction capacity of this system
with a previous study reported by Valds and coworkers.12
Experiments were carried out at 25 C (1 C), putting into contact under vigorous stirring equal volumes of TFA/IL and copper
aqueous solution (3 mL + 3 mL) for 45 min in order to reach
the equilibrium conditions. Na2 SO4 was added to the aqueous
solution in order to obtain 0.1 mol L-1 of SO4 -2 in solution and
to improve the phase separation. After the extraction run, both
phases were separated by centrifugation, the nal pH of the
aqueous solution was measured with a pH-meter and the nal
concentration of Cu(II) in the aqueous phase and IL was analysed
as explained above. In the second step, the IL phase loaded with
Cu(II) and recovered from the extraction experiments was placed
in a view cell to be contacted with supercritical carbon dioxide
in order to achieve the equilibrium conditions, regenerating the
extraction capacity of the IL by means of the removal of the
formed complexes.
The extraction performance was characterized by means of the
extraction percentage (%E) and the extracted mass of copper for
each extraction step (MEi ). These parameters are dened by the

MEi =

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R Seplveda, J Romero, J Snchez

by means of [bmim][Tf2 N] and [bmim][PF6 ] containing Htta

(4,4,4-triuoro-1-(2-thienyl)-1,3-butanedione) according to the
formation of a neutral complex. In this way, we have taken into
account this assumption to verify the complex formation mechanism in our system. Thus, the extraction of Cu2+ from the aqueous
phase would be described through the following equation at
equilibrium conditions:
+ 2TFA(IL) Cu (TFA)2(IL) + 2H+(aq)
Cu2+
(aq)

(3)

and its equilibrium constant of the extraction reaction would be

given by the following expression:
[

Kext

[ + ]2
] [ ]2
Cu (TFA)2 (IL) H+ (aq)
H (aq)
= [
=D
]
2
2+
[TFA]2(IL)
Cu (aq) [TFA](IL)

(4)

where the concentrations are the equilibrium values in the

aqueous (aq) and ionic liquid (IL) phases, and D is dened as the
dimensionless distribution coecient (D = [Cu(TFA)2 ](IL) /[Cu2+ ](aq) ).
A logarithmic form of this relationship allows Equation (4) to be
rewritten as follows:
)
(
(5)
Log D = 2pH + Log Kext [TFA]2(IL)
where the pH is considered at equilibrium condition. Thus, if the
cation exchange mechanism is observed under the stoichiometry
described in Equation (3), the slope of log D as a function of
the equilibrium pH would be equal to 2 according to Equation
(5). The AAS analysis done on the aqueous and IL phases after
each extraction allows calculation of the concentration related to
copper species, meanwhile the mass balance allows estimation of
the concentration of TFA under equilibrium conditions in order to
verify the y-intercept of Equation (5).
Supercritical extraction of metal-complexes formed in IL
After the separation of phases contacted in liquidliquid extraction, the IL phase loaded with Cu(II) and recovered from the
extraction experiments was placed in a 100 mL view cell to be
contacted with supercritical carbon dioxide at 18 MPa and 40 C
for 4 h to achieve equilibrium conditions. Supercritical extraction
tests to remove the copper complexes were done in a device specially designed for this purpose where a view cell containing the
IL phase was loaded with CO2 , which was pressurized with high
pressure air-driven pump Autoclave Engineers G35.
The ionic liquid was removed from the cell after this processing
and sent for analysis by AAS as an ethanol-based sample. Additional experiments were done using the same volume of ionic
liquid in cycles of liquidliquid extraction and supercritical regeneration of the IL phase in order to verify the feasibility to reuse
a constant volume of IL as solvent maintaining its extraction and
regeneration capacity.

RESULTS AND DISCUSSION

902

Extraction mechanism and stoichiometry

The rst step of this study involves elucidation of the extraction
mechanism when Ils are used as solvents. -diketones can show a
cation exchange behavior with the formation of neutral complexes
in conventional organic solvents, but this fact must be veried in
the imidazolium-based ILs selected in this work.

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Distribution ratio (D) was calculated as: complex concentration

in the IL phase/metal concentration in the aqueous phase; and the
linearization of the extraction constant equation makes it possible
to plot the value of log D as a function of the equilibrium pH (Fig. 2),
checking if the slope of the adjusted curve is coherent with the
extraction stoichiometry. Figure 2 shows the results obtained for
the correlations done for the experimental extractions data with
the dierent ionic liquids under the same initial conditions: initial
concentrations of Cu(II) and TFA were 250 mg L-1 and 310 mol m-3 ,
respectively; volumetric phase ratio was 1:1; initial concentration
of SO4 2- in the aqueous solution equal to 0.1 mol L-1 , and an initial
pH value of 5.3 0.2. Figure 2(A) and 2(B) show a good agreement
between the experimental data for [bmim][PF6 ] and [bmim][Tf2 N],
respectively, and the supposed stoichiometry related to the formation of a neutral complex Cu(TFA)2 through Equation (3). This
is not the case for the experiments done with [hmim][PF6 ] and
reported in Fig. 2(C), where the linear function of the supposed
stoichiometry couldnt be correctly correlated. This fact was conrmed by the results reported in Fig. 3, which shows the eect of
the concentration of TFA on the extraction percentage. The percentage extraction of copper for TFA-free [hmim][PF6 ] suggests an
additional mechanism with a direct interaction between the metal
cation and this IL, which could explain the solvation of the Cu(II)
ions in [hmim][PF6 ] or even a certain reactivity.
Eect of the concentration of TFA and copper
on the extraction performance
The eect of the initial concentration of extractant agent in the ILs
on the extraction capacity was assessed in experiments under similar conditions to the extractions reported in the previous section.
In this case, the concentration of TFA in the IL was varied between
0 and 310 mol m-3 . Since the veried extraction mechanism can
be described by Equation (1) for at least two of the three ILs, the
initial concentration values of TFA chosen for these experiments
was the stoichiometric concentration, which was 7.86 mol m-3 . The
results reported in Fig. 3, show a particular extraction behaviour
of [hmim][PF6 ], since this is the only IL capable of extracting a
signicant amount of Cu(II) without the presence of TFA and it
shows the highest extraction percentage values in these tests.
Moreover, as observed above, the extraction of experiments done
with [hmim][PF6 ] and reported in Fig. 2(C), show that the linear
function of the supposed stoichiometry couldnt be correctly
correlated as for the two other ILs. Nevertheless, this result could
represent a restriction in the use of this IL for this type of application, since if stable copper species are formed in the IL phase,
its removal from this phase could be more dicult, However,
additional studies must be done in order to identify the extraction
mechanism with [hmim][PF6 ].
On the other hand, [bmim][PF6 ] and [bmim][Tf2 N] both show
a clear cation exchange behaviour, but present dierent extraction capacity response when the concentration of TFA changes.
In Fig. 3, [bmim][PF6 ] shows relatively low Cu(II) extraction percentages when the concentration of TFA is equal to or lower
than the stoichiometric value. Despite the fact that the extraction percentage increases when the concentration of TFA increases
from the stoichiometric value 100 mol m-3 , further TFA concentration enhancement results in identical extraction capacity. This
result indicates that the TFAsolvent interaction plays a fundamental role because even if the extracting molecule concentration
increases, the maximum extraction capacity seems to have been
reached in this solvent.

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B 1.0

0.3
0.2

0.8
Log D

Log D

0.1
0.0
-0.1
y = 2.0799x3.723
R2 = 0.99317

-0.2
-0.3
1.0

1.5

2.0

2.5

0.6
0.4
y = 2.010x3.24
R2 = 0.997

0.2
0.0
1.0

3.0

1.5

2.0
Equilibrium pH

Equilibrium pH

2.5

3.0

C 0.8

Log D

0.7
0.6
0.5
y = 0.4146x0.25129
R2 = 0.37583

0.4
0.3
1.0

1.5

2.0

2.5

3.0

Equilibrium pH

Extraction percentage, %

Figure 2. Plots of log D as a function of pH for (A) [bmim][PF6 ]; (B) [bmim][Tf2 N]; (C) [hmim][PF6 ]. Initial concentration of Cu(II) and TFA, 250 mg L-1 and
310 mol m-3 respectively, phase rate 1:1 (3 mL of each solution), SO4 2- =0.1 mol L-1 , initial pH=5.3 0.2.

100
90
80
70
60
50
40
30
20
10
0
[bmim][PF6] [bmim][Tf2N] [hmim][PF6]
Ionic liquid
TFA free

Stoichiometric TFA

TFA = 100 mol/m3

TFA = 310 mol/m3

Figure 3. Eect of TFA concentration on the extraction percentage. Initial

concentration of Cu(II) 250 mg L-1 , phase rate 1:1 (3 mL of each solution),
SO4 2- = 0.1 mol L-1 , initial pH=5.3 0.2.

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903

The results obtained for extractions done with [bmim][Tf2 N]

show a dierent behaviour with a continuous increase of the
extraction percentage with increasing concentration of TFA from
0 to 310 mol m-3 . Indeed, [bmim][Tf2 N] seems to be the solvent
that generates the best extraction equilibrium condition among
the selected ones and it forms neutral complexes, which could be
extracted from the IL phase by contact with supercritical carbon
dioxide.
An additional set of experiments was done in order to verify the
eect of the initial concentration of Cu(II) in the aqueous phase on
the extraction performance. Figures 4 and 5 show the results for
extraction percentage and equilibrium concentration of copper,
respectively, for two dierent values of initial concentrations of

Cu(II): 250 and 500 mg L-1 . In this work, the concentration of

copper in the aqueous phase ranged from 250 to 500 mg L-1 ,
since this value may be considered representative of a wide
range of conditions in dierent types of processes. Meanwhile,
the concentration of TFA was held constant and equal to 310 mol
m-3 . This choice was made in order to use a signicant excess
of extractant on the metal ion. This concentration represents an
excess of 78.5 and 39.4 for 250 and 500 mg L-1 , respectively, times
on the stoichiometric amount. Moreover, this concentration of TFA
was chosen in a previous study of supercritical uid extraction
of Cu(II) ions.12 Thus, in that work CO2 was saturated with TFA
estimating its concentration at 310 mol m-3 .
Figures 4 and 5 show a slight dierence between the extraction percentages and equilibrium concentrations of Cu(II) when
[hmim][PF6 ] was used with and without TFA. These results conrm that most of the extraction of copper in [hmim][PF6 ] can be
explained by a direct interaction between the metal ion and the IL;
this particular and very interesting behaviour will be the subject of
future research.
Moreover, the selection of the best imidazolium-based salt
among the other two ILs, [bmim][PF6 ] and [bmim][Tf2 N], requires
more experiments in order to determine which IL has the highest
Cu(II) load capacity. These tests will be reported in the following
sections.
The extraction percentages obtained in this work can be considered relatively high compared with the extraction percentage
obtained using extractants and solvents that are commonly used
at industrial scale. Asghari and coworkers34 reported extraction
percentages of copper close to 93% from solutions with concentrations of 500 mg L-1 . These authors used an extraction phase
composed of LIX 984N and kerosene with a concentration of
extractant compound of 18% w/v. In this work, the concentration

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B 100
Extraction percentage, %

Extraction percentage, %

A 100

R Seplveda, J Romero, J Snchez

90
80
70
60
50
40
30
20
10
0

90
80
70
60
50
40
30
20
10
0

250
500
Cu(II) in the feed, mg L-1

250
500
Cu(II) in the feed, mg L-1

TFA = 310 mol m-3

TFA free

TFA free

TFA = 310 mol m-3

Extraction percentage, %

C 100
90
80
70
60
50
40
30
20
10
0
250
500
Cu(II) in the feed, mg L-1
TFA free

TFA = 310 mol m-3

Figure 4. Extraction percentage as a function of the initial concentrations of Cu(II)(aq) and TFA(IL) , (A) [bmim][PF6 ], (B) [bmim][Tf2 N] and (C) [hmim][PF6 ].
Phase rate 1:1 (3 mL of each solution), SO4 2- =0.1 mol L-1 , initial pH=5.3 0.2.

of TFA (310 mol m-3 ) was equivalent to 3.67% w/v, obtaining extraction percentages, which reached values between 35% and 60% for
the tested ILs in a single extraction step from aqueous solutions
containing 500 mg L-1 of Cu(II).
Eect of the aqueous solution medium on the extraction
capacity
In order to understand the phenomena related to metal ion transfer from the aqueous solution to the IL phase, a set of extraction runs were done modifying the anionic medium in the aqueous phase. Thus, parallel extractions were carried out with solutions prepared from CuSO4 and CuCl2 . Figure 6 compares the
experimental results in terms of the extraction percentages of
Cu(II) when chloride and sulphate media were used with and
without addition of TFA in the IL phase. Figure 6(A) shows the
extraction percentages for the three TFA-free ILs. Low extraction
percentage values observed for [bmim][PF6 ] and [bmim][Tf2 N]
in sulphate medium were slightly increased when the extractions were done in chloride medium. In contrast, extractions with
TFA-free [hmim][PF6 ] in chloride medium showed only half of the
extraction percentages reached in sulphate medium. When TFA
was added to the IL phase, this dierence between the media
was no longer observed. Thus, Fig. 6(B) shows practically the same
extraction percentage with all ILs when the extractions were done
in sulphate or chloride medium. In terms of applicability, the
removal of Cu(II) ions could be implemented in both media, but
the majority of solutions handled in industry contain sulphates.

904

Accumulative extraction capacity of the ILs

Selection of the best extraction solvent among the three
imidazolium-based ILs chosen in this work must be based on

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its accumulative extraction capacity. Indeed, the copper load

capacity of each ILs was assessed following a procedure similar to
that used for liquidliquid extraction tests described previously,
but with an accumulative extraction of Cu(II) ions in the same
volume of IL. For this purpose, the same IL was used consecutively
for the extraction of fresh aqueous solutions containing Cu(II)
ions, the process was carried out four times. Figure 7 reports
these results in terms of the extraction percentage (Fig. 7(A)) and
concentration of copper in the IL (Fig. 7(B)) for the three ILs when
the initial concentrations of Cu(II)(aq) and TFA(IL) were 250 mg L-1
and 310 mol m-3 , respectively. Every extraction step was done
with the same volumetric aqueous/IL ratio (1:1).
Figure 7(A) and 7(B) show that both [bmim][PF6 ] and [hmim][PF6 ]
did not show any increase in its copper content after the third
successive extraction step; these results indicate that the capacity of the TFA in both IL seems to be reached. Meanwhile, copper
content in [bmim][Tf2 N] continues to increase after four successive extractions. This higher extraction capacity is observed in the
IL with a larger anion and the cation with shortest 1-alkyl chain.
Kidani and Imura11 report dierences in the solubility values of
Cu(II) and Ni(II) complexes in [Cn mim][Tf2 N] having dierent 1-alkyl
chains in the cation. This range of solubility values and extraction
capacity could be explained by the dierent magnitudes of van der
Waals interactions and the change in the molar volume caused by
1-alkyl groups. However, there are still many unidentied characteristics of ionic liquids that require more fundamental studies oft
solubility, distribution, and solvation of metal ions, extractant compounds and complexes involved in the process.
From these results, the IL selected for sequential regeneration
steps with supercritical carbon dioxide and extraction cycles was
[bmim][Tf2 N].

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Copper ions removal by ionic liquids coupled to supercritical uid extraction

B
300

Cu(II) in the ionic liquid, mg L-1

Cu(II) in the ionic liquid, mg L-1

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250
200
150
100
50
0
250

300
250
200
150
100
50

500

0
250

Cu(II) in the feed, mg L-1

TFA = 310 mol m-3

Cu(II) in the ionic liquid, mg L-1

TFA free

500

Cu(II) in the feed, mg L-1

TFA free

TFA = 310 mol m-3

300
250
200
150
100
50
0
250

500

Cu(II) in the feed, mg L-1

TFA = 310 mol m-3

TFA free

Figure 5. Equilibrium concentration of Cu(II) in the aqueous phase as a function of the initial concentrations of Cu(II)(aq) and TFA(IL) , (A) [bmim][PF6 ], (B)
[bmim][Tf2 N] and (C) [hmim][PF6 ]. Phase relationship 1:1 (3 mL of each solution), SO4 2- =0.1 mol L-1 , initial pH=5.3 0.2.

100
90
80
70
60
50
40
30
20
10
0

Extraction percentage, %

Extraction percentage, %

[bmim][PF6] [bmim][Tf2N] [hmim][PF6]

100
90
80
70
60
50
40
30
20
10
0
[bmim][PF6] [bmim][Tf2N]

Ionic liquid
Chloride medium

[hmim][PF6]

Ionic liquid

Sulphate medium

Chloride medium

Sulphate medium

Figure 6. Extraction percentage for chloride and sulphate medium: (A) without TFA; (B) with TFA = 310 mol m-3 . Initial concentration of Cu(II) 250 mg L-1 ,
phase rate 1:1 (3 mL of each solution), SO4 2- =0.1 mol L-1 , initial pH=5.3 0.2.

J Chem Technol Biotechnol 2014; 89: 899908

with carbon dioxide at 180 bar and 40 C for 40 min. Then, the cell
was depressurized and the IL phase was recovered and analysed by
AAS as ethanol-based sample. Table 1 reports the concentration of
copper before and after recovery with supercritical carbon dioxide
for [bmim][Tf2 N] and [hmim][PF6 ]. Unfortunately, the [bmim][PF6 ]
sample could not be analysed, since it was not totally soluble
in ethanol. From these results, it is possible to verify the higher
extraction capacity of [bmim][Tf2 N], since the concentration of
copper measured in its sample was 212 mg L-1 against 196 mg
L-1 measured for the [hmim][PF6 ] sample. Nevertheless, this high
receiving capacity of [bmim][Tf2 N] involves a lower capacity to

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905

Copper complex removal from ILs with supercritical carbon

dioxide and extraction cycles
The second part of this study involved the removal of copper
complexes formed in the IL phase after the extraction using a
stripping phase of dense CO2 at supercritical conditions. A set of
experiments was implemented to remove copper complexes from
samples of ILs obtained after the liquidliquid extraction tests.
Specically, 3 mL samples of each IL with an initial concentration
of TFA equal to 310 mol m-3 and already used for the liquidliquid
extraction of copper (250 mg L-1 ) from aqueous solutions, were
placed in a 100 mL high-pressure extraction cell and contacted

Extraction percentage, %

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100
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60
50
40
30
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10
0
[bmim][PF6] [bmim][Tf2N] [hmim][PF6]
Ionic liquid
First load

Second load

Third Load

Fourth load

Cu(II) in the ionic liquid, mg L-1

B
800
700
600
500
400
300
200
100
0
[bmim][PF6]
First load

[bmim][Tf2N]
Ionic liquid

Second load

[hmim][PF6]

Third Load

Fourth load

Figure 7. (A) Accumulative extraction percentage and (B) mass concentration for test with four loads. Initial concentration of Cu(II) and TFA, 250 mg
L-1 and 310 mol m-3 respectively, phase rate 1:1 (3 mL of each solution),
SO4 2- =0.1 mol L-1 , initial pH=5.3 0.2.

Table 1. Concentration of copper in the IL before and after treatment

with supercritical carbon dioxide at 180 bar and 40 C, and removal
percentage

Ionic liquid
[bmim][Tf2 N]
[hmim][PF6 ]

Concentration of
copper
in the IL,mg L-1
212.0
196.0

Concentration of
copper in the
IL after
stripping with
SC CO2 mg L-1
133.0
71.0

Removal
percentage
37.26
63.78

906

remove the copper complexes formed during the extraction by

means of dense CO2 . After a regeneration step with supercritical
CO2 , the 37.26% of copper species in the IL phase were removed
from [bmim][Tf2 N], meanwhile 63.78% of these same species were
removed from [hmim][PF6 ]. This result could be explained by
higher anity between the metal complex and [bmim][Tf2 N].
Thus, a greater amount of copper is retained in [bmim][Tf2 N] after
the regeneration step even though the CO2 solubility in this ionic
liquid is higher than in [hmim][PF6 ].35,36
These last experiments were complemented with additional
tests for the assessment of the extraction capacity of the IL regenerated with SC CO2 . Thus, the IL samples stripped with dense CO2
in the view cell were recovered in order to conduct liquidliquid
extraction experiments with two types of IL samples: the rst one
using the regenerated IL and the second one by adding TFA to
obtain the same original concentration (310 mol m-3 ). The addition

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R Seplveda, J Romero, J Snchez

of fresh TFA was done under the assumption that all non-reacted
TFA in the rst extraction was removed from the IL during the treatment with SC CO2 . The comparative results of the copper extraction with and without TFA (310 mol m-3 ) for the rst extraction step
and using stripped ILs are reported in Table 2. According to the
previous experiments, [hmim][PF6 ] was the only TFA-free IL with
a signicant extraction capacity in the rst LL extraction step.
However, this capacity, expressed in terms of the extraction percentage, decreased when the IL was regenerated with dense CO2 .
This result could be explained by the direct interaction between
Cu(II) and [hmim][PF6 ], since the metal ions extracted in this form
are not extractable with SC CO2 from the IL phase and they remain
in this phase for the following LL extraction step.
Furthermore, the results for [bmim][PF6 ] and [bmim][Tf2 N] veried the negligible extraction capacity of these TFA free ILs.
Both IL show a decreasing extraction percentage close to 26.5%
when they were regenerated with dense CO2 and reused without addition of TFA. Nevertheless, both ILs recovered most of
their extraction percentage (58.68% on 66.53% and 82.23% on
87.60%) when fresh TFA was added after stripping with SC CO2 .
Thus, a signicant removal of non-reacted TFA during the supercritical regeneration step can be veried. Moreover, the regenerated [bmim][Tf2 N] + TFA is still the best choice for extraction cycles
among the three ILs tested.
After these experiments, cycles of liquidliquid extraction and
stripping with SC CO2 were done using the same original volume of IL. For this purpose, the [bmim][Tf2 N] was selected, since
it showed the highest accumulative extraction capacity of Cu(II)
in sequential liquidliquid extractions and the best regeneration
capacity. Figure 8 shows the extraction cycles, which considered
sequences of LL extraction coupled to supercritical regeneration steps of IL. LL extractions were done using fresh aqueous
CuSO4 solutions with an initial concentration of Cu(II) of 250 mg L-1 .
[bmim][Tf2 N] was regenerated after every LL extraction step by
means of SC CO2 at 180 bar and 40 C. Fresh TFA was added to the
recycled [bmim][Tf2 N] under the assumption that all non-reacted
TFA in the last extraction was removed from the IL during the treatment with SC CO2 . Extraction percentages reported in Fig. 8 for
extractionregeneration cycles with the same original volume of
[bmim][Tf2 N] remain practically constant after 6 cycles. Thus, this
procedure could become an interesting alternative for the extraction of dierent types of metal ions and hazardous species from
aqueous media. The diversity of ILs with dierent and functionalized structures as well as the improvement of the operating conditions in terms of the cation exchange equilibrium identied in this
work will be priority of our future research.

CONCLUSIONS
In this work, the extraction of Cu(II) ions from aqueous solution was done with three dierent imidazolium-based ILs:
[bmim][PF6 ], [hmim][PF6 ] and [bmim][Tf2 N], which contained
a specic -diketone as extractant agent. From L-L extraction
experiments, a predominant cation exchange mechanism with
the formation of a neutral copper complex Cu(TFA)2 was veried when [bmim][PF6 ] and [bmim][Tf2 N] were chosen as solvents.
Meanwhile, the extraction of Cu(II) ions in [bmim][PF6 ] seems to be
inuenced by the direct solubility of Cu2+ in the IL. Furthermore,
in LL extraction tests, [bmim][Tf2 N] showed higher extraction
capacity in terms of accumulative extraction percentage after
sequential loads of Cu(II) ions.

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Copper ions removal by ionic liquids coupled to supercritical uid extraction

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Table 2. Extraction percentage values obtained for the three ILs during the rst and second LL extraction step. Between these extraction steps the
IL phase was regenerated by contact with SC CO2
Extraction percentage
for the rst LL extraction step(fresh ILs)
Ionic liquid

CTFA = 310 mol m-3

TFA free

[bmim][PF6 ]
[bmim][Tf2 N]
[hmim][PF6 ]

12.40
13.60
51.60

66.53
87.60
73.78

Extraction percentage in the

second extraction step with stripped ILs
Without addition of fresh TFA
40.08
61.94
28.34

AddingTFA, CTFA = 310 mol m-3

58.68
82.23
66.88

Extraction percentage, %

Conditions of liquidliquid extraction: Cu(II) concentration 250 mg L-1 , phase ratio 1:1 (3 mL of each solution), pH = 5.3 0.2, SO4 2- = 0.1 mol L-1 .
Supercritical extraction conditions, PCO2 SC = 180 bar, T = 40 C, contact time = 40 min.

the Franco-Chilean international collaboration program

ECOS-CONICYT (Project number C10E05). Chilean researchers
R. Seplveda and J. Romero were supported by Project
ICM-P10-003-F, Interdisciplinary Center of Ionic Liquids, CILIS,
granted by Fondo de Innovacin para la Competitividad, del
Ministerio de Economa, Fomento y Turismo, Chile.

100
90
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70
60
50
40
30
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10
0

REFERENCES
1st

2nd

3rd

4th

5th

6th

Liquid-liquid extraction

Figure 8. Extraction percentage of Cu(II) for LL extraction cycles using

recycled [bmim][Tf2 N] regenerated with supercritical carbon dioxide, initial
concentration of Cu(II) in the aqueous phase 250 mg L-1 , initial concentration of TFA in IL 310 mol m-3 , phase volume ratio 1:1 (3 mL of each solution),
SO4 2- = 0.1 mol L-1 . Fresh TFA was added to the IL after every regeneration
step.

Additional extraction tests allow verifying that the eect of the

anionic medium of the aqueous solution (sulphate or chloride) on
the extraction percentage was not signicant.
Moreover, ILs used in LL extraction of Cu(II) ions were regenerated using supercritical carbon dioxide, which stripped the copper complexes formed in the IL phase. In these experiments,
[bmim][Tf2 N] is still the best solvent for this application, since it
was able to recover its extraction capacity after several extraction
cycles (close to 80%). The optional addition of fresh -diketone
(TFA) in the regenerated IL showed that the SC CO2 removes most
of the non-reacted TFA content with the metal complex. The addition of fresh TFA in the IL after every supercritical regeneration step
allows the recovery of most of its original extraction capacity.
The extraction performance of the process proposed in this
study is relatively high compared with conventional solvent
extraction processes, which involve concentrations of extractant
5 times higher than the ones applied in this study.
Future studies must be conducted in order to optimize the
operating conditions and reduce the concentration of extractant
and the required volume of IL. This research will be focused on
the chemical aspects related to extraction mechanism veried in
this work.

ACKNOWLEDGEMENTS

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907

This study has been developed in the framework of the

research project FONDECYT 1100305 (CONICYT Chile) and

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