minerals

Article
Metal Recovery from the Mobile Phone Waste by
Chemical and Biological Treatments
Yumi Kim, Hyunhee Seo and Yul Roh *
Department of Earth and Environmental Sciences, Chonnam National University, Gwangju 61186, Korea;
yumikim@jnu.ac.kr (Y.K.); seo_hyunhee@hanmail.net (H.S.)
* Correspondence: rohy@jnu.ac.kr; Tel.: +82-62-530-3458

Received: 30 November 2017; Accepted: 28 December 2017; Published: 2 January 2018

Abstract: Recycling electronic waste is an important subject not only from the point of view of waste
treatment, but also regarding the recovery of valuable metals. This research examined the stepwise
recovery of metals in mobile phone waste using chemical treatment via pH swing and the biological
method using biomineralization. In chemical treatment, the metal fraction attached to the printed
circuit board (PCB) and camera parts were separated from the mobile phone waste and were then
pulverized into particles with a size less than ~2 mm. The metal fraction was dissolved in aqua
regia, and the pH of the solution was increased to 10.5 by adding NH4 OH. The first precipitate was
iron oxide, produced by raising the pH to 3.1~4.2 with NH4 OH. Sequentially, copper chloride and
rare earth-metal complex were produced at pH 5.7~7.7 and 8.3~10.5, respectively. In the biological
method, the filtrate at pH 7.7 was added to a metal-reducing bacteria growth medium as a precursor.
After two weeks of incubation, rhodochrosite and calcite were precipitated as nano-sized minerals.
The results indicate that effective metal recovery of mobile phone waste is feasible using chemical
and biological treatments, and the recovered metals and rare earth metals can be recycled into raw
materials for various industries.

Keywords: metal recovery; electronic waste; urban mining; pH swing process; biomineralization

1. Introduction
The amount of generated waste of electrical and electronic equipment (WEEE) has been growing
due to rapid economic growth and technological advances all over the world. In the European
Union (EU), 9 million tonnes of WEEE were generated in 2005, and this figure is expected to grow
to more than 12 million tonnes by 2020 [1]. Recycling WEEE may provide a substantial source of
both (non) ferrous and precious metals. Although most metals are base metals such as copper, iron,
nickel, tin, lead, aluminum, and zinc, a significant amount of attention has been expended on the
recovery of precious metals, including gold, silver, and palladium [2]. Waste mobile phones usually
consist of a body, printed circuit board (PCB), liquid crystal display (LCD), camera, key board, etc.
Since the PCBs contain a great amount of useful and precious metals, including gold, silver, and
palladium, researchers have focused on PCBs for precious metal recovery [3,4]. However, camera
parts including neodymium magnets (NdFeB48 H) have rarely been studied despite the high need
for neodymium recovery [5]. Increasing the pH of metal leached solution to the desired value is
connected with the metal precipitation in the form of hydroxides. In a previous study, the selective
recovery of leached metals in acid mine drainage by NaOH addition resulted in the precipitation
rate of 97% Fe at pH 4.05, 95% Cu at pH range 4.49 to 6.11, and 89% Zn at pH range 5.5 to 7.2 [6].
Although hydrometallurgical processes using various reagents (e.g., cyanide, thiosulfate, aqua regia,
etc.) have shown high efficiency in metal recovery, their high cost and toxic byproducts remain to be
addressed [5–8]. To solve these cost-related and environmental disadvantages, some microbiological

Minerals 2018, 8, 8; doi:10.3390/min8010008 www.mdpi.com/journal/minerals

Minerals 2018, 8, 8 2 of 10
Minerals 2018, 8, 8 2 of 9

disadvantages, some microbiological

processes have recently been proposedprocesses have to
as alternatives recently
chemicalbeen proposed
methods. Someas microbes,
alternatives to
such
chemical methods.
as C. violaceum, A. Some microbes,Chromobacterium
ferrooxidansm, such as C. violaceum, A. ferrooxidansm,
violaceum, Chromobacterium
and Aspergillus sp. increased violaceum,
Au and
and Aspergillus sp. increased Au and Cu leaching/recovery from mobile phone
Cu leaching/recovery from mobile phone PCBs waste [9–13]. Also, Brandl et al. (2001) reported PCBs waste [9–13].
Also, Brandl et
that bacteria al. (2001)
such reported ferrooxidans
as Thiobacillus that bacteriaandsuchT.asthiooxidans
Thiobacillus ferrooxidans
and fungi suchandasT.Aspergillus
thiooxidansniger
and
fungi such as Aspergillus
and Penicillium niger and
simplicissimum werePenicillium simplicissimum
able to mobilize were able toof
high percentages mobilize
Cu, Sn,high percentages
Al, Ni, Pb, and
of
ZnCu, Sn, Al,from
particles Ni, Pb,
WEEEand [13].
Zn particles from
Therefore, WEEE
the [13]. Therefore,
combination the combination
of chemical and biologicalof chemical
methods and can
biological
increase themethods
efficiencycanofincrease the efficiency
metal recovery from of metalphone
mobile recovery
wastefromandmobile
achieve phone wasteofand
the effect an
achieve the effect of an environmentally-friendly treatment. Thus, the objectives of this
environmentally-friendly treatment. Thus, the objectives of this study were to investigate the stepwise study were
to investigate
separation and the stepwise
recovery separation
of metals andboth
including recovery of metals
(non) ferrous and including both from
precious metals (non)mobile
ferrous and
phone
precious
waste by metals fromchemical
combining mobile phone waste bymethods.
and biological combining chemical and biological methods.

2. Materials and Methods

2.1. Preparation
2.1. Preparation of
of the
the Metal
Metal Solution
Solution Using
Using Aqua
Aqua Regia
Regia
First, the
First, the camera
camera parts
parts and
and PCB
PCB parts
parts attached
attached toto the
the mobile
mobile phone waste were
phone waste were separated
separated andand
collected for the experiment (Figure 1). The process of separating and recovering
collected for the experiment (Figure 1). The process of separating and recovering metals, including metals, including
both ferrous
both ferrousand andnon-ferrous
non-ferrousmetals, as as
metals, well as precious
well metals
as precious fromfrom
metals the mobile phonephone
the mobile waste, waste,
is shown is
in Figure 2. The camera and the PCB parts separated from the mobile
shown in Figure 2. The camera and the PCB parts separated from the mobile phone waste were phone waste were crushed
in a pulverizer
crushed for 2 minfor
in a pulverizer and2 were divided
min and wereinto pulverized
divided particles and
into pulverized non-pulverized
particles materials
and non-pulverized
(e.g., copper
materials foil,copper
(e.g., insulationfoil,film, etc.). The
insulation non-pulverized
film, material was excluded
etc.). The non-pulverized materialbeforehand
was excluded and
then only the pulverized particles were sieved to test particles less than 2 mm.
beforehand and then only the pulverized particles were sieved to test particles less than 2 mm. Since Since these sieved
particles
these seemparticles
sieved to contain soluble
seem metals and
to contain insoluble
soluble metals materials (e.g., plastic)
and insoluble in aqua
materials regia,
(e.g., the particles
plastic) in aqua
were
regia,dissolved
the particles in the
were1/10 (g/mL)in
dissolved ratio
the in the(g/mL)
1/10 aqua regia
ratio at
inroom temperature
the aqua for 48temperature
regia at room h and only the for
48 h and only the supernatant was used for the experiments. As a metal solvent, aqua regia wasa
supernatant was used for the experiments. As a metal solvent, aqua regia was freshly prepared at
3:1 mixture
freshly of hydrochloric
prepared acid (HCl,
at a 3:1 mixture 35%, OCI, Seoul,
of hydrochloric acidKorea): nitricOCI,
(HCl, 35%, acid Seoul,
(HNO3Korea):
, 60~61%, JUNSEI,
nitric acid
Tokyo, Japan). The leached metal concentration in aqua regia was analyzed
(HNO3, 60~61%, JUNSEI, Tokyo, Japan). The leached metal concentration in aqua regia was via inductively coupled
plasma-atomic
analyzed emission spectroscopy
via inductively (ICP-AES). emission spectroscopy (ICP-AES).
coupled plasma-atomic

Figure 1. (a) Camera and (b) PCB parts separated from mobile phone waste.
Figure 1. (a) Camera and (b) PCB parts separated from mobile phone waste.
Minerals 2018, 8, 8 3 of 10
Minerals 2018, 8, 8 3 of 9

Figure 2. The
Figure process
2. The to separate
process and
to separate andrecover
recovermetals includingFe,
metals including Fe,Cu,
Cu, and
and rare
rare earth-metal
earth-metal complex
complex
from from
mobile phone
mobile waste
phone by by
waste combining
combiningchemical
chemical and
and biological methods.
biological methods.

2.2. Chemical Method for Metal Recovery

2.2. Chemical Method for Metal Recovery
The metal solution leached in aqua regia was a very strong acid. Ammonium hydroxide
The metal solution leached in aqua regia was a very strong acid. Ammonium hydroxide (NH4 OH,
(NH4OH, 28%, JUNSEI, Tokyo, Japan) solution was slowly added into the acidic metal solution to
28%, precipitate
JUNSEI, Tokyo,
ferrous,Japan) solution
non-ferrous, andwas slowly
precious added
metals withinto the acidic
gravity only andmetal
withsolution to precipitate
rapid stirring. The
ferrous, non-ferrous,
increase in pH with and
the precious
addition ofmetals
NH4OH with gravity
induced only and of
the formation with rapid stirring.
precipitates. When pH The increase
ranges
in pHwere
with the addition of NH 4 and 8.3~10.5, precipitates were formed with change in color. At thewere
reached at 3.9~4.2, 5.7~7.7,OH induced the formation of precipitates. When pH ranges
reached at 3.9~4.2,
pH ranges, 5.7~7.7,ofand
the addition NH8.3~10.5, precipitates
4OH into the suspensionwere formedbut
was stopped, with change
kept stirringinfor
color. At the pH
a sufficient
time.
ranges, the The suspension
addition of NH4was centrifuged
OH into to separate
the suspension wasinto a precipitate
stopped, but keptand a supernatant.
stirring The time.
for a sufficient
precipitate was
The suspension waswashed with distilled
centrifuged water
to separate three
into times and then
a precipitate and dried for mineralogical
a supernatant. analyses. was
The precipitate
Thewith
washed supernatant
distilledwas filtered
water threewith a syringe
times filterdried
and then (0.45 μm), and then the filtrate
for mineralogical was The
analyses. analyzed for
supernatant
the change in the concentration of metal ions via ICP-AES. The remaining supernatant was used to
was filtered with a syringe filter (0.45 µm), and then the filtrate was analyzed for the change in the
recover the other metal ions, and the experiment was continuously carried out in the same process.
concentration of metal ions via ICP-AES. The remaining supernatant was used to recover the other
metal2.3.
ions, and the
Biological experiment
Method for Metalwas continuously carried out in the same process.
Recovery
The Method
2.3. Biological metal-reducing
for Metalbacteria
Recovery(Suncheon-1) were enriched from intertidal flat sediments of
Suncheon in the Jeonnam province of South Korea. The medium for the bacterial growth contained
The metal-reducing
the following bacteria
ingredients (g/L): 2.5(Suncheon-1)
NaHCO3, 0.08 wereCaCl2∙2H enriched
2O, 1.0 NHfrom4Cl, intertidal
0.2 MgCl2∙6H flat
2O,sediments
10 NaCl, of
Suncheon in the
0.5 yeast Jeonnam
extract, province
7.2 HEPES of South Korea. The medium for the bacterial
(hydroxyl-ethylpiperazine-N′-2-ethanesulfonic acid),growth
10 mL containedtrace
mineral, and
the following 1 mL vitamin.
ingredients (g/L): Trace mineral3 , solution
2.5 NaHCO 0.08 CaCl 2 ·
contained
2H 2 O, the
1.0 following
NH 4 Cl, ingredients
0.2 MgCl 2 · 6H (g/L):
2 O, 1.5NaCl,
10
nitrilotriacetic acid, 0.2 FeCl ∙4H O, 0.1 MgCl ∙6H O, 0
0.02 sodium tungstate,
0.5 yeast extract, 7.2 HEPES (hydroxyl-ethylpiperazine-N -2-ethanesulfonic acid), 10 mL trace mineral,
2 2 2 2 0.1 MnCl 2 ∙4H 2 O, 0.1
and 1CoCl ∙6H2O, 1 Trace
mL 2vitamin. CaCl2∙2H 2O, 0.05 ZnCl2, 0.002 CuCl2∙2H2O, 0.005 H3BO3, 0.01 sodium molybdate, 1
mineral solution contained the following ingredients (g/L): 1.5 nitrilotriacetic
NaCl, 0.017 Na2SeO3, and 0.024 NiCl2∙6H2O. Also, vitamin solution contained the following
acid, 0.2 FeCl2 ·4H2 O, 0.1 MgCl2 ·6H2 O, 0.02 sodium tungstate, 0.1 MnCl2 ·4H2 O, 0.1 CoCl2 ·6H2 O,
1 CaCl2 ·2H2 O, 0.05 ZnCl2 , 0.002 CuCl2 ·2H2 O, 0.005 H3 BO3 , 0.01 sodium molybdate, 1 NaCl, 0.017
Na2 SeO3 , and 0.024 NiCl2 ·6H2 O. Also, vitamin solution contained the following ingredients (g/L):
0.02 biotin, 0.02 folic acid, 0.1 B6 (pyridoxine) HCl, 0.05 B1 (thiamine) HCl, 0.05 B2 (riboflavin),
Minerals 2018, 8, 8 4 of 9

Minerals 8, 8
2018, (g/L):
ingredients 0.02 biotin, 0.02 folic acid, 0.1 B6 (pyridoxine) HCl, 0.05 B1 (thiamine) HCl, 0.05 4 ofB2
10

(riboflavin), 0.05 nicotinic acid (niacin), 0.05 pantothenic acid, 0.001 B12 (cyanobalamine) crystalline,
0.05 nicotinic
0.05 PABA (P-aminobenzoic
acid (niacin), 0.05acid), and 0.05
pantothenic acid,lipoic acid(cyanobalamine)
0.001 B12 (thioctic) [14,15]. The medium
crystalline, was
0.05 PABA
pre-reduced by boiling and purging with nitrogen gas and dispensing into 125 mL
(P-aminobenzoic acid), and 0.05 lipoic acid (thioctic) [14,15]. The medium was pre-reduced by boilingserum bottles.
The purging
and bottles were
with sealed
nitrogenwith
gasbutyl rubber stoppers
and dispensing into 125and
mL autoclaved for 20The
serum bottles. min at 121°C
bottles wereand 1.2
sealed
kgf/cm 2. The final pH of the medium was about 8.0 [14,15]. In a previous study, Suncheon-1,
◦
with butyl rubber stoppers and autoclaved for 20 min at 121 C and 1.2 kgf/cm . The final pH of 2
consisting
the medium of was
Shewanella
about 8.0sp.,[14,15].
Clostridium
In a sp., and Vibrio
previous study,sp., reduced Fe(III),
Suncheon-1, Cr(VI),
consisting and Se(VI) sp.,
of Shewanella by
extracellularly
Clostridium forming
sp., and VibrioFe(II/III) minerals,
sp., reduced Cr(III) and
Fe(III), Cr(VI), hydroxide and
Se(VI) by amorphous forming
extracellularly elemental Se(0)
Fe(II/III)
minerals, Cr(III) hydroxide and amorphous elemental Se(0) nanoparticles, respectively, via glucose2
nanoparticles, respectively, via glucose fermentation [15]. To produce biogenic metal-precipitates,
mL of the filtrate
fermentation [15].at
TopH 7.7 was
produce added metal-precipitates,
biogenic to the medium containing
2 mL of 10
themM of glucose
filtrate at pH 7.7(Cwas
6H12O6) and 2
added to
mL medium
the of enriched metal-reducing
containing 10 mM of bacteria.
glucoseThe
(C6bacteria
H12 O6 ) were
and 2cultivated in a shaking
mL of enriched incubatorbacteria.
metal-reducing at 25°C
under an anoxic atmosphere for 2 weeks. ◦
The bacteria were cultivated in a shaking incubator at 25 C under an anoxic atmosphere for 2 weeks.

2.4. Analytical
2.4. Analytical Methods
Methods
The mineralogical
The mineralogical characteristics
characteristics of
of the
the precipitates formed during
precipitates formed during experiments
experiments were examined
were examined
using X-ray
using X-ray diffraction
diffraction (XRD)
(XRD) and
and scanning
scanning electron
electron microscopy (SEM) with
microscopy (SEM) with energy
energy dispersive
dispersive X-ray
X-ray
(EDS) analyses. The X-ray diffraction analysis was performed using an X’Pert PRO
(EDS) analyses. The X-ray diffraction analysis was performed using an X’Pert PRO (PANalytical, (PANalytical,
Almelo, The
Almelo, The Netherlands)
Netherlands) equipped
equipped with
with Cu
Cu KαKα radiation
radiation (40
(40 kV,
kV, 20
20 mA)
mA) at
at aa scan
scan speed
speed of
of 55 θ/min.
θ/min.
An SEM analysis was done on a JSM-7500F (JEOL, Tokyo, Japan) with an accelerating
An SEM analysis was done on a JSM-7500F (JEOL, Tokyo, Japan) with an accelerating voltage voltage of 200
kV to determine the morphology and elemental composition of the synthesized
of 200 kV to determine the morphology and elemental composition of the synthesized biogenicbiogenic precipitates.
The metal concentrations
precipitates. were measured
The metal concentrations wereusing inductively
measured coupled plasma
using inductively coupledatomic
plasmaemission
atomic
spectroscopy (ICP-AES) on an Optima 8300 (Perkin-Elmer, Waltham, MA, USA)
emission spectroscopy (ICP-AES) on an Optima 8300 (Perkin-Elmer, Waltham, MA, USA) following following the
standard method. Every experiment was run in triplicate, and the average values were
the standard method. Every experiment was run in triplicate, and the average values were used in theused in the
graph. The
graph. The minimum detection limit
minimum detection limit for
for the
the ICP-AES
ICP-AES of of the
the metals
metals was
was about
about 0.004
0.004 mg/L.
mg/L.

3. Results

3.1. Dissolution of
3.1. Dissolution of Metals
Metals in
in Aqua
Aqua Regia
Regia
The weight % of the initial leached metals from the camera and PCB parts into aqua regia were
determined via ICP-AES
ICP-AES (Figure
(Figure 3).3). The
The major
major metals
metals (over
(over 800
800 mg/L)
mg/L) leached from the camera parts
were
were CuCu (4610
(4610mg/L),
mg/L), FeFe (3380
(3380 mg/L),
mg/L), Zn (1930
(1930 mg/L),
mg/L), Ni (1690 mg/L),
mg/L), and Nd (874 mg/L),
mg/L), whereas
minor metals
metals (less than 200 mg/L) were Pr (200 mg/L), Cr (168 mg/L), Sn (114 mg/L), Dy (38 mg/L),
(less than 200 mg/L) were Pr (200 mg/L), Cr (168 mg/L), Sn (114 mg/L), mg/L),
and Tb (34 mg/L).
mg/L). InIn the
the case of the PCB parts, the major major leached
leached metals
metals (over
(over 2500
2500mg/L)
mg/L) were Cu
(23,600 mg/L),
mg/L), Fe (22,200 mg/L),
mg/L), Cr (4460 mg/L),mg/L), NiNi (4120 mg/L), and Zn (2800 mg/L),
mg/L), and mg/L), whereas the
minor metals (less than 500 mg/L) were Nd (425 mg/L), Pr (152 mg/L),
minor metals (less than 500 mg/L) were Nd (425 mg/L), Pr (152 mg/L), Ag (63.6 mg/L), Ag (63.6 mg/L), Mg (30.7
Mgmg/L),
(30.7
and Au and
mg/L), (20.9Au
mg/L).
(20.9Thus,
mg/L).the Thus,
types oftheleached
types metals showed
of leached similar
metals trends,similar
showed and thetrends,
concentrations
and the
of Cu and Fe were
concentrations the and
of Cu highest in both
Fe were thethe camera
highest inand the
both PCB
the parts.and
camera However,
the PCB theparts.
leaching rate of Nd
However, the
was relatively high in the camera due to the Nd-magnet attached to the part. Also,
leaching rate of Nd was relatively high in the camera due to the Nd-magnet attached to the part. the concentrations
of all leached
Also, metals in the
the concentrations of PCB were higher
all leached metalsthan those
in the PCB ofwere
the camera
higher parts, and precious
than those metalsparts,
of the camera such
as
andAg and Aumetals
precious were leached
such asoutAgonly
and from the PCB.
Au were leached out only from the PCB.

Figure
Figure 3.
3. The
The weight
weight %
% of
of the
the initial
initial leached
leached metals from (a)
metals from (a) camera
camera and
and (b)
(b) PCB
PCB parts
parts in
in aqua
aqua regia.
regia.
Minerals 2018, 8, 8 5 of 9

Minerals 2018, 8, 8 5 of 10
3.2. Chemical Recovery of Copper, Iron, and Rare Earth-Metal Complex
The pH of the metal solution with a strong acidic solution treatment was slowly increased by
3.2. Chemical Recovery of Copper, Iron, and Rare Earth-Metal Complex
injecting the ammonia solution dropwise. The metal solution from the camera part was dark green at
the initial
The pH pHofofthe
0.4. As the
metal pH increased,
solution with a strong the color
acidicbecame
solution darker, and was
treatment a brownslowly precipitate
increasedwas by
formed atthe
injecting pHammonia
4.2. The precipitate was separated
solution dropwise. The metal by centrifugation,
solution from and the supernatant
the camera part was was darkfiltered
green
using
at a syringe
the initial pH offilter
0.4. (0.45
As the μm).pHThe filtrate the
increased, wascolor
reacted
becamewithdarker,
the ammonia
and a brown solution in the same
precipitate was
manner.atWhen
formed pH 4.2.theThe
pHprecipitate
of the filtrate
wasgradually
separatedwas increased to pH
by centrifugation, and 7.7,
theit supernatant
transformedwas intofiltered
a light
blue precipitate.
using a syringe filterThe(0.45
precipitate
µm). Thewas alsowas
filtrate separated
reacted bywith centrifugation.
the ammonia solutionThe pH in ofthe
thesame
supernatant
manner.
was increased
When the pH ofusing the same
the filtrate method,
gradually wasand it turned
increased to pHto 7.7,
dark blue with theinto
it transformed formation of aprecipitate.
a light blue light gray
precipitate
The at pH
precipitate was10.5.
also separated by centrifugation. The pH of the supernatant was increased using
The method,
the same mineralogical
and it characteristics
turned to dark of bluethewithprecipitate were investigated
the formation of a light gray via XRD analysis.
precipitate at pH In the
10.5.
results,
Thethe brown precipitate
mineralogical formed at
characteristics of pH
the 4.2 was difficult
precipitate weretoinvestigated
identify in terms
via XRD of the mineral
analysis. Intype
the
due to the
results, the low
brown crystallinity
precipitate(Figure
formed4a), but 4.2
at pH ICP-AES analysis
was difficult to confirmed
identify in that
terms theofpoorly crystalline
the mineral type
minerals
due to thewere
low composed
crystallinity of (Figure
Fe, Cu, Cr,
4a),and
but Sn (Figureanalysis
ICP-AES 5a,b). Inconfirmed
particular,that
Fe, which was present
the poorly at a
crystalline
high concentration
minerals were composed in theofmetal
Fe, Cu,solution,
Cr, andwas found to
Sn (Figure haveIncompletely
5a,b). particular, precipitated
Fe, which was near 100%
present
removal
at from the solution
a high concentration in theatmetal
pH solution,
4.2. The was lightfound
blue precipitate formed precipitated
to have completely at pH 7.7 was nearmainly
100%
crystalline
removal from copper chloride
the solution at pH hydroxides
4.2. The light (Cublue
2Cl(OH) 3) (Figure
precipitate formed4b).at The
pH 7.7 elemental
was mainly analysis also
crystalline
showedchloride
copper that thehydroxides
concentration (Cuof2 Cu
Cl(OH)in the
3 ) supernatant
(Figure 4b). had
The greatly
elemental reduced
analysis (Figure
also 5a).
showed In the
that last
the
step, a small amount
concentration of Cu inof thegray precipitate
supernatant had that formed
greatly at pH(Figure
reduced 10.5 showed
5a). In no
thepeak in the
last step, XRD analysis
a small amount
and
of was
gray considered
precipitate thattoformed
be an amorphous
at pH 10.5 showed mineralno(Figure
peak in4c). theHowever,
XRD analysis the and
presence of rare earth
was considered to
mixed
be minerals mineral
an amorphous composed of Cu,
(Figure 4c). Nd, Pr, Dy,
However, theand Tb were
presence of rareconfirmed
earth mixed viaminerals
ICP-AES analysis
composed
(Figure
of Cu, Nd, 5a,b).
Pr, Dy, and Tb were confirmed via ICP-AES analysis (Figure 5a,b).

Figure 4.
Figure 4. XRD
XRD patterns
patternsof
ofthe
theprecipitate
precipitateseparated
separatedfrom
fromthe camera
the metal
camera solution
metal at (a)
solution pHpH
at (a) 4.2,4.2,
(b)
pHpH
(b) 7.7,7.7,
andand
(c) (c)
pHpH10.5.
10.5.
Minerals 2018, 8, 8 6 of 10
Minerals 2018, 8, 8 6 of 9

Figure
Figure 5.5.ICP-AES
ICP-AES results
results showing
showing metal contents
metal contents of the at
of the supernatant supernatant at (a)
different pHs: different pHs:
camera-major
(a) camera-major
elements; elements; (b)
(b) camera-minor; (c)camera-minor; (c) PCB-major
PCB-major elements; elements;
(d) PCB-minor (d) PCB-minor elements.
elements.

The chemical metal recovery experiments using PCB part were conducted in the same manner
The chemical metal recovery experiments using PCB part were conducted in the same manner as
as above. The PCB metal solution was also dark green at the initial pH of 0.4. As the pH increased,
above. The PCB metal solution was also dark green at the initial pH of 0.4. As the pH increased, the
the color became darker, and a brown precipitate was formed at pH 3.9. The precipitate was
color became darker, and a brown precipitate was formed at pH 3.9. The precipitate was separated
separated via centrifugation, and the supernatant was filtered using a syringe filter (0.45 μm).
via centrifugation, and the supernatant was filtered using a syringe filter (0.45 µm). Subsequently,
Subsequently, the pH of the filtrate gradually increased to pH 5.7 by injecting the ammonia solution,
the pH of the filtrate gradually increased to pH 5.7 by injecting the ammonia solution, and then a
and then a light blue precipitate formed. The precipitate was also separated via by centrifugation.
light blue precipitate formed. The precipitate was also separated via by centrifugation. The pH of the
The pH of the supernatant was increased using the same method, and it turned dark blue with the
supernatant was increased using the same method, and it turned dark blue with the formation of light
formation of light gray precipitates at pH 8.3. The mineralogical characteristics of the precipitate
gray precipitates at pH 8.3. The mineralogical characteristics of the precipitate were investigated via
were investigated via XRD and SEM-EDS analyses.
XRD and SEM-EDS analyses.
As results of the analyses, the brown precipitate formed at pH 3.9 was identified as poorly
As results of the analyses, the brown precipitate formed at pH 3.9 was identified as poorly
crystalline iron oxides (FeOOH) composed of Fe and O, and a small amount of Cu, Cr, and Sn
crystalline iron oxides (FeOOH) composed of Fe and O, and a small amount of Cu, Cr, and Sn
(Figure 6a,b). The ICP-AES analysis confirmed that the leached metals in the solution became
(Figure 6a,b). The ICP-AES analysis confirmed that the leached metals in the solution became
precipitated as minerals through the reduction of the element concentration in the supernatant
precipitated as minerals through the reduction of the element concentration in the supernatant
(Figure 5c,d). The light blue precipitate formed at pH 5.7 was identified as mainly crystalline copper
(Figure 5c,d). The light blue precipitate formed at pH 5.7 was identified as mainly crystalline copper
chloride hydroxides (Cu2Cl(OH)3), and the minerals were observed in the form of agglomerated
chloride hydroxides (Cu2 Cl(OH)3 ), and the minerals were observed in the form of agglomerated
particles of about 100 nm in size (Figure 6c,d). The elemental analysis also showed that the
particles of about 100 nm in size (Figure 6c,d). The elemental analysis also showed that the
concentration of Cu in the supernatant had greatly reduced (Figure 5c). In the last step, a minor
concentration of Cu in the supernatant had greatly reduced (Figure 5c). In the last step, a minor
amount of gray precipitate formed at pH 8.3 was difficult to identify the mineral due to the low
amount of gray precipitate formed at pH 8.3 was difficult to identify the mineral due to the low
crystallinity (Figure 6f). However, it was found that the metal-rare earth mixed minerals composed
crystallinity (Figure 6f). However, it was found that the metal-rare earth mixed minerals composed of
of Ni, Zn, Nd, Pr, Au, and Ag were confirmed through SEM-EDS and inversely correlated to
Ni, Zn, Nd, Pr, Au, and Ag were confirmed through SEM-EDS and inversely correlated to ICP-AES
ICP-AES analyses (Figures 5c,d and 6e).
analyses (Figures 5c,d and 6e).
These results indicated that the degree of acidity influences the order of the precipitation in this
These results indicated that the degree of acidity influences the order of the precipitation in
study: Fe precipitated in an acidic condition (pH 3.9~4.2), Cu precipitated in a slightly acidic to
this study: Fe precipitated in an acidic condition (pH 3.9~4.2), Cu precipitated in a slightly acidic to
neutral condition (pH 5.7~7.7), and the rare earth-metal complex precipitated in an alkaline
neutral condition (pH 5.7~7.7), and the rare earth-metal complex precipitated in an alkaline condition
condition (pH 8.3~10.5) using a simple chemical method. The tendency of metal precipitates of two
(pH 8.3~10.5) using a simple chemical method. The tendency of metal precipitates of two metal
metal leached solutions from the PCB part and the camera part was similar in order, but the degree
leached solutions from the PCB part and the camera part was similar in order, but the degree of pH to
of pH to precipitate in the PCB part was 1~2 order lower than which in the camera part.
precipitate in the PCB part was 1~2 order lower than which in the camera part.
Minerals 2018, 8, 8 7 of 10
Minerals 2018, 8, 8 7 of 9

Figure 6. SEM-EDS images and XRD patterns of the precipitate separated from the PCB metal
Figure 6. SEM-EDS images and XRD patterns of the precipitate separated from the PCB metal solution
solution at (a,b) pH 3.9, (c,d) pH 5.7, and (e,f) pH 8.3.
at (a,b) pH 3.9, (c,d) pH 5.7, and (e,f) pH 8.3.

3.3. Biological Recovery of Manganese and Calcium

3.3. Biological Recovery of Manganese and Calcium
In the experiment using the camera part, after removed Fe and Cu precipitates, the filtrate (pH
In the experiment using the camera part, after removed Fe and Cu precipitates, the filtrate (pH 7.7)
7.7) and the metal-reducing bacteria were reacted for 2 weeks. As a result, a small amount of white
and the metal-reducing bacteria were reacted for 2 weeks. As a result, a small amount of white
precipitate was formed (Figure 7a) and identified as rhodochrosite (MnCO3) and calcite (CaCO3) via
precipitate was formed (Figure 7a) and identified as rhodochrosite (MnCO3 ) and calcite (CaCO3 ) via
XRD (Figure 7b) and SEM-EDS analyses (Figure 7c–e). The calcite and manganese carbonate were
XRD (Figure 7b) and SEM-EDS analyses (Figure 7c–e). The calcite and manganese carbonate were
observed as cubic and spherical particles, respectively, and the particle size varied from 1 to 5 μm
observed as cubic and spherical particles, respectively, and the particle size varied from 1 to 5 µm
(Figure 7c–e). The morphology of these minerals was similar to those of previously reported
(Figure 7c–e). The morphology of these minerals was similar to those of previously reported microbial
microbial synthesized carbonate minerals [16,17].
synthesized carbonate minerals [16,17].
Minerals 2018, 8, 8 8 of 10
Minerals 2018, 8, 8 8 of 9

Figure 7. (a) A picture showing the white settled precipitate; (b) XRD patterns; and (c–e) SEM-EDS
Figure 7. (a) A picture showing the white settled precipitate; (b) XRD patterns; and (c–e) SEM-EDS
images of the biogenic carbonate minerals.
images of the biogenic carbonate minerals.

The results of ICP-AES analysis confirmed that the concentrations of Ca (24.26 mg/L to 14.3
mg/L),The results
Co. (1.83of ICP-AES
mg/L to 0.88analysis
mg/L),confirmed
Cu (21.52 thatmg/Lthetoconcentrations
9.05 mg/L), Niof(54.55
Ca (24.26
mg/L mg/L to 14.3
to 28.3 mg/L),
mg/L), and
Co (1.83 mg/L to 0.88 mg/L), Cu (21.52 mg/L to 9.05 mg/L), Ni (54.55 mg/L
B (1.02 mg/L to 0.55 mg/L) present with trace amount in the filtrate decreased, on average, by to 28.3 mg/L), and B (1.02
49%
mg/Lmicrobial
after to 0.55 mg/L) present
reaction, but Mn with trace
(5.86 amount
mg/L in the
to 5.78 filtrate
mg/L) decreased,
decreased on average,
by 1.4%. by 49%ofafter
The reduction the
microbial reaction, but Mn (5.86 mg/L to 5.78 mg/L) decreased by 1.4%.
metal concentration in the leached metals after pH swing process seemed to reflect mineral The reduction of the metal
concentrationof
composition inthe
the precipitates
leached metals by after pH swing
SEM-EDS and process
XRD, but seemed to reflect of
the reduction mineral composition
the metal of the
concentration
precipitates
in the growth by SEM-EDS
media was andnotXRD, but thecorrelated
directly reduction to of the
themetal concentration
components in the growth
of minerals. media
In addition,
was not directly correlated to the components of minerals. In addition, although
although the concentrations of diverse dissolved metals in the microbial growth media reduced by the concentrations of
diverse dissolved metals in the microbial growth media reduced
ICP-AES, only CaCO3 and MnCO3 in the precipitates were observed by SEM-EDS by ICP-AES, only CaCO and MnCO
3 and XRD. 3
in the precipitates
Therefore, only thewerechangeobserved
of the by SEM-EDS
metal and XRD.
concentrations wasTherefore,
unable toonly the change
conclude as theofamount
the metalof
concentrations
conversion of was unable
metal ionsto into
conclude as the amount
minerals. In the of conversion
biological of metalthe
process, ionsinteraction
into minerals. In the
between
biological process,
microorganisms themetal
and interaction between
ions might microorganisms
induce various and and metal ionspathways
complicated might inducesuch various and
as cell wall
complicated pathways such as cell wall adsorption, intracellular uptake, precipitation
adsorption, intracellular uptake, precipitation into amorphous phase, and mineral synthesis. into amorphous
phase,
Although and the
mineral synthesis. Although
metal-reducing bacteria did the metal-reducing
not form reduced bacteria did not
metal form reduced
minerals, metal
its metabolic
minerals, itssuch
byproducts metabolic byproducts
as bicarbonate such as bicarbonate
enhanced formation of enhanced
carbonatesformation
minerals of carbonates minerals
under an anaerobic
under an anaerobic environment [18]. These indicated that the metal ions remaining
environment [18]. These indicated that the metal ions remaining in the filtrate could be mineralized in the filtrate
could be mineralized by the metal-reducing
by the metal-reducing bacteria via diverse pathways. bacteria via diverse pathways.

4. Conclusions
4. Conclusions
These results
These results showed
showed that
that the
the metals
metals leached
leached in in aqua
aqua regia
regia could
could bebe recovered
recovered using
using aa simple
simple
chemical method, such as a pH swing. The order of precipitation
chemical method, such as a pH swing. The order of precipitation in metal leached solutions in metal leached solutions
appeared as
appeared as Fe
Fe precipitated
precipitatedin inan
anacidic
acidiccondition
condition(pH (pH3.9~4.2),
3.9~4.2),CuCu precipitated
precipitated in in a slightly
a slightly acidic
acidic to
to neutral condition (pH 5.7~7.7), and rare earth-metal complex precipitated in
neutral condition (pH 5.7~7.7), and rare earth-metal complex precipitated in an alkaline condition an alkaline condition
(pH
(pH 8.3~10.5),
8.3~10.5),respectively.
respectively.InInaddition,
addition, the the
pHspHs
of the ofprecipitation of the metal
the precipitation of theions
metaldiffered
ions between
differed
metal leached solutions in the PCB part and the camera part. The pH of the
between metal leached solutions in the PCB part and the camera part. The pH of the precipitate precipitate in the PCB in
metal solution was 1~2 order lower pH than which in the camera
the PCB metal solution was 1~2 order lower pH than which in the camera solution. solution.
Although most
Although mostprevious
previousstudies
studieshavehavefocused
focused ononthethe
recovery of precious
recovery of preciousmetals in theinPCB,
metals the there
PCB,
are disadvantages that complex processes and various toxic substances are
there are disadvantages that complex processes and various toxic substances are used only for used only for one or two
one
kinds of selective metal recovery. To recover precious metals effectively, it is necessary
or two kinds of selective metal recovery. To recover precious metals effectively, it is necessary to to concentrate
the precious the
concentrate andprecious
rare earth-metals that account for
and rare earth-metals thatmore thanfor
account 80% of the
more thantotal intrinsic
80% of the value, despite
total intrinsic
less than 1 wt % of the amount in the PCB. In this study, the rare earth-metal complex
value, despite less than 1 wt % of the amount in the PCB. In this study, the rare earth-metal complex obtained in
alkaline conditions
obtained in alkalinecould be materials
conditions could be suitable for suitable
materials the separation
for theand recovery
separation of recovery
and single precious or
of single
rare earth-metal.
precious or rare earth-metal.
Therefore, these results indicate that simple and effective metal recovery of the mobile phone
waste might be feasible via chemical and biological treatments, and the recovered metals such as Fe,
Cu, and rare earth-metal complex can be recycled as raw materials for diverse industries.
Minerals 2018, 8, 8 9 of 10

Therefore, these results indicate that simple and effective metal recovery of the mobile phone
waste might be feasible via chemical and biological treatments, and the recovered metals such as Fe,
Cu, and rare earth-metal complex can be recycled as raw materials for diverse industries.

Acknowledgments: This research was supported by the “Basic Science Research Program” of the National
Research Foundation of Korea funded by the Ministry of Education (NRF-2015R1D1A4A01016016 and
2016R1D1A1A09917588). We are grateful to Cho and Bae at KBSI-Gwangju Branch for SEM-EDS and ICP-AES
analyses, and Jung at CCRF in Chonnam National University for XRD analysis.
Author Contributions: Y.K. designed the experiments, performed analysis on all samples, interpreted data, wrote
manuscript; H.S. provided critical feedback and helped to evaluate and edit the manuscript; Y.R. conceived the
original idea, provided critical feedback, acted as corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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