metals
Article
Recovery of Copper(II) and Silver(I) from Nitrate Leaching
Solution of Industrial Dust via Solvent Extraction with LIX63
Pan-Pan Sun 1 , Tae-Young Kim 1 , Hyeon Seo 2 and Sung-Yong Cho 1, *






Citation: Sun, P.-P.; Kim, T.-Y.; Seo,
H.; Cho, S.-Y. Recovery of Copper(II)
and Silver(I) from Nitrate Leaching
Solution of Industrial Dust via
Solvent Extraction with LIX63. Metals
2021, 11, 1300. https://doi.org/
10.3390/met11081300
Academic Editors: Felix A. Lopez and
Jean François Blais
Received: 18 July 2021
Accepted: 13 August 2021
Published: 17 August 2021
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Attribution (CC BY) license (https://
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4.0/).
Metals 2021, 11, 1300. https://doi.org/10.3390/met11081300
1 Department of Environment and Energy Engineering, Chonnam National University, Gwangju 61186, Korea;
spp1227@jnu.ac.kr (P.-P.S.); tykim001@jnu.ac.kr (T.-Y.K.)
2 Department of Dental Materials, School of Dentistry, Chonnam National University, Gwangju 61186, Korea;
seohyeon@jnu.ac.kr
* Correspondence: swapoo@hanmail.net; Tel.: +82-62-530-1982
Abstract: A nitrate leachate containing Cu(II), Ag(I), Ni(II), Mg(II), and Al(III) was obtained during
the leaching of industrial dust, which arises during the pyrometallurgy of spent camera modules.
To separate and recover Cu(II) and Ag(I) from the leaching solution, solvent extraction experiments
using 5,8-diethyl-7-hydroxydodecan-6-oxime (LIX63) were conducted. LIX63 was found to selec-
tively extract Cu(II) and Ag(I) over other metal ions (Ni(II), Mg(II), and Al(III)) at low nitric acid
concentrations. The extraction efficiency of Cu(II) was more affected than that of Ag(I) by the acidity
of the feed solution and the LIX63 concentration in the organic phase. Cu(II) and Ag(I) were simulta-
neously extracted using 2 mol/L LIX63. Cu(II) was separated from the loaded LIX63 via stripping
with 4 mol/L HNO3 , whereas Ag(I) was recovered via stripping with 0.1 mol/L thiourea after the
removal of Cu(II). McCabe–Thiele diagrams for the extraction and stripping of Cu(II) and Ag(I)
were constructed. The complete extraction of Cu(II) and Ag(I) was confirmed via counter-current
extraction. Moreover, stripping simulation tests confirmed that higher than 99.99% of Cu(II) and
99.2% of Ag(I) were stripped. The purities of Cu(II) and Ag(I) in the recovered solution were 95.2%
and 99.993%, respectively. A process flow chart for the recovery of Cu(II) and Ag(I) from the nitrate
leachate of the target industrial dust was also provided.
Keywords: silver; copper; nitric acid; LIX63; separation; industrial dust
1. Introduction
Copper (Cu(II)) and silver (Ag(I)) are essential elements that are widely used in daily
life. In the industry, Cu(II) is used in the manufacture of electrical materials and telecom-
munication devices and in the construction, power generation, transportation, petroleum
refining, and electroplating industries [1–4]. Ag(I) has been employed in the production of
brazing alloys, electrical and electronic products, photographic paper and film, catalysts,
and other systems [5–7]. Cu(II) and Ag(I) are reported to be two common co-existing
valuable metals in industrial waste [8]. From economic and environmental perspectives,
the recovery of Cu(II) and Ag(I) from industrial waste is particularly important.
Hydrometallurgical methods have been widely used for the recovery/extraction of
Cu(II) and Ag(I) from various solutions. The results of studies on the extraction separation
of Cu(II)/Ag(I) from various resources are summarized in Tables 1 and 2. The extraction
of Cu(II) has been investigated using chelating extractants such as LIX84-IC, LIX622N,
LIX860N, LIX984N, LIX54, and LIX63 + Versatic10 + TBP [9–15], as well as acidic and
solvating extractants such as D2EHPA, Cyanex 272, Cyanex 301, Cyanex 302, Cyanex 921,
and Cyanex 923 from various media [16–20]. When Cyanex 301 is used as an extractant,
the stripping of Cu(II) is reported to be highly difficult and aqua regia is required as
a strippant [21]. LIX984 is added to Cyanex 301 to improve the efficiency of stripping
Cu(II) from Cyanex 301 systems [17]. It has been proven that the chelating extractant
https://www.mdpi.com/journal/metals
Metals 2021, 11, 1300 2 of 13

is the most effective among these extractants for Cu(II) extraction and is widely used
commercially [22].

Table 1. Summary of some studies on the extraction of Cu(II) using various extractants.

Extractant Media Diluent Remark Ref.

1. The extraction behavior of the two
extractants for copper(II) was compared.
LIX 84,
H2 SO4 kerosene 2. A copper(II) extraction of 95–99% was [9]
LIX 973N
achieved via three extraction stages with LIX
84 and two extraction stages with LIX 973N.
1. Cu(II) extractions of 98.64% and 99.95%
were obtained using LIX 84I and LIX 622N,
LIX 84I,
H2 SO4 kerosene respectively. [10]
LIX 622N
2. Stripping was conducted by using 2 mol/L
H2 SO4 .
1. The copper loading capacity order for four
extractants was LIX984N > LIX612N-LV and
LIX84-I, LIX612N-LV, XI04003 > LIX84-I.
XI-04003, HCl kerosene 2. At a pH of <0.5, copper extraction [11]
LIX984N efficiency increased quickly with increasing
pH, while at a pH value above 0.5, it
increased only slightly with increasing pH.
LIX 84-I, Extraction efficiency was much higher for
LIX 984N, Ammonia Escaid110 systems using hydroxy reagents than that [12]
LIX54-100 using β-diketone oximes.
1. Solvents cinnamate and a mixture of
β-diketone were suitable alternatives to
LIX 54.
LIX-54,
2. About 97.3%, 99.7%, and 99.6% of
cinnamate, Ammoniacal carbonate Arol-light [13]
copper(II) can be extracted using LIX 54,
β diketone
cinnamate, and β-diketone, respectively.
3. Stripping was conducted by using 2 mol/L
H2 SO4 .
1. Fe(III) and Pb(II) were co-extracted with
Cu(II) at pH 2.
LIX860N-I HCl kerosene [14]
2. Stripping was conducted using 1.5 mol/L
H2 SO4 .
1. Using a Versatic 10/LIX63/TBP system,
95% of Cu(II) and 12% of Ni(II), Zn(II), Co(II),
and Cl(I) were extracted.
LIX63 +
2. At pH 3–3.5, impurities of Ni(II), Zn(II),
Versatic10;
Co(II), and Cl(I) were stripped, and Cu(II)
LIX63 + HCl Shellsol D70 [15]
was transferred to a sulfate solution.
Versatic10
3. Cu(II) was recovered by electrowinning.
+ TBP
4. The Versatic 10/LIX63 system was used to
separate Cu(II) from Fe(III) in strong
chloride solutions.
1. Acetate ions greatly improved the Cu(II)
extraction efficiency.
D2EHPA Acetate buffer kerosene 2. At an initial pH value of 4.44, acetate ion [16]
concentration was 0.18 mol/L, and the single
stage extraction efficiency was >99.5%.
1. The extraction equilibria of Cu(II) with
Cyanex 301, LIX 984N, and their mixtures
Cyanex 301,
H2 SO4, kerosene were investigated. [17]
LIX 984N
2. Stripping efficiency was improved by the
addition of LIX 984N to Cyanex 301.
Metals 2021, 11, 1300 3 of 13

Table 1. Cont.

Extractant Media Diluent Remark Ref.

1. Cyanex 302 was a potential extractant for
the extraction of copper(II) from
H2 SO4 /
aqueous solutions.
Cyanex 302 HCl/ kerosene [18]
2. The endothermic nature of the extraction
HNO3
process for the three studied systems was in
the order: chloride > nitrate > sulfate media.
1. The solvent extraction of Cu(II) with
Cyanex 272,
H2 SO4 kerosene Na-Cyanex 272 was more efficient than that [19]
Na-Cyanex 272
with Cyanex 272
1. Cu(II) extraction was quantitative using
0.5 mol/L Cyanex 921 and 5 mol/L HCl.
Cyanex 921 HCl kerosene 2. By using using 0.2 mol/L H2 SO4 or [20]
0.5 mol/L HCl, 99.7% Cu(II) was recovered
from the loaded organic phase.
1. The extraction mechanism was
Cyanex 923 HCl kerosene [21]
investigated.

In the case of Ag(I), the applicability of calix(4)arene amide derivatives [23], ke-
tonic derivatives of calixarenes [24], Cyanex 272, Cyanex 302, Cyanex 301 [25], N,N-
diethyl-2,7-dihexyl-3,6-diazaoctanoic acid, 1,5-bis[2-(20 -carboxypentadecyloxy)phenoxy]-3-
oxapentane [26], bis-triazin-bi-pyridine (BTBP) [27], trioctylphosphine oxide (TOPO) [28],
and 5,8-diethyl-7-hydroxydodecan-6-oxime (LIX63) [29,30] for the extraction of Ag(I) has
been investigated. From a chloride-leaching solution of anode slimes containing Cu(II),
Ag(I), and Au(II), Cu(II) was recovered by extraction with LIX63, followed by stripping
with HCl, whereas Ag(I) was recovered via extraction with Alamine 336, followed by
stripping with an NH4 SCN solution [31]. Although Cu(II) and Ag(I) were simultaneously
extracted using Cyanex 301, their stripping from the loaded Cyanex 301 was difficult. The
efficient stripping of Cu(II) and Ag(I) was possible only by using aqua regia [31].

Table 2. Summary of some studies on the extraction of Ag(I) using various extractants.

Extractant Media Diluent Remark Ref.

Cyanex 272
Cyanex 302 HNO3 kerosene 1. Extraction mechanisms were investigated. [25]
Cyanex 301
1. Tetrameric ketone facilitated selective extraction of Ag(I) over
ketonic
HNO3 Pd(II) using ~1 mol/L HNO3 .
derivatives of / [26]
HCl 2. It effectively removed traces of Ag(I) from a large excess
calixarenes
of Pd(II).
1. The side group of the ligand affected the distribution of Ag(I).
Bis-triazin-bi-pyridine
HNO3 / 2. CyMe4-BTBP is a more efficient extractant for Ag(I) compared [27]
(BTBP)
to C2-BTBP.
1. TOPO selectively extracted Ag(I) over Al using 0.1 mol/L
Trioctyl HNO3 solution.
Phosphine 2. The selective stripping of Ag(I) was successful using a
HNO3 kerosene [28]
oxide 0.1 mol/L thiourea solution.
(TOPO) 3. TOPO was regenerated by stripping of co-loaded Al(III) using
3 mol/L HNO3 .
1. Ag(I) extraction followed a solvating extraction mechanism,
LIX63 HNO3 kerosene [29]
when the concentration of HNO3 was higher than 0.1 mol/L.
Metals 2021, 11, 1300 4 of 13

Table 2. Cont.

Extractant Media Diluent Remark Ref.

1. The selective extraction of Ag(I) over Zn(II) was achieved by
using LIX63, when the HNO3 concentration was 0.001–1 mol/L.
LIX63 HNO3 kerosene [30]
2. The stripping of Ag(I) was conducted by using
5 mol/L HNO3 .
1. Cu(II) was recovered by extraction with LIX 63 and stripping
with an HCl solution, while Ag(I) was recovered by extraction
LIX 63, with Alamine 336 followed by stripping with NH4 SCN solution.
Alamine 336; HCl kerosene 2. Cu(II) and Ag(I) were simultaneously extracted by [31]
Cyanex 301 Cyanex 301.
3. Stripping from Cyanex 301 was achieved using diluted
aqua regia.
1. LIX63 exhibited selectivity for the extraction of Cu(II) and
Ag(I) over Ni(II), Mg(II), and Al(III) at low concentrations
of HNO3 .
Present
LIX63 HNO3 kerosene 2. Cu(II) was selectively stripped over Ag(I) from the loaded
study
LIX63 using 4 mol/L HNO3 .
3. After the removal of Cu(II), Ag(I) was stripped from the
loaded LIX63 using 0.1 mol/L thiourea.

Herein, a simple and efficient process was developed for recovering Cu(II) and Ag(I)
from a nitrate-leaching solution of industrial dust that arises during the pyrometallurgy of
spent camera modules. In the proposed process, LIX63 was employed as an extractant to
simultaneously extract Cu(II) and Ag(I). Several parameters that affect the extraction and
stripping efficiencies, such as the acidity of the solution, concentration of the extractant,
species and concentration of the strippant, and volume ratio of the aqueous to organic
phases, were investigated. Moreover, the feasibility of the proposed process was verified
by performing a batch simulation of counter-current extraction and stripping experiments.

2. Materials and Methods

2.1. Leaching Procedure
The industrial dust composed of Cu(II), Ag(I), Ni(II), Mg(II), Al(III), Si (II), and C,
which arose during the pyrometallurgy of spent camera modules, was used. It was leached
using 1 mol/L of nitric acid at 70 ◦ C for 2 h. The pulp density used for leaching was 10 g/L.
The leaching solution contained 0.003 mol/L Ag(I), 0.02 mol/L Cu(II), 0.007 mol/L Ni(II),
0.001 mol/L Mg(II), and 0.003 mol/L Al(III).

2.2. Materials
AgNO3 (99.8%; Daejung), Cu(NO3 )2 ·2H2 O (99%; Daejung), Ni(NO3 )2 ·6H2 O (97%;
Junsei), Mg(NO3 )2 ·6H2 O (99%; Junsei), and Al(NO3 )3 ·9H2 O (98%; Daejung) were used to
prepare the leaching solution. The concentrations of metals Ag(I), Cu(II), Ni(II), Mg(II),
and Al(III) were fixed at 0.003, 0.02, 0.007, 0.001, and 0.003 mol/L, respectively, to main-
tain a composition identical to that of the leaching solution. HNO3 (60%; Daejung) was
used to adjust the acidity of the solution. Thiourea (98%; Junsei), HNO3 (60%; Daejung),
Na2 S2 O3 ·5H2 O (99.5%; Samchun), NH4 NO3 (99%; Daejung), (NH4 )2 SO4 (99%; Daejung),
and CH3 COONH4 (97%; Daejung) were used to prepare the strippant solution. The feed
and strippant solutions were prepared by dissolving the required quantity of reagents in
the desired volume of distilled water.
Extractant 5,8-diethyl-7-hydroxydodecan-6-oxime (LIX63) was purchased from Cognis
and used without further purification. Kerosene (90% distillation at 265 ◦ C; Daejung) was
used as a diluent.
Metals 2021, 11, 1300 5 of 13

2.3. Solvent Extraction and Stripping

In batch simulation extraction experiments, equal volumes (20 mL) of aqueous and
organic phases were mixed in a sealed bottle (100 mL) and shaken for 30 min using a wrist-
action shaker (Model 75, Burrell, Pittsburgh, PA, USA) at ambient temperature (24 ± 1 ◦ C).
The shaking speed was 200 rpm. The aqueous solution was collected, after the two
phases were well-separated in ~5 min using a separation funnel. Stripping was performed
through the same procedure by mixing the loaded organic phase and the strippant solution.
Subsequently, the concentration of metal ions in the aqueous phase was measured through
inductively coupled plasma optical emission spectrometry (Optima 8300, PerkinElmer,
Waltham, MA, USA). The concentration of metal ions in the organic phase was determined
by using a mass balance.

3. Results and Discussions

3.1. Effect of the HNO3 Concentration on the Extraction of Metal Ions
Metal ions were extracted from the synthetic leaching solution by using LIX63 and
varying the concentration of HNO3 from 0.001 to 3 mol/L. The concentrations of met-
als Ag(I), Cu(II), Ni(II), Mg(II), and Al(III) were fixed at 0.003, 0.02, 0.007, 0.001, and
0.003 mol/L, respectively. The concentration of LIX63 was maintained at 0.5 mol/L. The
aqueous-to-organic phase (A/O) ratio was fixed at 1:1.
Figure 1 shows the effect of the HNO3 concentration in the feed solution on the
extraction percentages of metal ions. LIX63 selectively extracted Cu(II) and Ag(I) over
other metal ions (Ni(II), Mg(II), and Al(III)) at low HNO3 concentrations. The extraction
percentage of Cu(II) decreased with an increase in the HNO3 concentration, whereas that
of Ag(I) first decreased with an increase in the HNO3 concentration to 0.1 mol/L and then
increased with a further increase in the HNO3 concentration to 1 mol/L. The extraction
efficiency was slightly changed by increasing the HNO3 concentration from 1 to 3 mol/L.
These results agree well with those of a previous study [29]. At a low acid concentration
([HNO3 ] < 0.1 mol/L), the extraction of Cu(II) and Ag(I) can be explained by the typical
cationic exchange theory, whereas at a higher acid solution ([HNO3 ] > 0.1 mol/L), the ex-
traction of Ag(I) followed the solvating extraction mechanism [29]. The reaction equations
for Cu(II) and Ag(I) can be represented as follows [12,29]:
i
[Ag + + [NO 3 ]aq + [H 2 R]org = [Ag(H 2 R)NO3 ]org , ([HNO3 ] > 0.1 mol/L) (1)
aq
i
2[Ag + + [H 2 R]org = [Ag 2 R]org + 2H+ , ([HNO3 ] < 0.1 mol/L) (2)
aq
i
[Cu + + [H 2 R]org = [CuR]org + 2H+ (3)
aq

where H2 R denotes LIX63.

The extraction percentages of Ni(II), Mg(II), and Al(III) in all the extraction experi-
ments were ~0%. Further experiments were performed using a 0.001 mol/L HNO3 solution.
 [Ag + ]aq + [NO3 ]aq + [H2R]org = [Ag(H2 R)NO3 ]org , ([HNO3] > 0.1 mol/L) (1)

2[Ag + ]aq + [H2R]org = [Ag 2R]org + 2H+ , ([HNO3] < 0.1 mol/L) (2)

[Cu+ ]aq + [H2R]org = [CuR]org + 2H+ (3)6 of 13

Metals 2021, 11, 1300

where H2R denotes LIX63.

100

90

Extraction percentage of metals (ex%)

80

70 Cu
Ni
60 Ag
Al
50 Mg
40

30

20

10

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
HNO3 concentration (mol/L)

Figure 1.
Figure 1. Effect
Effect of
of HNO
HNO3 3concentration
concentrationonon
metal extraction.
metal extraction.

The extraction
3.2. Effect percentages
of the LIX63 of Ni(II),
Concentration on theMg(II), and Al(III)
Extraction in all
of Cu and Agthe extraction experi-
ments were
The ~0%.ofFurther
effects experiments
the extractant were
(LIX63) performed using
concentration on thea extraction
0.001 mol/LofHNO 3 solu-
Cu(II) and Ag(I)
tion.
were investigated by varying the LIX63 concentration in the organic phase from 0.5 to
Metals 2021, 11, x FOR PEER REVIEW 6 of 13
2 mol/L. The HNO3 concentration in the feed solution was maintained at 0.001 mol/L.
3.2. Effect of the LIX63 Concentration on the Extraction of Cu and Ag
The metal ion concentrations were the same as those in the leaching solution (stated
The The effects
metal of the extractant
ion concentrations were (LIX63)
the sameconcentration onleaching
as those in the the extraction
solutionof(stated
Cu(II)inand
in Section 2.1).
Ag(I)
Sectionwere investigated by varying the LIX63 concentration in the organic
2.1). 2 shows that the extraction percentages of Cu(II) and Ag(I) increased phase from 0.5
Figure with an
to 2 mol/L.
Figure The HNO 3 concentration in the feed solution was maintained at 0.001 mol/L.
increase in 2the
shows thatconcentration
LIX63 the extraction percentages
from 0.5 toof2Cu(II)
mol/L.andNo Ag(I) increased
variation inwith an
the extraction
increase in the
percentages of LIX63
Ni(II),concentration from 0.5
Mg(II), and Al(III) wasto 2observed;
mol/L. Notheir
variation in the percentages
extraction extraction were
percentages of Ni(II), Mg(II), and Al(III) was observed; their extraction percentages were
~0%. (The data are not presented in the figure for brevity) The LIX63 concentration did
~0%. (The data are not presented in the figure for brevity) The LIX63 concentration did
not affect the extraction percentages of Ni(II), Mg(II), and Al(III), whereas higher than
not affect the extraction percentages of Ni(II), Mg(II), and Al(III), whereas higher than 90%
90% of Cu(II) and Ag(I) were extracted when the LIX63 concentration exceeded 2 mol/L.
of Cu(II) and Ag(I) were extracted when the LIX63 concentration exceeded 2 mol/L. This
This suggests
suggests the possibility
the possibility of the simultaneous
of the simultaneous separationseparation
of Cu(II) andofAg(I)
Cu(II) and
from theAg(I)
leach-from the
leaching solution.
ing solution.

100

80
Extraction percentage of metals (%)

60
Cu
Ag

40

20

0
0.5 1.0 1.5 2.0
LIX63 concentration (mol/L)

Figure Effectofofthe
Figure 2. Effect theLIX63
LIX63 concentration
concentration on extraction
on the the extraction of metals.
of metals.

3.3. Effect of the A/O Ratio on the Extraction of Cu(II) and Ag(I)
The effect of the aqueous-to-organic phase ratio (A/O) on the quantitative extraction
of Cu(II) and Ag(I) was investigated by varying the A/O ratio from 1:5 to 2:1. The concen-
Metals 2021, 11, 1300 7 of 13

3.3. Effect of the A/O Ratio on the Extraction of Cu(II) and Ag(I)
The effect of the aqueous-to-organic phase ratio (A/O) on the quantitative extraction
of Cu(II) and Ag(I) was investigated by varying the A/O ratio from 1:5 to 2:1. The concen-
trations of Cu(II), Ag(I), Ni(II), Mg(II), and Al(III) were the same as those in the leaching
solution list presented in the experimental section. The concentration of HNO3 in the feed
solution and that of LIX63 in the organic phase were fixed at 0.001 and 2 mol/L, respectively.
The results indicated that the extraction percentage of Cu(II) increased from 58% to
99% as the A/O ratio decreased from 2:1 to 1:5. However, the extraction percentage of
Ag(I) was higher than 90% for all the studied A/O ratios. Ni(II), Mg(II), and Al(III) were
not extracted in any of these experiments. The results for the extraction of Cu(II) and Ag(I)
are represented as the McCabe–Thiele diagrams in Figures 3 and 4, respectively. Figure 3
indicates that two stages were needed for the quantitative extraction of Cu(II) from a
0.001 mol/L HNO3 solution using 2 mol/L LIX63 at an A/O ratio of 1:2. Figure 4 suggests
Metals 2021, 11, x FOR PEER REVIEW 7 of 13
that the quantitative extraction of Ag(I) was achievable under the conditions identical to
those used for the quantitative extraction of Cu(II).

30
Cu(II) concentration in organic phase ( 10 mol/L)
-3

25

20

15

10

1/2
5 A/O =

0
0 5 10 15 20
-3
Cu(II) concentration in aqueous phase ( 10 mol/L)

Figure3.3.McCabe–Thiele
Figure McCabe–Thieleplot
plotfor
forCu(II)
Cu(II)extraction
extractionusing
using22mol/L
mol/L LIX63.
LIX63.

Based on the obtained results, a two-stage counter-current batch simulation test was
performed at an A/O ratio of 1:2 and using 2 mol/L LIX63. The test results indicated that
Ag(I) concentration in organic phase ( 10 mol/L)

after the two-stage counter-current extraction, neither Cu(II) nor Ag(I) was detected in the
6
raffinate, indicating that higher than 99.99% of Cu(II) and Ag(I) were co-extracted from
-3

the feed solution by using LIX63. The concentrations of Ni(II), Mg(II), and Al(III) after
extraction were the same as those before extraction.

/2
A/O = 1

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
-3
Ag(I) concentration in aqueous phase ( 10 mol/L)
 1/
5 A/O =

Cu(II
0
0 5 10 15 20
-3
Metals 2021, 11, 1300 Cu(II) concentration in aqueous phase ( 10 mol/L) 8 of 13

Figure 3. McCabe–Thiele plot for Cu(II) extraction using 2 mol/L LIX63.

Ag(I) concentration in organic phase ( 10 mol/L)

6

-3

/2
A/O = 1

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
-3
Ag(I) concentration in aqueous phase ( 10 mol/L)

Figure4.4.McCabe–Thiele
Figure McCabe–Thieleplot
plotfor
forAg(I)
Ag(I)extraction
extractionusing
using2 2mol/L
mol/LLIX63.
LIX63.
3.4. Selection of a Strippant for the Stripping of Cu(II) and Ag(I) from the Loaded LIX63
Based on the obtained results, a two-stage counter-current batch simulation test was
The
performedexperiments
at an A/Ofor stripping
ratio of 1:2 Cu(II) and Ag(I)
and using from
2 mol/L the loaded
LIX63. LIX63
The test were
results performed
indicated that
using various strippant solutions such as Na2 S2 O3 , NH4 NO3 , (NH4 )2 SO4 , CH3 COONH4 ,
after the two-stage counter-current extraction, neither Cu(II) nor Ag(I) was detected in the
HNO3 , and thiourea solutions. These solutions have been found to be effective for stripping
raffinate, indicating that higher than 99.99% of Cu(II) and Ag(I) were co-extracted from
of Ag(I) from LIX63 [29]. A synthetic leaching solution with 0.001 mol/L HNO3 was used
the feed solution by using LIX63. The concentrations of Ni(II), Mg(II), and Al(III) after
as a feed solution. The loaded organic phase was prepared by contacting the feed solution
extraction were the same as those before extraction.
and 2 mol/L LIX63 at an A/O ratio of 1:2. In the stripping experiments, the obtained
loaded LIX63 was in contact with each strippant solution at an A/O ratio of 1:1.
3.4. Selection of a Strippant for the Stripping of Cu(II) and Ag(I) from the Loaded LIX63
The experiment results indicated that NH4 NO3 , (NH4 )2 SO4 , and CH3 COONH4 failed
to stripThe experiments
Cu(II) for stripping
or Ag(I) from the loadedCu(II)
LIX63and Ag(I)
(Table from the Na
3). Although loaded LIX63 were per-
2 S2 O3 could be used
formed using various strippant solutions such as Na 2S2O3, NH4NO3, (NH4)2SO4,
to strip Cu(II) and Ag(I), its low selectivity limited its use in this process.

Table 3. Stripping of Cu(II) and Ag(I) from the loaded LIX63 with various strippants.

Stripping Percentage (%)

Strippants
Cu(II) Ag(I)
1 mol/L Na2 S2 O3 (pH 4.7) 63.89 98.90
1 mol/L NH4 NO3 (pH 4.6) 0.6 0.8
1 mol/L (NH4 )2 SO4 (pH 5.1) 2.1 6.7
0.5 mol/L CH3 COONH4 (pH 7.1) 0 0

The results of stripping with HNO3 and thiourea solutions are presented in
Figures 5 and 6, respectively. As shown in Figure 5, the stripping of Cu(II) over Ag(I)
was possible at HNO3 concentrations of <4 mol/L. When thiourea was used (Figure 6), no
selectivity in stripping Ag(I) over Cu(II) was observed because of the lower concentration
of Ag(I) than that of Cu(II) in the loaded LIX 63. However, the results in Figure 6 indicated
that the quantitative stripping of Ag(I) from the loaded LIX63 was possible.

Metals 2021, 11, 1300
The results of stripping with HNO3 and thiourea solutions are presented in Figures 5
and 6, respectively. As shown in Figure 5, the stripping of Cu(II) over Ag(I) was possible
at HNO3 concentrations of <4 mol/L. When thiourea was used (Figure 6), no selectivity in
stripping Ag(I) over Cu(II) was observed because of the lower concentration of Ag(I)9 of
than
13
that of Cu(II) in the loaded LIX 63. However, the results in Figure 6 indicated that the
quantitative stripping of Ag(I) from the loaded LIX63 was possible.

100

Stripping percentage of metals (%)

80

60

Cu
40
Ag

20

0
3 4 5 6 7
Metals 2021, 11, x FOR PEER REVIEW HNO3 concentration (mol/L) 9 of 13

Figure5.5.Stripping
Figure Strippingpercentages
percentagesof
ofCu(II)
Cu(II)and
andAg(I)
Ag(I)atatvarious
variousHNO
HNO33concentrations.
concentrations.

100

80
Stripping percentage of metals (%)

Cu
Ag

60

40

20

0
0.0 0.1 0.2 0.3 0.4 0.5
Thiourea concentration (mol/L)

Figure6.6.Stripping
Figure Strippingpercentages
percentagesofofCu(II)
Cu(II)and
andAg(I)
Ag(I)atatvarious
variousthiourea
thioureaconcentrations.
concentrations.

Thus,
Thus,ininthe
thesubsequent
subsequentstripping experiments,
stripping experiments,the separation of Cu(II)
the separation and Ag(I)
of Cu(II) and from
Ag(I)
the loaded
from LIX63 LIX63
the loaded was performed to remove
was performed Cu(II) first
to remove Cu(II) byfirst
usingby4using
mol/L4 HNO solution,
mol/L3 HNO 3 so-
followed by the stripping of Ag(I) by using 0.1 mol/L thiourea.
lution, followed by the stripping of Ag(I) by using 0.1 mol/L thiourea.
3.5. Effects of the A/O Ratio on the Stripping of Cu(II) and Ag(I)
3.5. Effects of the A/O Ratio on the Stripping of Cu(II) and Ag(I)
The effects of the A/O ratio on the stripping of Cu(II) and Ag(I) from the loaded
The effects of the A/O ratio on the stripping of Cu(II) and Ag(I) from the loaded LIX63
LIX63 using 4 mol/L HNO3 were investigated by varying the A/O ratio from 1:2 to 3:1.
using 4 mol/L HNO3 were investigated by varying the A/O ratio from 1:2 to 3:1. A two-
A two-stage counter-current extraction process at an A/O ratio of 1:2 was performed to
stage counter-current extraction process at an A/O ratio of 1:2 was performed to prepare
prepare the loaded LIX63. A synthetic leaching solution with 0.001 mol/L HNO3 was used
the loaded LIX63. A synthetic leaching solution with 0.001 mol/L HNO3 was used as a
as a feed solution, and 2 mol/L LIX63 was used as an extractant. The concentrations of
feed solution, and 2 mol/L LIX63 was used as an −extractant. The concentrations of Cu(II)
Cu(II) and Ag(I) in the loaded LIX63 were 1 × 10 2 and 1.5 × 10−3 mol/L, respectively.
and Ag(I) in the loaded LIX63 were 1  10−2 and 1.5  10−3 mol/L, respectively. Accordingly,
Accordingly, 4 mol/L HNO3 was used as a strippant in the stripping experiments.
4 mol/L HNO3 was used as a strippant in the stripping experiments.
The results (Figure 7) indicated that the stripping percentage of Cu(II) increased
sharply with an increase in the A/O ratio from 1:2 to 2:1 whereas that of Ag(I) increased
slightly. The complete stripping of Cu(II) was achieved, when the A/O ratio exceeded 2:1.
Over this A/O ratio range, the stripping percentage of Ag(I) was lower than 10%. Thus, in
Metals 2021, 11, 1300 10 of 13

The results (Figure 7) indicated that the stripping percentage of Cu(II) increased
sharply with an increase in the A/O ratio from 1:2 to 2:1 whereas that of Ag(I) increased
slightly. The complete stripping of Cu(II) was achieved, when the A/O ratio exceeded
2:1. Over this A/O ratio range, the stripping percentage of Ag(I) was lower than 10%.
Thus, in the subsequent stripping experiments, selective stripping of Cu(II) was performed
by using 4 mol/L HNO3 and an A/O ratio of 2:1 in one stage. Moreover, 10% of Ag(I)
was co-stripped, indicating that the purity of Cu(II) in the stripping solution was 95.2%.
Metals 2021, 11, x FOR PEER REVIEW
The removal of Ag(I) from the stripping solution by cementation with a copper sheet 10 is
of a13
potential method of increasing the purity of Cu(II) in the stripping solution.

100

80
Stripping percentage of metals (%)

60 Cu
Ag

40

20

0
0.5 1.0 1.5 2.0 2.5 3.0
A/O ratio

Figure
Figure 7. Effectsof of
7. Effects thethe
A/OA/O
ratioratio
on theonstripping
the stripping percentages
percentages of Cu(II)ofand
Cu(II)
Ag(I)and Ag(I)
using using
4 mol/L
4HNO 3. HNO3 .
mol/L

3.6.
3.6.Effects
Effectsofofthe
theA/O
A/ORatio
Ratioononthe
theStripping
StrippingofofAg(I)
Ag(I)with
withThiourea
Thiourea
After
After the removal of Cu(II) from the loaded LIX63,thiourea
the removal of Cu(II) from the loaded LIX63, thioureawas
wasemployed
employedfor forthe
the
stripping
stripping of Ag(I) from the loaded LIX63. To investigate the effect of the A/O ratio on on
of Ag(I) from the loaded LIX63. To investigate the effect of the A/O ratio the
the stripping
stripping of Ag(I),
of Ag(I), stripping
stripping experiments
experiments were were performed
performed by varying
by varying the A/O
the A/O ratioratio
from
from
1:2 to1:2
3:1.toThe
3:1.loaded
The loaded
LIX63,LIX63, as discussed
as discussed in Section
in Section 3.5, 3.5,
was was employed,
employed, and the and the
concen-
concentration of Ag(I) in the loaded LIX63 was 1.35 × 10−3 mol/L. Accordingly, 0.1 mol/L
tration of Ag(I) in the loaded LIX63 was 1.35  10 mol/L. Accordingly, 0.1 mol/L thiourea
−3
thiourea was used as a strippant in these stripping experiments.
was used as a strippant in these stripping experiments.
The results indicated that the stripping percentage of Ag(I) increased from 60% to
The results indicated that the stripping percentage of Ag(I) increased from 60% to
97.7% as the A/O ratio increased from 1:2 to 3:1. A McCabe–Thiele diagram for the
97.7% as the A/O ratio increased from 1:2 to 3:1. A McCabe–Thiele diagram for the strip-
stripping of Ag(I) was constructed to represent the results (Figure 8). Figure 8 indicates
ping of Ag(I) was constructed to represent the results (Figure 8). Figure 8 indicates that
that two counter-current stripping stages were required for the complete stripping of Ag(I)
two counter-current stripping stages were required for the complete stripping of Ag(I)
from the loaded LIX63 at an A/O ratio of 1:1. LIX63 can be regenerated after the stripping
from the loaded LIX63 at an A/O ratio of 1:1. LIX63 can be regenerated after the stripping
of Ag(I) using 0.1 mol/L thiourea.
of Ag(I) using 0.1 mol/L thiourea.
Two-stage counter-current batch simulation stripping experiments were performed to
verify the results obtained from the McCabe–Thiele diagram. The loaded LIX63 after the
removal of Cu(II) using 4 mol/L HNO3 at an A/O ratio of 2:1 in one stage was used. After
the two-stage counter-current stripping using 0.1 mol/L thiourea at an A/O ratio of 1:1,
99.2% of Ag(I) was stripped. The concentration of Ag(I) in the obtained stripping solution
was 1.34 × 10−3 mol/L. This indicated that the purity of Ag(I) was higher than 99.993%
(detection limit: 0.01 mg/L).
Metals 2021,11,
Metals2021, 11,1300
x FOR PEER REVIEW 11
11 of
of1313

Ag concentration in aquoeous phase (10 mol/L)

-3
2

= 1/1
A/O

0
0.0 0.5 1.0 1.5
-3
Ag concentration in organic phase (10 mol/L)

Figure8.8.McCabe–Thiele
Figure McCabe–Thieleplot
plotfor
forthe
thestripping
strippingofofAg(I)
Ag(I)using
using0.1
0.1mol/L
mol/L thiourea.
thiourea.

Compared to the reported results (Table 1) [31], the purity of Cu(II) in the recovered
Two-stage counter-current batch simulation stripping experiments were performed
solution was low (95.2%); however, by using the present process, Cu(II) and Ag(I) can be
to verify the results obtained from the McCabe–Thiele diagram. The loaded LIX63 after
separated and recovered using a unique extractant (LIX63). Further, when simultaneous
the removal of Cu(II) using 4 mol/L HNO3 at an A/O ratio of 2:1 in one stage was used.
extraction of Cu(II) and Ag(I) was achieved by using Cyanex 301, only aqua regia was
After the two-stage counter-current stripping using 0.1 mol/L thiourea at an A/O ratio of
suitable for their stripping from loaded Cyanex 301 [31]. Thus, the proposed process is
1:1, 99.2% of Ag(I) was stripped. The concentration of Ag(I) in the obtained stripping so-
advantageous in that the simultaneous extraction of Cu(II) and Ag(I) is achieved by using
lution was 1.34  10−3 mol/L. This indicated that the purity of Ag(I) was higher than
LIX63 and the stripping of Cu(II) and Ag(I) is achieved by using HNO3 and thiourea
99.993% (detection limit: 0.01 mg/L).
solutions, respectively.
Compared to the reported results (Table 1) [31], the purity of Cu(II) in the recovered
4.solution was low (95.2%); however, by using the present process, Cu(II) and Ag(I) can be
Conclusions
separated and recovered using a unique extractant (LIX63). Further, when simultaneous
A solvent-extraction process was developed to recover Cu(II) and Ag(I) from a nitrate
extraction
leaching of Cu(II)
solution and Ag(I) dust
of industrial was achieved by using
arising during the Cyanex 301, onlyofaqua
pyrometallurgy spentregia was
camera
modules. A flow chart for the proposed process is illustrated in Figure 9. From the leachingis
suitable for their stripping from loaded Cyanex 301 [31]. Thus, the proposed process
advantageous
solution, Cu(II) in
andthat the simultaneous
Ag(I) were selectivelyextraction
extractedofbyCu(II)
usingand Ag(I)
LIX63 at is
anachieved
A/O ratiobyof
using
1:2
LIX63
in and theleaving
two stages, stripping of Cu(II)
Ni(II), and
Mg(II), Ag(I)
and is achieved
Al(III) by usingThe
in the raffinate. HNO 3 and thiourea so-
complete stripping
lutions,
of Cu(II) respectively.
with a 10% stripping percentage of Ag(I) from the loaded LIX63 was achieved
by using 4 mol/L HNO3 at an A/O ratio of 2:1 in one stage. After the removal of Cu(II),
4. Conclusions
Ag(I) from the loaded LIX63 was recovered via stripping by using 0.1 mol/L thiourea at
an A/O A solvent-extraction
ratio of 1:1 in twoprocess
stages.was developed
Finally, to recover
the feasibility of Cu(II) and Ag(I)
this process wasfrom a nitrate
verified via
leaching
batch solution of industrial
counter-current simulationdust arisingand
extraction during the pyrometallurgy
stripping experiments. Aof spentsolution
Cu(II) camera
modules.
with A flow
a 95.2% chart
purity andfor the proposed
a Ag(I) solution process is illustrated
with a 99.993% inwere
purity Figure 9. From In
obtained. thefuture,
leach-
ing solution,
strategies Cu(II) and
to increase the Ag(I)
puritywere selectively
of the obtained extracted by using
Cu(II) solutions canLIX63 at an A/O ratio of
be developed.
1:2 in two stages, leaving Ni(II), Mg(II), and Al(III) in the raffinate. The complete stripping
of Cu(II) with a 10% stripping percentage of Ag(I) from the loaded LIX63 was achieved
by using 4 mol/L HNO3 at an A/O ratio of 2:1 in one stage. After the removal of Cu(II),
Ag(I) from the loaded LIX63 was recovered via stripping by using 0.1 mol/L thiourea at
an A/O ratio of 1:1 in two stages. Finally, the feasibility of this process was verified via
batch counter-current simulation extraction and stripping experiments. A Cu(II) solution
with a 95.2% purity and a Ag(I) solution with a 99.993% purity were obtained. In future,
strategies to increase the purity of the obtained Cu(II) solutions can be developed.
Metals 2021, 11, 1300 12 of 13
Metals 2021, 11, x FOR PEER REVIEW 12 of 13

Figure 9.
Figure 9. Flow
Flow chart
chart of
of the
the proposed
proposed process
process for
for the
the separation
separation of
of Cu(II)
Cu(II) and
and Ag(I)
Ag(I) from
from aa nitrate
nitrate leaching
leaching solution
solution of
of
industrial dust.
industrial dust.
Author Contributions: Methodology and editing, P.-P.S.
Author Contributions: P.-P.S. and S.-Y.C.;
S.-Y.C.; data
data support, T.-Y.K.
T.-Y.K. and
and H.S.;
writing—original
writing—originaldraft
draftpreparation,
preparation,P.-P.S. AllAll
P.-P.S. authors have
authors haveread andand
read agreed to the
agreed published
to the version
published ver-
sion
of theofmanuscript.
the manuscript.
Funding: This
Funding: This
workwork was supported
was supported by the BasicbyScience
the Research
Basic Science Research
Program (No. Program (No.
2020R1I1A3A04037308)
2020R1I1A3A04037308)
through throughFoundation
the National Research the NationalofResearch Foundation
Korea (NRF), fundedofbyKorea (NRF), funded
the Ministry by the
of Education,
Ministry
and of (P0015130)
Project Education, funded
and Project (P0015130)
by the funded
Korea Institute forbythe
the Korea Institute
Advancement for the Advancement
of Technology.
of Technology.
Acknowledgments: We gratefully thank the Gwangju branch of the Korea Basic Science (KBSI) for
Acknowledgments:
ICP data. We gratefully thank the Gwangju branch of the Korea Basic Science (KBSI) for
ICP data.
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.
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