Solvent Extraction and Ion Exchange

ISSN: 0736-6299 (Print) 1532-2262 (Online) Journal homepage: http://www.tandfonline.com/loi/lsei20

COPPER EXTRACTION FROM CHLORIDE SOLUTION

BY SOLVATING AND CHELATING EXTRACTANTS
Ryszard Cierpiszewski & Jan Szymanowski
To cite this article: Ryszard Cierpiszewski & Jan Szymanowski (2001) COPPER EXTRACTION
FROM CHLORIDE SOLUTION BY SOLVATING AND CHELATING EXTRACTANTS, Solvent Extraction
and Ion Exchange, 19:3, 441-456, DOI: 10.1081/SEI-100103279
To link to this article: http://dx.doi.org/10.1081/SEI-100103279

Published online: 15 Feb 2007.

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SOLVENT EXTRACTION AND ION EXCHANGE, 19(3), 441456 (2001)

COPPER EXTRACTION FROM CHLORIDE

SOLUTION BY SOLVATING AND
CHELATING EXTRACTANTS
Ryszard Cierpiszewski1 and Jan Szymanowski2,*
1

Poznan University of Economics, Faculty of Commodity

Science, al. Niepodleglosci 10, 60-967 Poznan, Poland
2
Institute of Chemical Technology and Engineering,
Poznan Technical University, Pl. Sklodowskiej-Curie 2,
60-965 Poznan, Poland

ABSTRACT
The extraction of Cu(II) from chloride solutions at constant
water activity aw and constant total concentration s of species
dissolved in the aqueous phase by di(2-ethylhexyl)pyridine-2,4dicarboxylate (S), ACORGA CLX-50 (S) and LIX 54 (HL) used
alone and in 1 : 1 mole=mole mixtures was studied. It was found
that solvating reagents have a high ability of copper extraction
from chloride solutions of low water activity and their extraction
ability strongly depends on the chloride concentration. The extraction of copper(II) by LIX 54 is low in all systems studied
(pH 2.43.9) and only slightly affected by chloride concentration. In the region of chloride concentration equal to 34 M
approximately 90 and 50% of extracted copper is bound in the
solvate with ACORGA CLX-50 for aw 0.617 and s 12 M,
*Corresponding author. E-mail: jan.szymanowski@put.poznan.pl
441
Copyright # 2001 by Marcel Dekker, Inc.

www.dekker.com

442

CIERPISZEWSKI AND SZYMANOWSKI

and aw 0.835 and s 8 M, respectively. Scrubbing with water

at equilibrium pH above 4 permits almost complete transfer of
chloride ions into the aqueous phase with the simultaneous conversion of copper(II) from the solvate CuCl2S2 in the chelate
CuL2. Copper can be then stripped with 2575 g=L H2SO4 and
the organic phase recycled.

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INTRODUCTION
In the 1980's ICI patented and developed a new reagent called ACORGA
CLX-50 and an associated process called CUPREX for copper extraction from
chloride solutions [13]. The reagent contains a diester of pyridine-3,5dicarboxylic acid as the active substance, and efciently extracts copper(II)
from chloride media of high concentration of chloride (49 M) and copper(II)
(4050 g=L) and of low water activity (high concentration of inorganic salts). The
proposed reagent is highly selective for copper(II) in the presence of other
common metals, including iron ions. Unfortunately, by carrying out electrowinning from a chloride solution granules of copper are obtained.
Recently it was proposed to use mixtures of reagents to extract copper(II)
from chloride solutions. The following options were considered: i) a mixture of
a chelating reagent HL, especially LIX 54, and a basic extractant (trialkylamine)
[4, 5], ii) a mixture of bifunctional reagent such as LIX 26 and KELEX 100,
which depending on the composition of the aqueous phase (concentration of
chloride and proton ions) can both act as a chelating and basic reagent [69], and
iii) a mixture of a chelating reagent (hydroxyoxime or b-diketone) and a solvating
extractant (pyridine-3,5-dicarboxylate) [10] or (pyridine carboxamide) [11].
Such mixtures efciently extract copper(II) from chloride solutions binding
it in appropriate ion pairs, e.g., CuCl4(R3NH)2 or solvates CuCl2S2. Scrubbing of
the organic phase with an aqueous solution of appropriate pH removes chloride
ions, simultaneously converting the liberated copper(II) into the chelate CuL2.
Stripping can then be carried out in the typical way using sulphuric acid of
appropriate concentration.
The rst two options (i.e., i and ii) have two signicant drawbacks. The
extraction of copper(II) is not selective with respect to iron ions, which form
strong chlorocomplexes with chloride ions. These anionic chlorocomplexes, e.g.
FeCl
4 , are extracted by protonated amines as metal ion pairs. In the strip stage
this basic reagent is protonated giving undesired hydrosulphate, e.g.,
R3NH
HSO4. Thus, before recycling to extraction, the reagent must be
transformed into the hydrochloride form R3NHCl.
The third option seems the most promising because copper(II) can be
selectively extracted in the presence of iron ions. However, some undesired

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COPPER EXTRACTION FROM CHLORIDE SOLUTION

443

protonation can occur in the stripping stage. As a result, the use of a weak
chelating extractant (e.g., LIX 54) instead of a strong extractant (e.g.,
hydroxyoxime) is favoured.
The aim of this work was to study the extraction of copper(II) from chloride
solutions with individual extractants (commercial ACORGA CLX-50, model
di(2-ethylhexyl)pyridine-2,4-dicarboxylate and commercial LIX 54) and their
equimolar mixtures. The work follows the previous one [11] in which a
pyridinecarboxamide derivative was used. Pyridine dicarboxylates [12] exhibit
better extraction performance with respect to pyridine carboxyamides [13, 14]
because they do not extract copper(II) from solutions having a low concentration
of chloride ions (below 2 mol=L). Their pyridine nitrogen is less basic and they
are more resistant to protonation than pyridine carboxamides.
EXPERIMENTAL
Reagents
ACORGA CLX-50, about 1 mol=L in kerosene, was kindly supplied by
Zeneca Specialities (Manchester, U.K.). LIX 54 was kindly supplied by Cognis
(Dusseldorf, Germany). Individual di(2-ethylhexyl)pyridine-2,4-dicarboxylate,
abbreviated further as ester, was synthesized according to the method described
previously [12]. The structure of the compounds is shown on page 444, where R
in LIX 54 contains seven carbon atoms in the hydrocarbon chains of different
structures [15] and R in ACORGA CLX-50 is an isododecyl group.
Toluene was used as the diluent. Copper(II) chloride, sodium chloride,
lithium chloride, sodium nitrate and magnesium nitrate were used to prepare
aqueous solutions. The salts used were all of analytical reagent grade.
Extraction Procedure
Equilibrium extractions of copper were carried out in two model systems of
constant water activity equal to 0.835 or 0.617 and constant total concentration of
ions and molecules dissolved in the aqueous phase equal to 8.0 or 12.0 M. The
activity of water equal to 0.835 was adjusted with NaCl, LiNO3 and NaNO3 [16].
The ionic strength was equal to 4.0 M.
The activity of water equal to 0.617 was adjusted with LiCl, NaNO3 and
Mg(NO3)2 [16] and the concentration of chloride was changed up to 6 M. The
ionic strength changed then from 6.0 up to 8.5 M.
Typically, extractions were carried out by shaking the phases at room
temperature for 1 h. The volume ratio of the organic and water phases was 1 : 1.

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CIERPISZEWSKI AND SZYMANOWSKI

Structure 1.

The concentration of copper was equal to 0.01 M and the concentration of

extractants in toluene was 0.1 or 0.2 M.
Copper concentration was determined in the initial aqueous solutions and
in the aqueous phases after extraction by atomic absorption spectroscopy using a
Varian Spektr AA 800 spectrometer. The metal concentration in the organic
phases was also measured by stripping copper into water (volume phase ratio
equal to 1 : 1) and analyzing the metal as mentioned before.
Chloride content in aqueous solutions was determined by the Mohr method
using 0.05 M AgNO3 [17].

RESULTS AND DISCUSSION

The extraction of copper(II) from chloride media by pyridine type
extractants (S) and the stripping of their complexes can be described by the
following reactions:
CuCl2w 2So CuCl2 S2o

COPPER EXTRACTION FROM CHLORIDE SOLUTION

445

with
1

Kex CuCl2 S2 o CuCl2 w So

2i

Cu2
w iClw CuCliw
2i

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bi CuCli

i
w Cu2 1
w Cl w

and i 1 to 4

where bi denotes the stability constants of copper(II) chlorocomplexes, subscripts

w and o denote the aqueous and organic phase, respectively.
By combining eqs. (2) and (4) and rearranging, the following equation for
the extraction constant is obtained:
Kex D

1 Sbi Cl iw

b2 Cl 2w S2o

The results of extraction depend signicantly on the composition of the

aqueous phase. By keeping constant the water activity (aw) and the total
concentration (s) of species dissolved in the aqueous solution one can eliminate
the inuence of the composition of the aqueous phase on the activity coefcients
of species [16, 18, 19].
The stability constants bi depend signicantly on the ionic strength, and the
effect can be predicted according to existing theories [20, 21].
Various computer programs are available which permit to recalculate the
stability constants for a desired ionic strength, e.g., MEDUSA program [22].
However, various values of b i constants are reported by different authors [23].
Some of them are reported in Table 1. They differ signicantly depending on the
experimental method used for their determination and=or the type of electrolyte
used to adjust the ionic strength.
Table 1.
System No.
1
2
3
4
5
6
7
8

Formation Constants for Chloride Complexes with Cu2

Ionic Strength

5
5
5
5
5

M
M
M
M
M

0 corr
0 corr
0.69
Na(Cl,ClO4)
Na(Cl,ClO4)
Na(Cl,ClO4)
Na(Cl,ClO4)
Na(Cl,ClO4)

b1

b2

b3

1
4.365
0.98
2.49
2.36
1.51
4
1.5

0.4
6.918
0.69
1.15
1.49
0.276
4.7
0.63

0.024
0.436
0.55
0.90
0.68
0.339
1.96
0.088

b4

Method

0.00024
0.00011
0.0
Ion exch.
0.025
Coulometry
0.0055

Calorim.
0.23
Spectr.
0.0032
Spectr.

Reference
[24]
[22]
[25]
[26]
[27]
[28]
[29]
[30]

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446

CIERPISZEWSKI AND SZYMANOWSKI

The electrolyte system used in our work (NaCl, LiCl, LiNO3, NaNO3,
Mg(NO3)2) differs signicantly from those used in fundamental studies (NaCl,
NaClO4). Therefore, for our computations we used the following two sets
of b i constants: b1 3.98, b2 0.398, and b1 0.89, b2 6.31, b3 0.05,
b4 0.0016 estimated in our previous work [16] for the same aqueous phases
characterised by water activities equal to 0.835 and 0.617, respectively. These
values were obtained from the best tting of the model (equations 14) to the
experimental extraction data for various pyridine carboxylate derivatives and the
considered compositions of the aqueous phase (water activity). They must be
considered as approximate values for the case where the water activity is adjusted
to 0.617 because the ionic strength changes from 6 to 8.5 M.
The extraction of copper with a chelating reagent HL can be described by
the equation:

Cu2
w 2HLo CuL2o 2Hw

with extraction constant:

2

Kex CuL2 o H w Cu2 w HLo

Figure 1. Extraction of copper(II) from chloride solutions with ACORGA CLX-50 (2),
LIX 54 (3), di(2-ethylhexyl)pyridine-2,4-dicarboxylate (1) used alone (aw 0.617,
s 12 M, extractant concentration 0.1 M, [Cu2] 0.01 M).

COPPER EXTRACTION FROM CHLORIDE SOLUTION

447

Introducing the expression for [Cu2], the following nal equation is

obtained:

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Kex D

H 2w 1 Sbi Cl iw
HL2o

Figures 1 and 2 show the effect of the chloride concentration on the

distribution coefcient of copper(II) from solutions at aw 0.617 and s 12 M.
When the concentration is increased, the distribution coefcient of copper
increases strongly for the solvating extractants (1 and 2), but decreases slightly
for the chelating extractant (3). The extraction of copper reaches 70% for an
aqueous feed containing 6 M chloride concentration.
A decrease of the content of electrolytes (aw 0.835, s 8 M, I 4 M)
affects negatively the extraction with solvating reagents but only slightly changes
the extraction with LIX 54 (Figures 3 and 4). Low values of distribution
coefcient are obtained both for solvating and chelating reagents. Systems of low
electrolyte content do not permit to achieve a high extraction of copper(II).

Figure 2. Extraction of copper(II) from chloride solutions with ACORGA CLX-50 (2),
LIX 54 (3), di(2-ethylhexyl)pyridine-2,4-dicarboxylate (1) used alone (aw 0.617,
s 12 M, extractant concentration 0.2 M, [Cu2] 0.01 M).

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CIERPISZEWSKI AND SZYMANOWSKI

Figure 3. Extraction of copper(II) from chloride solutions with ACORGA CLX-50 (2),
LIX 54 (3), di(2-ethylhexyl)pyridine-2,4-dicarboxylate (1) used alone (aw 0.835,
s 8 M, extractant concentration 0.1 M, [Cu2] 0.01 M).

Commercial extractant ACORGA CLX-50 permits a higher extraction of

copper(II) than di(2-ethylhexyl)pyridine-2,4-dicarboxylate as is reected in
extraction constants reported in Table 2. Moreover, the most important effect is
caused by the water activity and the Kex increases by a factor of about 2 when the
water activity decreases from 0.835 to 0.617.
It is obvious that the values of extraction constants depend on the stability
constants of chlorocomplexes used for computing. Therefore it is impossible to
obtain absolutely true values. For example, using the MEDUSA program to
calculate bi constants for the relevant values of the ionic strength, the following Kex
values are obtained: reagent 1 (Ester), 43.9  5.0 and 3.1  0.84 for aw 0.617 and
0.835, respectively, and reagent 2 (ACORGA CLX-50) 59.1  5.1 and 4.4  0.49
for aw equal to 0.617 and 0.835, respectively. These values do not agree with those
given in Table 2. However, the same conclusions can be formulated.
The extraction of copper(II) with solvating reagents at pH near 3 does not
depend on the acidity of the aqueous phase and the pH of the rafnate is equal to
the pH of the aqueous feed. However, when LIX 54 (alone or in a mixture) is
used, protons are liberated due to the formation of the chelate and the acidity of

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COPPER EXTRACTION FROM CHLORIDE SOLUTION

449

Figure 4. Extraction of copper(II) from chloride solutions with ACORGA CLX-50 (2),
LIX 54 (3), di(2-ethylhexyl)pyridine-2,4-dicarboxylate (1) used alone (aw 0.835,
s 8 M, extractant concentration 0.2 M, [Cu2] 0.01 M).

the aqueous phase increases (Table 3). These results conrm the previous
observations: i) the extraction of copper(II) with LIX 54 increases when the
concentration of chloride decreases (a lower pH of the rafnate is registered) and
ii) LIX 54 contributes to the extraction of copper(II) when used in a mixture with
ACORGA CLX-50 (a decrease of pH is also observed but is lower in comparison
to that observed for LIX 54 used alone).
The extraction of copper(II) with the equimolar mixtures of the extractants
amounts approximately to the sum of extraction by the individual reagents
(Figures 5 and 6). The total amount of copper extracted (e and r in Figures 5
and 6) always increases when the concentration of chloride ions increases. The
contribution of ACORGA CLX-50 in the extraction of copper depends mainly on
the water activity. The effect of the chloride concentration is signicantly lower.
In the chloride concentration range important for practical applications, i.e.,
[Cl ] 34 M, 8594% and 4554% of copper(II) is bound into the solvate with
ACORGA CLX-50 (, and . in Figures 5 and 6) for aw 0.617 and s 12 M
and aw 0.835 and s 8 M, respectively. The remaining part of the extracted
copper is bound into the chelate with LIX 54.

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CIERPISZEWSKI AND SZYMANOWSKI

Table 2. Extraction Constants (awWater Activity, sTotal Concentration of Ionic or

Molecular Species in the Aqueous Phase, cextr.Concentration of Extractants in the
Organic Phase)
Reagent
1

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aw

Cextr.

Kes *

0.835

0.617

12

0.835

0.617

12

0.835

0.617

12

0.1
0.2
0.1
0.2
0.1
0.2
0.1
0.2
0.1
0.2
0.1
0.2

16.5  7.9
11.5  6.8
35.6  7.1
30.1  4.2
19.2  9.2
19.5  7.2
44.8  8.4
43.5  5.7
(9.0  8.2)
10 5
(4.7  2.9)
10 5
(5.4  5.5)
10 4
(2.1  1.8)
10 4

* The sets of b i values given in the previous work [16] were used for computing.

Table 3.

Measured Equilibrium pH of Water Phase After Extraction

pH of Rafnate

[Cl ]

pH of Feed

M
4.
3.
2.
1.
0.1
6
5
4
3
2
1
0.1

M
8
8
8
8
8
12
12
12
12
12
12
12

Initial
3.87
3.89
3.9
3.83
4.04
3.44
3.38
3.33
3.34
3.18
2.67
2.42

3
0.1 M
2.54
2.48
2.43
2.34
2.24
2.15
2.11
2.16
1.99
1.87
1.65
1.49

2 3
0.2 M
2.19
2.18
2.13
2.08
1.98
1.83
1.80
1.73
1.63
1.50
1.39
1.22

0.1 M
2.90
2.93
2.99
3.06
3.25

0.2 M
2.30
2.29
2.26
2.16
2.11

Scrubbing with water removes almost completely the chloride ions from the
organic phase. Copper(II) is simultaneously converted from solvate CuCl2S2 into
the chelate with LIX154 (CuL2). However, important amounts of copper(II) at
[Cl ] 34 M (1832% and 7275% for aw 0.835 and aw 0.617,

451

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COPPER EXTRACTION FROM CHLORIDE SOLUTION

Figure 5. Extraction of copper(II) with 1 : 1 mol=mol mixture of ACORGA CLX-50 and

LIX 54 (aw 0.835, s 8 M, extractant concentration open symbols 0.2 M and solid
symbols 0.1 M, [Cu2] 0.01 M, u, jcopper scrubbed out with water; s, dcopper
remained in the organic phase in the form of the chelate CuL2 after scrubbing with water, ,,
.extracted copper bound into solvate CuCl2S2, e , rtotal amount of copper extracted).

CIERPISZEWSKI AND SZYMANOWSKI

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452

Figure 6. Extraction of copper(II) with 1 : 1 mol=mol mixture of ACORGA CLX-50 and

LIX 54 (aw 0.617, s 12 M, extractant concentration open symbols 0.2 M and solid
symbols 0.1 M, [Cu2] 0.01 M, u, jcopper scrubbed out with water; s, dcopper
remained in the organic phase in the form of the chelate CuL2 after scrubbing with water; ,,
.extracted copper bound into solvate CuCl2S2, e , rtotal amount of copper extracted).

COPPER EXTRACTION FROM CHLORIDE SOLUTION

453

Table 4. pH of the Scrubbed Water (2 : 3 1 : 1 mol=mol; Extractant Concentration 0.1

and 0.2 M, Initial pH 6.1)
[S] [HL] 0.1 M

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[Cl ]
0.1
1
2
3
4
5
6

aw 0.835
3.64
3.51
3.50
3.45
3.47

[S] [HL] 0.2 M

aw 0.617
3.0
2.86
2.88
2.96
2.93
2.90
2.80

aw 0.835
3.58
3.20
3.15
3.20
3.15

aw 0.617
2.60
2.52
2.47
2.43
2.55
2.56
2.45

Figure 7. Scrubbed copper(%) vs equilibrium pH (2 : 3 1 : 1 mol=mol, total concentration of extractants 0.2 M, aw 0.617, s 12 M; d, 4 M NaCl; s, 6 M LiCl; u, 0.1 M
NaCl).

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CIERPISZEWSKI AND SZYMANOWSKI

respectively) are also scrubbed out. The reaction probably occurs in the interfacial
region and some amounts of the liberated copper(II) are transferred into the
aqueous phase before complexation with LIX 54. The formation of the chelate
with LIX154 liberates free protons and the pH of the aqueous phase becomes as
low as 2.5 (Table 4). This indicates that stripping of copper from the chelate can
occur.
The undesired scrubbing of copper(II) with water can be avoided by a partial
neutralisation of the aqueous phase (Figure 7). The equilibrium pH of the scrub
solution must be above 4. At lower pH an abrupt stripping of copper is observed.
Copper(II) can be stripped from the organic phase with diluted sulphuric
acid (2575 g/L H2SO4) and the organic phase can be recycled. Emulsion is not
formed and protonation of the extractant is not observed in both experiments
carried out at the laboratory scale. This suggests that the organic phase can be
recycled to the extraction system without any treatment. Thus, the use of an
equimolar mixture containing dialkylpyridine dicarboxylate and LIX154 is more
advantageous than the use of a similar mixture containing pyridine carboxamide
derivative.
ACKNOWLEDGMENT
The work was supported by the Polish Scientic Committee KBN grant
No. 3 TO9B 051 14.
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Received September 27, 2000