Journal of Cleaner Production 232 (2019) 1251e1256

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Recovery of high-grade copper from waste printed circuit boards by

mechanical-grinding assisted flotation
Xiang-nan Zhu a, *, Chun-chen Nie a, Hao Zhang a, Xian-jun Lyu a, You-jun Tao b, Jun Qiu a,
Lin Li a, Guang-wen Zhang b
a
College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao, Shandong, 266590, China
b
School of Chemical Engineering and Technology, China University of Mining & Technology, Xuzhou, Jiangsu, 221116, China

a r t i c l e i n f o a b s t r a c t

Article history: Mechanical grinding combined flotation technology with renewable collector has been proposed to
Received 24 January 2019 recover high-grade copper from waste printed circuit boards (WPCBs). Surface morphology and element
Received in revised form distribution of copper particle section were analyzed using scanning electron microscopy and energy
4 June 2019
dispersive spectrometry (SEM þ EDS) technology. Results show that the copper particle is covered with a
Accepted 6 June 2019
Available online 6 June 2019
layer of micrometer-scale organic matter. Thermogravimetric analysis demonstrates the organic layer
commonly existed on all of the particle surfaces, which prove that the pyrolysis method was not feasible
for selectively removing the organic impurity. Mechanical grinding pretreatment was proposed to peel
Keywords:
Waste printed circuit boards
off the organic layer. Grinding experiment results show that impurity can be effectively separated from
Grinding pretreatment copper. Soap collector prepared from waste oil was used for flotation. The flotation results show that the
Pyrolysis characteristics copper grade of the concentrate first increased and then decreased with the increase of the grinding
Flotation time, while the recovery gradually decreased from 78.7% to 21.7%. Concentrate with 79.1% copper grade
Cleaner recovery and 71.5% recovery was obtained when the grinding time was 3 min. This study provides a physical
High-grade copper approach to recover high-grade copper from WPCBs.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction
The output of electronic waste has reached 41.8 Mt per year. In
Europe, the per capita e-waste is approximately 20.4 kg/person/
year, compared with 22.3 kg/person and 4.4 kg/person in the
United States and China, respectively (Isildar et al., 2019). Printed
circuit boards (PCBs) account for 4% of the electronic waste, which
are rich in gold, silver, copper and other metal elements (Li et al.,
2018). In previous studies, many innovative methods have been
proposed for the classification and utilization of different compo-
nents in waste WPCBs (Abdelbasir et al., 2018).
The reuse of organic and metal resources in WPCBs is of
increasing concern. Organic matter in WPCBs is usually effectively
utilized by pyrolysis. Bromine immobilization can be enhanced by
the co-pyrolysis of non-metallic components in WPCBs and red
mud (Chen et al., 2018). Microwave-assisted pyrolysis technology
was utilized to produce phenolics (Suriapparao et al., 2018). WPCBs
* Corresponding author.
E-mail address: zhuxiangnan1989@163.com (X.-n. Zhu).
were used to produce pyrolysis oil at 600  C and to synthetize oil-
based resins by pyrolysis. In addition, debromination pyrolysis
technology was reported to decompose the non-metallic compo-
nents in WPCBs to produce resins, reinforcing materials and
recover calorific values (Gao et al., 2019). Meanwhile, more atten-
tion has been paid to the resource utilization of metals in WPCBs.
Thermal transformation method was reported to synthetize
CueNieSn, CueSn base on the copper contained in WPCBs (Ulman
et al., 2018). High-value lead oxide and tin oxide particles was
prepared from WPCBs with sizes of 1 mm and 7 nm, respectively
(Tatariants et al., 2018). A slurry electrolysis technology, including
leaching and electrowinning methods, was proposed by Yang to
separate the metals and nonmetals in WPCBs, and the copper grade
of the concentrate reached 86.6% (Yang et al., 2018). The study re-
sults of Arshadi show that metals, such as copper and silver, are
mainly concentrated in particle with size less than 1 mm in
crushing products, and the plastic content of different WPCBs is
between 42% and 67% (Arshadi et al., 2018). Cyanide-based leaching
was always used for leaching precious metals such as gold and
silver (Ata et al., 2015). In addition, hydrometallurgical treatment
was also used for the recovery of metals component (Tuncuk et al.,

https://doi.org/10.1016/j.jclepro.2019.06.063
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
1252 X.-n. Zhu et al. / Journal of Cleaner Production 232 (2019) 1251e1256

2012).
Physical separation is also an alternative approaches for sepa-
rating electronic waste, including gravity separation and flotation
technology. The difference in the physicochemical properties of the
various components of the dissociation products of WPCBs can be
utilized for the separation of the metal and non-metal. These can be
magnetic, electrical, density, and hydrophobic differences (Zhang
et al., 2017). Gravity separation technology, including fluidized
bed and enhanced gravity separator, have been used for the puri-
fication of electronic waste (Zhang et al., 2018a; Zhu et al., 2018).
The dissociation of metal components and impurities can be ach-
ieved by applying shear force and impact force. Conventional
dissociation methods can usually break materials up to -1mm
(Duan et al., 2009). However, a deep dissociation method needs to
be explored. Moreover, finer granularity is helpful to dissociation,
but it will bring challenges to subsequent sorting (Xue and Xu,
2013). Therefore, the products of deep dissociation need to be
adapted to more efficient sorting methods, which is the focus of
this study.
Flotation is an effective method for separating fine coal (Lyu
et al., 2018; You et al., 2019) and minerals (Liu et al., 2018). Nano-
bubbles are used to improve flotation efficiency (Calgaroto et al.,
2015; Etchepare et al., 2017). The feasibility of using flotation in
the separation of electronic waste has also been proven (Zhu et al.,
2019a). Separation of LiCoO2 and graphite from spent lithium-ion
batteries was realized using flotation assisted by pyrolysis, with a
93% LiCoO2 grade (Zhang et al., 2018b). The flotation approach was
also used to separate indium tin oxide from waste LCD screen
(Wang et al., 2018). Flores-Campos discussed the effect of inverse
flotation on separation efficiency of nonmetallic fraction from
WPCBs, and showed that methyl isobutyl carbinol could enhance
the process (Florescampos et al., 2017). He et al. (2015) also utilized
reverse floatation with kerosene as the collector to recover metal
from WPCBs, and the metal grade reached 16.86% with a recovery
of 94.69% for 0.125e0.25 mm (He et al., 2015). In previous studies,
only medium-grade concentrates can be obtained by physical
separation. It is necessary to propose a technical scheme for
recovering high-grade copper. However, the morphology of organic
layer on the surface of copper particles has not been analyzed,
especially its pyrolysis characteristics.
In this study, 1-0.5 mm fraction with 30% copper content of the
dissociation products of WPCBs was used as experimental object. In
order to produce a higher-grade copper concentrate, mechanical
grinding combined flotation technology with renewable collector
was proposed. The surface morphology and element composition
of copper particles were analyzed using scanning electron micro-
scopy and energy dispersive spectrometry (SEM þ EDS), and the
pyrolysis characteristics of different components were detected by
thermogravimetric analysis. In order to make the flotation process
cleaner, renewable collectors prepared from waste oils in kitchen
waste were used in flotation experiments. An approach of recov-
ering high-grade copper from WPCBs by physical separation tech-
nology has been validated in this paper.
2. Materials and methods
with gold to improve its conductivity, and the detection was carried
out at high vacuum with room temperature.
2.2. Pyrolysis characteristics of different components in WPCBs
The pyrolysis characteristics of different components in libera-
tion products of WPCBs were analyzed, namely organic particle
(low density), glass fiber (middle density) and metal particles (high
density). The different components were obtained by density sep-
aration method. That is, the raw materials were added to organic
liquids of different densities successively, and the three densities of
particles were obtained. In addition, the thermogravimetric char-
acteristics of raw materials (mixture of three particles) were also
analyzed. The four samples were ground to 0.045 mm, and then
thermogravimetric analyzer (Mettler TGA 2, Mettler-Toledo,
Switzerland) was utilized to detect pyrolysis characteristics. The
temperature detection range was set to 30e950  C and the heating
rate was 10  C/min.
2.3. Grinding experiment
The feasibility of removing organic impurities by grinding was
verified. A dry method with vibration mill was used in this exper-
iment, where materials were crushed by extrusion and grinding
forces. Each feed was 20 g and grinding time was set to 1, 2, 3, 4, and
5 min. The particle size distribution of the ground products was
determined using a laser particle size analyzer with the standard
procedure. Alcohol was added before size distribution testing to
improve the dispersion of the particle groups. The grinding process
is shown in Fig. 1.
2.4. Flotation test
The ground products were separated by flotation, and the col-
lector used was soap collector prepared from waste oil by saponi-
fication reaction (Zhu et al., 2019b). In this test, a lab-used single
XFDIV (0.5 L) flotation machine was utilized. The key parameters
were set as follows: the spindle speed was 1920 r/min, and the air
flow rate was 0.15 m3/h. The sample mass in each experiment was
30 g. The dosage of collector was 1000 g/t. The water temperature
was controlled at 35  C to ensure adequate dissolution of the col-
lector. After separation, the concentrate (sink product) and tailings
(floated product) were collected, dried and crushed respectively.
The elemental composition of the particles was analyzed using an
X-ray fluorescence spectrometer (XRF, Axios, Panalytical,
Netherlands).
3. Results and discussion
3.1. Surface properties analysis of copper particles
Elemental analysis (point A and point B) of the cross section of
copper particles is shown in Fig. 2. The surface morphology and
elemental analysis of the copper particles, including both the

2.1. Materials

The WPCBs was crushed by hammer crusher and shear crusher.

Crushing products were screened, and 1e0.5 mm with copper
content of 30% was used for testing. The surface morphology and
element distribution of valuable recoverable components, namely
copper particles, were analyzed by scanning electron microscopy
(SEM, FEI, APREO, USA) and energy dispersive spectrometry (EDS,
XFlash, Bruker, Germany). The surface of the sample was sprayed Fig. 1. Grinding process of WPCBs by vibrating millstone.
X.-n. Zhu et al. / Journal of Cleaner Production 232 (2019) 1251e1256 1253

Fig. 2. SEM and EDS analysis of cross section of copper particle.

1254 X.-n. Zhu et al. / Journal of Cleaner Production 232 (2019) 1251e1256
Fig. 3. Element distribution and morphology of the copper surface.
positive and the reverse side, are shown in Fig. 3. Copper particle in
the detection was obtained by density separation.
Fig. 2 shows the cross section of copper particles. Elemental
analysis conducted by EDS shows that point A is high purity copper,
while region B is impurity rich in elements such as silicon,
aluminum and calcium. Fig. 2 can also clearly show that copper is
closely associated with impurities, and the thickness of copper is in
the micron level, while the thickness of impurities is larger than
that of copper sheets, which is related to the degree of dissociation.
(a) TG curves
(b) DTG curves
Fig. 4. Thermogravimetric analysis of the materials in WPCBs.
Fig. 3 shows two particles images, D represent the reverse side
of the copper particle, and E represents the positive side. It can be
clearly observed that the front of the particles is smooth, while the
reverse is rough. The results of the elemental analysis show that the
positive side of the particles is mainly enriched with copper, while
the reverse side is rich in carbon and silicon, which is mainly due to
insufficient dissociation.
3.2. Pyrolysis characteristics analysis of particles
Pyrolysis characteristics of raw materials, organic particle, glass
fibre particles, and copper particles are shown in Fig. 4.
Fig. 4 (a) shows the mass decreases with an increase in tem-
perature. The weight losses of the four kinds of particles are
significantly different, that is, the weight loss decreasing with an
increase in density. When the temperature is 300  C, the weight of
the organic particle decreases 100%e88.34% of the initial value, and
the other three particles change slightly. Further, mass loss mainly
occurred in 300e400  C, with the masses of the organic particle
decreasing from 88.34% to 50.78%, glass fibre particles decreasing
from 98.65% to 76.28%, and copper particles only decreasing to
86.78%. When the temperature is higher than 400  C, the mass of
glass fibre particles and copper particles are basically stable, with
masses of 74.33% and 84.25%, respectively. Meanwhile, the mass of
the organic particle is reduced to 28.77%. It can be seen that the four
particles have the same initial weightlessness peak, i.-e., between
300  C and 400  C from Fig. 4 (b). This indicates that the organic
layer exists on the surface of all particles. It also shows that there
are two weightlessness peaks for the organic particles, and only one
for the other density particles.
Based on the thermogravimetric analysis, it can be inferred that
it is not feasible to remove the organic matter by pyrolysis because
of its widespread coverage, which is verified by the same weight-
lessness peaks at 320  C of all particles. Pyrolysis treatment will
lead to a significant reduction in the floatability of all the particles
and selectivity loss of the flotation process.
3.3. Particle size distribution of grinding products
Size distribution of grinding products with different grinding
time is shown in Fig. 5.
Fig. 5 illustrate that the particle size gradually decreases with an
increase in the grinding time, which is reflected in the gradual in-
crease in the slope of the fine-grained part. With an increase in the
Fig. 5. Size distribution of grinding products.
 X.-n. Zhu et al. / Journal of Cleaner Production 232 (2019) 1251e1256
Fig. 6. Surface morphology and element distribution of grinding products (3 min).
grinding time, the grinding fineness (particle content with less than
35 mm) yields are 59.49%, 68.38%, 75.89%, 93.41%, and 100%. In or-
der to analyze the dissociation of copper and impurities by
grinding, the morphology and element distribution of grinding
products were analyzed by SEM þ EDS. The results are shown in
Fig. 6.
The results of Fig. 6 show that after grinding treatment, impurity
and metal can be effectively liberated by comparing Figs. 2 and 3.
Therefore, ideal dissociation is realized. Mechanical grinding can
effectively remove organic matter from the surface of copper par-
ticles, which contributes to the subsequent upgrading of copper
concentrate grade.
3.4. Flotation experiments
Influence of grinding time on concentrate yield and recovery is
shown in Fig. 7. The yield is equal to the ratio of concentrate quality
to feed quality. The recovery rate is equal to the ratio of the total
amount of copper in concentrate (yield multiplied by grade) to the
total amount of copper in feed.
Fig. 7 shows that yield of concentrate decrease with the increase
of grinding time, decrease from 38.93% to 9.40% corresponding
with recovery decrease from 78.67% to 21.73%. When the grinding
time increases from 3 min to 4 min, the grinding fineness increases
from 75.89% to 93.41%, and the yield decreases sharply from 27.37%
Fig. 7. Effect of grinding time on concentrate yield and copper recovery.
1255
to 14.88%. This may be due to the entrainment of ultrafine particles.
With the increase of grinding time, excessive ultrafine particles are
produced. During the flotation process, ultrafine particles easily
enter into the floats product with the water flow, which leads to the
loss of metal. Although the long grinding time is favorable for
dissociation, it is not conducive to the flotation precision. Therefore,
suitable grinding time is necessary.
Fig. 8 shows that the copper grade of the concentrate first in-
creases and then decreases with an increase in the grinding time,
while the copper grade of the tailings increases. The copper grade
of concentrate increased from 61.1% to 79.06%, and then decreased
to 70.48%. The copper grade of the tailings increased from 10.56% to
26.35%. With increase in the grinding fineness, the dissociation of
organic matter gradually increased. However, the copper grade of
the tailings gradually increased, which indicates that the ultrafine
copper particles are lost in tailing. Although the increase of
grinding fineness contributes to the dissociation of copper particles
and impurities, the over-fine particles will reduce the accuracy of
flotation process, which is reflected in the improvement of tailings
grade. Therefore, suitable grinding fineness is necessary to achieve
the balance of concentrate grade and recovery. In this study, when
the grinding time is 3 min, the copper grade in concentrate reaches
79.06%, with recovery of 71.47%.
4. Conclusion
WPCBs are rich in valuable metals and have potential economic
value. In order to recover high-grade copper, the method of
grinding-assisted flotation has been proposed in this study, and
renewable collector prepared from waste oil has been applied in
flotation process.
The causes of the low grade of the concentrate, i.e., the
morphology and element distribution on the copper surface, were
analyzed by scanning electron microscopy and energy dispersive
spectrometry (SEM þ EDS). The results show that the copper par-
ticle surface is covered with a layer of organic matter, which leads
to an increase in the hydrophobicity of the copper particle and the
loss of copper in the tailings. The pyrolysis characteristics of
different components were tested by thermogravimetric analysis.
Results show that all particles exhibit significant weight loss peaks
near 320  C, which indicates that organic matter exists on the
surface of all particles. Thus, it is not feasible to selectively remove
the organic layer on the copper surface by pyrolysis.
Fig. 8. Effect of grinding time on copper grade in tailing and concentrate.
1256 X.-n. Zhu et al. / Journal of Cleaner Production 232 (2019) 1251e1256
The method of grinding assistance was proposed to realize the
dissociation of copper particles and impurities through mechanical
force. Subsequently, the flotation process of grinding products was
carried out to achieve copper recovery. The flotation results show
that the copper grade of concentrate first increase and then
decrease with an increase in the grinding time, increasing from
61.1% to 79.06% and then decreasing to 70.48%. The recovery
decreased from 78.67% to 21.73%. Copper concentrate with 79.06%
grade corresponding with 71.47% recovery can be obtained when
the grinding time is 3 min. It is established that grinding-assisted
flotation is an alternative approach to recover high-grade copper
from WPCBs.
Acknowledgement
This work was supported by Natural Science Foundation of
Shandong Province (ZR2019BEE055), supported by the Scientific
Research Foundation of Shandong University of Science and Tech-
nology for Recruited Talents (2017RCJJ035), National Natural Sci-
ence Foundation of China (Grant 51674161), and supported by
SDUST Research Fund (Grant No. 2018TDJH101).
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