INTRODUCTION
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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
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following equations:
(
)
Amount of extracted metal
%E =
Initial amount of the metal in the aqueous solution
100
(1)
(2)
i=1
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MEi =
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(3)
Kext
[ + ]2
] [ ]2
Cu (TFA)2 (IL) H+ (aq)
H (aq)
= [
=D
]
2
2+
[TFA]2(IL)
Cu (aq) [TFA](IL)
(4)
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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
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B 100
Extraction percentage, %
Extraction percentage, %
A 100
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 free
TFA free
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
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.
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B
300
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250
200
150
100
50
0
250
300
250
200
150
100
50
500
0
250
TFA free
500
300
250
200
150
100
50
0
250
500
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, %
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.
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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Extraction percentage, %
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100
90
80
70
60
50
40
30
20
10
0
[bmim][PF6] [bmim][Tf2N] [hmim][PF6]
Ionic liquid
First load
Second load
Third Load
Fourth load
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.
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
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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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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
TFA free
[bmim][PF6 ]
[bmim][Tf2 N]
[hmim][PF6 ]
12.40
13.60
51.60
66.53
87.60
73.78
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.
100
90
80
70
60
50
40
30
20
10
0
REFERENCES
1st
2nd
3rd
4th
5th
6th
Liquid-liquid extraction
ACKNOWLEDGEMENTS
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