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Waste Manage Res 2006: 24: 234241

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Waste Management & Research

ISSN 0734242X

Treatment of copper industry waste and production

of sintered glassceramic
Copper waste is iron-rich hazardous waste containing heavy
metals such as Cu, Zn, Co, Pb. The results of leaching tests
show that the concentration of these elements exceeds the
Turkish and EPA regulatory limits. Consequently, this waste
cannot be disposed of in its present form and therefore
requires treatment to stabilize it or make it inert prior to disposal. Vitrification was selected as the technology for the treatment of the toxic waste under investigation. During the vitrification process significant amounts of the toxic organic and
inorganic chemical compounds could be destroyed, and at the
same time, the metal species are immobilized as they become
an integral part of the glass matrix. The copper flotation waste
samples used in this research were obtained from the Black
Sea Copper Works of Samsun, Turkey. The samples were vitrified after being mixed with other inorganic waste and materials. The copper flotation waste and their glassceramic
products were characterized by X-ray analysis (XRD), scanning
electron microscopy and by the toxicity characteristic leaching procedure test. The products showed very good chemical
durability. The glassceramics fabricated at 850C/2 h have a
large application potential especially as construction and
building materials.

Semra oruh
Osman Nuri Ergun
Department of Environmental Engineering, Ondokuz Mayis
University, Samsun, Turkey

Ta-Wui Cheng
Department of Materials & Mineral Resources Engineering,
National Taipei University of Technology, Taipei, Taiwan

Keywords: Copper flotation waste, vitrification, glassceramic,

heavy metals, wmr 8575

Corresponding author: Semra oruh, Department of Environmental Engineering, Ondokuz Mayis University, 55139 Samsun,
Turkey.
Tel: +90 362 457 60 20 ext1328; fax: +90 362 457 60 35;
e-mail: semcoruh@omu.edu.tr
DOI: 10.1177/0734242X06062600
Received 6 April 2005; accepted in revised form 28 November 2005

Introduction
Copper occasionally occurs pure and is found in many minerals such as cuprite, malachite, bornite, chalcopyrite, covellite
and azurite. The most important types of copper ores are the
sulphides, oxides and carbonates. From these, copper is obtained
by smelting, leaching and by electrolysis.
Copper flotation waste which is the product of pyrometallurgical production of copper from copper ores contain materials such as iron, alumina, calcium oxide, silica, etc. According to Gorai et al. (2003), about 2.2 tonnes of copper flotation
waste is generated for each ton of metal production. Consequently, approximately 24.6 million tonnes of copper flotation waste is generated each year, based on the world copper

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Waste Management & Research

production. Copper slag and the flotation waste are generally

disposed of without any prior solid waste treatment in areas
around the industrial facility at which they are generated.
Dumping of such large amounts of copper slag causes economic, environmental and space problems and therefore, governments have implemented policies that give mining and
metallurgical companies the responsibility for reducing the
volume of solid waste deposition by promoting the material
recycling and re-utilization. Due to these strict environmental regulations and the reduction or eventual elimination of
the cost of copper slag deposition, copper smelters are looking for technological innovation, which involves utilization

Treatment of copper industry waste and production of sintered glassceramic

of the copper slag (Kersch et al. 2004, Gonzales et al. 2005).

In particular, the development of new ceramic, glass and glass
ceramic materials, made by recycling waste, is of specific importance (Scarinci et al. 2000). Vitrification is one of the best
technical processes for the immobilization and destruction of
environmentally dangerous components in waste materials.
Furthermore, the vitrification process usually results in a large
reduction in the volume of the waste, with evident benefits
in terms of long-term storage or dumping. Toxic organic and
inorganic chemical compounds are destroyed and hazardous
metal components in the waste are converted into non-hazardous oxides by the vitrification process at temperatures
above 1300C. The metal species present in the waste are
immobilized as they become an integral part of the glass
matrix (Karamanov et al. 1999, Rincon et al. 1999). It is necessary to know the chemical composition of the waste in order
to design the mixture to be vitrified and consequently for the
characteristics of the glass or glassceramic products resulting from the vitrification. In this perspective, it is important that waste materials of different origin and composition are simultaneously vitrified, so that each of them may
contribute the appropriate quantities of vitrifying (SiO2,
Al2O3, ), melting (Na2O, K2O, ) and stabilizing (CaO,
MgO, ZnO, PbO, ) agents in the final glass in order that
suitable physicalchemical properties are obtained (Barbieri
et al. 2000).
The Black Sea Copper Works, which is situated in the
metropolitan city centre of Samsun, was established in 1973
and has an annual capacity of 37 800 tonnes of blister copper,
which is obtained by treating 170 000 tonnes of lump sulphide ores with 22% Cu grade. The obtained slag is treated
by a millingflotation process, which each year generates
increasing amounts of copper flotation waste and has reached
about 150 000 tonnes year1 for the last 10 years. As a result
of this activity, about 1.52 million tonnes of slag and copper
flotation waste have been disposed of on the flood plain of the
Yesilirmak River Delta, currently without any environmental
pollution control. Hence, as a result of leaching, metals such
as Cu, Zn, Co, Fe and Pb are present in the waste pollute surface and groundwater resources (Pelino et al. 2004).
In a recently conducted study, the characterization of the
microstructure of the vitrified copper flotation waste product
and the chemical composition of a glass and glassceramic
material obtained from copper flotation waste was investigated. The microstructure materials were characterized by
the toxicity characteristic leaching procedure (TCLP). The
TCLP was selected as the batch leaching test, because it simulates conditions similar to those prevailing at landfills that
have acidic drainage (US EPA 1989). X-ray fluorescence
(XRF), X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses were used to characterize the micro-

structure and chemical composition of heat-treated copper

flotation waste.

Experimental procedure
The samples of copper flotation waste were obtained from
The Black Sea Copper Works in Samsun, Turkey. The other
waste and the raw material used in this study were fly ash and
perlite. The fly ash was obtained from Ktahya Seyitmer
thermal plant and the perlite was obtained from Etibank
Izmir Comaovasi Perlit Factory, both in Turkey. Table 1 illustrates the chemical composition of the investigated perlite as
raw material and the copper and fly ash waste. The chemical
compositions of the waste materials were evaluated by using
X-ray fluorescence techniques (Spectro-Xepos). Copper flotation waste has a black colour and glassy appearance and its
specific gravity was 3100 kg m3. The absorption capacity of
the waste material was typically very low (0.13%). As can be
seen in Table 1, the copper flotation waste contained significant levels of Fe2O3 (67.68%) and SiO2 (24.87%), whereas
the contents of other metal oxides were much less than 10%.
The hazardous oxides in the copper flotation waste included
ZnO, CuO, PbO and CoO.
The crystalline phase composition of the material was investigated using X-ray diffractometry (RIGAKU, D/Max-IIIC)
with CuK radiation. The X-ray diffraction pattern shown in
Table 1: Chemical composition (wt. %) of the copper flotation waste
and other materials.
Copper flotation
waste

Perlite

SiO2

24.87

72.90

59.09

Fe2O3a

67.68

0.53

12.06

Al2O3

0.92

11.90

17.05

TiO2

0.08

CaO

0.69

0.79

9.44

CuO

0.98

ZnO

2.78

PbO

0.21

Cr2O3

0.12

SO3

2.18

0.98

K2O

0.48

4.47

0.59

MgO

0.36

0.18

1.33

BaO

0.10

CoO

0.21

Na2O

3.29

P 2O 5

0.02

MnO

0.12

0.05

LOIb

5.87

a
b

Fly ash

Iron oxides are present as Fe2O3.

Loss on ignition.

Waste Management & Research

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S. oruh, O.N. Ergun, T.-W. Cheng

Fig. 1: XRD patterns of the copper flotation waste.

Table 2: Weight % component ratios in the studied glass compositions.

Copper flotation waste

Perlite

Fly ash

Na2CO3

SiO2

CaCO3

MgO

100

F60

60

30

10

F160

60

30

10

F260

60

20

Figure 1 revealed fayalite (Fe2SO4), magnetite (Fe3O4), copper sulphide ((Fe, Cu) S2) and cuprospinel (Cu Fe2O4) and
SiO2 to be the main phases present in the slag. As the metals
are most stable in oxide and silicate forms, construction material produced from copper slag is very resistant against corroding. Knowledge of the chemical composition of the waste
is necessary in order to design the input mixture for vitrification and consequently the characteristics of the glass and glass
ceramic products produced. As the copper flotation waste
does not contain enough glassnetwork-forming agents, it
was mixed with raw materials and other residues in order to
obtain a glass with suitable properties. The similarity of perlite to sodium feldspar means that it is also a suitable material
for the glass and ceramic industry. This study therefore dealt
mainly with the four most representative investigated glass
compositions, namely F, F60, F160 and F260. The mixtures
for vitrification were mixed together in the ratios reported in
Table 2. The chemical composition of the four glass mixtures
obtained is shown in Table 3.

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Waste Management & Research

Table 3: Chemical composition (wt. %) of the investigated glasses

F60

F160

F260

SiO2

47.10

43.30

44.30

Fe2O3

28.72

31.82

29.29

Al2O3

6.20

7.10

5.30

CaO

0.62

3.84

9.78

Na2O

10.34

9.02

4.32

CuO

1.61

0.63

0.59

ZnO

0.70

0.72

0.71

MgO

0.57

1.02

2.88

P 2O 5

0.01

0.01

0.02

K2O

2.40

1.46

1.14

The glasses are non-crystalline substances formed from a

melt by cooling. They can be regarded as supercooled liquids
and their crystallization can be achieved by controlling the
nucleation and crystal growth rates. The materials investigated
were placed in a graphite crucible and induction-heated on

Treatment of copper industry waste and production of sintered glassceramic

air. The molten samples were kept at 1550C for 30 min to

ensure complete melting. They were subsequently quenched
in water to obtain glass frit. The frits were dried and ground
to grain sizes below 400 mesh. The frits were dried in an oven
at 150C for 3 h to eliminate the moisture. The ground samples were pressed into 1 cm 1 cm 0.2 cm stainless steel
moulds without using any binder and applying a pressure of
250 kg cm2. The pressed samples were sintered for 2 h at different temperatures such as 650, 750, 850, 950, and 1050C
and then cooled down to room temperature. The obtained
glassceramics were subjected to various analytical procedures: the chemical analysis was performed by using X-ray
fluorescence (XRF) spectroscopy; the crystalline phase of the
material was investigated using X-ray diffractometry (XRD);
the chemical durability was assessed by TCLP leaching tests;
microstructure/morphology observation was performed by using
a scanning electron microscopy (SEM).

Result and discussion

TCLP test on copper flotation waste and vitrified waste
The metal ions selected for the study were Cu, Zn, Pb, Co
and Cr. They were selected because of their presence in the
copper flotation waste and also their toxic nature, which
requires proper handling under the Turkish Environmental
Quality Regulations.
The TCLP is used by the EPA as the basis for the promulgation of best demonstrated available technologies (BDAT)
treatment standards included in the land disposal restrictions
programme. The copper flotation waste samples were subjected to US EPA TCLP tests to determine the leachability
characteristics for heavy metals in the raw waste and in waste
which has been treated thermally at several temperatures
such as 200, 400, 600, 800, 1000 and 1200C. This procedure
allows the chemical resistance of the waste and glassceramic
materials to be assessed.
The raw waste and waste treated thermally at different temperatures were exposed to the TCLP test. To obtain TCLP
extracts, 5 g copper flotation waste was agitated in glass jars

Table 4: Changes in Cu, Zn, Pb, Co and Cr concentrations (mg L1) in

the TCLP leaching test solutions from raw copper flotation waste as a
function of treatment temperature.
Thermal treatment
temperature (C)

Cu

Zn

Pb

Co

Cr

Room temperature

138

17

1.5

0.8

0.2

200

152

18.5

1.8

1.3

0.4

400

285

28

2.1

1.8

0.9

600

345

54

23

3.5

1.2

800

18

11

21

3.9

0.9

1000

5.2

3.2

0.5

0.1

1200

2.5

2.8

0.3

0.07

containing 100 mL of extracting medium for the specified time

period of 18 h. The pH adjustment was made with 0.1 N acetate
buffer containing 64.3 mL of 1.0 N sodium hydroxide (NaOH)
and 5.7 ml glacial acetic acid in 1 L water. Under this condition, the final pH of the solution was buffered at 4.93 0.02.
The copper flotation waste was heated for 3 h at different
temperatures to determine the amount of metal released as a
function of rising temperature. According to literature the
metal solubility in copper flotation waste containing both
oxide and sulphide of Cu decreases with increasing treatment
temperature (Spira 1969). The Cu, Zn, Pb, Co and Cr leachate concentrations for the raw waste and the waste treated at
200, 400, 600, 800, 1000 and 1200C are summarized in
Table 4. The results indicated leachate concentrations of
138 mg L1 for Cu, 17 mg L1 for Zn, 1.5 mg L1 for Pb,
0.8 mg L1 for Co, and 0.2 mg L1 for Cr, respectively. The
values for Cu, Zn and Pb exceed the limits of Turkish standards and EPA standards (see Table 5). As expected, the
release of Cu in raw copper flotation waste was considerably
higher than the releases of Zn, Co and Cr. In this study, metals released from the copper flotation waste increased with
increasing temperature of treatment up to 600C. At this
temperature, Cu, Zn, Pb, Co and Cr releases were found to be
345, 54, 23, 3.5 and 1.2 mg L1, respectively. Metal releases
decreased for samples treated at temperatures of 800C or
higher due to the glassy matrix obtained, and were lowest at a

Table 5: TCLP leaching test results for the waste glasses vitrified at 1550C.
Elements
Cu

F
(mg L1)

F60
(mg L1)

F160
(mg L1)

F260
(mg L1)

Turkish limits
(mg L1)

EPA limitsa
(mg L1)

0.13

0.007

0.011

0.024

nr

Zn

0.28

0.59

0.067

0.34

4.30

Pb

0.005

0.003

0.004

0.002

0.4

0.75

Co

0.35

0.38

0.44

0.04

nr

nr

Cr (VI)

0.13

0.15

0.14

0.13

0.60

a
Federal Register V63 100, 28 May 1998.
nr, not regulated.

Waste Management & Research

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S. oruh, O.N. Ergun, T.-W. Cheng

Fig. 2: XRD patterns of copper flotation waste (650; 750; 850 and 950C). H, haematite; M, maghamite; P, pyroxene; F, fayalite.

treatment temperature of 1200C. The levels of Cu, Zn, Pb,

Co and Cr released from samples treated at 1200C were 2.5,
2, 2.8, 0.3 and 0.07 mg L1, respectively.
The results of leaching analysis of vitrified materials (waste
glasses) at 1550C are summarized in Table 5 and show that
Cu, Zn, Pb, Co and Cr releases from F and F60 samples were
found to be 0.13, 0.28, 0.005, 0.35 and 0.13; and 0.007,
0.59, 0.003, 0.38 and 0.15, respectively. Similar results were
also obtained for the F160 and F260 samples. The levels of the
analysed elements were within the US EPA and Turkish regulatory limits. Only small amounts of Cu released from the vitrified mixed copper flotation waste were assessed. This behaviour can be explained due to the formation of stable crystal
phases with an increasing content of SiO2 in the residual
glass. Similar results have also been reported for a zinc
hydrometallurgy waste in Italy (Pisciella et al. 2001; Pelino et
al. 2002; Park & Heo 2002).
Characterization of crystalline phases
in the glassceramic
By thermal treatment of the glasses, nucleation and crystallization took place in a controlled manner, leading to the for-

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Waste Management & Research

mation of crystalline phases throughout the bulk of the sample. In the kinetics of glass crystallization, the nucleation
process requires particular attention since an efficient rate of
nucleation greatly affects the final properties of the glass
ceramic.
After the re-crystallization experiments, the samples were
investigated by using XRD and SEM. Macroscopically, the
samples identified as F, F60, F160 and F260 showed a tendency from reddish brown to chocolate brown and darker
with increasing temperatures and annealing times. The crystallization of a super-cooled liquid is controlled by the rate of
nucleation and crystal growth. XRD analysis of the bulktreated glassceramic samples showed different tendencies
towards crystallization as a function of thermal treatment
temperatures. The XRD results for flotation waste are shown
in Figure 2. The XRD spectrum of the glassceramic samples
shows the formation of magnetite spinel and pyroxene solid
solution (FeO.SiO2, Fe3O4 and Ca (Fe, Mg) (SiO3)2).
Figure 3 shows that different crystalline phases are present
depending on the glassceramic composition and thermal treatment performed, but the pyroxene (FeOx.MgO1x.CaO.2SiO2),
diopside (Ca(Mg, Al) (Si, Al)2O6) and wollastonite (W)

Treatment of copper industry waste and production of sintered glassceramic

Fig. 3: XRD patterns recorded on F, F60, F260 glass-ceramics treated at 850C for 2 h. H, hematite; M, maghamite; P, pyroxene; W, wollastonite.

(CaSiO3) are the main phases present in the glassceramic

samples.
SEM observations of microstructure materials after heat
treatment at several temperatures were performed. SEM results

of F260 samples treated at various temperatures (650, 750,

850, 950 and 1050C) and F, F60, F260 samples treated at
850C are shown in Figures 4 and 5, respectively. The influence of the sintering temperature on the evolution of the

Fig. 4: Scanning electron microscopic (SEM) micrograph of microstructure material sample F260 heat treated for 2 h at (a) 650C; (b) 750C; (c)
850C; (d) 950C; (e) 1050C.

Waste Management & Research

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S. oruh, O.N. Ergun, T.-W. Cheng

Fig. 5: Scanning electron microscopic (SEM) micrograph of F, F60, F260 microstructure material sample heat treated for 2 h at 850C.

porous structure can obviously be assumed. This microstructure seems to indicate that the crystal size increased with
increasing heat-treatment temperature. When the microstructure materials were heat treated at 1050C, both the crystal
growth rate and crystal size improved. As one possibility, rapid
heating provides better sintering. Another possibility for
controlling the relative rates of sintering and crystallization of
the glass powders is to chemically treat the glass particle surfaces (Boccaccini 2000).

Conclusions
Treatment and characterizations of the copper flotation
waste by using vitrification technology have been carried
out. Vitrification is one of the most promising technological options and recognized as an environmentally acceptable solution for the treatment of industrial waste since it
improves the potential chemical resistance of the product
and also reduces the volume of the waste for disposal. An
accurate selection and adequate ratios of the waste materials
used allows the properties of the vitrification product to be
varied.
In this study, the copper flotation waste obtained from
The Black Sea Copper Works of Samsun, Turkey was thermally treated and vitrified by itself and with the addition of
other waste materials and reagents. Copper flotation waste
was heat-treated at different temperatures and it was found
that metal releases decreased for samples treated at temperatures higher than 800C because of the formation of a glassy

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Waste Management & Research

matrix, and that releases were minimal at a treatment temperature of 1200C. Using TCLP procedures the releases of
Cu, Zn, Pb, Co and Cr for samples treated at 1200C were
2.5, 2, 2.8, 0.3 and 0.07 mg L1, respectively. The amounts of
Cu, Zn and Cr released for samples treated at this temperature did not exceed the limits of Turkish and EPA standards.
In this regard, heat-treated copper flotation waste cannot be
classified as a hazardous waste under the principles of Resource
Conservation and Recovery Act (RCRA).
Cu, Zn, Pb, Co and Cr releases from F, F60, F160 and
F260 samples were found to be 0.13, 0.28, 0.005, 0.35 and
0.13 mg L1; 0.007, 0.59, 0.003, 0.38 and 0.15 mg L1;
0.011, 0.067, 0.004, 0.44 and 0.14 mg L1; and 0.024,
0.34, 0.002, 0.04 and 0.13 mg L1, respectively. The glasses
obtained, particularly with fly ash perlite and additives
SiO2, CaCO3 and MgO were effective in confining heavy
metal ions from the leaching. These glasses showed good
chemical resistance and passed the US EPA and Turkish
regulatory limits for TCLP tests. According to Scarinci et
al. (2000), a similar result was also reported for production
of glass fibres using industrial and natural waste materials.
The results clearly show that glass and glassceramic products of acceptable quality can be produced by vitrification of
the copper flotation waste. Microstructure materials with
improved physical and mechanical properties were obtained
after heat treatment at low temperatures such as 650 and
750C. Microstructure materials have a wide range of potential applications especially for construction and building
materials.

Treatment of copper industry waste and production of sintered glassceramic

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