Recovery of metal values from copper

slags by flotation and roasting with pyrite

G. Bulut, K.T. Perek, A. Gl, F. Arslan and G. nal

Assistant professor, research assistant, assistant professor, professor and professor, respectively, Mining
Engineering Department, Mineral and Coal Processing Division, Istanbul Technical University, Istanbul, Turkey

Abstract

The recovery of copper and cobalt from ancient copper slags from the Kre region of Turkey was investigated.
A fayalitic-type of ancient copper slag containing 1.24% Cu, 0.53% Co and 53.16% Fe were subjected to an
experimental study. Two different routes were followed to recover the metal values. The first route was roasting
the slag with pyrite followed by leaching. The second route was flotation of the slags, roasting of the flotation
tailings with pyrite and leaching. The second route was found to be suitable for the treatment of the copper slag
studied. In the flotation step, a copper concentrate containing approximately 11% Cu was produced with a 77%
recovery while 93% of the cobalt stayed in the tailings. In the roasting experiments, the effects of roasting time,
pyrite:slag ratio and roasting temperature on the dissolution efficiencies of Cu and Co were investigated, and the
optimum conditions were determined. In the tests, 87% of the cobalt dissolution was observed after one hour of
roasting at 500C with a pyrite:slag ratio of 3:1. The copper dissolution in the tests was 31%. Based on the results
of this study, a process flowsheet is proposed for the evaluation of these slags.
Keywords: Copper slag, Cobalt, Flotation, Roasting

Introduction

Various slags are produced as byproducts in metallurgical

processes or as residues in incineration processes. Slags
usually contain a quantity of valuable metals, and such
slags can actually be a secondary resource of metals rather
than an end waste. They have been applied as a resource
material in many areas. In addition, for some applications,
slags have comparable or even better properties than their
competitive materials.
There are a variety of nonferrous slags produced from
nonferrous smelters. Extensive studies on metal recovery
from nonferrous slags have been carried out over the
last several decades. Most of the studies were on metal
recoveries from copper slags. The chemical compositions
of copper slags from different origins are quite different
depending on factors such as the type of ores processed,
the type of furnaces used and the cooling methods. When
copper slag is crystalline, the major phases are usually
fayalite along with other silicates. In most cases Ni and
Co are in the form of oxides. Some studies show that Co
distribution in the slags is very homogeneous. However,
the forms of Cu minerals are different in different copper
slags. They may be in the form of oxides or sulfides or a
mixture of them. Copper sulfide minerals are also different
in different copper slags.

A number of methods for metal recovery from copper

slag are briefly reviewed (Ycel et al., 1992; Bipra and
Jana, 2003; Shen and Forssberg, 2003). Basically, they
can be classified into the following three categories:
flotation, leaching and roasting. In principle, copper slag
flotation is the same as sulfide ore flotation (Osborn et
al., 1986; Giray et al., 1996; Arslan et al., 2002; Sarrafi
et al., 2003; Bruckard et al. 2004). This means that only
metallic Cu and sulfide minerals can be floated effectively.
Because in some slags Cu occurs in the oxide form (Co is
in homogenous distribution) and is disseminated in small
amounts in the slag matrix, the application of flotation to
copper slag processing could be limited, and the flotation
method will not be effective for the recovery of Co, Ni
and oxide Cu. In spite of some positive attributes of hydroxametes, which are known as collectors for nonsulfide
minerals (Lee et al., 1998), they may not be efficient in
the flotation of oxide copper in the ores and slags.
Leaching is another method for the extraction of metals from copper slags. Leaching with nitric, perchloric,
hydrochloric and sulfuric acids; ferric chloride; ferric
sulfate; cyanide; SO2; and ammonia solutions and the use
of pressure leaching were among the hydrometallurgical
processes studied (Herreros, et al., 1998; Banza et al.,
2002). The combination of the pyrometallurgical process

Paper number MMP-06-016. Original manuscript submitted online February 2006. Revised manuscript accepted for publication June 2006. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications
Dept. prior to Aug. 31, 2007. Copyright 2007, Society for Mining, Metallurgy, and Exploration, Inc.

MINERALS & METALLURGICAL PROCESSING

013-018MMP06-016Bulut.indd 13

13

Vol. 24, No. 1 February 2007

1/9/07 4:11:31 PM

The second route was flotation of the slag followed by roasting of the flotation tailings with pyrite. The pyrite used in
the roasting experiments contained 0.22% Cu, 0.034% Co
and 44.73% Fe and was in the size range of -0.1 mm. In the
pyrite roasting tests with slag, the effects of roasting time,
the pyrite:slag ratio and the roasting temperature on the dissolution efficiencies of copper and cobalt were investigated.
The pyrite roasting was followed by hot water or diluted acid
leaching and filtration.
The roasting experiments with pyrite were carried out as
follows: the slag/pyrite mixtures were placed in a porcelain
dish and roasted in a muffle furnace preheated to the required
temperature. After the samples were cooled to room temperature, leaching was carried out at the following conditions: 300
mL water, 70C, a stirring speed of 450 rpm and a leaching
time of one hour.
In the diluted acid leaching experiments, the effect of acid
concentration was investigated. Standard glassware, a heater
plus magnetic stirrer and a contact thermometer were used in
the leaching experiments. After leaching, the leach slurry was
filtered and all chemical analyses were made on the filtrates
using an atomic absorption spectrometer.

Table 1 Chemical composition of the Kre copper

slag.
Element

Cu
Co
Ni
Zn

Content, %
1.24
0.53
0.0035
0.232

Element
Pb
S
SiO2
Fe

Content, %
Nil
1.67
21.27
53.16

with leaching was also investigated. These methods consist

of roasting with ferrous sulfate, ferric sulfate, pyrite, ammonium sulfate and sulfuric acid followed by water leaching
(Arslan, 1982, Sukla et al., 1986; Tmen and Bailey, 1990;
Altundoan and Tmen, 1997; Ziyadanoullar, 2000; Arslan
and Arslan, 2002; Gl et al., 2003; Bulut et al., 2004; Giray
et al., 2005).
There are 2.5 Mt (2.75 million st) of ancient copper slags
located in the Kre region of Turkey, and they contain considerable amounts of Cu (1.24%) and Co (0.53%). The aim
of this experimental study was to investigate the possibilities
of recovering Cu and Co from these ancient copper slags by
applying flotation and roasting of the flotation tailings with
pyrite followed by leaching.

Results and discussions

Flotation experiments. In the flotation tests the optimum

conditions were determined to be as follows: pH 7 to 7.2,
a particle size of -0.1-mm, 300 g/t Na2S and 200 g/t collector. The results of the flotation tests performed at optimum
conditions with different collectors are given in Table 2. The
results after distribution of middlings (using Aero 211 collector) are shown in Table 3. As can be seen from Tables 2 and
3, a copper concentrate containing approximately 10.7% Cu
can be produced with a recovery of 76.7% (after middlings
was distributed), while cobalt is distributed evenly among the
products. A low flotation recovery (92.6% cobalt remained in
the tailings) of cobalt was probably due to the formation of
nonfloatable cobalt spinels and silicates in the slag. Therefore,
the pyrite roasting method was conducted with the tailings to
recover the remaining cobalt.

Material and methods

The ancient copper slags taken from the Kre region of Turkey
contain considerable amounts of copper and cobalt. Representative samples were taken from stockpiles of these ancient
slags. Physical, chemical and mineralogical properties of the
slag sample were determined prior to the concentration tests.
The chemical analysis results are given in Table 1.
Mineralogical studies of the slag sample indicated the
existence of 60% to 65% fayalite (Fe2SiO4), 15% to 17%
wustite (FeO), 5% to 6% leucite (K(AlSi2O6)), 5% to 6%
hercynite (FeAl2O4), 4% to 5% vitreous phase and 4% to
5% other minerals and metals such as magnetite (Fe3O4),
pyrrhotite (FeS), limonite (FeO-OH), chalcopyrite (CuFeS2),
digenite (Cu9S5), chalcocite (Cu2S), covellite (CuS), metallic
copper, metallic iron, hematite (Fe2O3), pyrite (FeS2), wurtzite ((Zn,Fe)S) and cuprite (Cu2O). The maximum size of the
sulfide minerals in the slag was measured to be 50 to 60 m
using an optical microscope. Although Co minerals were not
observed during the microscopic examinations, some copper
and cobalt oxide minerals were determined by XRD analyses
(Bulut, 2006). On the other hand, it is known that this type
of slag, which is usually fayalitic based, contains Cu and Co
in the form of silicates and ferrites (Arslan and Arslan, 2002;
Shen and Forssberg, 2003).
In this study, flotation and roasting were applied for recovering the main metallic values, such as the copper and
cobalt in the slag. Flotation experiments using a conventional
flotation unit (Denver flotation machine) were performed
under the following conditions: 15% solids in pulp and an
agitation speed of 1,300 rpm. Hostaflot M-91, Potassium
Amyl Xanthate (KAX), Hostaflot X-231, Hostaflot LSB and
Aero 211 were used as collectors; Na2S (300 g/t) was used
as sulfidizing control reagent; and methyl isobutyl carbinol
(MIBC) was used as frother. The effects of particle size, pH,
type of collector and amount of collector on flotation were
systematically investigated. Two-stage cleaning was applied
in all flotation tests.
Two different routes were followed in the roasting experiments. The first route was roasting of the slags with pyrite.
February 2007 Vol. 24 No. 1

013-018MMP06-016Bulut.indd 14

Pyrite roasting experiments. Pyrite roasting experiments were

carried out on slags and flotation tailings that were discarded
from the flotation experiment with Aero 211 collector. The flotation tailings contain 0.29% Cu, 0.57% Co and 51.43% Fe.
Pyrite roasting of slags: In the roasting experiments on the
slags, the effects of roasting time, pyrite:slag ratio and roasting
temperature were investigated. In the leaching tests, the effect
of sulfuric acid concentration on the dissolution efficiencies
of Cu and Co was investigated.
The effect of temperature was investigated at pyrite:slag
ratios of 1:2 and 1:1 for a roasting time of one hour. The results
are shown in Figs. 1 and 2, respectively. Increasing the roasting temperature above 450C caused the metal dissolutions
to decrease.
The effect of pyrite:slag ratio was investigated at roasting
temperatures of 450 and 500C for one hour. The results are
illustrated in Figs. 3 and 4, respectively. Increasing the pyrite:
slag ratio resulted in a gradual increase in Co dissolution, while
Cu and Fe dissolution efficiencies started to decrease at a 1:1
pyrite:slag ratio.
The effect of roasting time was investigated at a pyrite:
slag ratio of 1:1 at roasting temperatures of 450 and 500C.
The results are given in Figs. 5 and 6, respectively. In both
cases, after one hour of roasting (even 30 minutes at 500C),
dissolution efficiencies stayed almost the same.
14

MINERALS & METALLURGICAL PROCESSING

1/9/07 4:11:31 PM

Figure 1 Effect of roasting temperature on metal dissolutions for a pyrite:slag ratio of 1:2.

Figure 2 Effect of roasting temperature on metal dissolutions for a pyrite:slag ratio of 1:1.

Table 2 The effect of collector type on the flotation of slag sample.

Collector type
Product

Weight,
%

Copper
Content,
%

Cobalt

Recovery,
%

Content,
%

Recovery,
%

M-91+KAX

Concentrate
Middlings
Tailings
Total

5.4
21.1
73.5
100.0

9.57
1.78
0.36
1.16

44.7
32.4
22.9
100.0

0.54
0.46
0.50
0.49

5.9
19.6
74.5
100.0

M-91+X-231

Concentrate
Middlings
Tailings
Total

11.2
23.3
65.5
100.0

5.31
1.14
0.28
1.04

57.0
25.4
17.6
100.0

0.53
0.50
0.48
0.49

12.1
23.5
64.4
100.0

M-91+LSB

Concentrate
Middlings
Tailings
Total

3.0
24.7
72.3
100.0

10.35
1.90
0.44
1.10

28.7
42.5
28.8
100.0

0.43
0.48
0.50
0.49

2.6
24.3
73.1
100.0

Aero 211

Concentrate
Middlings
Tailings
Total

7.0
8.8
84.2
100.0

10.68
1.66
0.29
1.14

65.6
12.9
21.5
100.0

0.51
0.49
0.57
0.55

6.3
7.7
86.0
100.0

Table 3 Distribution of middlings.

Collector type
Product

Aero 211

Concentrate
Tailings
Total

MINERALS & METALLURGICAL PROCESSING

013-018MMP06-016Bulut.indd 15

Copper

Cobalt

Weight,
%

Content,
%

Recovery,
%

Content,
%

Recovery,
%

8.2
91.8
100.0

10.68
0.29
1.14

76.7
23.3
100.0

0.51
0.57
0.56

7.4
92.6
100.0

15

Vol. 24, No. 1 February 2007

1/9/07 4:11:31 PM

Figure 3 Effect of pyrite:slag ratio on metal dissolutions

at a roasting temperature of 450C.

Figure 5 Effect of roasting time on metal dissolutions at

roasting temperature of 450C.

Figure 4 Effect of pyrite:slag ratio on metal dissolutions

at a roasting temperature of 500C.

Figure 6 Effect of roasting time on metal dissolutions at

a roasting temperature of 500C.

In the hot water leaching step following the roasting step,

the effect of acid concentration was investigated at a pyrite:
slag ratio of 3:1, a roasting temperature of 500C and a roasting time of one hour. The results are shown in Fig. 7. The best
result was obtained at an acid concentration of 10 g/L, where
cobalt dissolution was 83.5% and the copper dissolution was
38%. The direct application of pyrite roasting on slag resulted
in high cobalt dissolution efficiencies but very poor copper
dissolution efficiencies. Therefore, pyrite roasting would be
a more efficient method for recovering cobalt after copper is
recovered by flotation.
Pyrite roasting of flotation tailings: Pyrite roasting experiments were also carried out on flotation tailings to recover
cobalt. The pyrite:slag ratio and acid concentration were found
to be the most effective parameters for cobalt dissolution in

the earlier tests. Therefore, only the effects of these parameters

were investigated on the dissolution of metals from the flotation tailings. The effect of pyrite/tailings ratio is shown in Fig.
8, while the effect of acid concentration in hot water leaching
after roasting is given in Fig. 9. When the acid concentration
increases, the dissolution efficiency of cobalt increases up to
86.5%, while copper dissolution efficiency is 31.4% and iron
dissolution efficiency is 22.4%.
The leach residue after roasting pyrite and leaching was
also analyzed to determine the possibility of being used in
the iron and steel industry as a raw material. Table 4 shows
the chemical composition of the leach residue compared to
the charge material used in the iron industry. All analyses fit
within the range for of the charge material used in the iron
industry except for sulfur.

February 2007 Vol. 24 No. 1

013-018MMP06-016Bulut.indd 16

16

MINERALS & METALLURGICAL PROCESSING

1/9/07 4:11:32 PM

Figure 7 Effect of acid concentration on hot water leaching after roasting.

Figure 9 Effect of acid concentration on metal dissolutions from the tailings.

Table 4 Chemical compositions of the leach residue

and charge material used in the iron industry.




Element

Figure 8 Effect of pyrite/flotation tailings ratio on metal

dissolutions at a roasting temperature of 500C.

Conclusions

Based on the results of this experimental study, the flotation

of slags followed by roasting of the flotation tailings with
pyrite prior to its leaching was found to be the most efficient
process for the treatment of the ancient copper slag studied.
In the flotation of slags, a copper concentrate containing approximately 10.68% Cu can be produced with a 77% recovery,
while 93% of the cobalt stayed in tailings. Therefore, pyrite
roasting was conducted on the flotation tailings to recover the
remaining cobalt. Cobalt was leached with an 86.5% dissolution
efficiency at a roasting temperature of 500C, a roasting time
of one hour and a pyrite:slag ratio of 3:1. An attempt will be
made to recover the metals, especially cobalt, by roasting the
material together with the pyrite concentrate now produced in
the copper ore beneficiation plant in Kre-Turkey.
MINERALS & METALLURGICAL PROCESSING

013-018MMP06-016Bulut.indd 17

Fe
Mn
P
S
SiO2
Al2O3
CaO
MgO
Sn
Ti
As
Sb
Cu
Pb and Zn
K2O+Na2O
Cr2O3

Charge material
used in the
iron industry
(ztrk et al., 2005),
%

Leach residue
after roasting with
pyrite followed
by leaching,
%

50.0-65.0
0.1-2.0
(0.05-0.3)
0.05-2.0
1.0-15.0
1.0-10.0
0.3-3.0
0.05-3.0
<0.08
<0.1
<0.1
<0.1
<0.1
<0.1
<0.25
<1.0

61.04
0.015
0.021
2.36
7.66
1.96
0.09
0.16
0.0004
0.13
0.0097
0.0001
0.028
0.037
0.21
0.077

Using this technique, it will be possible to leach the valuable

metals from the roasted products and simultaneously produce
H2SO4 from the gaseous product. Leach residue containing
61% Fe and a low amount of impurities can also be used in
the iron industry as a raw material. Thus, copper slags can
be efficiently evaluated without any waste production. The
proposed flowsheet shown in Fig. 10 was developed for recovering Cu and Co from the Kre ancient copper slags. With
the application of this process to these slags, approximately
250,000 t (275,000 st) of Cu and 8,500 t (9,400 st) of Co could
be recovered. This would be very important to the economy
of Turkey and would also be important from waste treatment
17

Vol. 24, No. 1 February 2007

1/9/07 4:11:32 PM

Arslan, C., and Arslan, F., 2002, Recovery of copper, cobalt, and zinc from copper
smelter and converter slags, Hydrometallurgy, 2083, pp. 1-7.
Arslan, F., Giray, K., nal, G., and Grkan, V., 2002, Development of a flowsheet
for recovering copper and tin from copper refining slags, The European Journal
of Mineral Processing and Environmental Protection, Vol. 2, pp. 94-102.
Arslan, C., 1982, Evaluation of Black Sea Copper Works Smelter Slag Via Acid
Roasting Method, MSc. Thesis, Istanbul Technical University, Istanbul (in
Turkish).
Banza, A.N., Gock, E., and Kongolo, K., 2002, Characterization of copper smelter
slag from Lubumbashi for the recovery of valuable metals, Extended Abstracts
of the IX International Mineral Processing Symposium, Cappadocia, Turkey,
18-20 September, pp. 5-7, Published by Kozan Ofset, Ankara.
Bipra Gorai, Jana, R.K., and Premchand, 2003, Characteristics and utilisation
of copper slag a review, Resources, Conservation and Recycling, 39, pp.
299-313.
Bruckard, W.J., Somerville, M., and Hao, F., 2004, The recovery of copper, by
flotation, from calcium-ferrite-based slags made in continuous pilot plant
smelting trials, Minerals Engineering, Vol. 17, pp. 495-504
Bulut, G., Gl, A., Kangal, O., and nal, G., 2004, Evaluation of metallic values
from ancient slags, COM 2004, The Conference of Metallurgists, Materials:
The Future of Manufacturing in A Sustainable Environment, Proceedings of
the fifth International Symposium on Waste Processing and Recycling in
Mineral and Metallurgical Industries, Ontario, Canada, August 22-25, 2004,
pp. 417-427.
Bulut, G., 2006, Recovery of copper and cobalt from ancient slag, Waste
Management & Research, Vol. 24, pp.118-124.
Giray, K., nal, G., Arslan, F., and Grkan, V., 1996, Recovery of copper and tin
from copper fire refining slags, Proceedings of the 6th International Mineral
Processing Symposium, Kusadasi, Turkey, A.A. Balkema, Rotterdam, NL.,
24-26 September, pp. 301-306.
Giray, ., Kangal, M.O., and Arslan, F., 2005, Recovery of metal values from
copper refining dust, 12th International Metallurgy-Materials Congress and
Fair, Abstract Book, 28 Sept-2 Oct., Istanbul, p. 83.
Gl, A., Bulut, G., Kangal, O., and nal, G., 2003, Beneficiation of ancient copper
slags, Proceedings of X Balkan Mineral Processing Congress, Varna, Bulgaria,
Published by Djiev Trade ltd., Sofia, 15-20 June, 2003, pp. 831-836.
Herreros, O., Quiroz, R., Manzano, E., Bou, C., and Vinals, J., 1998, Copper
extraction from reverberatory and flash furnace slags by chlorine leaching,
Hydrometallurgy, Vol. 49, pp.87-101.
Lee, J.S., Nagaraj, D.R., Coe, J.E., 1998, Practical aspects of oxide copper recovery
with alkyl hydroxamates, Minerals Engineering, Vol. 11, pp. 929-939.
Osborn, G. A., Garner F. A., and Veasey, T. J., 1986, Recovery of metal values
from secondary copper slags, Proceedings of the 1st International Mineral
Processing Symposium, Izmir, Turkey, 29 September-1 October, pp. 46-64.
ztrk, H., Kahriman, A., and Hanili, N., Behaviours of impurity elements
which come with the charge materials in the blast furnace, Proceedings
of Symposium on Existent Problems, Geology, and Mining of Turkish Iron
Deposits, 23-25 June, Istanbul, 2005, pp. 374-385.
Sarrafi, A., Rahmati, B., Hassani, H.R., and Shirazi, H.H.A., 2003, Recovery of
copper from reverberatory furnace slag by flotation, Minerals Engineering,
17, pp. 457-459.
Shen, H., and Forssberg, E., 2003, An overview of recovery of metals from
slags, Waste Management, Vol. 23, pp. 933-949.
Sukla, L.B., Panda, S.C. and Jena, P.K., 1986, Recovery of cobalt, nickel and
copper from converter slag through roasting with ammonium sulphate and
sulphuric acid, Hydrometallurgy, Vol. 16, pp. 153-165.
Topkaya, Y.A., 1990, Extraction of Co and Cu from historical slags of Kre,
ATB Metall, Vol. 30, pp. 23-28.
Tmen, F., and Bailey, N.T., 1990, Recovery of metal values from copper smelter
slags by roasting with pyrite, Hydrometallurgy, Vol. 25, pp. 317-328.
Ycel, O., Addemir, O., Tekin, A., and Nizamoglu, S., 1992, Recovery of cobalt
from copper slags, Mineral Processing and Extractive Metallurgy Review,
Vol. 10, pp. 99-107.
Ziyadanogullar, B., 2000, Recovery of copper and cobalt from concentrate
and converter slag, Separation Science and Technology, Vol. 35, pp. 9631971.

Figure 10 Proposed flowsheet for the evaluation of Kre

ancient copper slag.

and environmental viewpoints. The results of this research

may also help in evaluating similar types of slags located in
the Samsun and Ergani regions of Turkey, as well as slags that
exist in other parts of the world.

Acknowledgments

The authors thank Istanbul Technical University-Scientific Research Project Center (BAP) for the support provided
throughout this research.

References

Altundogan, H.S., and Tmen, F., 1997, Metal recovery from copper converter slag
by roasting with ferric sulphate, Hydrometallurgy, Vol. 44, pp. 261-267.

February 2007 Vol. 24 No. 1

013-018MMP06-016Bulut.indd 18

18

MINERALS & METALLURGICAL PROCESSING

1/9/07 4:11:33 PM