metals

Article
Improvement of Copper Metal Leaching in Sulfuric
Acid Solution by Simultaneous Use of Oxygen and
Cupric Ions
Kyoungkeun Yoo 1, * , Yujin Park 1 , Sanghyeon Choi 2 and Ilhwan Park 3
1 Department of Energy & Resources Engineering, Korea Maritime and Ocean University (KMOU), 727,
Taejong-ro, Yeongdo-gu, Busan 49112, Korea; jinee00@kmou.ac.kr
2 Division of Sustainable Resources Engineering, Graduate School of Engineering, Hokkaido University,
Sapporo 060-8628, Japan; cshshow351@gmail.com
3 Division of Sustainable Resources Engineering, Faculty of Engineering, Hokkaido University,
Sapporo 060-8628, Japan; ihp2035@gmail.com
* Correspondence: kyoo@kmou.ac.kr; Tel.: +82-51-410-4686




Received: 28 April 2020; Accepted: 26 May 2020; Published: 28 May 2020


Abstract: A new concept for copper (Cu) metal leaching by the simultaneous use of cupric ions
(Cu2+ ) and oxygen (O2 ) was proposed to improve Cu metal leaching in sulfuric acid. According to
this concept, Cu2+ oxidizes Cu metal into cuprous ion (Cu+ ), and O2 oxidizes Cu+ into Cu2+ .
The improvement in Cu leaching efficiency from Cu metal was investigated experimentally in the
sulfuric acid solution using Cu2+ and O2 simultaneously. Furthermore, the result was compared with
that for the sulfuric acid solution containing neither Cu2+ nor O2 and with the sulfuric acid solution
without Cu2+ and O2 . When both Cu2+ and O2 were used in the leaching solution, the leaching rate
of Cu from Cu metal powder was higher than at other leaching conditions, and the leaching efficiency
of Cu increased to more than 99.9% in 1 mol/L sulfuric acid solution at 400 rpm and 50 ◦ C with
≤75 µm Cu metal powder, 1% pulp density, 10,000 mg/L initial Cu2+ concentration, and 100 cc/min
O2 introduction. These results indicated that the leaching of Cu from Cu metal could be accelerated
by adding Cu2+ and O2 in the sulfuric acid solution.

Keywords: copper; leaching; oxygen; cupric ion; sulfuric acid

1. Introduction
The International Copper Study Group (ICSG) reported that 33% of global copper use came from
recycled copper in 2017 [1]. Although more than 70% of refined copper is produced by smelter [1,2],
there have been many studies to recover copper from secondary sources such as printed circuit boards
(PCBs) using hydrometallurgical ways, which have some advantages such as less gas emission and lower
capital cost than pyrometallurgical processes [3–12]. Leaching is the first step of hydrometallurgical
process for copper recovery from secondary sources, where copper metal must be oxidized into copper
ion such as cuprous ion (Cu+ ) or cupric ion (Cu2+ ) because copper in the secondary sources is present
as elemental copper [3,4].
The standard reduction potential of copper is +0.34 V (Cu2+ + 2e = Cu) [13], which is higher than
that of hydrogen (0 V); therefore, copper cannot be oxidized by sulfuric acid. Hence, strong oxidants
such as nitric acid, hydrogen peroxide, and ferric ion have been investigated to oxidize copper for
the leaching of copper [3,14–18]. These oxidants have the following disadvantages: NOx gas could
be generated from nitric acid leaching [3]; hydrogen peroxide has been found to be unstable and
expensive [3,14–16]; and when Fe3+ ion is used as an oxidant, an additional process after leaching is
required to separate the Cu ion from Fe ions [17,18].

Metals 2020, 10, 721; doi:10.3390/met10060721 www.mdpi.com/journal/metals

Metals 2020, 10, 721 2 of 8

Cupric ions (Cu2+ ) have been recognized as an alternative to the strong oxidants [4,19–21].
Metals 2020, 10, 721 2 of 8
However, it was reported that the cupric ions can act as oxidants only in hydrochloric acid or ammonia
solutions. The oxidation reaction can be summarized as follows [19,20]:
Cupric ions (Cu2+) have been recognized as an alternative to the strong oxidants [4,19–21].
However, it was Cureported
2+
+ Cuthat the +cupric
= 2Cu ions can act
(in hydrochloric acidasoroxidants
ammoniaonly in hydrochloric
solution ), acid (1)
or
ammonia solutions. The oxidation reaction can be summarized as follows [19,20]:
where the cuprous ion + plays a key role in the reaction because the reaction cannot proceed
Cu(Cu+ )Cu = 2Cu (in hydrochloric acid or ammonia solution), (1)
without Cu+ . Generally, Cu+ ions can exist as complex ions in hydrochloric acid or ammonia solutions.
whereions
These the are
cuprous ionin(Cu
unstable
+) plays a key role in the reaction because the reaction cannot proceed
a sulfuric acid solution; hence, it is understood that the reaction represented
without
by Cu+.(1)
Equation Generally, Cuto
is unlikely
+ ions can exist as complex ions in hydrochloric acid or ammonia solutions.
occur in a sulfuric acid solution.
These Inions are unstable
conventional in a sulfuric
studies [22–24],acid solution; hence,
the instability it is understood
of cuprous that theacid
ions in a sulfuric reaction represented
solution has been
by Equation (1) is unlikely to occur in a sulfuric acid solution.
reported by examining the leaching behavior of Cu from cuprous oxide (Cu2 O). When Cu2 O was leached
In conventional
in a sulfuric studies
acid solution under[22–24],
anoxicthe instabilitythe
conditions, of Cu
cuprous
+ ionsions in a sulfuric
dissolved out from acid
Cusolution has
2 O, but they
been immediately
were reported by examining
transformed theinto
leaching
Cu2+ behavior
ions and ofCuCu duefrom cuprous
to their oxide (Cu
instability. The2O). When Cu2O
transformation
was leached in a sulfuric acid solution under
reaction can be represented as follows [22–24]: anoxic conditions, the Cu + ions dissolved out from Cu2O,

but they were immediately transformed into Cu2+ ions and Cu due to their instability. The
+ follows
transformation reaction can be represented
Cu2 O + 2Has = Cu2+ [22–24]:
+ Cu + H2 O. (2)
Cu O + 2H = Cu + Cu + H O. (2)
As shown in Figure 1a, under anoxic conditions, when one of the two Cu+ ions, which are
+ ions, +which are
As shown
dissolved in Figure
out from 1a, under
Cu2 O, oxidizes to anoxic
cupric ion (Cu2+ ) bywhen
conditions, losingone of the two
an electron, theCu
other Cu ion gains
dissolved
the electronout
andfrom Cu2O, oxidizes
is transformed to cupric ion
into elemental (Cu (Cu
copper 2+ 0
) by).losing
Thus, an electron,chemical
a balanced the otherreaction
Cu+ ionoccurs.
gains
the electron and is transformed into elemental copper (Cu 0). Thus, a balanced chemical reaction
Figure 2 shows the XRD data of Cu2 O reagents (before leaching) and leaching residue (after leaching),
occurs. Figure
respectively, 2 shows
where the XRD
Cu metal data
peaks of Cu
were 2O reagents
observed after (before
leaching. leaching) and leaching residue (after
leaching), respectively, where Cu metal peaks were observed after leaching.

1. Leaching behavior of copper from Cu22O

Figure 1. O in sulfuric
sulfuric acid leaching
leaching under
under (a) anoxic and (b)
conditions.
aerated conditions.
 Metals 2020, 10, 721 3 of 8

Metals 2020, 10, 721 3 of 8

Figure 2. XRD peaks of leaching residue and Cu2 O reagent. Leaching conditions; 1 mol/L sulfuric acid
without aeration,
Figure 50 ◦ C, of
2. XRD peaks 400 rpm, 2%
leaching pulp density
residue and Cu[23].
2O reagent. Leaching conditions; 1 mol/L sulfuric acid

without aeration, 50 °C, 400 rpm, 2% pulp density [23].

In the previous study [23], the leaching tests with and without oxidants (1000 cc/min air) were
performed to previous
In the investigate the leaching
study behaviors
[23], the leaching of Cu
tests from
with andreagent
withoutCu 2 O in 1 (1000
oxidants mol/Lcc/min
sulfuric acid
air) were
solution ◦
performed to investigate the leaching behaviors of Cu from reagent Cu2O in 1 mol/L sulfuric to
at 400 rpm and 30–90 C with 2% pulp density. The leaching efficiency of Cu increased acid
100% withinat60
solution 400min
rpmwith
andthe aeration,
30–90 while
°C with 2% apulp
lower leaching
density. Theefficiency
leaching was observed
efficiency of Cuwithout the to
increased
introduction
100% withinof air. The with
60 min leaching
the with aeration
aeration, was
while given leaching
a lower by efficiency was observed without the
introduction of air. The leaching with aeration
1 was given by
Cu2 O + 4H+ + O2 = 2Cu2+ + 2H2 O, (3)
Cu O + 4H2 + O = 2Cu + 2H O, (3)
where
whereoxygen
oxygen in the air air
in the actsacts
as an electron
as an acceptor,
electron as shown
acceptor, as shownin Figure 1b.1b.
in Figure Thus, all all
Thus, thethe
cuprous
cuprousionsions
could be be
could oxidized
oxidized to cupric ions
to cupric during
ions duringCuCu
2 O 2leaching.
O leaching.Park et al.
Park reported
et al. reported that thethe
that leaching
leachingefficiency
efficiency
of Cu from
of Cu fromCuCu2 O 2increased
O increased to 100%
to 100%under
under aerated leaching
aerated leachingconditions
conditions [23].
[23].
AsAsdiscussed previously, due to the instability of the Cu + ions, it is understood that the reaction
discussed previously, due to the instability of the Cu ions, it is understood that the reaction
+
represented
represented by byEquation
Equation(1) (1)
is unlikely to occur
is unlikely in sulfuric
to occur in sulfuricacid. However,
acid. However, thethe
behavior
behaviorhashasnotnot
been
been
investigated in detail. We assumed that the oxidation of copper metal by cupric
investigated in detail. We assumed that the oxidation of copper metal by cupric ions has taken placeions has taken place
in the sulfuric
in the sulfuricacid solution
acid solutionwithout
withoutoxygen,
oxygen, and thethe
and new concept
new concept of of
copper
copperleaching
leaching is shown
is shown in in
Figure 3b. Although copper metal could be oxidized by the cupric ion in
Figure 3b. Although copper metal could be oxidized by the cupric ion in sulfuric acid as shownsulfuric acid as shown in in
Equation (1), the Cu + ions oxidize to Cu2+ ions or reduce to Cu0 , as shown in Figure 3a. This is because
Equation (1), the Cu+ ions oxidize to Cu2+ ions or reduce to Cu0, as shown in Figure 3a. This is because
thethe + ions of the reaction product are unstable in sulfuric acid. These reactions can be summarized
CuCu + ions of the reaction product are unstable in sulfuric acid. These reactions can be summarized
by by
thethe
following
following equation:
equation:

Cu2+ +CuCu →
+ Cu
2Cu→+2Cu →2+Cu+ Cu
→ Cu + Cu
(in(in sulfuric
sulfuric acid
acid solution).
solution ). (4) (4)
Equation (4) indicates that even if the Cu2+ ions could oxidize Cu metal in the sulfuric acid solution,
Equation (4) indicates that even if the Cu2+ ions could oxidize Cu metal in the sulfuric acid 2+
it may appear that no reactions have occurred because the Cu+ ions transform immediately into Cu
solution, it may appear that no reactions have occurred because the Cu+ ions transform immediately
ions or Cu. As shown in Figure 3b, when oxygen is introduced into the system, the oxygen oxidizes
into Cu2++ions or Cu. As shown in Figure 3b, when oxygen is introduced into the system, the oxygen
the Cu ions,+which are generated by the oxidation of Cu metal by the Cu2+ ions. The reactions can be
oxidizes the Cu ions, which are generated by the oxidation of Cu metal by the Cu2+ ions. The reactions
represented as follows:
can be represented as follows:
Cu + Cu = 2Cu (in sulfuric acid solution), (5)
Cu2+ + Cu = 2Cu+ (in sulfuric acid solution), (5)
1 (6)
2Cu + 2H1 + O = 22Cu + H O,
2Cu + 2H + O2 2= 2Cu + + H2 O,
+ +
(6)
2
Metals 2020, 10, 721 4 of 8

Metals 2020, 10, 721 4 of 8

where the Cu+ ions act as an intermediate. Hence, the overall reaction can be rearranged as follows:
where the Cu+ ions act as an intermediate. Hence, 1the overall reaction can be rearranged as follows:
Cu2+ + Cu + 2H+ + O2 = 2Cu2+ + H2 O, (7)
Cu + Cu + 2H +2 O = 2Cu + H O, (7)

Figure 3. The proposed concept

concept of
of leaching
leaching behavior
behaviorof
ofcopper
copperfrom
fromCu
Cumetal
metalby Cu2+
byCu 2+ ions in sulfuric

acid leaching: (a) without aeration and (b) with aeration.

Equation (7) 2+ 2+
(7) indicates
indicates that
that the
thecombination
combinationof ofCu
Cu2+ ions
ions and
and O O22 could
could leach
leach the
theCuCu2+ ions from
copper 2+
copper metal.
metal. However,
However, the the effects
effectsofofthe
theaddition
additionofofthe
theCu
Cu2+ ions and introduction of oxygen on the
enhancement of copper leaching have have not been investigated in
not been investigated in aa sulfuric
sulfuric acid
acid solution.
solution. Since oxygen
has a relatively
relatively high
highstandard
standardredoxredoxpotential
potentialtotooxidize
oxidize copper
copper metal
metal (O(O + 22H
2 +22H 4e+
O +2 O − =4e− =− 4OH− ,
4OH , + 0.40
+V)0.40 V) [13], only O can oxidize copper and has been used in de-copperization
[13], only O2 can 2oxidize copper and has been used in de-copperization from the anode slime. from the anode slime.
Therefore,
Therefore, in in this
this study,
study, four
four experimental
experimental conditions
conditions were
were compared
compared to to investigate
investigate thethe oxidation
oxidation of
copper metal powder in in the
the sulfuric
sulfuric acid
acidsolution.
solution.These
Theseconditions
conditionswere wereasasfollows:
follows: thethe addition
addition of
of Cu 2+ ions with the introduction of O , the addition of 2+ Cu 2+ ions with the introduction of N ,
Cu ions with the introduction of O2, the
2+ 2 addition of Cu ions with the introduction of N2, the 2
the introduction
introduction of Oof O2 without
2 without the addition
the addition of Cuof Cu2+and
2+ ions, ions,
theand the introduction
introduction of N2 the
of N2 without without the
addition
addition of Cu 2+ 2+ ions and O was
of Cu2+ ions. Thus,ions. Thus, theeffect
the synergistic synergistic effect
produced byproduced
using the Cu by 2+using the Cu
ions and O2 was investigated2 for
investigated for
copper metal leaching.copper metal leaching.

2. Materials and
2. Materials and Methods
Methods
Two
Two different
different sizes
sizes (≤
(≤ 75
75 µmµm (≥(≥ 95%,
95%, Junsei
Junsei Chemical Co., Ltd.,
Chemical Co., Ltd., Tokyo,
Tokyo, Japan)
Japan) and
and 150–420
150–420 µm µm
(99.5%, Alfa Aesar Chemical Co., Ltd, Ward Hill, MA, USA)) of the copper
(99.5%, Alfa Aesar Chemical Co., Ltd, Ward Hill, MA, USA)) of the copper metal powder were metal powder were used in
used
this study. ForFor
leaching tests, 1 mol/L sulfuric acid acid
solutions with with
and without 10,00010,000
mg/L Cu 2+
in this study. leaching tests, 1 mol/L sulfuric solutions and without mg/Lwere Cu2+
prepared by dissolving CuSO
were prepared by dissolving CuSO 4 ·5H O (99.0%, Junsei Chemical Co., Ltd., Tokyo, Japan) in sulfuric
2 4·5H2O (99.0%, Junsei Chemical Co., Ltd., Tokyo, Japan) in sulfuric acid
(≥ 95%,
acid Junsei
(≥ 95%, Chemical
Junsei Co., Ltd.,
Chemical Tokyo,
Co., Ltd., Japan)
Tokyo, and distilled
Japan) and deionized
and distilled water.water.
and deionized The solutions were
The solutions
transferred to a 500 cm 3 four-necked Pyrex glass reactor (Daihan Scientific Co., Ltd, Wonju, Korea) and
were transferred to a 500 cm four-necked Pyrex glass reactor (Daihan Scientific Co., Ltd, Wonju,
3

the temperature
Korea) of the solutions
and the temperature was
of the maintained
solutions was at 50 ◦ C using
maintained at a50heating
°C usingmantle. The mantle.
a heating reactor wasThe
fitted with a stirrer, gas inlet/outlet tubes, and a reflux condenser. In addition, 100 cc/min
reactor was fitted with a stirrer, gas inlet/outlet tubes, and a reflux condenser. In addition, 100 cc/min of O 2 , air and
Nof2Ogas were introduced through the inlet tube during the leaching tests, and the purity of all gases is
2, air and N2 gas were introduced through the inlet tube during the leaching tests, and the purity
99.99%. When
of all gases the temperature
is 99.99%. When theoftemperature
the solution of was
thestabilized, 2 g ofstabilized,
solution was Cu metal 2powder
g of Cuwas added
metal into
powder
the
wassolutions,
added into and thesolutions,
the solutionsand werethewithdrawn
solutions at designated
were withdrawn times. The solutions
at designated wereThe
times. filtered with
solutions
awere
0.45 filtered
µm membrane filter and subsequently diluted with
with a 0.45 µm membrane filter and subsequently diluted 5% HNO 3 for ICP-OES (inductively coupled
with 5% HNO3 for ICP-OES
plasma
(inductively coupled plasma optical emission spectrometer, PerkinElmer, Inc.analysis.
optical emission spectrometer, PerkinElmer, Inc. Waltham, MA, USA) Waltham, MA, USA)
analysis.
Metals 2020,
Metals 10, 721
2020, 10, 721 5 of5 8of 8

3. Results and Discussion

3. Results and Discussion
In Equations (5)–(7), the +Cu+ ions play a key role as an intermediate. However, it is difficult to
In Equations (5)–(7), the Cu ions play a key role as an intermediate. However, it is difficult to
detect the Cu+ ions in the sulfuric acid solution due to their instability. Therefore, the improvement
detect the Cu+ ions in the sulfuric acid solution due to their instability. Therefore, the improvement2+in
in copper metal leaching was verified experimentally in sulfuric acid solution by adding the Cu ions
copper metal leaching was verified experimentally in sulfuric acid solution by adding the Cu2+ ions
and introducing O2. Four leaching conditions were used according to the addition of the Cu2+ ions
and introducing O2 . Four leaching conditions were used according to the addition of the Cu2+ ions
and introduction of O2, and the leaching behavior of Cu from Cu metal was investigated.
and introduction of O2 , and the leaching behavior of Cu from Cu metal was investigated.
Figure 4 shows the leaching behavior of Cu in 1 mol/L sulfuric acid solution at 50 °C and 400
Figure 4 shows the leaching behavior of Cu in 1 mol/L sulfuric acid solution at 50 ◦ C and
rpm with 1% pulp density and < 75 µm Cu metal powder. The leaching efficiencies of Cu increase
400 rpm with 1% pulp density and < 75 µm Cu metal powder. The leaching efficiencies of Cu increase
rapidly when O2 is introduced into the solution, while they increase gradually when N2 is introduced
rapidly when
into the O2 is introduced
solution. The leachinginto efficiency
the solution, while
of Cu they increase
increases more gradually
rapidly inwhen N2 is
the case ofintroduced
the solutions
intocontaining
the solution. Themg/L
10,000 leaching
Cu 2+ efficiency
ions than of the
in Cu increases
case of more
the rapidly
solutions incontaining
not the case of10,000
the solutions
mg/L Cu2+
containing 10,000 mg/L Cu 2+ ions than in the case of the solutions not containing 10,000 mg/L Cu2+ ions.
ions. Moreover, the leaching efficiency of Cu increased to more than 99.9% within 60 min in the
Moreover,
sulfuric the
acidleaching
solutionefficiency
containing of Cu increased
10,000 mg/L Cuto more than 99.9% within 60 min in the sulfuric acid
2+ ions.
solution containing 10,000 mg/L Cu2+ ions.

Figure 4. Leaching behaviors of Cu in 1 mol/L sulfuric acid solution at 50 ◦ C and 400 rpm with 1%
Figure
pulp 4. Leaching
density behaviors
and ≤75 µm Cu metalof powder.
Cu in 1 mol/L sulfuric acid solution at 50 °C and 400 rpm with 1%
pulp density and ≤75 µm Cu metal powder.
Figure 5 shows the leaching behavior of Cu in 1 mol/L sulfuric acid solution at 50 ◦ C and 400 rpm
with 1%Figure
pulp density andthe
5 shows 150–420 Cu metal of
µmbehavior
leaching powder.
Cu in 1The leaching
mol/L of Cu
sulfuric is slower
acid with
solution at150–420
50 °C andµm400
than with
rpm 751%
with Cu density
µmpulp metal powder, as observed
and 150–420 after powder.
µm Cu metal comparingTheFigures
leaching4 of
and
Cu5.is slower
When oxygen
with 150–
is introduced into the 75
solution, 2+ ions is
420 µm than with µm Cuthemetalimprovement
powder, asinobserved
Cu metalafter
leaching by adding
comparing the Cu
Figures 4 and 5. When
remarkable,
oxygen is as shown in into
introduced Figure
the5.solution,
Further,the
theimprovement
leaching efficiency
in Cu of Cu in
metal the solution
leaching containing
by adding the Cu2+
10,000 2+
ionsmg/L Cu ions as
is remarkable, increases
shown to in 54.8%
Figureafter 120 min,the
5. Further, while that of
leaching the solution
efficiency of Cunotincontaining
the solution
10,000 2+ ions increases
mg/L Cu10,000
containing mg/L Cu2+ to
ions35.6%.
increases to 54.8% after 120 min, while that of the solution not
containing 10,000 mg/L Cu2+ ions increases to 35.6%.
 Metals 2020, 10, 721 6 of 8
Metals 2020, 10, 721 6 of 8

Figure 5. Leaching behaviors of Cu in 1 mol/L sulfuric acid solution at 50 ◦ C and 400 rpm with 1%
pulpFigure 5. and
density Leaching behaviors
150–420 of Cu in 1 mol/L sulfuric acid solution at 50 °C and 400 rpm with 1%
µm Cu powder.
pulp density and 150–420 µm Cu powder.
In Figures 4 and 5, in the cases of N2 gas introduction, the leaching efficiencies of Cu are lower
than thoseIn Figures
with O24 gas and introduction.
5, in the cases The
of Nleaching
2 gas introduction,
efficienciesthe withleaching efficiencies and
N2 introduction of Cu<75 areµmlower
Cu than
metalthose
powder withincrease
O2 gas introduction.
to 9.8% and 35.5%The leaching
without efficiencies
and with 10,000 with mg/L 2+
N2 introduction
Cu ions, and <75 µm Cu
respectively,
metal
after powder
120 min. increase
In the case ofto 150–420
9.8% andµm 35.5%
Cu without and with
metal powder, the10,000
leachingmg/L Cu2+ ions, were
efficiencies respectively,
2.0% and after
8.8%120 min. Inand
without thewith
case10,000
of 150–420
mg/L µmCu2+ Cuions,
metal powder, the
respectively, leaching
after 120 min. efficiencies
Althoughwere 2.0%cannot
Cu metal and 8.8%
without and
be dissolved with 10,000bymg/L
theoretically Cu2+acid,
sulfuric ions,therespectively,
dissolutionafter of Cu120would
min. Although
result from Cuthemetal cannot be
following
twodissolved
reasons. (1)theoretically
The surface byofsulfuric
Cu metal acid, the dissolution
powder of Cu would
could be partially result
oxidized from
into Cuthe
2 O following
as reported two
reasons.
before (1) The
[25]; thus, surface
even of Cu
sulfuric metal
acid couldpowder could
dissolve the be partially
oxidized oxidized
copper into Or,
surface. Cu2(2)O as reported
a vortex before
could
[25]; thus,
be formed duringevenagitation;
sulfuric acid coulda dissolve
therefore, small amountthe oxidized copper surface.
of air (oxygen), which was Or,introduced
(2) a vortex could
into the be
formed
leach during
solution, couldagitation;
act as antherefore, a smallstudy
oxidant. Further amount willofbeair (oxygen),
required which waswhat
to investigate introduced into the
factors affect
the leach solution,
leaching could
efficiency act as
under thean oxidant. Further study will be required to investigate what factors
condition.
affect the6 leaching
Figure shows the efficiency
leaching under the condition.
efficiencies of Cu with different gases such as O2 , air, N2 , and without
Figure 6 under
gas introduction shows the thefollowing
leaching efficiencies
conditions: of Cu with
1 mol/L H2 SOdifferent gases such
4 concentration, 400asrpm
O2, agitation
air, N2, and
without
speed, ◦
50 Cgas introduction
temperature, 1%under
pulp density, < 75 µm-sized
the following conditions: 1 mol/L
Cu metal H2SO4and
powder, concentration,
10,000 mg/L400 Cu2+ rpm
agitation speed,
concentration. When5010,000
°C temperature, 2+
mg/L Cu ions 1% pulp density,
are added, the<leaching
75 µm-sized Cu metal
efficiency powder,
increases to more andthan
10,000
mg/L
99.9% Cumin
in 60 2+ concentration. When 10,000 mg/L Cu2+ ions are added, the leaching efficiency increases to
with 100 cc/min of O2 introduction. In addition, the leaching efficiency increases to
more
98.1% than
after 12099.9% in 60 100
min with mincc/min
with 100 cc/min
of air of O2 introduction.
introduction. The oxygen In addition,
in Equation the(7)
leaching
indicatesefficiency
the
increases
dissolved to 98.1%
oxygen, andafter 120 min efficiency
the leaching with 100 cc/min
is higher of with
air introduction.
O2 than with Theairoxygen
becauseinthe Equation
partial (7)
indicates
pressure the dissolved
is higher during Ooxygen, and the The
2 introduction. leaching efficiency
leaching is higher
efficiency withto
increases O279.1%
than after
with 120air because
min
the partial
without pressure is higher
gas introduction because during O2 introduction.
it is caused by the inflowThe leaching
of air due efficiency
to vortex increases
formation to 79.1%
during after
120 minThe
agitation. without gas introduction
dissolution because it is
of Cu was suppressed bycaused by theNinflow
introducing 2 gas toof air
avoid due
O 2 to vortex
inflow. formation
during agitation. The dissolution of Cu was suppressed by introducing N2 gas to avoid O2 inflow.
 Metals 2020, 10, 721 7 of 8
Metals 2020, 10, 721 7 of 8

Figure 6. Effects of the introduction of gases on the leaching behaviors of Cu in 1 mol/L sulfuric acid
Figure 6. Effects of the introduction of gases on the leaching behaviors of Cu in 1 mol/L sulfuric acid
solution at 400 rpm with 1% pulp density, ≤75 µm Cu powder, and 10,000 mg/L Cu2+ ions.
solution at 400 rpm with 1% pulp density, ≤75 µm Cu powder, and 10,000 mg/L Cu2+ ions.
4. Conclusions
4. Conclusions
The leaching process of copper metal in sulfuric acid solution with both Cu2+ and O2 was proposed
to avoidThe leaching
the use of nitric process
acid orof copper metal
hydrochloric acidin
andsulfuric acid solution
the addition of oxidantswith
suchboth Cu
as Fe and
3+2+for O2 was
copper
metal leaching. The leaching of Cu metal was enhanced by adding Cu ions and introducing as
proposed to avoid the use of nitric acid or hydrochloric acid and the addition of oxidants such O2Fe
2+ 3+

for sulfuric
in the copper acidmetal leaching.
solution; e.g.The
the leaching of Cu metal
leaching efficiency of Cuwas enhanced
increased by adding
to more Cu within
than 99.9%
2+ ions and
introducing O in the sulfuric acid solution; e.g. the leaching efficiency
2+
30 min in 1 mol/L sulfuric acid solution with 10,000 mg/L Cu at 400 rpm with 1% pulp density,
2 of Cu increased to more than
<7599.9% withinsize,
30 min andin100
1 mol/L
cc/minsulfuric acidalso
solution with that
10,000 mg/L Cu at 400 rpm with 1%the pulp
2+
µm particle O2 . It was observed a smaller particle size increases
density, <75 µm particle size, and 100 cc/min O
leaching efficiency of Cu. In this case, it is suggested that the added Cu ions oxidize Cu metal intosize
2 . It was also observed
2+ that a smaller particle
Cu+increases
ions, andthetheleaching efficiency
intooftheCu. In thisacid
case,solution
it is suggested the Cu+Cu
that the added ionsionsintooxidize
2+
O2 introduced sulfuric further oxidizes the
Cu Cuions.
metal into Cuof ions,
Cu andionsthe
andOO2 introduced into the sulfuric acid solution further oxidizes the Cu+
2+ + 2+
The use 2 is for Cu metal leaching would leave no impurity in solution
ions
after into the Cu ions. The use of Cu ions and O2 is for Cu metal leaching would leave no impurity
leaching.
2+ 2+

in solution after leaching.

Author Contributions: Methodology, S.C. and K.Y.; writing—original draft preparation, I.P. and K.Y.; project
Author Contributions:
administration and funding Methodology, S.C.
acquisition, K.Y.; and
data K.Y.; writing—original
curation, draft preparation,
Y.P. and K.Y.; writing—review I.P. andproviding
and editing, K.Y.; project
administration
ideas, andhave
K.Y. All authors funding acquisition,
read and agreed toK.Y.; data curation,
the published versionY.P. and
of the K.Y.; writing—review and editing,
manuscript.
providing ideas, K.Y. All authors have read and agreed to the published version of the manuscript.
Funding: This work was supported by the National Research Foundation of Korea (NRF) grant funded by the
Korea government
Funding: (MSIP)
This work was(No. 2019R1I1A3A01060907).
supported by the National Research Foundation of Korea (NRF) grant funded by the
Korea of
Conflicts government (MSIP)
Interest: The (No.declare
authors 2019R1I1A3A01060907).
no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.
References
1. References
International Copper Study Group (ICSG). The World Copper Facebook 2019; International Copper Study
1. Group (ICSG): Lisbon,
International CopperPortugal, 2020; pp.
Study Group 9, 52. The World Copper Facebook 2019; International Copper Study
(ICSG).
2. Park, H.; Kang,
Group J.; Lee,
(ICSG): T.; Lee,
Lisbon, J.; Kim,
Portugal, Y. Ap.review
2020; 9, 52. on the demand and supply of major non-ferrous metals
2. and their recycling of scraps during 2014–2018
Park, H.; Kang, J.; Lee, T.; Lee, J.; Kim, Y. A review on theJ. demand
in Korea. Korean Inst. Resour. of
and supply Recycl.
major 2019, 28, 68–76.
non-ferrous metals
[CrossRef]
and their recycling of scraps during 2014–2018 in Korea. J. Korean Inst. Resour. Recycl. 2019, 28, 68–76,
3. Jung, M.; Yoo, K.; Alorro, R.D. Dismantling of electric and electronic components from waste printed circuit
doi:10.7844/kirr.2019.28.3.68.
3. boards byM.;
Jung, hydrochloric acid leaching
Yoo, K.; Alorro, with stannic
R.D. Dismantling ions. Mater.
of electric Trans. 2017,
and electronic 58, 1076–1080.
components [CrossRef]
from waste printed circuit
4. Kang,
boards by hydrochloric acid leaching with stannic ions. Mater. Trans. 2017, 58, trend
L.; An, H.; Kang, H.Y.; Lee, C.G. Analysis of commercial recycling technology and research for
1076–1080,
waste Cu scrap in Korea. J. Korean
doi:10.2320/matertrans.M2017096. Inst. Resour. Recycl. 2019, 28, 3–14. [CrossRef]
5. 4. Chi,Kang,
T.D.; Lee, J.C.;
L.; An, H.;Pandey, B.D.; Yoo,
Kang, H.Y.; K.; Jeong,
Lee, C.G. J. Bioleaching
Analysis of gold
of commercial and copper
recycling from waste
technology mobile phone
and research trend for
PCBs by using a cyanogenic bacterium. Miner. Eng. 2011, 24, 1219–1222. [CrossRef]
waste Cu scrap in Korea. J. Korean Inst. Resour. Recycl. 2019, 28, 3–14, doi:10.7844/kirr.2019.28.1.3.
5. Chi, T.D.; Lee, J.C.; Pandey, B.D.; Yoo, K.; Jeong, J. Bioleaching of gold and copper from waste mobile phone
PCBs by using a cyanogenic bacterium. Miner. Eng. 2011, 24, 1219–1222.
Metals 2020, 10, 721 8 of 8

6. Kim, E.Y.; Kim, M.S.; Lee, J.C.; Jha, M.K.; Yoo, K.; Jeong, J. Effect of cuprous ions on Cu leaching in the
recycling of waste PCBs, using electro-generated chlorine in hydrochloric acid solution. Miner. Eng. 2008, 21,
121–128. [CrossRef]
7. Yoo, J.M.; Jeong, J.; Yoo, K.; Lee, J.C.; Kim, W. Enrichment of the metallic components from waste printed
circuit boards by a mechanical separation process using a stamp mill. Waste Manag. 2009, 29, 1132–1137.
[CrossRef]
8. Kim, E.Y.; Kim, M.S.; Lee, J.C.; Yoo, K.; Jeong, J. Leaching behaviour of copper using electro-generated
chlorine in hydrochloric acid solution. Hydrometallurgy 2010, 100, 95–102. [CrossRef]
9. Kumar, M.; Lee, J.C.; Kim, M.S.; Jeong, J.; Yoo, K. Leaching of metals from waste printed circuit boards
(wpcbs) using sulfuric and nitric acids. Environ. Eng. Manag. J. 2014, 13, 2601–2607.
10. Bae, M.; Lee, H.; Kim, S.; Yoo, K. Destruction of cyanide and removal of copper from waste printed circuit
boards leach solution using electro-generated hypochlorite followed by magnetite adsorption. Metals 2019,
9, 963. [CrossRef]
11. Cho, B.G.; Cho, Y.J.; Lee, J.C.; Yoo, K. Korea’s metal resources recycling research project-valuable recycling.
Geosyst. Eng. 2019, 22, 48–58. [CrossRef]
12. Lee, J.C.; Zhu, T.; Jha, M.K.; Kim, S.K.; Yoo, K.; Jeong, J. Solvent extraction of Cu(I) from waste etch chloride
solution using tri-butyl phosphate(TBP) diluted in 1-octanol. Sep. Purif. Technol. 2008, 62, 596–601. [CrossRef]
13. Brett, C.M.A.; Brett, A.M.O. Electrochemistry; Oxford University Press Inc.: New York, NY, USA, 1993;
pp. 416–419.
14. Moon, G.; Yoo, K. Separation of Cu, Sn, Pb from photovoltaic ribbon by hydrochloric acid leaching with
stannic ion followed by solvent extraction. Hydrometallurgy 2017, 171, 123–127. [CrossRef]
15. Jeon, S.; Yoo, K.; Alorro, R.D. Separation of Sn, Bi, Cu from Pb-free solder paste by ammonia leaching
followed by hydrochloric acid leaching. Hydrometallurgy 2017, 169, 26–30. [CrossRef]
16. Yoo, K.; Lee, K.; Jha, M.K.; Lee, J.; Cho, K. Preparation of nano-sized tin oxide powder from waste Pb-free
solder by direct nitric acid leaching. J. Nanosci. Nanotechnol. 2016, 16, 11238–11241. [CrossRef]
17. Lee, S.; Yoo, K.; Jha, M.K.; Lee, J. Separation of Sn from waste Pb-free Sn-Ag-Cu solder in hydrochloric acid
solution with ferric chloride. Hydrometallurgy 2015, 157, 184–187. [CrossRef]
18. Xing, W.; Lee, S.; Lee, M. Solvent extraction of Li(I) from weak HCl solution with the mixture of neutral
extractants containing FeCl3 . J. Korean Inst. Resour. Recycl. 2018, 27, 53–58. [CrossRef]
19. Lim, Y.; Kwon, O.; Lee, J.; Yoo, K. The ammonia leaching of alloy produced from waste printed circuit boards
smelting process. Geosyst. Eng. 2013, 16, 216–224. [CrossRef]
20. Oishi, T.; Koyama, K.; Konishi, H.; Tanaka, M.; Lee, J. Influence of ammonium salt on electrowinning of
copper from ammoniacal alkaline solutions. Electrochim. Acta 2007, 53, 127–132. [CrossRef]
21. Sohn, H. Recycling of copper scrap. J. Korean Inst. Resour. Recycl. 2019, 28, 3–14. [CrossRef]
22. Majima, H.; Awakura, Y.; Enami, K.; Ueshima, H.; Hirato, T. Kinetic study of the dissolution of cuprite in
oxyacid solutions. Metall. Trans. B 1989, 20, 573–580. [CrossRef]
23. Park, I.; Yoo, K.; Alorro, R.D.; Kim, M.; Kim, S. Leaching of copper from cuprous oxide in aerated sulfuric
acid. Mater. Trans. 2017, 58, 1500–1504. [CrossRef]
24. Youzbashi, A.A.; Dixit, S.G. Leaching of Cu2 O with aqueous solution of sulfur dioxide. Metall. Trans. B 1993,
24, 563–570. [CrossRef]
25. Choudhary, S.; Sarma, J.V.N.; Pande, S.; Ababou-Girard, S.; Turban, P.; Lepine, B.; Gangopadhyay, S.
Oxidation mechanism of thin Cu films: A gateway towards the formation of single oxide phase. AIP Adv.
2018, 8, 055114. [CrossRef]

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).