Beruflich Dokumente
Kultur Dokumente
ISSN 0734242X
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
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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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
235
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.
236
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
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
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.
237
Fig. 2: XRD patterns of copper flotation waste (650; 750; 850 and 950C). H, haematite; M, maghamite; P, pyroxene; F, fayalite.
238
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)
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.
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.
239
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
240
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.
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