Mineral Processing and Extractive Metallurgy

Transactions of the Institutions of Mining and Metallurgy: Section C

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Characterisation of copper slag in view of metal

recovery

X. Wang, D. Geysen, S. V. Padilla Tinoco, N. D'Hoker, T. Van Gerven & B.

Blanpain

To cite this article: X. Wang, D. Geysen, S. V. Padilla Tinoco, N. D'Hoker, T. Van Gerven & B.
Blanpain (2015) Characterisation of copper slag in view of metal recovery, Mineral Processing
and Extractive Metallurgy, 124:2, 83-87

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 Characterisation of copper slag in view
of metal recovery
X. Wang*1,2, D. Geysen1, S. V. Padilla Tinoco1, N. D’Hoker2, T. Van Gerven2 and
B. Blanpain1
In this study, the copper bearing particle of a fayalitic copper slag was assessed using
quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN) and X-ray
computed tomography (CT). The copper content of the slag was ,0?87 wt-%. Copper in this slag
was present as sulphidic droplets. The content and particle size distribution of the major sulphide
phases (bornite, chalcopyrite and chalcocite/digenite) were quantified using QEMSCAN. The
copper bearing particles had a wide particle size distribution from a few micrometres up to
millimetre level. Large copper bearing particles (.100 mm) were composed mainly of bornite and
chalcocite/digenite and tended to accumulate in the lower part of the slag layer. As characterised
Mineral Processing and Extractive Metallurgy 2015.124:83-87.

with CT, ,70% of the copper value was present in these large copper bearing particles.
Keywords: Copper slag, Characterisation, QEMSCAN, Copper sulphides, Particle size distribution, CT

Introduction non-destructive characterisation technology, which can

Metal slags generated from metallurgical processes are a
group of promising recyclable sources of metal. Each year,
a large amount of copper slag is produced worldwide.
Copper slag usually contains a certain quantity of valuable
metals, such as copper, nickel, cobalt and iron (Gorai et al.,
2003). Therefore, it can be treated as a secondary resource
for metal extraction rather than as a waste. Numerous
studies have been carried out on metal recovery from
copper slag using hydro- and/or pyrometallurgical
methods (Altundogan et al., 2004, Banza et al., 2002,
González et al., 2005, Das et al., 2010, Kucharski et al.,
2014, Yang et al., 2014, Heo et al., 2014).
Characterisation of feed material to determine the
expected concentrate grade and metal recovery is essential
for the design of separation flow sheets and achieving
sustainable development in the utilisation of resources
(Jan D. Miller et al., 2009). Extensive research has been
performed to characterise copper slags in view of metal
recovery through various techniques (Li et al., 2009, Das
et al., 2010, Cardona et al., 2011). For the sake of metal
recovery, the mineralogy and particle size of metal phases
are the key metallurgical parameters. Quantification of
minerals can be performed by quantitative evaluation of
minerals by scanning electron microscopy (QEMSCAN).
It is an automated image analysis system using back-
scattered electron (BSE) and energy dispersive X-ray
(EDX) signals from a scanning electron microscope
(SEM). QEMSCAN has been widely applied in the study of
mineral properties (Pascoe et al., 2007, Liu et al., 2005,
Matjie et al., 2011). X-ray computed tomography (CT) is a
1
Department of Metallurgy and Materials Engineering, KU Leuven,
Leuven, Belgium
2
Department of Chemical Engineering, KU Leuven, Leuven, Belgium
*Corresponding author, email xuan.wang@cit.kuleuven.be
provide direct volumetric data acquisition and quantitative
analysis in three dimensions (3D) with a reasonably short
analysis time and limited sample preparation
(Jan D. Miller and Lin, 2004). CT scanning has been
applied to characterise different properties of rocks and
ores (J. D. Miller et al., 2003, Remeysen, 2006, Ghorbani
et al., 2011). CT scanning and QEMSCAN are powerful
characterisation tools that have not yet been applied in the
study of copper slag. In this work, the species and distri-
bution of copper bearing phases were characterised
through QEMSCAN. In addition, the distribution of
copper bearing grains was studied through CT scanning.
Once the mineralogy and distribution of copper bearing
particles are understood, the suitable slag processing
techniques and conditions can be designed in view of
copper recovery.
Experimental
The copper slag was generated by the El Teniente pro-
cess and cooled in the ambient air. It was received as
fragments with a size from *100 mm up to 7 cm.
In preparation of chemical and mineralogical analysis,
the slag was crushed down to 5–10 mm with a jaw
crusher. Further milling was performed with a tungsten
carbide ring mill and a McCrone micronising mill down
to v10 mm. The overall chemical composition of the
slag was determined with X-ray fluorescence (XRF,
Philips PW 2400) and inductively coupled plasma mass
spectroscopy (ICP-MS, Thermo Elemental type X
Series). The mineralogical composition of the slag was
characterised with X-ray diffraction (XRD, Siemens
D500). The quantification of phases was carried out with
Rietveld refinement (Mertens, 2009). The microstructure
of the slag was characterised with SEM (Philips XL30
FEG, coupled with EDX detector).

Ñ 2015 Institute of Materials, Minerals and Mining and The AusIMM

Published by Maney on behalf of the Institute and The AusIMM
Received 22 May 2014; accepted 21 March 2015 Mineral Processing and Extractive
DOI 10.1179/1743285515Y.0000000004 Metallurgy (Trans. Inst. Min. Metall. C) 2015 VOL 124 NO 2 83
 Wang et al. Copper slag in view of metal recovery
The distribution and portion of copper bearing phases
were obtained through QEMSCAN. The distribution of
copper sulphide particles in the horizontal direction of a
slag layer is rather homogenous and can therefore be
considered to be randomly dispersed. A piece of slag,
representing the structure of the whole slag layer, was
cut through the vertical direction of the slag layer. The
cross-section was then polished and coated with carbon
for QEMSCAN measurement. The scanning area
was *5|50 mm, and the resolution was 1 mm2 per pixel
for a total measurement time of *2 h. In total,
14 064 copper sulphide particles were analysed. The
detection limit in this scan is generally 1–3 wt-%. The
two-dimensional (2D) particle size distribution obtained
by QEMSCAN was transferred into a 3D particle size
through the stereological programme CSDCorrections
1?40 (Higgins, 2000). The distribution of copper bearing
particles inside the identical slag piece applied in
QEMSCAN scanning was characterised with
CT (GE Nanotom). The sample, a cylinder with 5 mm
diameter and length of 5 cm, was prepared for
CT scanning by cutting through the vertical direction of
the slag layer (*5 cm thick). Nine sections (each
Mineral Processing and Extractive Metallurgy 2015.124:83-87.
*5 mm in length) were scanned from the top to the
bottom of the cylinder. Voxel size of 2|2|2 mm3 was
acquired, and 830 024 copper bearing particles were
analysed in total. The scanning images were reconstructed
with phoenix datos|x (GE Measurement & Control)
and analysed through CT-Analyser (SkyScan). As most
of the copper bearing particles are in a droplet form,
it is a reasonable assumption that the shape of copper
bearing particles will be spherical. With this assumption,
the relevant particle size (diameter) of individual
particles can be calculated from the volume results.
Results and discussion
Morphology
The cross-sections representing the internal structure are
shown in Fig. 1. Large copper sulphide particles (shiny
droplets) as well as pores and cracks could be observed.
The size of the copper sulphide particles in the slag
varied from a few micrometres (observed by SEM) up to
the millimetre level. The majority of the large copper
1 Cross-section of fragmented slag
84 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
sulphide particles were located in the lower part of the
slag layer. This may be due to the long solidification time
of the thick slag layer, which allowed the sedimentation
and accumulation of copper sulphide particles in the
lower part of the slag layer, while the upper part of the
slag layer was more quickly cooled by air.
Chemical composition
The chemical composition of the slag is presented in
Table 1. The most abundant elements in the slag were
iron (*42 wt-%) and silicon (*14 wt-%). This was in
line with the fayalitic nature of the copper slag. The
concentration of copper was close to 0?9 wt-%,
which is higher than that of certain copper ores
(Davenport et al., 2002).
Mineralogical composition
The XRD pattern of the copper slag is shown in Fig. 2.
The calculated quantitative XRD results are listed in
Table 2.
Fayalite was the major crystalline mineral present in
the slag taking up to 52 wt-% of the system. Besides
fayalite, 13 wt-% magnetite was present due to the
overoxidation of iron oxide (Jalkanen et al., 2003). The
large amorphous phase content (35 wt-%) suggested that
the slag had undergone a relatively fast cooling process
and/or had relatively high silica content.
Figure 3 shows the microstructure of the slag. Faya-
lite, magnetite (spinel), copper sulphides and glassy
phase could be distinguished. The copper sulphide
phases existed as spherical particles with diverse particle
sizes (from a few micrometres to several hundred
micrometres). All the copper bearing phases observed
were sulphides, having an overall Cu–Fe–S composition.
However, the Cu–Fe–S stoichiometry varied among the
copper bearing particles. No metallic copper was
observed in the slag.
As shown in Fig. 3, different crystal shapes could be
observed within the same slag fragment, which may be
caused by the change in cooling rate at different
positions. In the part close to the top of the slag layer
(Fig. 3b), the liquid slag was in direct contact with the
air. As a result, the cooling rate in this part was higher.
Skeletal/dendritic fayalite crystals coexisted with fine
magnetite, and copper sulphide particles could form
during the solidification. The solidified slag might act as
an insulator and slow down the cooling of the middle
and bottom part of the slag layer (Fig. 3a) (Pandelaers,
2011). Hence, the slag in these parts could develop into
larger grains.
Mineral phase distribution
Detailed study of the distribution of copper bearing
phases was carried out using a QEMSCAN system.
As shown in Table 3, bornite was the most abundant
copper sulphide phase, followed by chalcopyrite and
chalcocite/digenite. Trace concentrations of idaite
(Cu5FeS6) were also found.
2D grain size analysis was performed to determine the
size distribution of the various copper bearing grains.
Figure 4 was compiled from data obtained across the
entire scanned surface of the sample (5 mm|45 mm).
Only bornite and chalcocite/digenite occurred in grain
sizes of w20 mm, while chalcopyrite only appeared in
grain sizes v20 mm. Chalcocite/digenite had a roughly
2015 VOL 124 NO 2
 Wang et al. Copper slag in view of metal recovery

Table 1 Chemical composition of copper slag

Major element Concentration/wt-% Standard deviation Trace element Concentration/ppm Standard deviation

Al 1.5 ,0.1 As 238 1

Cu 0.87 0.02 Ba 116 4
Fe 42 3 Ca 480 80
K 0.88 0.01 Cl* 600 300
Mg 0.56 ,0.01 Co 160 10
Na 0.28 0.02 Cr 71 2
Mo 0.12 ,0.01 Mn 162 5
S* 0.43 ,0.01 Sr 76 ,1
Si* 13.6 0.3 Ni 45 6
Ti 0.37 ,0.01 Pb 340 20
Zn 0.20 ,0.01 Sb 254 7
O{ 39 n.a. Sr 76 ,1
V 55 4
W 93 6

* XRF data.
{ Calculated based on the listed data; all others by ICP-MS.
The standard deviation was calculated with three replicates. n.a., not analysed.
Mineral Processing and Extractive Metallurgy 2015.124:83-87.

2 XRD pattern of copper slag: F, fayalite; S, spinel (magnetite); Z, zincite (internal standard)

Table 2 Quantitative XRD results of slag sample

Mineral Chemical formula Concentration/wt-%
Fayalite Fe2SiO4 52
Magnetite Fe3O4 13
Glassy phase 35
bimodal size distribution, with a significant percentage
of grains in size ranges w40 mm.
However, the grain size here only refers to the size of
the individual copper sulphide mineral grain. The copper
bearing particles, especially large particles (w100 mm),
were aggregates of various copper sulphides in most
cases. Hence, a copper bearing particle could be several
times larger than a copper sulphide grain. Chalcocite/
digenite and bornite were the major components of large
copper bearing particles and were, therefore, potentially
easier to be liberated. Chalcopyrite, on the other hand,
was randomly distributed in the slag samples as fine
grains. Figure 5 demonstrates a typical aggregate copper
bearing particle with complex texture.
Particle size distribution
The particle size distribution of copper bearing particles,
in the identical slag piece applied in QEMSCAN
characterization, was studied through CT scanning.
The volume of copper bearing particles in nine sections,
from top to bottom, is illustrated in Fig. 6, where
the ‘top’ means the surface of the slag layer and the
‘bottom’ means the base of the slag layer. As can be
observed, *60 vol.-% of copper bearing particles accu-
mulated in the lower (depth w50%) part of the slag
layer. The section near the bottom (depth between 80
and 90%), illustrated as point B in Fig. 6, contained
w25 vol.-% of the copper sulphides, while the part close
to the top (depth between 20 and 30%), illustrated as
point A in the figure, contained only *8 vol.-% of the
copper sulphides. As can be concluded, large particles
tended to accumulate in the lower part of the slag layer.
Comparison of QEMSCAN and CT data
The cumulative copper sulphide volume distributions
versus particle size of the whole cross-section, obtained
through different methods, are plotted in Fig. 7. In the 3D
data obtained through CT scanning, *70% of the total
copper sulphides appeared in particles with sizes w100 mm.
Extra-large copper sulphide particles (w300 mm) could
also be observed. The data directly obtained from QEM-
SCAN, which is a 2D means, show different results. In this
case, only *32% of the copper sulphides appeared in
particles with size w100 mm and no extra-large particle
could be observed. After 3D transformation of QEM-
SCAN data, the obtained curve (with triangle dots) fits the

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2015 VOL 124 NO 2 85
 Wang et al. Copper slag in view of metal recovery

3 SEM-BSE image of copper slag: F, fayalite; S, magnetite (spinel); G, glass; C, copper sulphides; P, pores (Wang et al., 2011)

Table 3 Volume abundance of copper bearing phases in

slag

Abundance/
Mineral Processing and Extractive Metallurgy 2015.124:83-87.

Mineral Chemical formula vol.-%

Bornite Cu5FeS4 0.23

Chalcocite/digenite Cu2S/Cu9S5 0.14
Chalcopyrite CuFeS2 0.27
Idaite Cu5FeS6 0.01
Copper bearing 0.65
phases in total
Other phases in slag 99.35 5 Large aggregate copper bearing particle composed of
various copper sulphides

6 Copper sulphide volume distribution along depth of slag

layer: (A) section near top of slag layer; (B) section near
bottom of slag layer

4 Copper sulphide grain size distribution (2D)
CT scanning curve relatively well v200 mm. However, the
curve deviates from the CT scanning data in the larger
particle size range (w200 mm). This deviation may be due
to the ‘section size’ nature of the QEMSCAN data. Large
particles have a larger diameter, and therefore a greater
probability of intersection with the sample plane (Peterson,
1996). The particle sizes deduced from other intersection
planes are not an accurate representation of the true par-
ticle size as they tend to be smaller, even after stereological
transformation. Hence, compared to the data from
CT scanning, QEMSCAN data, in this case, under-
estimated the volume and size of the large copper bearing
particles. Relative accurate size distribution could only be
obtained through calculations based on numerous 2D
intersection scans, which require enormous time and
sample reparation steps, while 3D scanning can provide the
accurate particle size distribution of the sample through
only one scan.
The integration of QEMSCAN and CT scanning can
provide the mineralogy and particle size distribution
respectively, which are crucial metallurgical factors for
the recovery of copper from slag. The optimum grinding
size should be set according to the size distribution of the

86 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2015 VOL 124 NO 2

7 Cumulative copper sulphide volume versus copper
bearing particle size plotted with CT scanning and QEM-
SCAN data before (2D) and after (3D) transformation
copper bearing particles to achieve high liberation of
Mineral Processing and Extractive Metallurgy 2015.124:83-87.
copper sulphide minerals. The following processing con-
ditions, such as flotation reagents, should be selected
based on the mineralogy of the copper sulphides.
Conclusion
The fayalitic copper slag studied in this work contained
0?87 wt-% Cu. This indicated the potential to recover
copper from this slag. QEMSCAN and CT scanning
could provide the mineralogy and particle size distri-
bution respectively, which are crucial for the design of
the following metal recovery processes. According to
study performed with QEMSCAN, copper pre-
dominantly existed in the form of bornite, chalcocite and
chalcopyrite. Large copper bearing particles were
aggregates of various copper sulphides, mainly bornite
and chalcocite. Based on the observations, the
distribution of copper sulphide phases was random in
the horizontal direction of the slag layer but inhomo-
geneous in the vertical direction of the slag layer. Large
copper sulphide particles tended to settle down during
solidification. The grain size of copper bearing particles
and its distribution are important parameters for the
selection of appropriate beneficiation techniques. Based
on the analysis performed through CT scanning, most of
the copper value existed in the copper sulphide
particles w100 mm. The integration of QEMSCAN and
CT scanning can provide the mineralogy and particle
size distribution respectively, which are crucial
metallurgical factors for the recovery of copper from
slag, as well as other metal containing residues.
Acknowledgements
We are grateful to Mr Matthew D. Dye and
Dr Katharina Pfaff for the QEMSCAN analysis
performed in Colorado School of Mines, and Dr Greet
Kerckhofs and the Materials Performance and
Non-destructive Testing research group (MTM,
K.U.Leuven) for providing the CT scanning device and
training. Financial and material support from Group
Machiels is also acknowledged.
Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)
Wang et al. Copper slag in view of metal recovery
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