Separation and Purification Technology 222 (2019) 22–29

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Separation and Purification Technology

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

Selective extraction of copper from Cu-Zn sulfate media by new generation T

extractants
⁎
Przemysław Aksamitowski, Kinga Filipowiak, Karolina Wieszczycka
Poznan University of Technology, Institute of Chemical Technology and Engineering, Berdychowo St. 4, 60-965 Poznan, Poland

A R T I C LE I N FO A B S T R A C T

Keywords: The selective recovery of copper(II) from Cu-Zn sulfate solutions using solvent extraction and N,N-dialkyl-N′-
Solvent extraction hydroxypyridine-2-carboximidamides as extractants was investigated. Three compounds were synthesized and
Copper their extractability toward copper(II) and zinc(II) was studied. The influence of process parameters such as the
Zinc pH of aqueous phase, shaking time, diluent type and also extractant’s structure and concentration on efficiency
Selective recovery
of both metals ions extraction was presented. Results indicated that the equilibrium pH and type of the organic
diluent had the biggest impact on the copper(II) extraction efficiency, its selectivity over zinc(II), and the
stoichiometry of formed copper complex. Obtained experimental data were used to develop a method of copper
(II) extraction from Zn-Cu sulfate solution composed of 40.9 g/L Zn(II) and 1.2 g/L Cu(II). A flowsheet was tested
in laboratory-scale reactors and the conducted test confirmed the possibility to selective recover of Cu(II) over Zn
(II), and the concentration of Cu(II).

1. Introduction
The growing demand of industry for metals leads to the rapid ex-
haustion of the best or the simplest available resources, which stimulate
the search for new environmental - friendly solutions. The basis of
hydrometallurgy is justified not only by economical, but also ecological
considerations. Hydrometallurgical processes have been widely used in
separation, purification, and recovery of metal not only from ores but
also from solid wastes and wastewaters [1–4]. A great deal of emphasis
has recently been put on the recovery of metals such as Cu and Zn from
low-grade ores [5]. Both metals are also among the most common
heavy metals in industries wastewaters and electronic scrap [6,7].
Solvent extraction is also the most used method that separates and
concentrates metallic ions in aqueous solution [8–11]. Reactive liquid-
liquid extraction has become an effective and widely used separation
technique, because of its speed, ease, selectivity, and cost effective.
More than 20% of the world copper production is generated directly at
mine sites through heap leaching of oxide ores followed by solvent
extraction and electrowinning to high quality cathode [12]. Selective
copper extraction from acidic sulfate solutions is typically accomplished
using commercial hydroxyoxime extractants such as LIX 63, LIX 64N,
LIX 65, SME 529, M5397, LK-C2. The Cu(II) extraction with the hy-
droxyoxime extractants can be successfully done at low pH values with
high selectivity towards Zn, Fe, Ni [13–17], but the selectivity is
sensitive to the changes of pH. Moreover, the main shortcoming of these
reagents is low stability in contact with acidic solutions or at higher
temperature [18,19]. The potential of the oxime reagents was a moti-
vation to synthesize novel complexing agents such as pyridine ketox-
imes and pyridineamidoxime derivatives. The extraction ability of the
pyridylketoximes towards copper(II), zinc(II), cadmium(II), iron(III),
nickel(II) and cobalt(II) has been widely investigated [20–27]. The
most interesting studies have mainly focused on extraction with 1-(2-
pyridyl)tridecan-1-one oxime, which shows excellent phase separation,
low entrainment losses to a raffinate, very high selectivity, and stability
against temperature, acidity and light. Disadvantage of this reagent is
the stability of extracted copper complex, which decomposition re-
quires presence of oxalate ions. N-alkyloxypyridinecarboximidamides
and N,N-dialkyl-N'-hydroxypyridinecarboximidamides are also capable
to coordinate metals ions in different aqueous solutions [28–30]. Ex-
ample of such extractants is N,N-dihexyl-N'-hydroxypyridine-2-carbox-
imidamide (DH2PIA) showing very good extractive property towards
copper(II) and selectivity over iron ions. While DH2PIA is very suitable
to apply for recovery of copper in the presence of iron(II) and iron(III)
[30], its application to recovery of copper(II) from Cu-Zn sulfate solu-
tions has not been proposed so far. Therefore, the present work has
aimed to test the N,N-dialkyl-N'-hydroxypyridine-2-carboximidamides
(Fig. 1) as extractants of copper over zinc from the Cu-Zn sulfate media.
In order to establish the optimal extraction and separation of copper

⁎
Corresponding author.
E-mail address: karolina.wieszczycka@put.poznan.pl (K. Wieszczycka).

https://doi.org/10.1016/j.seppur.2019.03.100
Received 18 December 2018; Received in revised form 24 March 2019; Accepted 30 March 2019
Available online 05 April 2019
1383-5866/ © 2019 Published by Elsevier B.V.
P. Aksamitowski, et al.
Fig. 1. Structure of tested compounds.
and zinc, the following process parameters have been investigated:
extractant type, pH of aqueous feed, phase ratio, and number and se-
quence of the extraction-stripping stages.
2. Experimental
2.1. Reagents
2.1.1. Extraction
Toluene (p.a., POCH), heptane (p.a., POCH, Poland), Exxsol® D80
(AZ) (aliphatic hydrocarbon solvent, producer Brenntag, Poland),
Solvesso® 100 (AZ) (aromatic content of 99%, producer Brenntag,
Poland), and synthesized DB2PIA (N,N-dibutyl-N′-hydroxypyrydine-2-
carboximidamide), DH2PIA (N,N-dihexyl-N′-hydroxypyridine-2-car-
boximidamide), and D2EH2PIA (N,N-bis(2-ethylhexyl)-N′-hydro-
xypyrydine-2-carboximidamide) were used as compounds of the or-
ganic phase solutions.
Copper(II) sulfate (CuSO4·5 H2O, p.a., CHEMPUR, Poland), and zinc
(II) sulfate (ZnSO4·7 H2O, p.a., Sigma-Aldrich), sulfuric acid (purity
99.8%, CHEMPUR, Poland), sodium hydroxide, (p.a., CHEMPUR,
Poland) and ultra-pure water (18.2 MΩ cm, Arium Pro DI, Sartorius)
were used as compounds of the aqueous solutions.
2.1.2. Extractants synthesis
Pyridine-2-carbonitrile (purity 98%, Sigma Aldrich, Germany), hy-
droxylamine hydrochloride (purity 99.8%, POCH), sodium bicarbonate
(p.a., POCH, Poland), sodium nitrite (a.r., CHEMPUR, Poland), trie-
thylamine (purity 99%, Sigma Aldrich, Germany) dibutylamine (98%,
Aldrich, Germany), dihexylamine (purity 98%, Merck, Germany) and
bis(2-ethylhexyl)amine (98%, Aldrich, Germany) were used as reagents
in the N,N-dialkyl-N′-hydroxypyridine-2-carboximidamides synthesis.
The reaction was conducted using hydrochloric acid (38%, p.a., POCH,
Poland), NaNO2 (p.a., POCH, Poland), and ethanol (purity 99.8%,
POCH, Poland). Ethanol was dried by molecular sieves 3 Å (Sigma
Aldrich, Germany).
2.2. Procedures
2.2.1. Extractants synthesis
N,N-dibutyl-N′-hydroxypyrydine-2-carboximidamide, N,N-dihexyl-
N′-hydroxypyridine-2-carboximidamide, N,N-bis(2-ethylhexyl)-N′-hy-
droxypyrydine-2-carboximidamide were synthesized according to a
three-step procedure described in the previous papers [28,31]. The
procedure consisted of synthesis of N′-hydroxypyridine-2-carbox-
imidamide (I), which next reacted with sodium nitrite at 0 °C to obtain
pyridine-2-hydroximoyl chloride (II). The final compounds (III) were
obtained from the reactions of dihexylamine, dibutylamine or bis(2-
23
Separation and Purification Technology 222 (2019) 22–29
Fig. 2. Scheme of tested compounds synthesis.
ethylhexyl)amine with the synthesized pyridine-2-hydroximoyl
chloride in the presence of triethylamine as the catalyst (Fig. 2). Both
N,N-dibutyl-N′-hydroxypyrydine-2-carboximidamide, N,N-dihexyl-N′-
hydroxypyridine-2-carboximidamide, as well as N,N-bis(2-ethylhexyl)-
N′-hydroxypyrydine-2-carboximidamide were obtained as yellow-or-
ange oils in 89–90% yield. Purities (99.9%) were determined by FT-IR
and NMR (1H, 13C) spectroscopy (see Table S.1 of the Supplementary
Information for details).
2.2.2. Extraction
The experiments at a two phase system were carried out by vigor-
ously stirring equal volumes (25 mL) in appropriate time (1–30 min) of
the two phases in glass reactor using a T50 titrator (Mettler Toledo) at
room temperature (22 ± 1 °C). The pH of the aqueous phase was
varied from 1 to 4.5. The pH was measured using combined glass pH
electrode with a ceramic frit for aqueous media (DGi111-SC, Mettler
Toledo) which was coupled with T50 titrator. The electrode was cali-
brated by a three-point method using appropriate buffer solutions. The
volume ratio of the aqueous to organic phase O/A was varied from 1 to
10 for the extraction isotherm and was kept at 1:1 for the other equi-
librium experiments. The two phases after achieving the desired pH
value were equilibrated for 5 min, allowed for complete separation and
analyzed. To determine the selectivity of the extractant, the organic
phases were contacted with the solutions containing changes con-
centrations of Cu(II) and Zn(II) (0.01–0.08 mol/L). All extraction ex-
periments were carried out three times, and the reproducibility was
found to be 5%.
2.2.3. Stripping
Stripping was carried using the loaded organic phases and sulfuric
acid solutions as stripping agent ([H2SO4] = 1, 5, 10 and 20%). The
stripping experiments were also conducted using the glass reactor
equipped with the T50 titrator. Both phases were mixed for 15 min at
different O/A ratios (1–10). The stripping experiments were repeated to
achieve the highest reproducibility.
2.2.4. Analysis
Concentration of copper(II) and zinc(II) were determined by using
atomic absorption spectroscopy (AAS) method by high-resolution,
continuum source atomic absorption spectrometer (ContrAA 300,
Analytik Jena AG).
2.2.5. Calculations
Distribution ratio (D) and percentage extraction (%E) of the metals
P. Aksamitowski, et al. Separation and Purification Technology 222 (2019) 22–29

were calculated using the following formula:

[M(II)]org,eq Vaq
D= ·
[M(II)]aq,eq Vorg (1)

[M(II)]aq,0 − [M(II)]aq,eq
%E = × 100%
[M(II)]aq,0 (2)

Percentage extraction (%E) of Cu(II) or Zn(II) was calculated from

the contents of the metal in the aqueous phase before and after ex-
traction. The concentration of the metal ions in the organic phase was
calculated by the difference in concentration before and after extrac-
tion. Distribution ratio was the ratio of metal concentration in the or-
ganic phase to that in the aqueous phase after the extraction. The se-
paration factor (β) was calculated using the following formula:
DCu (II )
β=
DZn (II ) (3)

3. Results and discussion

3.1. Influence of equilibrium pH and type of organic diluent

The influence of pH on the extraction of Cu(II) and Zn(II) from the

mixture of both metals was examined by varying equilibrium pH from 1
to 5. The obtained results shown in Figs. 3 and 4 indicate the marked
influence of the pH on the copper(II) extraction. In the case of DB2PIA,
irrespective of the solvent used, the Cu-complex formed was completely
soluble in the acidic aqueous phase, therefore this reagent was elimi-
nated from further studies. In the case of the rest considered imida- Fig. 4. Influence of pH on extraction of Cu(II) and Zn(II) by DH2PIA (A) and
mides the dissolution in the aqueous phase as well as precipitation of D2EH2PIA (B) dissolved in toluene ([Extractant] = 0.1 mol/L; [Cu(II)] = [Zn
the complexes in the organic phase have not been observed, even after (II)] = 0.01 mol/L; [SO42−] = 0.05 mol/L; T = 303.15 K; dashed lines re-
present approximations).

Fig. 3. Influence of pH on extraction of Cu(II) and Zn(II) by DH2PIA (A) and
D2EH2PIA (B) dissolved in heptane ([Extractant] = 0.1 mol/L; [Cu(II)] = [Zn
(II)] = 0.01 mol/L; [SO42−] = 0.05 mol/L; T = 303.15 K; dashed lines re-
present approximations).
contact with strong acidic solutions. The obtained results also reveal
that regardless on pH of the aqueous phase, used organic diluents and
on structure of the reagents the extraction of Zn(II) does not exceed 5%.
In the case of copper(II) the extraction percentage is found to increase
as the equilibrium pH increases to the level dependent on the diluent
type and the imidamide structure.
In heptane, DH2PIA shows a high yield of extraction already at the
equilibrium pH of 1.5 (E = 75%), and further increase in the pH results
in reaching the maximum just at pH of 2 (Fig. 3A). D2EH2PIA in
heptane forms complex with Cu(II) with lower yield than using DH2PIA
(Fig. 3B). At pH of 1.5 Cu(II) is extracted in 50%, while the maximum
extraction is achieved above pH of 3.5.
When using toluene as a diluent, maximum of the Cu(II) extraction
by using DH2PIA and D2EH2PIA as the extractants are shifted towards
higher equilibrium pH values (Fig. 4). In the case of DH2PIA at pH of
1.5 Cu(II) is extracted in 15%, while the maximum extraction is ob-
served at pH of 4. The extraction curve obtained for D2EH2PIA also
shows inconsiderable extraction at pH of 1.5 (%E = 12%), and the
maximum extraction is observed around pH of 4.
The changes of the diluent from aliphatic to aromatic also influences
the value of pH0.5. This parameter determines the value of equilibrium
pH of the aqueous phase at which 50% of the metal is transported to the
organic phase. It was shown that the pH0.5 values for copper decreases
as diluent changes from heptane to toluene. In the case of DH2PIA the
pH0.5 values were found to be 1.2 and 2.8 in the heptane and toluene
solution, respectively, while for D2EH2PIA 1.4 and 2.9, respectively.
The replacement of heptane and toluene by their industrial coun-
terparts (Exxsol D80 and Solvesso 100, respectively) does not affect
significantly the change in the efficiency of copper(II) extraction
(Fig. 5). In the case of D2EH2PIA dissolved in Exxsol D80 at pH of 1.5
Cu(II) is extracted in 60%, while the maximum extraction is ob-
served ≥ pH of 3, and using Solvesso 100 as the diluent at pH of 1.5 the

24
P. Aksamitowski, et al.
Fig. 5. Influence of pH on extraction of Cu(II) and Zn(II) by D2EH2PIA dis-
solved in Exxsol D80 (A) and Solvesso 100 (B) ([Extractant] = 0.1 mol/L; [Cu
(II)] = [Zn(II)] = 0.01 mol/L; [SO42−] = 0.05 mol/L; T = 303.15 K; dashed
lines represent approximations).
21% extraction is observed, while the maximum yield is indicated at pH
greater than 3.5. Moreover, the extraction of zinc(II) using both com-
mercial diluents is also inconsiderable.
The differences in the extraction efficiencies depend on type of di-
luent have been studied by various researchers [32–36]. They have
indicated that the metal extraction kinetic strictly depends on physical
properties of the diluents e.g., dipole moment, solubility parameter,
dielectric constant. Especially diluents with a high dipole moment such
as toluene can interact strongly with an extractant, then the extractant
impose an additional energy barrier for the extractant to leave the di-
luent environment and take part in metal complex formation. In the
case of the chelate extractant, such as the studied imidamides, the in-
teraction with toluene causes an additional energy barrier counter-
acting the dissociation of –OH. Therefore, the formation of the metal
oxime complex can be less preferred than using the aromatic diluent.
Similar effect has been observed for 2-hydroxy-4-octylox-
ybenzophenone oxime, for which better equilibrium performance and
kinetics have been found for the aliphatic than for the aromatic diluent
[37].
3.2. Effect of diluent on stoichiometry of extracted species
The previous paper have shown that the extraction of Cu(II) by
DH2PIA as extractant is based on the cationic exchange reaction, but
the stoichiometry of the extracted species depends on the type of di-
luent. In toluene copper(II) is extracted as CuL (HL) , while in heptane as
CuL (HL)2 [30]. In the case of D2EH2PIA the graphical analysis was also
conducted using similar assumption as stated for DH2PIA (Eqs. (4)–(7)).
The extraction reaction of Cu(II) by D2EH2PIA can be written as
follows:
2+ (2+) − n +
Cuaq + (n + m) HLorg = (CuLn (HL)m )org + nHaq (4)
25
Separation and Purification Technology 222 (2019) 22–29
Fig. 6. Logarithmic relation between distribution ratio of Cu(II) and equili-
brium pH obtained for D2EH2PIA dissolved in different diluents
([D2EH2PIA] = 0.1 mol/L, dashed lines represent linear regressions).
According Eq. (4) the extraction equilibrium and the distribution
ratio (D) can be written as follows:
[(CuLn (HL)m)(2+) − n][H+]n
K ex =
¯ ](n + m)
[Cu2 +][HL (5)
[(CuLn (HL)m )(2+) − n]
D=
[Cu2 +] (6)
Eq. (6), after rearrangement and logarithmic transformations, can be
rewritten as Eq (7) and used to estimate of n and m values:
logD = (n + m)log[D2EH2PIA] + logKex + npH (7)
The results of the conducted analysis presented in Fig. 6, indicate
that in the case of heptane, Exxsol D80 and Solvesso 100 used as or-
ganic diluent, the slopes of the lines obtained from the plot logD versus
pH was close to 1 (0.785, 0.710 and 0.659, respectively), which in-
dicates that during extraction one H+ is released in the aqueous
medium. Using Exxsol D80 as diluent, the slope obtained is milder
(0.421, R2 = 0.997). This value can suggests that in Exxsol D80 the H+
release is observed but further transport to the aqueous phase is hin-
dered by limited interfacial activity of the diluent. The released hy-
drogen ion from cation exchange enhances the acidity of solution, and if
the transport is limited the effect on the equilibrium of metal extraction
is also limited.
The experimental data was also plotted as relation logD–pH and log
[D2EH2PIA], and presented in Fig. 7. As observed, the obtained lines
are straight with slopes of 2.073 (R2 = 0.996) and 2.096 (R2 = 0.998)
for heptane and Exssol D80, respectively, and these values indicate that
in the aliphatic diluent 2 molecules of D2EH2PIA participate in the
extracted copper complex. In the case of toluene and Solvesso 100, the
obtained lines are also straight with slopes indicating copper co-
ordination by 1 molecule of ligand or mixture of the complexes in
which Cu is coordinated by 1 and 2 molecules of D2EH2PIA (slopes
P. Aksamitowski, et al. Separation and Purification Technology 222 (2019) 22–29

-3
y = 2.073x - 1.489 y = 2.096x - 1.641
R² = 0.996 R² = 0.998
-4
y = 1.486x - 2.923
logD-pH

R² = 0.999

Heptane
-5
Exxsol D80
Toluene
y = 1.418x - 3.232
R² = 0.998 Solvesso 100
-6
-2.0 -1.5 -1.0 -0.5 0.0
log[D2EH2PIA]

Fig. 7. Relation between logD-pH and D2EH2PIA concentration. ([Cu

(II)] = 0.01 mol/L, pH = 4.3–4.7; dashed lines represent linear regressions).

1.486 with R2 = 0.999 and 1.418 with R2 = 0.998 for toluene and
Solvesso 100, respectively).

3.3. Selectivity

The selectivity of Cu(II) extraction over Zn(II) using DH2PIA and

D2EH2PIA as the extrctants were carried out using the mixture of both
metals in concentration of 0.01 mol/L. The results are presented in
Fig. 8. Comparing results obtained for DH2PIA dissolved toluene and
heptane (Fig. 8A), it can be observed that the selectivity factor values
increase with the increase of pH achieving the highest values of β above
pH of 3.5. Moreover it is also observed that DH2PIA dissolved in hep-
tane reveals much higher selectivity towards Cu(II) than in toluene (at
pH of 4.8–4.9 β = 614 and 151, respectively).
In the case of D2EH2PIA, the differences in the β values in term of
type of diluent used are less significant. Moreover, individual values of
the parameter for each diluent are higher than those observed for
DH2PIA. As presented in Fig. 8B, the β values increase with the increase
of pH up to β = 692 (at pH of 4.8) and up to β = 985 (at pH of 4.4)
using as the diluent toluene and heptane, respectively. The selectivity
was also considered using D2EH2PIA dissolved in Exxsol D80 and
Solvesso 100, and also the maximum β values are comparable for both
used diluents (Fig. 8C). For D2EH2PIA dissolved in Exxsol D80
β = 962, while for D2EH2PIA dissolved in Solvesso 100 β = 927.
The effect of copper(II) and Zn(II) concentration on the extraction
selectivity was also studied. The experiments were carried out using
two aqueous solutions: (I) aqueous solutions containing various con- Fig. 8. pH dependence of selectivity factor (β) by using as extractant DH2PIA
centration of copper(II) (from 0.01 to 0.08 mol/L) and the constant Zinc (A) dissolved in heptane (○) and toluene (□), and D2EH2PIA (B) dissolved in
(II) concentration equal to 0.01 mol/L, and II) aqueous solutions con- heptane (○) and toluene (□), (C) dissolved in Exxsol D80 (△) and Solvesso 100
taining various concentration of zinc(II) (from 0.01 to 0.08 mol/L) and (▴) (dashed lines represent approximations).
the constant copper(II) concentration equal to 0.01 mol/L. The studies
were conducted at the constant concentration of sulfate ions (0.1 mol/ 3.4. Stripping
L) and at the constant value of pH equal to 4.
The experimental results, shown in Fig. 9, indicate the reducing Stripping studies were carried out using the loaded organic phases
effect of Cu(II) concentration on the Cu(II) extraction. In the case of the containing 0.6 g/L Cu(II), and 0.03 g/L Zn(II), 5.12 g/L Cu(II) and
zinc extraction the increasing Cu(II) concentration does not affect 1.20 g/L Zn(II), and the organic phases containing 1.90 g/L Cu(II) and
amount of the zinc(II) transferred from the aqueous to the organic 0.03 g/L Zn(II). The results obtained using as stripping agents water and
phase. This phenomenon probably results from the high affinity of the aqueous solutions of sulfuric acid (1–25%) are summarized in Table 1.
extractant towards Cu(II), but not towards Zn(II). From presented results it is observed that water can wash out the co-
In the case of the increasing Zn(II) concentration, the presented extracted zinc(II), while the extracted copper(II) requires sulfuric acid
results indicate the negative effect of Zn(II) concentration on the Cu(II) in the concentration depending on the concentration of copper in the
extraction, but the decrease is ∼ 10% (Fig. 10). It is also observed a loaded organic phase. Using the organic phase containing 0.6 g Cu(II)
several percent increase in amounts of extracted Zn(II), and finally the stripping with 5% H2SO4 is sufficient, however much more con-
using the solution containing 0.08 mol/L Zn(II) and 0.01 mol/L Cu(II), centrated organic phase required the 20% H2SO4 solution.
zinc(II) is extracted in 4%.
The obtained results also allows determination of the tested com-
pound capacity. The conducted calculation indicated that the capacity 3.5. Flowsheet for recovery of copper from Cu-Zn sulfate solution
of D2EH2PIA dissolved in toluene is 20 g Cu(II) per one mole of the
extractant. Based on the presented results, a flow-sheet for selective recovery of
copper(II) from Cu-Zn sulfate solution containing 40.9 g/L Zn(II) and

26
P. Aksamitowski, et al. Separation and Purification Technology 222 (2019) 22–29

Table 1
Cu(II) and Zn(II) stripping from loaded organic phase after extraction with
DH2PIA and D2EH2PIA (0.1 M) dissolved in toluene or Solvesso 100.
Organic phase

Stripping O/A DH2PIA O/A D2EH2PIA

agent ratio diluent: toluene ratio diluent: toluene
0.58 g/L Cu(II) 0.61 g/L Cu(II)
0.03 g/L Zn(II) 0.03 g/L Zn(II)

Cu Zn Cu Zn

Water 1 < 1% 100% 1 < 1% 100%

1% H2SO4 1 47% 100% 1 42% 100%
5% H2SO4 1 95% 100% 1 93% 100%
10% H2SO4 1 99% 100% 1 98% 100%

Organic phase

Stripping O/A D2EH2PIA O/A D2EH2PIA diluent:

agent ratio diluent: Solvesso 100 ratio Solvesso 100
5.12 g/L Cu(II) 1.90 g/L Cu(II)
1.20 g/L Zn(II) 0.03 g/L Zn(II)

Cu Zn Cu Zn

Washing with 0.2 < 1% 100% 0.2 < 1% 100%

water
20% H2SO4 5 46% – 2 40% –
10 30% – 4 35% –
45% H2SO4 3 57% – 3 59%

Fig. 9. Effect of increasing Cu(II) concentration on amounts of Cu(II) and Zn(II)

transferred to organic phase by D2EH2PIA dissolved in Solvesso 100 (dashed
lines represent approximations).

Fig. 10. Effect of increasing Zn(II) concentration on amounts of Cu(II) and Zn

(II) transferred to organic phase by D2EH2PIA dissolved in Solvesso 100 (da-
shed lines represent approximations).

Fig. 11. Flowsheet for recovery of copper(II) from solution containing 40.9 g/L
Zn(II) and 1.18 g/L Cu(II) using as extractant D2EH2PIA dissolved in Solvesso
100.

27
P. Aksamitowski, et al.
1.18 g/L Cu(II) [38] was proposed and tested.. In this stage of studies as
the organic phase D2EH2PIA (0.1 mol/L) dissolved in Solvesso 100 was
used. Using this method, it has been proposed that the extraction of
copper(II) from Cu-Zn sulfate solution can be carried out in one stage at
the phase ratio A/O = 0.2, and then the loaded organic phase is con-
tacted with water to wash out the co-extracted Zn(II). After the washing
stage, the extracted Cu is stripped in two counter-current stages using
20% H2SO4 and the phase ratio A/O = 0.2. The results are presented in
Fig. 11. The conducted test confirmed the applicability of the proposed
method to selective recover of Cu(II) over Zn(II). Moreover, the test
confirmed that the regenerated organic phase can be used repeatedly in
subsequent processes. The efficiency of the process after 10-fold ap-
plication of the same organic phase varies within 5%.
4. Conclusions
In this paper, the hydrophobic N,N-dialkyl-N′-hydroxypyridine-2-
carboximidamides were tested as extractants of copper from the Cu-Zn
sulfate media. The results indicated that only DH2PIA and D2EH2PIA
can be used successfully to recover copper(II) from Cu-Zn mixture. The
copper complex with DB2PIA revealed the affinity to aqueous phase
and that resulted in the extractant loss. The equilibrium studies con-
ducted using DH2PIA and D2EH2PIA as the extractants indicated that
the copper extraction and stripping kinetics were reasonably fast. The
obtained results indicated the marked influence of the pH and the type
of diluent on the extraction efficiency. The values of pH0.5 also de-
pended on the type of diluent, and varied from ∼ 1.3 for aliphatic
to ∼ 2.8 for aromatic. The selectivity studies revealed that the used
extractants enabled to recovery of copper with high selectivity, which
also depended on the type of diluent. In heptane the selectivity was
much higher than in toluene. Moreover, in the case of D2EH2PIA the
differences in the β values in term of diluent type are much lower than
in the case of DH2PIA. The experimental data also showed that the
increasing Cu(II) concentration did not adversely affect on the se-
lectivity. The increasing Zn(II) concentration influences negatively the
copper extraction, but the decrease was not higher than 10%. The
stripping of Cu(II) from the loaded organic phase was accomplished
with sulfuric acid solutions in the concentration depending on the
concentration of copper in the loaded organic phase. However, the co-
extracted Zn(II) can be removed from the loaded phase by washing with
water. Based on the obtained results the flow-sheet for the selective
recovery of copper(II) from Cu-Zn sulfate solution using D2EH2PIA
dissolved in Solvesso 100 was proposed. The conducted test confirmed
the possibility to selective recover of Cu(II) over Zn(II), and the con-
centration of Cu(II) to the value of 25 g/L (using enriched in Cu(II)
stripping phase).
Acknowledgements
The work was financed by a statutory activity subsidy from the
Polish Ministry of Science and Higher Education for the Institute of
Chemical Technology and Engineering of Poznan University of
Technology.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.seppur.2019.03.100.
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