metals

Article
A New Recycling Process for Tungsten Carbide Soft
Scrap That Employs a Mechanochemical Reaction
with Sodium Hydroxide
Jaeryeong Lee *, Suyun Kim and Byoungjin Kim
Department of Energy & Resources Engineering, Kangwon National University, Chuncheon 24341, Korea;
syoon0270@kangwon.ac.kr (S.K.); iybj90@kangwon.ac.kr (B.K.)
* Correspondence: jr-lee@kangwon.ac.kr; Tel.: +82-33-250-6252

Received: 2 June 2017; Accepted: 19 June 2017; Published: 22 June 2017

Abstract: WC soft scrap, including Co used as a binder, thermally oxidized at 600 ◦ C, was subjected
to grinding with NaOH in a mechanochemical reaction, followed by water leaching to establish
an effective recycling process. Na2 WO4 was synthesized through a mechanochemical (MC) reaction
with oxidized scrap, and Na2 CO3 was formed when the mixing ratio of NaOH increased. These
as-synthesized compounds were water-soluble. When the weight ratio of soft scrap to NaOH was
1:0.5, 99.2% W was extracted by water leaching, while the extraction yield of Co was limited to 3.57%
under the same conditions.

Keywords: WC soft scrap; thermal oxidation; mechanochemical reaction; sodium hydroxide;

water leaching

1. Introduction
Tungsten is one of the most important refractory metals, and tungsten carbide (WC) is used in
a variety of products, such as cutting tools, wear parts, and mining drill bits, because of its superior
toughness and hardness. Moreover, other refractory carbides, such as TiC and TaC, are frequently
combined with WC alloys along with a metal binder or cementing agent, typically cobalt (Co),
which holds the hard carbide grains together in a dense composite structure. In this regard, sustainable
hard metal production is important to and supports modern industry, especially as it expands with
global population growth and elevating standards of living. Concurrently, it is important to reduce
the environmental impact of industrial processes because emission remediation costs have escalated;
some harmful processes have been completely outlawed. The majority of tungsten (W) produced
is used to meet the demand for hard metals, so it is critical to consider the W supply chain. Over
the past decade, W precursor prices have undergone a dramatic escalation (an eight-fold increase)
and industrial electricity costs (a major production expense) have increased significantly (by 30%).
In this regard, W production via the recycling of hard-metal scrap, which allows for reduced cost,
energy consumption, and environmental impact, has been in the limelight. The recycling ratio of W
has increased continuously, but still is no greater than approximately 25% due to the physical and
chemical diversity of various types of scrap (e.g., materials that have reached the end of their life or
more prevalently those that are generated during the manufacturing of W materials (including WC)).
This scrap can be classified by shape; (1) powder (soft scrap) or (2) bulky (hard scrap) [1–10].
Worn tools, such as cutting and drilling bits made of WC hard metals, are generally classified
as hard scrap. Soft scrap does not have a defined shape and is composed mainly of unsintered WC
powder. Typically, this scrap is the waste product of W manufacturing, and it includes wires, coils,
powders, and turnings. Soft scrap contains more metallic impurities than hard scrap, but does not need

Metals 2017, 7, 230; doi:10.3390/met7070230 www.mdpi.com/journal/metals

Metals 2017, 7, 230 2 of 9

to be crushed like hard scrap. To enhance the recycling efficiency and increase the selective recovery of
valuable metals, soft scrap should be treated with special care [11].
Researchers have investigated the recycling process of WC soft scrap via two main processes:
alkali treatment and acid treatment [12–14]. Alkali treatment is typically executed in one of two ways:
(1) transformation of WC to sodium tungstate, which is soluble in water, via an alkali fusion process
using sodium nitrate/nitrite and sodium carbonate, or (2) dissolution of the oxidized scrap using
a sodium hydroxide solution followed by the removal of impurities, the precipitation of tungstic
acid, and dissolution by ammonia. In acid treatment, cobalt (which is utilized as a binder material)
is extracted, first leaving an insoluble WC residue [15–18]. There are challenges to using both of
these methods in an industrial process for recycling WC soft scrap. The alkali treatment requires a
high-temperature fusion step and the separation of cobalt from the residue, which consume a large
amount of energy. In the case of the acid treatment, the purity of the recovered WC is often too low for
it to be reused as a raw material in hard metal manufacturing processes; high temperature alkali fusion
processes or oxidation are needed to augment tungsten recovery [19,20]. In addition, the tungsten
product may be contaminated by the incomplete leaching of cobalt. Moreover, after such treatments,
W and Co must be recovered from the solution. For these reasons, we have developed a new process
that involves a mechanochemical (MC) reaction and that enables us to recover tungsten selectively
from oxidized soft scrap.
Here, we provide information and the optimal conditions that can be employed for the effective
and economic recycling of WC soft scrap, enabling the facile recovery of tungsten.

2. Experimental Procedure

2.1. Starting Materials and Characterization

The soft scrap used in this study consisted of a hard metal sludge generated in the manufacturing
process of turning tools composed of WC, and it was provided by TaeguTec Co., Daegu, Korea.
This scrap contained not only the components generated as a byproduct in the manufacturing process,
but also foreign substances, such as paper and organic dust, introduced during collection. To separate
these substances, the scrap was screened with a #500 sieve (aperture size: 25 µm) for 1 h using a sieve
shaker (J-VSS, JISICO Co., Seoul, Korea). As a result, 77.33 wt % of the as-received scrap was acquired,
and this portion was used as the starting material. The chemical composition of the starting materials
was analyzed by X-ray fluorescence spectrometry (XRF, ZSX Primus II, Rigaku Co., Tokyo, Japan)
(Table 1). The major elements detected were as follows: tungsten (W, 54.3 wt %), oxygen (O, 16.6 wt %),
carbon (C, 15.7 wt %), cobalt (Co, 5.25 wt %), silicon (Si, 1.95 wt %), and iron (Fe, 1.56 wt %). For the
major components (W, Co) in the soft scrap, the leaching tendencies were surveyed, and a method to
selectively recover W was presented.

Table 1. Chemical composition of the soft scrap used as a starting material in this study.

Element Content (wt %) Element Content (wt %)

W 54.3 Al 0.19
Co 5.25 Cu 0.07
Si 1.95 V 0.05
Fe 1.56 Mo 0.05
Cr 0.28 C 15.7
Nb 0.24 O 16.6
Ni 0.23 Others (B, Na, P, K) 3.56

2.2. Experimental Procedure

The recovery of W from the soft scrap proceeded in three steps: (1) thermal treatment to
oxidize WC, (2) MC treatment with NaOH, and (3) water-leaching of the MC-treated scrap (Figure 1).
 Metals 2017, 7, 230 3 of 9

2.2. Experimental Procedure

The7,recovery
Metals 2017, 230 of
W from the soft scrap proceeded in three steps: (1) thermal treatment to oxidize
3 of 9
WC, (2) MC treatment with NaOH, and (3) water-leaching of the MC-treated scrap (Figure 1). The
oxidation for the WC soft scrap should be carried out before the MC treatment because the WC
The oxidation for the WC soft scrap should be carried out before the MC treatment because the WC
powder, which is characterized by strength and hardness, may cause excessive abrasion of the
powder, which is characterized by strength and hardness, may cause excessive abrasion of the grinding
grinding ports and media.
ports and media.

WC soft-scrap Passed #500 sieve

Oxidation 500~650℃ for 1 hour in air

Mechanochemical With NaOH using planetary mill at 700 rpm

Reaction for various grinding time

Water leaching By water at room temperature (pulp density: 10 g/L)

Figure1.1.Flow
Figure Flowchart
chartofofexperimental
experimentalprocedures.
procedures.

The starting material (WC soft scrap) was thermally oxidized using an electric furnace. The scrap
The starting material (WC soft scrap) was thermally oxidized using an electric furnace. The scrap
(100 g) was placed in an alumina boat and heated for 1 h in air at temperatures ranging from 500 to
(100 g) was placed in an alumina boat and heated for 1 h in air at temperatures ranging from 500 to
650 °C. Sodium hydroxide (NaOH) was used as an additive to induce the MC reaction (Junsei
650 ◦ C. Sodium hydroxide (NaOH) was used as an additive to induce the MC reaction (Junsei Chemical
Chemical Co., Ltd., Tokyo, Japan). The thermally treated scrap was mixed with sodium hydroxide
Co., Ltd., Tokyo, Japan). The thermally treated scrap was mixed with sodium hydroxide (NaOH) in
(NaOH) in different weight ratios (soft scrap: NaOH), ranging from 1:0.3 to 1:0.5, and these mixtures
different weight ratios (soft scrap: NaOH), ranging from 1:0.3 to 1:0.5, and these mixtures were stored
were stored in a desiccator. A planetary mill (Pulverisette-7, Fritsch Gmbh, Idar-Oberstein, Germany)
in a desiccator. A planetary mill (Pulverisette-7, Fritsch Gmbh, Idar-Oberstein, Germany) was used
was used to grind the mixture for the MC reaction. The mill contained a pair of pots composed of
to grind the mixture for the MC reaction. The mill contained a pair of pots composed of zirconia
zirconia installed on a rotating disc driven by an electric motor. The mixture (4 g) was placed in the
installed on a rotating disc driven by an electric motor. The mixture (4 g) was placed in the port (45 cm3
port (45 cm3 inner volume) with seven zirconia balls (15 mm in diameter) and ground in air at 700
inner volume) with seven zirconia balls (15 mm in diameter) and ground in air at 700 rpm for certain
rpm for certain periods of time. Subsequently, the ground mixture was leached in distilled water
periods of time. Subsequently, the ground mixture was leached in distilled water under the following
under the following conditions: room temperature, 10 g/L slurry density, and stirring with a magnetic
conditions: room temperature, 10 g/L slurry density, and stirring with a magnetic bar. During the
bar. During the leaching procedure, 1 mL leaching liquor samples were taken between 5 s and 1 h.
leaching procedure, 1 mL leaching liquor samples were taken between 5 s and 1 h. To acquire more
To acquire more accurate data, the total content of the two components (W, Co) was calculated for
accurate data, the total content of the two components (W, Co) was calculated for each sample. For this
each sample. For this reason, the content of the components (W, Co) in both the leached solution and
reason, the content of the components (W, Co) in both the leached solution and leached residue was
leached residue was analyzed. To dissolve the residue completely, a chemical digestion method was
analyzed. To dissolve the residue completely, a chemical digestion method was used. The leachability
used. The leachability was determined via the following equation:
was determined via the following equation:
M content A
Leachability of M % = M content A)content B × 100 (1)
Leachability of M (%) = M content A +(M × 100 (1)
M content (A) + M content (B)
where M denotes the two components (W, Co) in this study, M content (A) is the M mass calculated
from M
where thedenotes
M concentration in the leached
the two components solution,
(W, Co) in thisand M content
study, (B) (A)
M content represents
is the Mthe M calculated
mass mass in the
leached
from the Mresidue after complete
concentration in thedissolution.
leached solution, and M content (B) represents the M mass in the
leached residue after complete dissolution.
2.3. Characterization
2.3. Characterization
Thermogravimetric and differential thermal analysis (TG-DTA, DTG-60H, Shimadzu Co.,
Thermogravimetric
Kyoto, Japan) using a and differential
heating rate ofthermal analysis
10 °C/min (TG-DTA,
in air DTG-60H,
flow (100 mL/min)Shimadzu
scanningCo.,
fromKyoto,
room
Japan) using a heating rate of 10 ◦ C/min in air flow (100 mL/min) scanning from room temperature up
temperature up to 800 °C was utilized to determine the optimal temperature for oxidizing the soft
to 800 ◦ C was utilized to determine the optimal temperature for oxidizing the soft scrap. The starting
soft scrap and the treated mixtures were characterized by high resolution X-ray diffraction (HRXRD,
Metals 2017, 7, 230 4 of 9
Metals 2017, 7, 230 4 of 9
scrap. The starting soft scrap and the treated mixtures were characterized by high resolution X-ray
diffraction (HRXRD, X’pert-Pro MPD, PANalytical, Almelo, The Netherlands) using Cu-Kα radiation
X’pert-Pro MPD, PANalytical, Almelo, The Netherlands) using Cu-Kα radiation (λ = 1.5406 Å) to
(λ = 1.5406 Å) to identify how the phases changed after thermal and MC treatment. The leachability
identify how the phases changed after thermal and MC treatment. The leachability of the two major
of the two major components (W, Co) was measured using an inductively coupled plasma
components (W, Co) was measured using an inductively coupled plasma spectrometer (ICP, OPTIMA
spectrometer (ICP, OPTIMA 7300DV, Perkin Elmer, Waltham, MA, USA).
7300DV, Perkin Elmer, Waltham, MA, USA).
3.3.Results
Resultsand
andDiscussion
Discussion

3.1.
3.1.Oxidation
Oxidationofofthe
theStarting
StartingSample,
Sample,Soft
SoftScrap
ScrapPassed
Passedby
by#500
#500Sieve
Sieve
Figure
Figure22shows
showsthe theXRD
XRDpattern
patternofofthe
thestarting
startingsample,
sample,which
whichwas
waspassed
passedthrough
throughaa#500
#500sieve
sieve
(aperture
(aperture size: 25 µm). Despite the various elements comprising this scrap (Table 1), only
size: 25 µm). Despite the various elements comprising this scrap (Table 1), only two
two
compositions,
compositions,WC WC(JCPDs
(JCPDsNo.No.73-0471)
73-0471)and
andCoC
CoCxx(JCPDs
(JCPDsNo.No.44-0962),
44-0962),were
wereobserved
observedininthe
thepattern.
pattern.
Further,
Further, the
the main
main peaks
peaks were
were associated
associated with
with WC
WC and
and only
only aa single
single weak
weak peak
peak associated
associated with
with CoC
CoCxx
was
was observed. Peaks corresponding to the other components were not detected, likely owing totheir
observed. Peaks corresponding to the other components were not detected, likely owing to their
relatively
relativelysmaller
smaller particle
particle size
size (≤25
(≤25µm)
µm)andandlower
lowercrystallinity.
crystallinity.

WC CoCx
Intensity (arbitrary unit)

10 20 30 40 50 60 70 80
(Cu-Kα)

X-raydiffraction
Figure2.2.X-ray
Figure diffraction(XRD)
(XRD)pattern
patternof
ofthe
thestarting
startingsample
sampleused
usedin
inthis
thisstudy.
study.

To
To determine
determine the oxidation conditionsconditionsfor forthe
thesamples,
samples,TG-DTATG-DTAanalysisanalysiswaswascarried
carriedout
out (Figure
(Figure 3).
3).
AsAs shown
shown in Figure
in Figure 3a, weight
3a, the the weight
of theofsample
the sample decreased
decreased by asbymuchas much as 2.26%
as 2.26% at approximately
at approximately ◦
320 C.
320
Then,°C.itThen, it increased
increased gradually gradually with increasing
with increasing temperaturestemperatures
up to 650up ◦ Ctoby650 °C byas
as much as14.87%.
much asAs 14.87%.
for the
As for the thermal
differential differential thermal
analysis analysis
(Figure (Figure
3b), three 3b), three
exothermic peaks exothermic
were observed peaksat were observed310,
approximately at
approximately ◦
410, and 570 C,310, 410, and 570to°C,
corresponding thecorresponding
combustion of the to the combustioninofthe
oil component thesludge,
oil component in the
the oxidation of
sludge, the oxidation
cobalt carbide, and the ofoxidation
cobalt carbide, and the
of tungsten oxidation
carbide, of tungsten
respectively carbide,
(recovery respectively
of WC from hard (recovery
material
of WC from
sludge). hard material
The weight sludge).
loss observed viaThe weight loss observed
thermogravimetric analysisvia thermogravimetric
at temperatures 318 ◦atC
analysis
lower than
temperatures
can be attributed lower tothan 318 °C can
the removal be attributed
of moisture and to oilthe removal ofthe
components; moisture
weightand oilobserved
gain components; the
between
weight
320 andgain ◦ C can bebetween
650observed attributed320toandthe650 °C can be
oxidation attributed
of WC-Co to the oxidation
carbide. Thus, thermalof WC-Co carbide.
treatment was
Thus,
carried thermal
out fortreatment
1 h between was 500carried
andout 650for◦ C1toh oxidize
betweenand 500eliminate
and 650 °C thetocombustible
oxidize and eliminate
impuritiesthe so
combustible
that the optimal impurities
treatmentso that the optimal
temperature treatment
could temperature
be determined. XRD could be determined.
patterns XRD patterns
of the thermally treated
of the are
scrap thermally
presented treated scrap4.are
in Figure presented
When the scrap in was
Figure 4. When
treated at 500the◦ C,scrap was treated
the pattern at 500
of peaks was°C, the
similar
pattern
to that ofof the
peaks was similar
starting to thatthe
scrap (except of the startingdiffered).
intensities scrap (except the intensities
However, when thediffered).
scrap wasHowever,
treated at
550 ◦ C,
when thepeaks
scrapcorresponding
was treated at to 550 °C, peaks
a new phasecorresponding
(WO3 and CoWO to a4new
) were phase (WO3and
detected andtheir
CoWO 4) were
intensities
detected
increasedand withtheir intensities
increasing increased
treatment with increasing
temperature. Peakstreatment temperature.
corresponding Peaks corresponding
to the starting material were
to
notthe starting when
observed material were
it was not observed
treated betweenwhen 550 andit was ◦ C, implying
650treated between 550the
that and 650 °C,scrap
starting implying
should that
be
the starting
treated scrap should
thermally at 550 be ◦ C treated
or higher thermally
(for 1 h in at 550
air) °C or changed
to be higher (for from1 hainmixture
air) to be
of changed
WC and CoC fromx
ainto
mixture of WC
a mixture ofand
WOCoC 3 and x into
CoWO a mixture
4 phases. of WO3 and CoWO4 phases.
Metals 2017, 7, 230 5 of 9
Metals 2017, 7, 230 5 of 9
Metals 2017, 7, 230 5 of 9

120 250
120 (a) TG 250 (b) DTA
(a) TG 200 (b) DTA
568.95 ℃
115 200
Weight change +14.873% 568.95 ℃
115 150
Weight change/ wt%

Weight change +14.873%

150
Weight change/ wt%

100

uVuV
110
100 311.39 ℃
110

flow/
50 311.39 ℃

flow/
50
105
0

Heat
105 409.08 ℃
0

Heat
409.08 ℃
-50
100 -50
100 Weight change -2.262%
Weight change -2.262% -100
-100
318.76 ℃
318.76 ℃
95 -150
095 200 400 600 800 1000 -150 0 200 400 600 800 1000
0 200 400 600 800 1000 0 200 400 600
800 1000
Temperature/ oo o oC
Temperature/CC Temperature/
Temperature/ C

Figure
Figure 3.
Figure TG-DTA
3. 3. TG-DTA(thermogravimetric
TG-DTA (thermogravimetric and
(thermogravimetric and differential
and differential thermal analysis)
thermalanalysis)
differential thermal profiles
analysis)profiles for
profilesfor
for the
the
the soft
soft
soft scrap
scrap
scrap
of WC.
of of
WC.WC.

WO3 3
WO WC CoC
CoCx x CoWO
CoWO
4 4

650℃
650℃
unit)
(arbitraryunit)

600℃
600℃
Intensity(arbitrary

550℃
550℃
Intensity

500℃
500℃

-500mesh
-500mesh

10 20 30 40 50
10 20 30
(Cu-Kα) 40 50
(Cu-Kα)
Figure 4. XRD pattern of the samples treated thermally from 500 to 650 ◦ C for 1 h in air.
Figure 4. XRD pattern of the samples treated thermally from 500 to 650 °C for 1 h in air.

3.2.3.2.
MC Figureof4.the
Reaction XRD pattern Scrapof the samples treated thermally from 500 to 650 °C for 1 h in air.
MC Reaction of theOxidized
Oxidized ScrapwithwithNaOH
NaOH
Scrap samples treated atat550, 600, and 650 ◦ C were ground with NaOH to induce an MC reaction.
3.2. MC Reaction
Scrap of the
samples Oxidized
treated Scrap
550, with
600, andNaOH
650 °C were ground with NaOH to induce an MC reaction.
Each
Eachof of
these
these scraps
scraps waswasmixed
mixedwithwithNaOH
NaOHat at aa weight ratio of
weight ratio of 1:0.4.
1:0.4.Four
Fourgrams
gramsofofthethe mixture
mixture was
was
ground Scrap
at samples
700 rpm treated
for 2 h. at 550, grinding,
After 600, and 650 °C were
these ground
mixtures were with NaOH
dried at to induce
105 ◦ C for 2anh MC
to reaction.
eliminate
ground at 700 rpm for 2 h. After grinding, these mixtures were dried at 105 °C for 2 h to eliminate
Each of these
moisture so so scraps
that they was mixed with NaOH
could at a weight ratio of 1:0.4. Four grams of the mixture was
moisture that they couldbebeanalyzed
analyzedusing
usingXRD.
XRD.
groundThe at 700
XRD rpm
patternsfor 2 h. After grinding, these mixturesinwere dried at 105corresponding
°C for 2 h to eliminate
The XRD patternsofofthe theground
groundmixtures
mixtures areare shown
shown Figure
Figure 5. 5. Peaks
Peaks corresponding toto WOWO3 3
moisture
andandCoWO
CoWOso that
could they
not could
be be
found, analyzed
and using
those of XRD.
sodium tungsten oxide (Na WO ) were seen regardless
4 4 could not be found, and those of sodium tungsten oxide (Na2WO 2 4)4were seen regardless

of The
of treatmentXRD
treatment patterns
temperature.
temperature. of the groundaamixtures
However,
However, small WC
small arepeak
shown
peak wasin
was Figure for
detected
detected 5.
forPeaks
the corresponding
thescrap
scrap treated
treatedat at
550to WO
◦ C.3
°C.
550
and CoWO4 could not be found, and those of sodium tungsten oxide (Na2WO4) were seen regardless
of treatment temperature. However, a small WC peak was detected for the scrap treated at 550 °C.
Metals 2017, 7, 230 6 of 9
Metals 2017, 7, 230 6 of 9

These
These results imply that
results imply that the
the oxide
oxide (Na
(Na2WO 4) shall be formed in the mechanochemical reaction as
2 WO4 ) shall be formed in the mechanochemical reaction as
expressed by Equation (2).
expressed by Equation (2).
WO3 + 2NaOH → Na2 WO4 + H2 O (2)
WO3 + 2NaOH → Na2 WO4 + H2 O (2)
Moreover, the peak for WC was indicative of incomplete oxidation (Figure 5a). Therefore, an
MC reaction
Moreover,and
thesubsequent water-leaching
peak for WC was indicativeshould be carried
of incomplete out for(Figure
oxidation the scrap
5a). treated at 600
Therefore, °C
an MC
or higher.
reaction ◦
and subsequent water-leaching should be carried out for the scrap treated at 600 C or higher.

WC Na2WO4
(c) with the scrap treated at 650℃
Intensity (arbitrary unit)

(b) with the scrap treated at 600℃

(a) with the scrap treated at 550℃

10 20 30 40 50 60 70 80

(Cu-Kα)
Figure 5. XRD patterns of the ground mixture, NaOH, and the scrap thermally treated at (a) 550 ◦ C,
Figure 5. XRD patterns of the ground mixture, NaOH, and the scrap thermally treated at (a) 550 °C,
(b) 600 ◦ C, and (c) 650 ◦ C.
(b) 600 °C, and (c) 650 °C.

For the
the scrap
scrap treated
treated atat 600 ◦ C, its MC reactivity was investigated under various grinding
For 600 °C, its MC reactivity was investigated under various grinding
conditions (different mixing ratios
conditions (different mixing ratios (scrap: NaOH (scrap: NaOH = 1:0.3–1:0.5)
= 1:0.3–1:0.5) and grinding
and grinding timesmin)).
times (5–30 (5–30Figure
min)).
Figure 6(1) shows the XRD patterns of the scrap mixture treated at 600 ◦ C with NaOH (1:0.3) for
6(1) shows the XRD patterns of the scrap mixture treated at 600 °C with NaOH (1:0.3) for various
various grinding
grinding times (5, times15, and(5,3015, andAs30shown
min). min). inAs shown
Figure in Figure
6(1-a), peaks 6(1-a),
correspondingpeaks corresponding
to the unreacted to
the unreacted scrap, such
scrap, such as WO3 (JCPDS No. 43-1035)as WO 3 (JCPDS No. 43-1035) and CoWO
and CoWO4, (JCPDS No. 72-0479), 4 , (JCPDS No. 72-0479),
were observed. After 5 were
observed.
min After new
of grinding, 5 min of grinding,
peaks for Na2WO new peaks No.
4 (JCPDS for Na 2 WO4appeared.
70-1040) (JCPDS No. Upon 70-1040) appeared.
increasing Upon
the grinding
increasing the grinding time, the intensities of these new peaks increased,
time, the intensities of these new peaks increased, while the intensities of the peaks corresponding to while the intensities of
the peaks corresponding to the unreacted compounds decreased gradually.
the unreacted compounds decreased gradually. For the scrap ground for 30 min (Figure 6(1-c)), only For the scrap ground for
30 min
one CoWO(Figure4 peak 6(1-c)),
was only one CoWO
discernible, and4the peak waspeaks
other discernible, and the to
corresponded otherNa2peaks
WO4. corresponded
For the samples to
Na
with WO .
2 a mixing
4 For the samples with a mixing ratio of 1:0.4 (Figure 6(2)), peaks corresponding
ratio of 1:0.4 (Figure 6(2)), peaks corresponding to Na2WO4 were identified regardless to Na 2 WO 4
were
of identified
grinding time, regardless of grinding
and the changes in thetime, and the of
intensities changes in the were
those peaks intensities of those peaks
unperceivable. The peakswere
unperceivable. to
corresponding TheNapeaks corresponding
2CO3 (JCPDS No. 77-2082)to Nacould
2 CO3 (JCPDS
be observedNo. 77-2082)
in the XRD could be observed
pattern in the
of the ground
XRD pattern of the ground mixture with a ratio of 1:0.5 (Figure 6(3)). For
mixture with a ratio of 1:0.5 (Figure 6(3)). For the mixture ground for 5 min Figure 6(3-a), only peaksthe mixture ground for 5 min
Figure
of Na2WO 6(3-a),
4 were only peaks
found of Nato
(similar 2 WO were found
the4pattern of Figure(similar to the
6(2-a)), pattern
but with of Figure
noticeable 6(2-a)), but
differences with
in their
noticeable differences in their intensities. With increasing grinding time
intensities. With increasing grinding time (15 min or longer), the peaks corresponding to Na2WO4 (15 min or longer), the peaks
corresponding
increased, and to theNa 2 WO4ofincreased,
peaks Na2CO3 were and the alsopeaks
found. of Na 2 COresults
These 3 were also
imply found. These
that the results
mixing imply
ratio of
that thedictates
NaOH mixing ratio the MCof NaOH
reactiondictates
with the
the MC reaction
oxidized with
soft the and
scrap, oxidized soft scrap,isand
the reactivity the reactivity
improved with
is improved
increasing with increasing
NaOH. NaOH.ratio
For the mixing For ofthe1:0.3
mixing (theratio of 1:0.3
lowest amount(the oflowestNaOH amount
used of NaOH
here), theused
MC
here), the MC reaction did not proceed until all of
reaction did not proceed until all of the scrap (CoWO4) had reacted. These the scrap (CoWO 4 ) had reacted. These
peaks corresponding peaksto
corresponding
the unreacted to the unreacted
scrap disappeared scrap asdisappeared
the NaOH as wasthe increased
NaOH wasthroughincreased through amorphization
amorphization and MC
reaction (Figure 6(2)). Moreover, Na2CO3 could be formed in the ground mixture (1:0.5) by the
progressive reaction between residual carbide/carbonate components and NaOH (Figure 6(3)).
Metals 2017, 7, 230 7 of 9

and MC reaction (Figure 6(2)). Moreover, Na2 CO3 could be formed in the ground mixture (1:0.5) by
the progressive
Metals 2017, 7, 230 reaction between residual carbide/carbonate components and NaOH (Figure 6(3)).
7 of 9
Metals 2017, 7, 230 7 of 9

WO3
WO CoWO4
CoWO Na2WO
Na WO4 Na2CO
Na CO3
3 4 2 4 2 3
(1-c)
(1-c) (2-c) (3-c)
unit)

(2-c) (3-c)
(arbitraryunit)
Intensity(arbitrary

(1-b)
(1-b) (2-b)
(2-b) (3-b)
(3-b)

(1-a) (2-a) (3-a)

Intensity

(1-a) (2-a) (3-a)

10
10 20
20 30
30 40
40 50 10
50 10 20
20 30
30 40
40 50 10
50 10 20
20 30
30 40
40 50
50
(Cu-Kα)
(Cu-Kα)
Figure
Figure 6.XRD
Figure6.6. XRDpatterns
XRD patternsof
patterns ofthe
of the ground
the ground mixture:
ground mixture: (1) mixing
mixture: (1) mixingratio
ratioof
ratio ofsoft
of softscrap:
soft scrap:NaOH
scrap: NaOH===1:0.3,
NaOH 1:0.3,(2)
1:0.3, (2)1:0.4,
(2) 1:0.4,
1:0.4,
(3)
(3) 1:0.5
1:0.5 with
with (a)
(a) grinding
grinding time:
time: 55 min,
min, (b)
(b) 15
15 min,
min, and (c) 30 min.
(3) 1:0.5 with (a) grinding time: 5 min, (b) 15 min, and (c) 30 min.

3.3.Water-Leaching
3.3.
3.3. Water-Leachingfor
Water-Leaching forthe
for theGround
the Ground Mixture
Mixture of
of the
the Soft
Soft Scrap
Scrap and
Scrap and NaOH
and NaOH
NaOH
Figure777shows
Figure
Figure showsthe
shows theleaching
leaching trends
trends of of W
W and
W and
andCoCo according
Coaccording
accordingto to the
tothe mixing
themixing ratio
mixingratio and
ratioand grinding
andgrinding time.
grindingtime.
time.
Forthe
For
For theground
the groundmixture
ground mixturewith
mixture withaa ratio
ratio of of 1:0.3
1:0.3 (Figure
1:0.3 (Figure 7a),
(Figure7a), the
7a),the leachability
theleachability
leachabilityof of W
ofW increased
Wincreased proportionally
increasedproportionally
proportionally
withgrinding
with
with grindingtime
grinding timeand
time andits
and itsdissolution
its dissolutionmostly
dissolution mostlystopped
mostly stopped
stopped within
within
within 2 min.
min.
2 2min. Unusually,
Unusually,
Unusually, the the
the extraction
extraction
extraction of
ofof
WW Wfor
for
the the mixture
for mixture
the mixture
ground ground
ground for
for 5for
min 5 min
5 min
barely barely
barely increased
increased
increased during
during
during 60 min
60 min
60 min of leaching.
of leaching.
of leaching. MoreMore
More
W was W was
W was extracted
extracted
extracted with
with
with
the the(Figure
the
1:0.4 1:0.4 (Figure
1:0.4 (Figure 7b) mixture
7b)
7b) mixture mixture
than thanthan with
with with1:0.3
the the 1:0.3
the 1:0.3 mixture,
mixture,
mixture, reaching
reaching
reaching aa maximum
maximum
a maximum of 98%of 98%
of 98% within
within
within 60
60
60 min.
min.
min.
For the For
For the 1:0.5
the(Figure
1:0.5 (Figure
1:0.5 (Figure 7c) mixture,
7c) mixture,
7c) mixture, the leachability
the leachability
the leachability of W was of
of WW was
as was
highas as high
ashigh
95% asas 95%
in 95% in the
in the
the early early stages
earlyofstages
stages of
of
leaching
leaching (within
leaching1 (within
(within min) and 1 min)
1 min) and as
and as much
as much much
99.2% as as
was 99.2%
99.2% was extracted
was extracted
extracted in less
in less
in less than than
60 than
min of 60 min of water-leaching.
60 water-leaching.
min of water-leaching.Co was
Co
Co was
was difficult
difficult to
to extract,
extract, and
and its
its leachability
leachability was
was rarely
rarely more
more than
than 3.5%
3.5% under
under
difficult to extract, and its leachability was rarely more than 3.5% under any of the conditions explored. any
any of
of the
the conditions
conditions
explored.
explored.
100 100 100
100 100 100
(a)
(a) (b)
(b) (c)
(c)
90 90
%

90
90 90
Leachability//%

90

80 80 80
80 80 80
Leachability

70 70 70
70 70 70

60 60 60
60 60 60
W,55min
W, min Co,55min
Co, min W,55min
W, min Co,55min
Co, min W,55min
W, min Co,55min
Co, min
50 50 50
50 W,15
15min
min Co,15
15min
min 50 W,15
15min
min Co,15
15min
min 50 W,15
15min
min Co,15
15min
min
W, Co, W, Co, W, Co,
40 W,30
W, 30min
min Co,30
Co, 30min
min 40 W,30
W, 30min
min Co,30
Co, 30min
min 40 W,30
W, 30min
min Co,30
Co, 30min
min
40 40 40

0 0 0
0 0 0
0 0.1 1 10 60 0 0.1 1 10 60 0 0.1 1 10 60
0 0.1 1 10 60 0 0.1 1 10 60 0 0.1 1 10 60

Leaching time
Leaching time // min
min

Figure
Figure7.
Figure 7.Effect
7. Effectof
Effect ofmixing
of mixing ratio
mixing
(soft
ratio (soft
ratio
scrap:
(soft scrap: NaOH)
scrap: NaOH)
NaOH) andand grinding
and grinding duration
duration on
grinding duration
onthe
thedissolution
on the
dissolutionof
ofW
dissolution of
Wand
W and
and
Co via
Covia water-leaching:
viawater-leaching: (a)
water-leaching:(a) 1:0.3,
(a)1:0.3, (b)
1:0.3,(b) 1:0.4,
(b)1:0.4, and
1:0.4,and (c)
and(c) 1:0.5
(c)1:0.5 (pulp
1:0.5(pulp density:
(pulpdensity: 10
density:10 g/L,
10g/L, room
g/L,room temperature,
roomtemperature, stirring
temperature,stirring
stirring
Co
speed:
speed: 400
400 rpm).
rpm).
speed: 400 rpm).

InInsummary,
In summary,the
summary, theleaching
the leaching of
leaching of W
W increased
increased with
with increasing
with increasing NaOH
increasing NaOH
NaOHandand increasing
andincreasing grinding
increasinggrinding time,
grindingtime,
time,
and
and
andCoCo could
Cocould not
notnot
could easily
easily be extracted
be extracted
easily regardless
regardless
be extracted of
of theof
regardless the conditions
conditions of
of grinding
the conditions grinding or
or leaching
of grinding leaching
or that that
were that
leaching used.
were used.
were used.

4. Conclusions
4. Conclusions
We developed
We developed aa new
new process
process that
that involves
involves aa mechanochemical
mechanochemical (MC)
(MC) reaction
reaction which
which enables
enables the
the
recovery of tungsten with a high yield as well as the extraction of tungsten selectively from oxidized
recovery of tungsten with a high yield as well as the extraction of tungsten selectively from oxidized
soft scrap
soft scrap by
by using
using only
only water
water as
as aa leaching
leaching agent.
agent. Soft
Soft scrap
scrap was
was screened
screened with
with aa #500
#500 sieve,
sieve, then
then
Metals 2017, 7, 230 8 of 9

4. Conclusions
We developed a new process that involves a mechanochemical (MC) reaction which enables
the recovery of tungsten with a high yield as well as the extraction of tungsten selectively from
oxidized soft scrap by using only water as a leaching agent. Soft scrap was screened with a #500 sieve,
then subjected to oxidation, MC reaction, and water-leaching in turn to provide information and the
optimal conditions to achieve effective recycling.
The oxidation of the soft scrap proceeded at 550 ◦ C (for 1 h in air) to transform it into WO3 and
CoWO4 (according to TG and XRD analysis). It was essential for the scrap to be treated at 600 ◦ C to
eliminate unreacted WC.
Sodium tungsten oxide (Na2 WO4 ) was synthesized through a solid-state MC reaction between
oxidized scrap and NaOH with grinding under atmospheric conditions. The MC reaction proceeded
as grinding progressed and was bolstered by the addition of NaOH. With increasing NaOH, Na2 CO3
and Na2 WO4 were synthesized after only 10 min of grinding. This progression had a critical effect on
the subsequent room temperature water-leaching step.
The leachability of W in the ground mixture increased as the ratio of NaOH increased during the
MC treatment. Consequently, 99.2% of W was extracted from the ground mixture of oxidized scrap by
water-leaching for 60 min with a mixing ratio of 1:0.5 (scrap: NaOH), while the extraction of Co was
limited to 3.57% under the same conditions.

Acknowledgments: This study was supported by the R&D Center for Valuable Recycling (Global-Top R&BD
Program) of the Ministry of Environment (Project No. 2016002230002). This work was also supported by Korea
Energy and Mineral Resources Engineering Program funded by the Ministry of Trade, Industry and Energy.
Author Contributions: Jaeryeong Lee and Suyun Kim conceived and designed the experiments; Suyun Kim and
Byoungjin Kim performed the mechanochemical reaction experiments and analyzed the ICP, TG-DTA, and XRD
data; Jaeryeong Lee wrote the paper and modified the paper; all authors contributed equally to the discussion.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Penrice, T.W. Alternative binders for hard metals. J. Mater. Shap. Technol. 1987, 5, 35–39. [CrossRef]
2. Ogwu, A.A.; Davies, T.J. Proposed selection rules for suitable binders in cemented hard metals with possible
applications for improving ductility in intermetallics. J. Mater. Sci. 1992, 27, 5382–5388. [CrossRef]
3. Paul, R.L.; Te Riele, W.A.M.; Nicol, M.J. A novel process for recycling tungsten carbide scrap. Int. J.
Miner. Process. 1985, 15, 41–56. [CrossRef]
4. Grzesik, W. Advanced Machining Processes of Metallic Materials: Theory, Modelling and Applications, 1st ed.;
Elsevier: Oxford, UK, 2008.
5. Prakash, L.J. Application of fine grained tungsten carbide based cemented carbides. Int. J. Refract. Met. Hard
Mater. 1995, 13, 257–264. [CrossRef]
6. Lee, D.J.; Yoo, C.S. Predicting a promising fusion technology in geoscience and mineral resources engineering
using Korean patent data. Geosyst. Eng. 2014, 17, 34–42. [CrossRef]
7. Nakamura, T. E-Scrap recycling system and technologies in Japan. Geosyst. Eng. 2014, 17, 104–112. [CrossRef]
8. Shibata, J.; Murayama, N.; Niinae, M. Recovery of tungsten and cobalt from tungsten carbide tool waste by
hydrometallurgical method. Geosyst. Eng. 2014, 17, 120–124. [CrossRef]
9. Han, K.N.; Kellar, J.J.; Cross, W.M.; Safarzadeh, S. Opportunities and challenges for treating rare-earth
elements. Geosyst. Eng. 2014, 17, 178–194. [CrossRef]
10. Kim, J.R.; Song, Y.E.; Munussami, G.; Kim, C.M.; Jeon, B.H. Recent applications of bio electrochemical
system for useful resource recovery: Retrieval of nutrient and metal from wastewater. Geosyst. Eng. 2015, 18,
173–180. [CrossRef]
11. Lee, J.R.; Lee, J.W.; Kim, B.J.; Kim, Y.J. Leaching behavior of Al, Co and W from the Al-alloying treated
WC-Co tool as a new recycling process for WC hard scrap. Metals 2016, 6, 174. [CrossRef]
12. Walraedt, J. The coldstream process: A new powder production equipment. Powder Metall. Int. 1970, 3, 24–27.
Metals 2017, 7, 230 9 of 9

13. Barnard, P.G.; Heine, K. Reclamation of Refractory Carbides from Carbide Materials. U.S. Patent 3,595,484,
27 July 1971.
14. Edward, M.T. Process of Separating Hard Constituents from Sintered Hard Metals. U.S. Patent 2,407,752,
17 September 1946.
15. Kojima, T.; Shimizu, T.; Sasai, R.; Itoh, H. Recycling process of WC-Co cermets by hydrothermal treatment.
J. Mater. Sci. 2005, 40, 5167–5172. [CrossRef]
16. Malyshev, V.V.; Gab, A.I. Resource-saving methods for recycling waste tungsten carbide-cobalt cermets and
extraction of tungsten from tungsten concentrates. Theor. Found. Chem. Eng. 2007, 41, 436–441. [CrossRef]
17. Ghandehari, M.H.; Faulkner, J.K.; Schussler, M. Selective dissolution of the binder phase alloy (Co-W) from
WC-Co cemented carbides in particulate bed electrode systems. J. Electrochem. Soc. 1982, 129, 2666–2668.
[CrossRef]
18. Brookes, K.J.A. Reclaimed tungsten powders with ‘virgin’ properties. Met. Powder Rep. 1990, 45, 131–132.
[CrossRef]
19. Venkateswaran, S.; Schubert, W.D.; Lux, B.; Ostermann, M.; Kieffer, B. W-scrap recycling by the melt bath
technique. Int. J. Refract. Met. Hard Mater. 1996, 14, 263–270. [CrossRef]
20. Gu, W.H.; Jeong, Y.S.; Kim, K.M.; Kim, J.C.; Son, S.H.; Kim, S.J. Thermal oxidation behavior of WC-Co hard
metal machining tool tip scraps. J. Mater. Process. Technol. 2012, 212, 1250–1256. [CrossRef]

© 2017 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/).