Journal of Environmental Chemical Engineering 1 (2013) 12691274

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Journal of Environmental Chemical Engineering

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Solvent extraction recovery and separation of cadmium and copper

from sulphate solution
Ehsan Bidari a,*, Mehdi Irannejad a, Mahdi Gharabaghi b
a
Department of Mining & Metallurgical Engineering, Amirkabir University of Technology, Tehran, Iran
b
School of Mining Engineering, College of Engineering, University of Tehran, Iran

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

Article history: In this study solvent extraction process has been used for separation of cadmium and copper from
Received 12 July 2013 sulphate solution. A phosphoric acid extractant (D2EHPA) and an oxime extractant (MEX) in kerosene
Accepted 19 September 2013 diluent were used as cadmium and copper extractants, respectively. The results showed that 1 g/L
cadmium could be extracted by 3035% (v/v) D2EHPA at the pH of 3.54. Cadmium separation factor
Keywords: over copper with D2EHPA was calculated 4.04 in best condition of pH (=2). On the other hand 3% MEX
Solvent extraction separated 1 g/L copper over cadmium optimally at the pH of 3.5 and under this condition of pH, copper
Copper
separation factor is calculated 4495.5. Loading capacity studies showed that copper existence in
Cadmium
cadmium aqueous solution reduces cadmium extraction with D2EHPA up to 10% whilst copper
Phosphoric acid
Oxime extraction percentage with MEX does not vary considerably in the presence of cadmium.
2013 Elsevier Ltd. All rights reserved.

Introduction extracted from the by-products of zinc metallurgy among which

Elimination of heavy metals from industrial wastes at the point
of environmental aspects was always important. Furthermore
there is an attitude toward the recovery of precious metals from
low-grade or complex ores, secondary resources and industrial
wastes because of the reduction of worlds high grade resources
and metals high prices.
Generally, hydrometallurgical route (leachingsolvent extrac-
tionelectro winning) is found suitable to process lower grade ores,
wastes such as slag, tailings and recycled solutions [1]. Solvent
extraction is now a very well-established process in hydrometal-
lurgy. It is used for the hydrometallurgical processing of copper,
nickel, cobalt, zinc, uranium, molybdenum, tungsten, vanadium,
rare earths, zirconium, hafnium, niobium, tantalum, indium,
gallium, germanium, the platinum group metals, boron, reproces-
sing nuclear fuels, purication of wet process phosphoric acid,
nitric acid recovery, etc. [2].
In this study recovery and separation of cadmium and copper
were considered. Cadmium and its compounds are toxic and
poisoning occurs through inhalation and ingestion. In spite of its
toxicity, it is used in different industries such as electroplating,
pigments, synthetic chemicals, ceramics, metallurgical and photo-
graphic products, electronics and other industries [3]. Cadmium is
coppercadmium slag, cadmiumrich dust and also from the spent
Ni-Cd batteries. Pure cadmium can be recovered through solvent
extraction, electrolysis rening or vacuum distillation [4].
Among the available processing alternatives, solvent extraction
is a technique that not only meets the strict environmental
regulations but also high purity value added products could be
produced. Acidic extractants, including carboxylic acids, dialkyl
phosphoric and dialkyl phosphinic acids, can be used to extract
cadmium (II). The extraction of cadmium (II) is selective in the
presence of Zn(II), Ni(II), Co(II), Mn(II), Fe(II), Ca(II) and Mg(II) with
DpH0.5(Me/Cd) = 1.5 where Me = Zn (II), and not less than 2.5 for
the remainder of these cations. However, copper (II) and lead (II)
can be co-extracted [5]. Different kinds of extractant were used to
extract cadmium from aqueous solution and a comprehensive
literature about them are available [3,6].
Among phosphoric acids, (Di(2-ethylhexyl)) phosphoric acids
(D2EHPA) which is successfully used as cadmium extractant in
several industrial and experimental works, is used in this study and
the extraction mechanism of the metal ion (in this case cadmium)
with D2EHPA which is diluted in kerosene may be expressed as
follows [7]:
n p
Mn H2 A2 org @ MAn HA p org nH (1)
2

where (H2A2) is extractant in dimeric form, M is metal, n is valence

* Corresponding author. Tel.: +98 914 8224306. of the metal or metal complex ion and (n + p) number of molecules
E-mail address: e.bidari@aut.ac.ir (E. Bidari). of extractant engaged in reaction. Working with concentrations

2213-3437/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jece.2013.09.016
1270
E. Bidari et al. / Journal of Environmental Chemical Engineering 1 (2013) 12691274
lower than or equal to 0.2 mol L1 (22.48 g/L) of cadmium in the
organic phase, according to the literature [8], the chemical
reactions can be expressed as:
2
Cd 2H2 A2 org @ CdA2 H2 A2 org 2H
In addition of zinc processing residues cadmium and copper co-
existence is seen in different metal processing plants. For instance
the dense fumes, which come from smelters of metal bearing ores,
are rich in metallic pollutants, such as Cd, Cu, Pb, and Zn [9]. A
study which was done in the vicinity of Sarcheshmeh (the largest
porphyry copper deposit in Iran) copper smelting plan showed that
Sarcheshmeh soil samples are enriched in As, Cu, Mo, Zn, Cd, and Pb
[10]. Whereas copper solvent extraction is a well-established route
in copper processing plants, copper extractants can also be
considered useful in the separation of cadmium and copper. The
copper-specic extractants used to extract copper from other base
metals in acidic sulphate liquors are known as hydroxyoximes, and
the interaction is known as chelation. The basic structures of
modern oxime extractants are shown in Fig. 1 and the complexa-
tion of copper by these extractants is shown schematically in Fig. 2.
Today modied aldoximes and aldoximeketoxime mixtures are
the most widely used copper extractant systems [11]. In this study
a cadmium common extractant compared with a copper extractant
at the point of their ability in selective separation of cadmium and
copper and also on their loading capacity toward each and both of
these elements.
Materials and methods
Reagent
The aqueous feed solution containing cadmium and copper was
prepared by dissolving appropriate amount of their sulphate salt in
distilled water. Sulphuric acid (H2SO4) and sodium hydroxide
(NaOH) solutions were used in order to maintain desired
equilibrium pH of the solution during extraction. All chemicals
used were analytical reagent grade. All inorganic reagents were
purchased from Merck. MEX reagent from SOIL Company was
used for solvent extraction of copper. This extractant based on
aldoxime and ketoxime molecules: 5-nonylsalicylaldoxime, 5-
nonyl-2-hydroxyacetophenone oxime. Di-(2-ethylhexyl) phos-
phoric acid (D2EHPA), from the Luoyang Zhongda Chemical Co.
Ltd. was of chemical reagent quality with a purity >95.0%, was
used as cadmium extractant. Commercial grade kerosene was used
as diluent for organic extractant.
Procedure
Experimental studies were carried in two steps. At rst,
optimum condition of pH and extractant concentration for
extracting of cadmium with D2EHPA and copper with MEX from
their pure sulphate solution of each metal were determined. In this
stage we have investigated the extraction process in order to
[(Fig._1)TD$IG]
obtain optimum conditions of pH and extractants concentrations
Fig. 1. Modern oxime extractant.
[(Fig._2)TD$IG]
(2)
Fig. 2. Complexation of copper with oxime extractants.
([HA]), whereas optimum condition of each desired parameter (pH
or [HA]) was determined by varying that parameter whilst all other
parameters kept xed. The condition at which highest extraction
percentage happened, were chosen as optimum condition.
After that, a solution of both metals was prepared and contacted
with organic phases (extractant which diluted in kerosene). Metals
concentrations in all aqueous phases were 1 g/L. Equal volumes
(25 mL) of aqueous and organic phase were shaken using incubator
shaker (stirring rate: 100 rpm) for 20 min in each test. Aqueous
solution pH was varied from 1 to 4.5 and all tests were carried in
room temperature.
After extraction process organic and aqueous phases were
separated using separatory funnel. The solutes (Cd or Cu), which
initially was dissolved in aqueous phase (with initial concentration
of [A0]aq) distributes between the two phases. Sample was taken
from aqueous phase and its metal content ([A1]aq) was measured
using Unicam 939 atomic absorption spectrophotometer. The
ame conditions were those recommended by the instrument
manufacturer (wavelengths 324.8 nm and 228.8 nm, respectively,
for copper and cadmium). The quantication limits were 0.096 mg/
L and 0.03 mg/L and the detection limits were 0.29 mg/L and
0.01 mg/L for copper and cadmium, respectively.
The distribution ratio of the solute can be calculated as
following:
Aeq org A0 aq  A1 aq
D
Aeq aq A1 aq
For practical purposes, as in industrial applications, it is often
more popular to use the percentage extraction %E (sometimes
named the extraction factor), which is given by:
100D
%E
1D
Results and discussion
Determination of optimum pH and extractant concentration
Acidic extractants include simple reagents such as carboxylic
acids and organophosphorus acids, as well as chelating acids,
extraction occurs by a change of the acidity in solution; thus,
increasing the pH of solution increases extraction. Acidic
extractants extract metals generally according to the following
equilibrium reaction:
Mz
aq zAHorg @ MAzorg zHaq (3)
 [(Fig._4)TD$IG]
E. Bidari et al. / Journal of Environmental Chemical Engineering 1 (2013) 12691274 1271
The extent of extraction also depends on the magnitude of the
metalextractant formation constant and concentration of extrac- 100
tant. These factors can be combined with the distribution 90
coefcient in the following equation derived from Eq. (1) and 80

Cadmium Extraction%
the law of mass action [11]: 70
60
log D log K f z logHA zpH (4)
50

whereas D and Kf are the distribution coefcient of metal and the 40

equilibrium constant of reaction (3), respectively. Subsequently, 30
pH and extractant concentration have signicant effect on metal 20
extraction and have been reported frequently as main parameters 10
in metals extraction and separation [6,12,13].
0
0 10 20 30 40
Optimum condition of cadmium extraction using D2EHPA D2EHPA Concentration(v/v)%

Effect of pH. The effect of pH on cadmium extraction from synthetic Fig. 4. Effect of D2EHPA concentration on cadmium extraction percentage; 1 g/L
sulphate solution was examined in the range 0.54.5 at different cadmium aqueous solution; aqueous phase pH = 3.5; O/A phase ratio = 1:1; shaking
D2EPHA concentrations. It was observed from Fig. 3 that the time = 20 min and in the room temperature.
percentage extraction depends mainly on the pH of the aqueous
phase. The extraction of cadmium starts at pH values around 0.5
and reaches quantitative extraction at initial aqueous phase pH Separation studies
3.54.0.
The selectivity of one metal over the other(s) is the ease of
Effect of D2EPHA concentration. A plot of cadmium extraction using isolating that metal from the mixed electrolyte solution and is
different concentrations of D2EHPA is presented in Fig. 4 at initial expressed in terms of the separation factor, SM1=M2 :
aqueous phase pH = 3.5. It was observed that the D2EHPA
DM1
concentration had a signicant effect on the cadmium extraction. SM1=M2
Cadmium extraction increased by increasing D2EPHA concentra- DM2
tion up to optimum level whereas in which 1 g/L cadmium where
extracted quantitatively by using 3035% (v/v) D2EPHA.
Mn
org
Dn
M
Optimum condition of copper extraction using MEX Mn
aq

Effect of pH. Initial experiments on the extraction of copper from n

Dn
M is the distribution coefcient of the metal, M , between the
synthetic sulphate solutions were conducted in the initial aqueous organic and aqueous phases. The distribution coefcient per se is
phase pH range 0.54.5 using different concentrations of MEX. As it not useful in industrial applications since its value depends on the
is shown in Fig. 5 extraction was controlled by pH similar to operating conditions such as pH, temperature, extractant concen-
cadmium extraction and copper quantitatively extracted at tration, aqueous concentrations, phase ratio, etc. The separation
aqueous pH = 3.5. factor, on the other hand, is a very useful variable in the
commercial applications, though its value also depends on the
Effect of MEX concentration. Based on the previous results, the operating conditions. It is an indication of the ease of separating
effect of the concentration of MEX on the extraction of copper was mixed electrolyte systems under a given set of operating
evaluated at distinct pH level (3.5), as shown in Fig. 6 the increase conditions. The higher the separation factor, the easier it is to
in the concentration of MEX resulted in higher metal extraction perform selective extraction with little or no co-extraction of other
whereas 1 g/L copper quantitatively extracted using 3% (v/v) MEX. metals [14].
[(Fig._3)TD$IG]
[(Fig._5)TD$IG]
100
90 100
D2EHPA 5%
80
D2EHPA 15%
70 80
D2EHPA 25% MEX 3%
Extraction%

60 MEX 1%
Extraction %

50 60
40
30 40

20
10 20

0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 0
pH 0 1 2 3 4 5
pH
Fig. 3. Effect of pH on cadmium extraction percentage; 1 g/L cadmium aqueous
solution; O/A phase ratio = 1:1; shaking time = 20 min and in the room Fig. 5. Effect of pH on copper extraction percentage; 1 g/L copper aqueous solution;
temperature. O/A phase ratio = 1:1; shaking time = 20 min and in the room temperature.
[(Fig._6)TD$IG]
1272 [(Fig._7)TD$IG]
E. Bidari et al. / Journal of Environmental Chemical Engineering 1 (2013) 12691274

100 1.1
1
90
0.9
80 0.8
O/A=1:1
Copper Extraction%

70

[Cd]org g/L
0.7
0.6
60
0.5
50 0.4
3 1
40 0.3
30 0.2
0.1 2
20 0
10 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 1.2 1.3 1.4
0 [Cd]aq g/L
0 1 2 3 4 5 6
Fig. 7. Calculation of the number of theoretical stages of extraction by the method of
MEX Concetration(v/v)% McCabeThiele (pH 3.5, [D2EHPA] = 30% (v/v), O/A phase ratio = 1:1).
[(Fig._8)TD$IG]
Fig. 6. Effect of MEX concentration on copper extraction percentage; 1 g/L copper
aqueous solution; aqueous phase pH = 3.5; O/A phase ratio = 1:1; shaking 90
time = 20 min and in the room temperature.
80
70
Cadmium separation over copper with D2EHPA
An aqueous phase of both metals was contacted with D2EHPA 60

Extraction%
(30%) in different pH conditions. It was considered that maximum 50
separation factor occurs at more acidic condition (pH = 2) than
40
cadmium optimum extraction pH (ca. 4). The results are shown in Cu
Table 1. The pH1/2 values calculated from 50% extraction of 30
Cd
cadmium and copper are 1.6 and 3, respectively, demonstrating 20
the possible quantitative separation of cadmium and copper from
10
their mixtures.
It is important to make a decision regarding the staging 0
requirements, as it is directly related to the cost of operation and 0 5 10 15 20 25
maintenance. The McCabeThiele diagram helps to set the number Time/min
of extraction stages needed in a mixer-settler for the extraction of
Fig. 8. Effect of contact time on cadmium and copper extraction with 30% D2EHPA;
cadmium from the copper solution. Extraction isotherm was O/A phase ratio = 1:1 and in the room temperature.
obtained by contacting the metals solution and 30% D2EHPA (v/v),
at different A/O phase ratios from 1 to 5 and O/A from 1 to 5 at an
initial aqueous phase pH of 3.5. Fig. 7 indicates that 3 stages of Copper separation over cadmium with MEX
extraction would be sufcient to extract 100% cadmium from the Same solution with previous separation test was contacted with
solution having starting cadmium concentration of 1 g/L at an MEX in order to study its capability in copper separation over
O = A ratio of 1.0. cadmium. The metals solution was subjected to copper extraction
Kinetic of cadmium and copper extraction also was studied in in single stage at different initial aqueous phase pH and A/O ratio of
which the effect of contact time on metals extraction has been 1:1 using 3% (v/v) MEX. Results which are shown in Table 2
considered using 30% (v/v) D2EHPA and pH = 3.5. The results indicated that MEX is a very selective extractant for copper
obtained are shown in Fig. 8. The extraction of cadmium and whereas copper would be easily separated over cadmium in pH
copper was rapid and attained the equilibrium in less than 10 min. range of 24.5. Furthermore, optimum separation pH occurs at the
It was also observed that prolong contact time had no adverse same pH of maximum extraction percentage, so a quantitative
effect on extraction or separation. recovery and separation would be possible in pH around 3.5 in
Fig. 9 shows the effect of stirring rate on metals extraction. As it single stage.
is clear stirring rate do not have a considerable effect on extraction
percentage of cadmium nor copper. This indicates that the effect of Loading capacity
the uid to particle mass transfer resistance is negligible in both
cadmium and copper extraction with D2EHPA in stirring rates Loading capacity of D2EHPA and MEX were studied in the
higher than 50 rpm. optimum conditions of pH and extractant concentration which

Table 1
Cadmium separation over copper with D2EHPA.

pH Distribution coefcient of cadmium Distribution coefcient of copper Cadmium separation factor over copper Cadmium extraction %

1 0.07 0
1.5 0.7 0.22 3.18 41.2
2 2.1 0.52 4.04 67.4
2.5 3.05 0.89 3.43 75.3
3 3.42 1 3.42 77.4
3.5 4.18 1.17 3.57 80.1
4 4.27 1.22 3.5 81.1
4.5 4.15 1.17 3.55 80.6
[(Fig._9)TD$IG] [(Fig._1)TD$IG]
E. Bidari et al. / Journal of Environmental Chemical Engineering 1 (2013) 12691274 1273

80 100
70
Cd
60 80
Cu

Copper Extraction%
Extraction%

50
40 60

30
20 40

10
20
0
0 50 100 150 200
Stirring rate/rpm 0
0 1 2 3 4 5
Fig. 9. Effect of stirring rate on cadmium and copper extraction with 30% D2EHPA;
pH
O/A phase ratio = 1:1; shaking time = 20 min and in the room temperature.
[(Fig._10)TD$IG] Fig. 11. Copper extraction with 30% D2EHPA; 0.1 g/L copper aqueous solution;
different pH of aqueous phase; O/A phase ratio = 1:1; shaking time = 20 min and in
100 the room temperature.
90 [(Fig._12)TD$IG]
80
100
70
Extraction %

60
90
50
Cd and Cu soluon
40
Extraction% 80
30
20 Cd soluon Cu soluon
70
10 Cu and Cd soluon
0
60
0 1 2 3 4 5
pH
50
Fig. 10. Effect of copper impurity on cadmium extraction percentage; different pH 0 1 2 3 4 5
of aqueous phase; O/A phase ratio = 1:1; shaking time = 20 min and in the room
pH
temperature.

Fig. 12. Effect of cadmium impurity on copper extraction percentage with 3% MEX;
different pH of aqueous phase; O/A phase ratio = 1:1; shaking time = 20 min and in
the room temperature.

were determined previously. It was found that cadmium extrac-

tion percentage increases with raising of D2EHPA concentration
(Fig. 4) and 3035% D2EHPA can extract cadmium from cadmium zinc hydrometallurgical plants whereas only removing of cadmi-
pure sulphate solution whilst copper existence in the solution um and copper from wastes, because of their environmental
reduces cadmium extraction percentage up to 10% (Fig. 10). problems, was important).
D2EHPAs capacity for copper extraction was found approxi- It was also found that copper extraction efciency increases
mately 10 times less than of its capacity toward cadmium with rising of MEX concentration (Fig. 6) and 2.53% MEX can
extraction and as Fig. 11 shows only 0.1 g/L copper can extract extract copper quantitatively in the optimum condition of solution
with 30% D2EHPA. Then D2EHPA can use for co-extraction of pH. Fig. 12 shows that cadmium existence in the solution has no
cadmium and copper whereas cadmium concentration in the noticeable effect on copper extraction, and then MEX is very
solution is several times more than copper concentration (e.g. in suitable solvent for separation of copper over cadmium.

Table 2
Copper separation over cadmium with MEX.

pH Distribution coefcient of copper Distribution coefcient of cadmiuma Copper separation factor over cadmium Copper extraction %

1 4.29 0 81.1
1.5 20.74 0.02 1037 95.4
2 51.63 0.02 2581.5 98.1
2.5 65.67 0.02 3283.5 98.5
3 82.33 0.02 4116.5 98.8
3.5 89.91 0.02 4495.5 98.9
4 82.33 0.02 4116.5 98.8
4.5 82.33 0.02 4116.5 98.8
a
Whereas all cadmium distribution coefcients were in the range of 0.02  0.005, approximate distribution coefcient (0.02) was taken to avoid the probable error.
1274 E. Bidari et al. / Journal of Environmental Chemical Engineering 1 (2013) 12691274
Conclusion
Optimal cadmium separation over copper with D2EHPA occurs
at more acidic and restricted pH than cadmium optimum
extraction pH, whilst MEX separated copper over cadmium with
grater separation factor and extended domain of pH. Loading
capacity studies revealed that 1 g/L cadmium and 1 g/L copper
could be extracted by using 3035% D2EHPA and 2.53% MEX,
respectively. Then, whereas separation and recovery of these
elements was aimed, MEX is more effective extractant. Co-
extraction studies demonstrated that MEX has inconsiderable
extraction capability toward cadmium whilst D2EHPA can extract
both metals, although, D2EHPAs capacity for copper is almost 10
times less than cadmium. So, whenever only removing of these
elements from wastes was concerned, D2EHPA can be more
suitable.
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