recycling
Article
Precious Metal Recovery from Waste Electrical and Electronic
Equipment through Oxidative Refining
Eunmi Park 1 , Minji Kim 1,2 , Min-Wook Pin 1 , Hyunsik Park 3 and Yong-Hwan Kim 1, *
Citation: Park, E.; Kim, M.; Pin,
M.-W.; Park, H.; Kim, Y.-H. Precious
Metal Recovery from Waste Electrical
and Electronic Equipment through
Oxidative Refining. Recycling 2023, 8,
80. https://doi.org/10.3390/
recycling8050080
Academic Editors: Dechao Hu
and Zhixin Jia
Received: 23 August 2023
Revised: 22 September 2023
Accepted: 8 October 2023
Published: 16 October 2023
Copyright: © 2023 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 (https://
creativecommons.org/licenses/by/
4.0/).
Recycling 2023, 8, 80. https://doi.org/10.3390/recycling8050080
1 Korea Institute of Industrial Technology, Incheon 21999, Republic of Korea; epark@kitech.re.kr (E.P.);
minji99@kitech.re.kr (M.K.); minwook.pin@rist.re.kr (M.-W.P.)
2 Department of Materials Science and Engineering, Inha University, Incheon 22212, Republic of Korea
3 Korea Institute of Geoscience and Mineral Resources, Daejeon 34132, Republic of Korea;
hyunsik.park@kigam.re.kr
* Correspondence: yhkim@kitech.re.kr
Abstract: This study delves into the application of oxidative refining for the recovery and concentra-
tion of precious metals, namely palladium (Pd) and gold (Au), from waste electrical and electronic
equipment by WEEE recycling, leveraging pyrometallurgical techniques. The primary objective is
to optimize refining parameters, encompassing variations in gas pressure, temperature, and gas
composition, to maximize the extraction and purification of precious metals from recycled materials.
Through an array of comprehensive characterization techniques, encompassing microstructural anal-
ysis, elemental composition assessment, and metal concentration measurement, this study scrutinizes
the potential of oxidative refining. The conclusive findings underscore the remarkable potential
of oxidative refining in augmenting the efficiency and effectiveness of metal recovery from waste
printed circuit boards (PCBs), with a pronounced emphasis on the concentration of Pd and Au. This
research not only highlights the promise of oxidative refining but also concludes that optimizing
process parameters, such as a N2 /O2 mixed gas pressure of 4 L/min, a process time of 40 min, and
a temperature of 1400 ◦ C, is imperative for achieving the highest efficiency in metal recovery from
electronic waste, especially precious metals like Pd and Au. It further contributes to the sustainable
management of electronic waste and the strategic extraction of valuable precious metals.
Keywords: WEEE; recycling; precious metals; recovery; refining; pyrolysis
1. Introduction
Waste electrical and electronic equipment (WEEE) recycling is of paramount impor-
tance in tackling the escalating issue of electronic waste and its detrimental environmental
consequences [1–4]. With the proliferation of electronic devices worldwide, the proper
disposal and recycling of electronic waste have become imperative [5–7]. In 2019, global
e-waste generation reached a staggering 53.6 metric tons (Mt), and this figure is projected
to surge to 74.7 Mt by 2030, with a potential further increase to 110 Mt by 2050 [8]. How-
ever, only 17% of the e-waste generated in 2019 was collected and recycled, resulting in
the loss of valuable materials amounting to a staggering $57 billion USD. Approximately
44.3 Mt of e-waste flows remain unaccounted for, likely being dumped, traded, or recycled
in an inappropriate manner [9]. The primary objective of WEEE recycling is to mitigate
the environmental impact associated with electronic waste and delay the depletion of
valuable resources by extracting and recycling precious metals from discarded electronic
devices [10,11].
WEEE materials are known to contain precious metals such as gold (Au), silver (Ag),
and the platinum group metals (PGMs), which possess superior characteristics including
high melting points, corrosion resistance, and excellent electrical conductivity [12,13].
The recovery of these precious metals not only helps to preserve valuable resources but
also reduces the need for extracting virgin ores, thereby mitigating the environmental
https://www.mdpi.com/journal/recycling
Recycling 2023, 8, 80 2 of 13

impact associated with conventional mining practices [14,15]. Pyrometallurgical recycling

processes have been considered as highly effective methods for the recovery of valuable
metals from WEEE [16–18]. This approach utilizes high-temperature thermal processes to
extract and separate metals from electronic waste, providing an efficient and reliable means
of metal recovery [19,20]. Valuable metals such as copper (Cu), gold (Au), silver (Ag),
palladium (Pd), and platinum (Pt) can be successfully recovered from complex electronic
waste streams using pyrometallurgical techniques [21–24].
The refining stage is a crucial step in the pyrometallurgical recycling process, aiming
to purify and concentrate the recovered metals to ensure their quality and market value.
During refining, impurities and contaminants are selectively removed, while valuable
metals are recovered and refined to high purity levels [25]. The oxidative refining process
follows the principles outlined in the Ellingham diagram, which illustrates the formation of
metal oxides as a function of pO2 and temperature. Base metals exhibit stronger affinities
for oxidation compared to precious metals, making them more susceptible to oxidation and
elimination during the refining process [26]. This process is essential to obtain metals that
meet industry specifications and can be reintroduced into the production cycle. Oxidative
refining has emerged as a promising technique for the purification and concentration of
metals in the pyrometallurgical recycling of WEEE [27]. The oxidative refining process
selectively oxidizes impurities such as iron (Fe), aluminum (Al), silicon (Si), and lead (Pb),
while preserving and enhancing the concentration of valuable metals [28]. This method
has shown great potential in improving the efficiency and effectiveness of metal recovery
from electronic waste, as it allows for targeted removal of impurities while maximizing the
concentration of valuable metals.
This study focuses on exploring the oxidative refining process as an effective method
for recovering and concentrating precious metals, such as Pd and Au, from waste printed
circuit boards (PCBs), through pyrometallurgical techniques. The study aims to optimize
the refining parameters to maximize the concentration of precious metals in the recov-
ered metals. Comprehensive characterization techniques, including scanning electron
microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD),
and inductively coupled plasma (ICP) analysis, were employed to assess the microstructure,
elemental composition, and concentration of the refined metals recovered from waste PCBs
through the oxidative refining process. These techniques provide valuable insights into the
effectiveness of the oxidative refining process and its potential for enhancing the recovery
of precious metals from electronic waste.

2. Materials and Methods

Waste PCBs and lead frames were collected and mechanically shredded to reduce
their size for subsequent processing. The resulting shredded PCBs and lead frames were
subjected to smelting, where the material was heated to high temperatures, causing the
metals to melt and separate from the slag layer. Figure 1a shows the pyrometallurgical
recycling process including smelting and refining process. In order to form a slag layer
to recover metals from PCBs and lead frames during the smelting process, a slag former,
which is 15Al2 O3 -40CaO-45SiO2 , was introduced. PCBs and lead frames mixed with the
slag former were subjected to a high-density carbon crucible in an electric arc furnace,
which is powered by a three-phase electrical supply. Then, they were heated until the
temperature reached 1500 ◦ C. After they were completely melted, the melt was kept for
0.5 h at 1500 ◦ C. Throughout the smelting process, the organic components of the materials,
such as plastics and resins, decomposed into gaseous products. Additionally, impurities
and undesired elements like calcium (Ca), phosphorus (P), Si, and Al were separated from
the molten metals and formed the slag layer.
 Recycling2023,
Recycling 2023,8,8,80x FOR PEER REVIEW 33 of
of1317

Figure 1. (a) A flow chart of the recycling processes and (b) schematic diagram of the oxidative
Figure 1. (a) A flow chart of the recycling processes and (b) schematic diagram of the oxidative
refining process.
refining process.

Theseparated
The separatedmetals
metals were
were subjected
subjected to to oxidative
oxidative refining
refining processes
processes aimed
aimed at remov-
at removing
ing residual impurities and concentrating the precious metals. The
residual impurities and concentrating the precious metals. The oxidative refining process oxidative refining pro-
cess is shown schematically in Figure 1b. A 300 g master alloy
is shown schematically in Figure 1b. A 300 g master alloy obtained from the smelting obtained from the smelting
processwas
process wasprepared
preparedand andintroduced
introducedinto intoaahigh-density
high-densityaluminaaluminacrucible
cruciblewith withaasize
sizeofof
47Φ×× 120
47Φ 120 mm.
mm. For Forthe
therefining
refiningprocess,
process,aagas gasmixture
mixtureofofoxygen
oxygen(O (O 2) and nitrogen (N2)
2 ) and nitrogen (N2 )
was used. The sample was heated using a MoSi2 heater system withheating/cooling
was used. The sample was heated using a MoSi 2 heater system with a a heating/cooling rate
of 5 °C/min.
◦ When the temperature reached the desired processing
rate of 5 C/min. When the temperature reached the desired processing temperature, the temperature, the mix-
ture of of
mixture O2Oand N2 gases were directly injected to the melt through the alumina tube. To
2 and N2 gases were directly injected to the melt through the alumina tube. To
optimizethe
optimize theoxidative
oxidative refining
refining process,
process, several
several parameters
parameters werewere varied.
varied. Firstly,
Firstly, the pro-
the process
cess duration
duration was adjusted
was adjusted between between
10 and 1040andmin.40 Secondly,
min. Secondly,the gas theinjection
gas injection
pressurepressure
was
was controlled
controlled by regulating
by regulating the gas the gasrate,
flow flowand rate,the
and thegas
total total gasrate
flow flowofrate theof the mixed
mixed gas wasgas
was varied
varied betweenbetween
3 and3 4and 4 L/min.
L/min. TheThe
flow flowraterate
of O of2 O 2 gas
gas waswas kept
kept constant
constant atat 2.5L/min,
2.5 L/min,
whilethe
while theflow
flowraterateofofNN gaswas
2 2gas wasadjusted
adjustedwithin
withinthe therange
rangeofof0.50.5toto1.5
1.5L/min.
L/min.Lastly,
Lastly,the
the
processtemperature
process temperaturewas wasalsoalsovaried
variedbetween
between1300 1300 C◦ °Candand1400
1400 C
◦ °Ctotoinvestigate
investigateits itseffect
effect
onthe
on theoxidative
oxidativerefining
refiningprocess.
process.
ToToanalyze
analyzethe themicrostructure
microstructureofofthe theobtained
obtainedmetals
metalsand andslag
slagafter
afterthe therefining
refiningpro-pro-
cess,scanning
cess, scanningelectron
electronmicroscopy
microscopy(SEM, (SEM,Quanta
Quanta200 200FEG,
FEG,FEI FEICompany,
Company,Hillsboro,
Hillsboro,OR, OR,
USA)was
USA) was employed.
employed. The Thephase
phaseformation
formationininthe theslag
slagwaswascharacterized
characterized using X-ray
using dif-
X-ray
fraction (XRD, SmartLab 9 kW, Rigaku, Japan). The components of the resulting metals
diffraction (XRD, SmartLab 9 kW, Rigaku, Japan). The components of the resulting metals
andslags
and slagswere
wereidentified
identifiedand andquantified
quantifiedusingusingwavelength
wavelengthdispersive
dispersiveX-ray X-rayfluorescence
fluorescence
spectroscopy(WD-XRF,
spectroscopy (WD-XRF,ARL ARLPERFORM’X,
PERFORM’X,Thermo ThermoFisherFisherScientific,
Scientific,Basel,
Basel,Switzerland).
Swi erland).
Additionally,inductively
Additionally, inductively coupled
coupled plasma
plasma optical
optical emission
emission spectroscopy
spectroscopy (ICP-OES,
(ICP-OES, Inte-
Integra
graGBC
XL, XL, GBC Scientific,
Scientific, Braeside,
Braeside, Australia)
Australia) analysis
analysis was conducted
was conducted to accurately
to accurately deter-
determine
mine
the the content
content of precious
of precious metals metals
within within the recovered
the recovered metal. metal.

3.3.Results
Resultsand
andDiscussions
Discussions
3.1. Characterization of A Master Alloy
3.1. Characterization of A Master Alloy
The metals obtained from the smelting process were used as the master alloy for the
The metals obtained from the smelting process were used as the master alloy for the
oxidative refining process. The composition of the metal was analyzed using WD-XRF
oxidative refining process. The composition of the metal was analyzed using WD-XRF
analysis, and the results are presented in Table 1. The analysis confirmed that the master
analysis,
alloy and the
consisted of aresults are presented
high quantity of Cu in Table 1. impurities
including The analysis confirmed
such as Si, Fe,that theand
P, Pb master
Al.
alloy consisted of a high quantity of Cu including impurities
Additionally, precious metals like Pd and Au were also present. such as Si, Fe, P, Pb and Al.
Additionally, precious metals like Pd and Au were also present.
Recycling 2023, 8, 80 4 of 13
Recycling 2023, 8, x FOR PEER REVIEW 4 of 17

Table 1. The mass compositions of master alloy analyzed by WD-XRF measurement.

Table 1. The mass compositions of master alloy analyzed by WD-XRF measurement.
Elements Cu Si Ni Fe P Pb Pd Al Au
Wt.% 89.20 4.20Elements3.42 Cu Si
1.72 Ni0.63 Fe 0.37 P Pb
0.28 Pd 0.13 Al Au
0.06
Wt.% 89.20 4.20 3.42 1.72 0.63 0.37 0.28 0.13 0.06

Figure
Figure 22 shows
shows thethe microstructures
microstructures of of the
the master
master alloy
alloy along
along with the EDX
with the EDX results,
results,
revealing the distribution of impurities within the Cu-rich grains. The
revealing the distribution of impurities within the Cu-rich grains. The Cu-rich grains Cu-rich grains
con-
contained a small
tained a small amountamount
of Si of Si (4.20
(4.20 wt%),wt%),
whichwhich is expected
is expected to be removed
to be removed during
during the oxi-
the oxidative refining process. Along the grain boundaries, two phases
dative refining process. Along the grain boundaries, two phases were observed, repre- were observed,
represented
sented by darkby dark
gray gray
color,color, as shown
as shown in Figure
in Figure 2. The2. phase
The phase
withwith a darker
a darker graygray
colorcolor
was
was composed of a high quantity of Fe, while the other phase, richer in
composed of a high quantity of Fe, while the other phase, richer in Ni, appeared withNi, appeared witha
alighter
lightergray
graycolor.
color.These
TheseFe-Fe-
andand Ni-rich
Ni-rich phases
phases also
also contained
contained other
other impurities
impurities such
such as as
Si
Si and P. Although precious metals were present in very small quantities in the WD-XRF
and P. Although precious metals were present in very small quantities in the WD-XRF
result, they were not detectable through EDX analysis.
result, they were not detectable through EDX analysis.

Figure 2.
Figure 2. SEM
SEM micrographs
micrographsand
andEDX
EDXresults
resultsofofa master
a master alloy
alloy obtained
obtained from
from thethe
arcarc smelting
smelting pro-
process.
cess. Pa erns of EDX analysis can be found in Figure A1.
Patterns of EDX analysis can be found in Figure A1.

To investigate
To investigate the
the thermal
thermal behavior
behavior ofof the
the master
master alloy, DSC analysis
alloy, DSC analysis was
was performed,
performed,
and the
and the results
resultsare
areshown
shownininFigure
Figure3.3.During
Duringthe the heating
heating process,
process, a significant
a significant endother-
endothermic
mic peak
peak waswas observed
observed at temperatures
at temperatures above
above 1000
1000 °C,indicating
◦ C, indicatingaacharacteristic
characteristic melting
melting
reaction. This observation confirmed that the melting point of the master alloy is 1046 °C.
reaction. This observation confirmed that the melting point of the master alloy is 1046 ◦ C.
Consequently, it was determined that the process temperature for the oxidative
Consequently, it was determined that the process temperature for the oxidative refining refining
needs to
needs to be
beset
setwithin
withina higher temperature
a higher temperature range to ensure
range proper
to ensure processing
proper of theofmas-
processing the
ter alloy.
master alloy.

3.2. Effect of Process Time on Oxidative Refining

The temperature for the oxidative refining process was determined as 1300 ◦ C, based
on the DSC result shown in Figure 3, which is a typical converting temperature of Cu. A
gas mixture of O2 and N2 with a 1:1 ratio was injected at a fixed total flow rate of 3 L/min.
To establish an appropriate process duration, the time was varied between 10 min and
40 min. After the oxidative refining process, the master alloy was separated into a slag
layer and a metal layer.
Figure 4 shows the microstructures and EDX results of the recovered metals obtained
after the oxidative refining process. After the 10 min process, distinct black and dark gray
phases were observed along the boundaries of the Cu grains, identified as Fe-rich and
Ni-rich phases, respectively, from the EDX mapping analysis. Inside the Cu grains, a small
amount of Si (4.1 wt.%) was found, consistent with the observations made in the master
alloy (as shown in Figure 2). With an increase in the process duration up to 40 min, the Cu
grain sizes grew larger, leading to a decrease in the volume fraction of grain boundaries.
Recycling 2023, 8, 80 5 of 13

Consequently, this reduction in grain boundaries resulted in a decrease in the volume

fraction of the Fe-rich and Ni-rich phases. However, the composition of the Cu grains
remained largely unchanged, retaining impurities such as Si and Ni. Therefore, while the
Recycling 2023, 8, x FOR PEER REVIEW 5 of 17
extended process duration effectively reduced impurities at the Cu grain boundaries, it
had minimal impact on the impurity content within the Cu grains themselves.

Recycling 2023, 8, x FOR PEER REVIEW 6 of 17

Figure 3.
Figure 3. DSC curve of a master alloy
alloy recovered
recovered from
from the
the arc
arc smelting
smeltingprocess.
process.

3.2. Effect of Process Time on Oxidative Refining

The temperature for the oxidative refining process was determined as 1300 °C, based
on the DSC result shown in Figure 3, which is a typical converting temperature of Cu. A
gas mixture of O2 and N2 with a 1:1 ratio was injected at a fixed total flow rate of 3 L/min.
To establish an appropriate process duration, the time was varied between 10 min and 40
min. After the oxidative refining process, the master alloy was separated into a slag layer
and a metal layer.
Figure 4 shows the microstructures and EDX results of the recovered metals obtained
after the oxidative refining process. After the 10 min process, distinct black and dark gray
phases were observed along the boundaries of the Cu grains, identified as Fe-rich and Ni-
rich phases, respectively, from the EDX mapping analysis. Inside the Cu grains, a small
amount of Si (4.1 wt.%) was found, consistent with the observations made in the master
alloy (as shown in Figure 2). With an increase in the process duration up to 40 min, the Cu
grain sizes grew larger, leading to a decrease in the volume fraction of grain boundaries.
Consequently, this reduction in grain boundaries resulted in a decrease in the volume
fraction of the Fe-rich and Ni-rich phases. However, the composition of the Cu grains re-
mained largely unchanged, retaining impurities such as Si and Ni. Therefore, while the
extended process duration effectively reduced impurities at the Cu grain boundaries, it
had minimal impact on the impurity content within the Cu grains themselves.
Figure 4. SEM micrographs and EDX mapping and elemental analysis including Cu, Fe, Ni, P, and
Figure
Si 4. SEM
of refined micrographs
metals andon
depending EDX
the mapping and elemental
refining process time foranalysis including
(a) 10 min, Cu, Fe,
(b) 30 min, andNi,
(c)P,40and Si
min.
of refined metals depending on the refining process
Pa erns of EDX analysis can be found in Figure A2. time for (a) 10 min, (b) 30 min, and (c) 40 min.
Patterns of EDX analysis can be found in Figure A2.
XRF analysis was performed to analyze the composition of the metals and slag ob-
XRF analysis was performed to analyze the composition of the metals and slag ob-
tained after the refining process. Figure 5 presents the results of the XRF analysis, with (a)
tained after the refining process. Figure 5 presents the results of the XRF analysis, with
and (b) representing the analyzed results of the metals and slag, respectively. The metals
(a) and (b) representing the analyzed results of the metals and slag, respectively. The metals
were primarily composed of Cu along with impurities and precious elements. After a 10-
were primarily composed of Cu along with impurities and precious elements. After a
min process, there was a slight increase in Cu content accompanied by an increase in Si
10-min process, there was a slight increase in Cu content accompanied by an increase in Si
content. This suggests that, initially, Cu oxidation was the dominant process. As the pro-
content. This suggests that, initially, Cu oxidation was the dominant process. As the process
cess time increased, the Cu content showed a slight increase while the Si content de-
time increased, the Cu content showed a slight increase while the Si content decreased.
creased. Impurities such as Fe, Ni, and P exhibited a continuous decrease over time. How-
Impurities such as Fe, Ni, and P exhibited a continuous decrease over time. However, even
ever, even after a 40 min process, the impurities were not completely removed, and the
contents of precious metals (Pd and Au) did not exhibit significant changes. Regarding the
slag layer, copper oxide (CuO) was predominantly formed during the initial 10 min of the
process. Subsequently, the content of other oxides, such as silicon oxide (SiO2), aluminum
oxide (Al2O3), iron oxide (Fe2O3), and nickel oxide (NiO), started to increase, and their
Recycling 2023, 8, 80 6 of 13

after a 40 min process, the impurities were not completely removed, and the contents of
precious metals (Pd and Au) did not exhibit significant changes. Regarding the slag layer,
copper oxide (CuO) was predominantly formed during the initial 10 min of the process.
Subsequently, the content of other oxides, such as silicon oxide (SiO2 ), aluminum7oxide
Recycling 2023, 8, x FOR PEER REVIEW of 17
(Al2 O3 ), iron oxide (Fe2 O3 ), and nickel oxide (NiO), started to increase, and their mass
fraction rapidly increased over time.

Figure
Figure 5.5. WD-XRF measurement results
WD-XRF measurement resultsof
of(a)
(a)metals
metalsand
and(b)
(b)slags
slags obtained
obtained after
after thethe refining
refining pro-
process.
cess. (c) X-ray
(c) X-ray diffraction
diffraction pa of
patterns erns
theofslags
the slags obtained
obtained from from the refining
the refining process.
process.

The
The X-ray
X-ray diffraction
diffraction pa erns of
patterns of the
the slag
slagobtained
obtained after
after the
theoxidative
oxidativerefining
refining process
process
are
are displayed
displayed in in Figure
Figure 5c.
5c. The
The diffraction
diffraction peaks
peaks ofof Cu
Cu22OO and
and CuO
CuO were
were observed
observed with
with
high
high intensities,
intensities, indicating
indicating thethe predominant
predominant formation
formation of of copper
copper oxides.
oxides. Additionally,
Additionally,
low-intensity
low-intensity diffraction
diffraction peaks
peaks ofof SiO
SiO33,, Fe
Fe33O4,
O4, and
and FeFe33SiO
SiO44 were
weredetected.
detected. These
These findings
findings
suggest that, during the oxidative refining process, not only were copper oxides formed
suggest that, during the oxidative refining process, not only were copper oxides formed
predominantly, but there was also partial oxidation of Si and Fe.
predominantly, but there was also partial oxidation of Si and Fe.
This
This result
result indicates
indicates that
that duration
duration time
time was
wasnotnotthetheonly
onlyvariable
variabletotocontrol
controlthetheim-
im-
purity during the refining process for the selective control of the elements
purity during the refining process for the selective control of the elements (Fe, Si, and P). (Fe, Si, and P).
Although increasing the process time allowed for selective oxidation of
Although increasing the process time allowed for selective oxidation of undesired ele- undesired elements,
it was evident
ments, that additional
it was evident variable
that additional controlcontrol
variable is necessary to enhance
is necessary the effectiveness
to enhance the effective-of
impurity removal and the concentration of precious elements.
ness of impurity removal and the concentration of precious elements.
3.3. Effect of Injected Mixed Gas Pressure
3.3. Effect of Injected Mixed Gas Pressure
For a higher efficiency of the refining process, the total pressure of the injected gas
For a higher efficiency of the refining process, the total pressure of the injected gas
was differentiated. This was achieved by controlling the flow rates of O2 and N2 gases.
was differentiated. This was achieved by controlling the flow rates of O2 and N2 gases. The
The flow rate of O2 gas was maintained at a constant 2.5 L/min, while the flow rate of
flow
N2 gasrate of O
was 2 gas was maintained at a constant 2.5 L/min, while the flow rate of N2 gas
varied from 0.5 to 1.5 L/min. As a result, the total gas flow rate ranged from
was
3 to 4varied
L/min,from 0.5 to
while the1.5 L/min.ofAs
supply O2a gas
result, the total
remained gas flow rate
consistent. Theranged
oxidativefrom 3 to 4
refining
L/min, while the supply of O 2 gas◦ remained
process was performed at 1300 C for a duration of 40 min. consistent. The oxidative refining process was
performed at 1300 °C for a duration of 40 min.
The micrographs and EDX results of the refined metals are presented in Figure 6.
The micrographs
In Figure and EDX results
6a, which corresponds to theofmetals
the refined metals
refined withare presented
a gas flow ratein Figure 6. In
of 3 L/min,
Figure 6a, which corresponds to the metals refined with a gas flow rate
similar observations to those discussed in Figure 4 were made. Black and dark gray phases, of 3 L/min, similar
observations
indicative of to thoseand
Fe-rich discussed
Ni-richin Figurerespectively,
phases, 4 were made. were Black and dark
observed alonggray
thephases, in-
Cu grains.
dicative of Fe-rich and Ni-rich phases, respectively, were observed
Additionally, the Cu grains contained small amounts of impurities such as Si, Ni, and Fe. along the Cu grains.
Additionally,
Conversely, inthe theCu grains
sample contained
refined with small amounts
a gas flow of3.5
rate of impurities
L/min, nosuch as Si,
other Ni, andwere
elements Fe.
Conversely, in the sample refined with a gas flow rate of 3.5 L/min,
detected within the Cu grains. The volume fractions of Fe-rich and Ni-rich phases along the no other elements
were detected
Cu grains werewithin the Cureduced,
significantly grains. Thewithvolume fractions
no distinct of Fe-rich
separation and the
between Ni-rich
two phases
phases.
along the Cu grains
Furthermore, when the were significantly
total flow rate was reduced, withtono
increased distinctFe-rich
4 L/min, separation between
or Ni-rich the
phases
two
werephases. Furthermore,
barely observed, andwhen the totalwere
no impurities flow detected
rate was within
increased theto
Cu4 grains.
L/min, Fe-rich
Therefore,or Ni-
the
rich phases
increase were
in gas barely observed,
injection and no impurities
pressure effectively decreased were detected
impurities within
such theNi,
as Fe, CuSi,grains.
and P.
Therefore, the increase in gas injection pressure effectively decreased impurities such as
Fe, Ni, Si, and P.
Recycling 2023, 8, x FOR PEER REVIEW 8 of 17
Recycling 2023, 8, 80 7 of 13

Figure 6. SEM micrographs, EDX mapping, and elemental analysis of recovered metals after refin-
Figure 6. SEM micrographs, EDX mapping, and elemental analysis of recovered metals after refining
ing process with a total gas flow rate of (a) 3 L/min, (b) 3.5 L/min, and (c) 4 L/min. The analysis
includeswith
process a total
Cu, Fe, Ni,gas flowSirate
P, and of (a) 3 Pa
elements. L/min,
erns(b) 3.5 L/min,
of EDX andcan
analysis (c) be
4 L/min. The
found in analysis
Figure A3.includes
Cu, Fe, Ni, P, and Si elements. Patterns of EDX analysis can be found in Figure A3.
The compositions of the metal and slag obtained from the refining process were an-
The compositions of the metal and slag obtained from the refining process were
alyzed using WD-XRF analysis, as shown in Figure 7a,b, respectively. With an increase in
analyzed using WD-XRF analysis, as shown in Figure 7a,b, respectively. With an increase in
the total gas flow rate, the Cu content in the metal significantly increased. Conversely, the
the total gas flow rate, the Cu content in the metal significantly increased. Conversely, the
contents of Si, Ni, Fe, and P decreased. For the sample refined with a total gas flow rate of
contents of Si, Ni, Fe, and P decreased. For the sample refined with a total gas flow rate of
4 L/min, the impurity contents were greatly reduced to below 1 wt.%, and some impurities
4 L/min, the impurity contents were greatly reduced to below 1 wt.%, and some impurities
such as Fe, P, Pb, Al, and Sn were not detected at all. In the slags, the CuO content did not
such as Fe, P, Pb, Al, and Sn were not detected at all. In the slags, the CuO content did
show significant changes with an increase in the total gas flow rate. However, the contents
not show significant changes with an increase in the total gas flow rate. However, the
of Fe2O3, NiO,
contents of Fe2and
O3 , PNiO,
2O5 gradually increased as the total gas flow rate increased. In conclu-
and P2 O5 gradually increased as the total gas flow rate increased.
Recycling 2023, 8, x FOR PEER REVIEW 9 of 17
sion, as the totalasgas
In conclusion, theflowtotalrate
gasincreased, impurities impurities
flow rate increased, such as Fe, such
Ni, and P were
as Fe, selectively
Ni, and P were
oxidized and
selectively transferred
oxidized from the metal
and transferred fromlayer to thelayer
the metal slag layer.
to the slag layer.

Figure 7. (a,b) WD-XRF measurement results of metals and slags, respectively, and (c) X-ray diffrac-
Figure 7. (a,b) WD-XRF measurement results of metals and slags, respectively, and (c) X-ray diffrac-
tion
tion patterns
pa erns of
of the
the slags
slags obtained
obtainedfrom
fromthe
therefining
refiningprocess
processwith
withvarying
varyinggas
gasflow
flowrate.
rate.

Figure 7c illustrates the XRD patterns of the slag obtained from the refining process.
Figure 7c illustrates the XRD pa erns of the slag obtained from the refining process.
All obtained slags exhibited prominent peaks corresponding to the Cu2 O phase, indicating
All obtained slags exhibited prominent peaks corresponding to the Cu2O phase, indicat-
its predominant formation. Additionally, diffraction peaks corresponding to CuO, SiO2 ,
ing its predominant formation. Additionally, diffraction peaks corresponding to CuO,
and Fe2 SiO4 were observed. In the sample refined with a total gas flow rate of 4 L/min,
SiO2, and Fe2SiO4 were observed. In the sample refined with a total gas flow rate of 4
diffraction peaks of Fe3 O4 were also detected. These findings suggest that during the early
L/min, diffraction peaks of Fe3O4 were also detected. These findings suggest that during
the early stages of the refining process, Fe and Si were oxidized, leading to the formation
of an Fe2SiO4 composite. It can be assumed that the oxidation of Fe facilitated the removal
of Si from the metal layer and the subsequent formation of the Fe2SiO4 phase, as reported
by Uchikoshi et al. [28]. As the process progressed, the remaining Fe underwent further
Recycling 2023, 8, 80 8 of 13

stages of the refining process, Fe and Si were oxidized, leading to the formation of an
Fe2 SiO4 composite. It can be assumed that the oxidation of Fe facilitated the removal of
Si from the metal layer and the subsequent formation of the Fe2 SiO4 phase, as reported
by Uchikoshi et al. [28]. As the process progressed, the remaining Fe underwent further
oxidation, resulting in the formation of Fe3 O4 . Therefore, supplying the injected gas at a
high pressure is necessary to achieve complete oxidation of the Fe element.
Increased gas pressure accelerated the refining process. This improvement was due
to the enhanced distribution of the mixed O2 /N2 gas within the melt at higher pressures,
leading to accelerated oxidation reactions. The higher gas pressure promotes a more
efficient removal of impurities, such as Ni, P, Si, and Fe, resulting in a more refined and
purified metal product.

3.4. Effect of Oxidative Refining Process Temperature

In the previous sections, influences of the refining process time and total gas pres-
sure were clarified. However, the concentration of precious metals was not significantly
increased. Further study of temperature control was necessary, as this might reduce
the viscosity of Cu melt, which renders easier movement of precious metals between
molten slag and liquid metal [29]. The process temperature was increased from 1300 ◦ C
to 1400 ◦ C, but the process time and total gas pressure were maintained as 40 min and
4 L/min, respectively.
The microstructure and EDX results of the recovered metals are presented in Figure 8.
As shown in Figure 8a, the EDX measurement detected only Cu in the recovered metal
after refining at 1300 ◦ C. However, for the recovered metal refined at 1400 ◦ C, in addition
to Cu, significant amounts of Pd and Au were observed through EDX analysis, as shown in
Figure 8b, indicating the remarkable concentration of precious metals within the recovered
metal. This observation highlights the effectiveness of the refining process at 1400 ◦ C in
enriching the recovered metal with valuable Pd and Au. No other phases, such as Fe-rich
Recycling 2023, 8, x FOR PEER REVIEW 10 of 17
or Ni-rich phases, were observed, while Cu oxides were formed and distributed within the
Cu matrix phase.

Figure 8. SEM micrographs and EDX measurement results of recovered metals from the refining
Figure 8. SEM micrographs and EDX measurement results of recovered metals from the refining
process at (a) 1300 °C and (b) 1400 °C. Pa erns of EDX analysis can be found in Figure A4.
process at (a) 1300 ◦ C and (b) 1400 ◦ C. Patterns of EDX analysis can be found in Figure A4.
Figure 9a presents the XRF analysis results of the recovered metals from the refining
Figure 9a presents the XRF analysis results of the recovered metals from the refining
process, while an enlarged image is displayed in Figure 9b. Upon refining at 1300 °C, a
process, while an enlarged image is displayed in Figure 9b. Upon refining at 1300 ◦ C, a sig-
significant increase in Cu content was observed, indicating successful reduction in impu-
nificant increase in Cu content was observed, indicating successful reduction in impurities
rities such as Fe, Si, Ni, P, and Pb, which oxidized and were separated into the slag layer.
such as Fe, Si, Ni, P, and Pb, which oxidized and were separated into the slag layer. Further-
Furthermore,
more, there wasthere was increase
a slight a slight increase in the of
in the contents contents
Pd andofAu,
Pdfrom
and 0.28
Au, from 0.28
to 0.31 to and
wt.% 0.31
wt.% and from 0.06 to 0.13 wt.%, respectively. When the refining process was conducted
from 0.06 to 0.13 wt.%, respectively. When the refining process was conducted at 1400 ◦ C,
at 1400
the °C, the
impurity impurity
levels were levels
furtherwere further
reduced andreduced and nearly reaching
nearly eliminated, eliminated, reaching
below be-
0.5 wt.%.
low 0.5 wt.%. In contrast, the contents of Pd and Au exhibited substantial increases, reach-
ing 1.35 and 0.48 wt.%, respectively. In the slag layer, the content of Cu oxides significantly
increased after the refining process at 1400 °C, as shown in Figure 9c. This finding is con-
sistent with the XRD results presented in Figure 9d, which indicate the predominant de-
velopment of diffraction peaks corresponding to the Cu2O phase with high intensities.
 Recycling 2023, 8, 80 9 of 13

In contrast, the contents of Pd and Au exhibited substantial increases, reaching 1.35 and
0.48 wt.%, respectively. In the slag layer, the content of Cu oxides significantly increased
after the refining process at 1400 ◦ C, as shown in Figure 9c. This finding is consistent with
the XRD results presented in Figure 9d, which indicate the predominant development of
Recycling 2023, 8, x FOR PEER REVIEWdiffraction peaks corresponding to the Cu O phase with high intensities. Consequently,11 of 17
2
these results support the conclusion that the Cu melt at higher temperatures can undergo
facile oxidation due to its lower viscosity.

Figure
Figure9.9.(a)
(a)XRF
XRFmeasurement
measurement results of recovered
results of recoveredmetal
metalwith
withvarying
varying thethe process
process temperature
temperature (full
(full measurement regime); (b) Zoomed-in view of the weight percent (wt.%) between 0 and 5; (c)
measurement regime); (b) Zoomed-in view of the weight percent (wt.%) between 0 and 5; (c) XRF
XRF measurement
measurement result;
result; andand
(d) (d)
XRD XRD pa erns
patterns of slags
of slags obtained
obtained after
after the the refining
refining process.
process.

3.5.Concentration
3.5. ConcentrationBehavior
BehaviorofofPrecious
PreciousMetals
Metals
ICPanalysis
ICP analysiswas
was performed
performed toto quantitatively
quantitatively determine
determine thethe precious
precious metal
metal contents,
contents,
and the results are presented in Figure 10. A 1 g sample was extracted from
and the results are presented in Figure 10. A 1 g sample was extracted from the recovered the recovered
metalalloy
metal alloyandandthen
then dissolvedinin
dissolved a preparedaqua
a prepared aqua regiasolution
regia solution(HCl:HNO
(HCl:HNO 3 in a 3:1 ratio).
3 in a 3:1 ratio).
Prior to the measurements, standard Pd and Au samples were analyzed for reference
Prior to the measurements, standard Pd and Au samples were analyzed for reference pur-
purposes. Prior to the refining process, the master alloy contained 0.19 wt.% of Pd and
poses. Prior to the refining process, the master alloy contained 0.19 wt.% of Pd and 0.05
0.05 wt.% of Au. Figure 10a depicts the normalized concentration of Pd and Au as a function
wt.% of Au. Figure 10a depicts the normalized concentration of Pd and Au as a function
of the process duration, indicating that their concentrations remained relatively stable
of the process duration, indicating that their concentrations remained relatively stable
with increasing process time. However, when the gas injection pressure was increased, a
with increasing process time. However, when the gas injection pressure was increased, a
slight increase in the concentrations of Pd and Au was observed, reaching 0.23 wt.% and
slight increase in the concentrations of Pd and Au was observed, reaching 0.23 wt.% and
0.08 wt.%, respectively, as shown in Figure 10b. The influence of process temperature on
0.08 wt.%, respectively, as shown in Figure 10b. The influence of process temperature on
the concentration of Pd and Au is presented in Figure 10c. Following the refining process at
the concentration of Pd and Au is presented in Figure 10c. Following the refining process
1300 ◦ C, the concentrations of Pd and Au exhibited an increase. Subsequently, after refining
at 1300 °C, ◦ the concentrations of Pd and Au exhibited an increase. Subsequently, after re-
at 1400 C, their concentrations were further elevated, reaching 0.57 wt.% and 0.22 wt.%,
fining at 1400 °C, their concentrations were further elevated, reaching 0.57 wt.% and 0.22
respectively. These results demonstrate the successful concentration of Pd and Au elements
wt.%, respectively.
through These
the oxidative resultsprocess
refining demonstrate
at 1400the
◦ C.successful concentration of Pd and Au
elements through the oxidative refining process at 1400 °C.
Recycling 2023, 8,
Recycling 2023, x FOR PEER REVIEW
8, 80 1010of
of 13
13

Figure
Figure 10.
10. Normalized
Normalizedconcentration
concentration(C (Cr/C 0) 0
r /C of) of
PdPd
and andAuAucalculated based
calculated on on
based the the
ICPICP
analysis re-
analysis
sults, depending
results, depending on on
(a) (a)
process time,
process (b) total
time, gas flow
(b) total gas flowrate rate
and (c)
andprocess temperature.
(c) process temperature.C0 repre-
C0
sents the concentration
represents of the
the concentration of master alloy,
the master while
alloy, Cr Crepresents
while representsthe concentration
the concentrationofofthe
the recovered
recovered
r
metal after the refining process.
metal after the refining process.

4.
4. Conclusions
Conclusions
In
In conclusion,
conclusion, this this study
studyprovides
providesvaluable
valuableinsights
insightsinto
intothethe oxidative
oxidative refining
refining pro-
process
cess applied
applied to metals
to metals recovered
recovered from waste
from waste PCBs and PCBs and
lead lead frames.
frames. The demonstrate
The results results demon- the
strate the significant
significant impact of
impact of various various parameters
parameters on theand
on the efficiency efficiency and effectiveness
effectiveness of this refining of
this refining
technique. technique.
First and foremost,First and foremost,
our study our study
uniquely utilizeduniquely utilized
real electronic real electronic
scraps, including
scraps,
PCBs and including PCBs and
lead frames, lead frames,
providing a directproviding a directofrepresentation
representation practical recyclingof practical re-
scenarios.
cycling scenarios. This authentic input material enhances the relevance and applicability
This authentic input material enhances the relevance and applicability of our findings in
of our findings in the field of electronic waste recycling.
the field of electronic waste recycling.
Importantly, the results showcase that the refining refining efficiency
efficiency significantly
significantly improves
with an increase in the total gas pressure. This observation underscores the critical role of
gas
gas distribution
distribution within
within thethe melt
melt for
for accelerating
accelerating oxidation
oxidation reactions,
reactions, which
which is is aa key
key insight
insight
derived from our study. Furthermore, our comprehensive analysis, including XRD XRF,
derived from our study. Furthermore, our comprehensive analysis, including XRD and and
XRF,
reveals reveals the formation
the formation of copper
of copper oxidesoxides
in the in theand
slag slag and
the the selective
selective oxidationoxidation of im-
of impurities
purities
such as Fe, suchNi,asSi,Fe,
andNi,P.Si, andnotably,
Most P. Mostour notably, our study successfully
study successfully achieved the achieved the con-
concentration of
centration of precious metals, namely Pd and Au, through the refining process, particu-
precious metals, namely Pd and Au, through the refining process, particularly at a higher
temperature of 1400 ◦ C.
larly at a higher temperature of 1400 °C.
In summary, this work notonly
In summary, this work not onlycontributes
contributestotothe theunderstanding
understanding ofof
oxidative
oxidative refining
refin-
processes but also presents a practical and scalable approach to electronic
ing processes but also presents a practical and scalable approach to electronic waste recy- waste recycling.
The optimized
cling. The optimizedrefining conditions
refining defined
conditions definedin this study,
in this namely,
study, an an
namely, oxidative
oxidative refining
refin-
process with a N /O mixed gas pressure of 4 L/min (with
ing process with2a N22/O2 mixed gas pressure of 4 L/min (with 2.5 L/min and 2.5 L/min and 1.5 L/min
1.5 of O
L/min of2
and N , respectively), a process time of 40 min, and a temperature of 1400 ◦ C, hold great
O2 and2 N2, respectively), a process time of 40 min, and a temperature of 1400 °C, hold
promise for reducing impurities and concentrating precious elements. The merits of our
great promise for reducing impurities and concentrating precious elements. The merits of
work lie in its real-world applicability and holistic approach to electronic waste recycling,
our work lie in its real-world applicability and holistic approach to electronic waste recy-
making it a valuable contribution to the field.
cling, making it a valuable contribution to the field.
Author Contributions: Conceptualization, Y.-H.K.; methodology, E.P. and M.-W.P.; investigation,
Author Contributions: Conceptualization, Y.-H.K.; methodology, E.P. and M.-W.P.; investigation,
E.P., M.K. and M.-W.P.; data curation, E.P., M.K. and M.-W.P.; writing—original draft preparation, E.P.;
E.P., M.K. and M.-W.P.; data curation, E.P., M.K. and M.-W.P.; writing—original draft preparation,
writing—review and editing, H.P.; visualization, E.P.; supervision, Y.-H.K.; project administration,
E.P.; writing—review and editing, H.P.; visualization, E.P.; supervision, Y.-H.K.; project administra-
Y.-H.K.; funding acquisition, Y.-H.K. All authors have read and agreed to the published version of
tion, Y.-H.K.; funding acquisition, Y.-H.K. All authors have read and agreed to the published version
the manuscript.
of the manuscript.
Funding: This research received no external funding.
Funding: This research received no external funding.
Data Availability Statement: The data that support the findings of this study are available from the
Data Availability Statement: The data that support the findings of this study are available from the
corresponding author upon reasonable request.
corresponding author upon reasonable request.
Acknowledgments: This
Acknowledgments: Thiswork
workwaswassupported
supportedbybythe
theKorea
Korea Institute
Institute of of Energy
Energy Technology
Technology Eval-
Evalua-
uation and Planning (KETEP) grant funded by the Korea government (MOTIE) (20217510100080,
tion and Planning (KETEP) grant funded by the Korea government (MOTIE) (20217510100080, De-
velopment of critical metal recovery technologies (capacity of 200 kg/day) from low grade solid
wastes for the foundation of open access recycling platform).
Recycling 2023, 8, 80 11 of 13

Recycling 2023, 8, x FOR PEER REVIEW 13 of 17

Development of critical metal recovery technologies (capacity of 200 kg/day) from low grade solid
wastes for the foundation of open access recycling platform).

Conflicts of
Conflicts of Interest:
Interest: The
The authors
authors declare
declare no
no conflict
conflict of
of interest.
interest.

Recycling 2023, 8, x FOR PEER REVIEW 14 of 17

Appendix A
A
Appendix
The patterns
The pa erns of
of EDX
EDX analysis
analysis were
were presented.
presented.

Figure A1. Pa erns of the EDX results of the master alloy shown in Figure 2. (a) Inside of Cu grain,
Figure A1. Patterns of the EDX results of the master alloy shown in Figure 2. (a) Inside of Cu grain,
(b,c) grain boundaries.
(b,c) grain boundaries.

Recycling 2023, 8, x FOR PEER REVIEW 15 time,

Figure A2. Pa erns of the EDX results of refined metals depending on the refining process of 17
Figure A2. Patterns of the EDX results of refined metals depending on the refining process time,
shown in Figure 4. (a) 10 min, (b) 30 min, and (c) 40 min.
shown in Figure 4. (a) 10 min, (b) 30 min, and (c) 40 min.

Figure A3. Pa erns of the EDX results of recovered metals after refining process, shown in Figure 6.
Figure A3. Patterns of the EDX results of recovered metals after refining process, shown in Figure 6.
(a) 3 L/min, (b) 3.5 L/min, and (c) 4 L/min of total gas pressure.
(a) 3 L/min, (b) 3.5 L/min, and (c) 4 L/min of total gas pressure.
 Recycling
Recycling 2023,
2023, 8, 8,
80x FOR PEER REVIEW 16 ofof1317
12

FigureA4.
Figure A4.Patterns
Pa ernsofofthe
theEDX
EDXresults
resultsofofthe
therecovered
recoveredmetals
metalsafter
afterrefining
refiningprocess
processatat(a)(a)1300
1300◦ C°C
and (b) 1400
◦ °C, shown in Figure
and (b) 1400 C, shown in Figure 6. 6.

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