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Abstract
Copper slag, which is produced during pyrometallurgical production of copper from copper
ores contains materials like iron, alumina, calcium oxide, silica etc. For every tonne of metal
production about 2.2 ton of slag is generated. Dumping or disposal of such huge quantities of
slag cause environmental and space problems. During the past two decades attempts have
been made by several investigators and copper producing units all over the world to explore
the possible utilisation of copper slag. The favourable physico-mechanical characteristics of
copper slag can be utilised to make the products like cement, fill, ballast, abrasive, aggregate,
roofing granules, glass, tiles etc. apart from recovering the valuable metals by various
extractive metallurgical routes. This paper gives a review of characteristics of copper slag as
well as various processes such as pyro, hydro and combination of pyro-hydrometallurgical
methods for metal recovery and preparation of value added products from copper slag.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Copper slag; Environmental problems; Utilisation; Recovery of metals; Preparation of value
added products
1. Introduction
Since the beginning of the industrial era, slags the glassy materials left over when
metals are pyrometallurgically extracted from ores, have been considered waste. One
such material is copper slag which is produced during matte smelting and converting
300
(1)
301
(2)
(3)
DG 0
from which KE at smelting temperature (:/
4:576T 0 K
1200 8C) is 104. This high value of KE shows that Cu2O is completely sulfidised to
Cu2S by FeS at smelting temperature. Eq. (1) can also be used for recovering copper
from converter slags. These slags are recycled to the smelting furnace where their
oxide is sulfidised to Cu2S. Oxidised copper may be present in the form of CuO,
CuSO4, CuO /CuSO4 or CuO /Fe2O3. These compounds also react to form Cu2S
during smelting. In short, the entire amount forms Cu2S. CuS and FeS2 are unstable
at high temperature due to their high sulphur pressures (CuS: p S2 :/100 atm at
600 8C; FeS2: pS2 /5 atm at 700 8C). These decompose during smelting to form
Cu2S and FeS. (Biswas and Davenport, 1980).
KE is given by logKE
(4)
The sulphide shows no tendency to form these anion complexes and hence they
remain as distinct covalent matte phase, quite dissimilar to the silicate slag. Silica is
added directly for the most complete isolation of copper in the matte which occurs at
near saturation concentration with SiO2 (Shi and Qian, 2000). Certain amount of
lime and alumina are added to stabilize the slag structure. The molten slag is
discharged from the furnace at 1000 /1300 8C. When liquid slag is cooled slowly, it
forms a dense, hard crystalline product where as quick solidification by pouring
Table 1
Copper slag generation in various regions
Regions
Asia
North America
Europe
South America
Africa
Oceania
7.26
5.90
5.56
4.18
1.23
0.45
302
molten slag into water gives amorphous granulated slag. Trade names of copper
slags include Kleen Blast and Tru-Grit. The copper slag that is usually found is an
impure iron silicate glass with small inclusions of copper and copper sulphide. The
chemical composition of slag varies with the types of furnace or process of treatment.
The typical composition of copper slag is given below. Fe: 30 /40%, SiO2: 35/40%,
Al2O3: 0/10%, CaO: 0/10%, Cu: 0.5 /2.1%.
Table 2
Typical physical and mechanical properties of copper slag
Appearance
Unit weight
Absorption, %
Bulk density
Conductivity
Sp. gravity
Hardness
Moisture
Water soluble chloride
Abrasion loss, %
Sodium sulphate soundness loss, %
Angle of internal friction
Emery (1986), Hughes and Haliburton (1973), Das et al. (1993) and Feasby (1975).
Origin
Fe, %
SiO2, %
CaO, %
MgO, %
Al2O3, %
S, %
Cu, %
Co, mg/kg
Mn, mg/kg
Ni, mg/kg
Zn, mg/kg
1
2
3
4
5
6
7
8
9
10
44.78
39.65
41.53
47.8
44.7 /47.7
47.13
44
47.8
44.8 (oxide)
34.62(oxide)
40.97
31.94
37.13
29.9
28.5 /32
/
28
26.1
24.7
27.16
5.24
3.95
/
/
1.6 /3.9
/
/
0.7
10.9
17.42
1.16
2.82
/
/
/
/
/
1.0
1.7
3.51
3.78
2.4
/
/
/
/
/
6.8
15.6
14.7
1.06
/
0.11
/
0.3 /0.9
1.47
/
1.5
0.28
0.33
/
1.01
0.79
0.7
0.5 /0.95
0.68
0.6
0.82
2.1
1.64
/
1040
/
/
Tr /8
2200
1300
4000
/
/
/
420
/
/
/
300
/
/
4000 (oxide)
4900 (oxide)
/
150
/
/
14 /20
500
600
/
/
/
/
7220
/
/
1700 /2850
500
/
1500
/
/
(1) Iranian National Copper Industries Co, (Marghussian and Maghsoodipoor, 1999). (2) Etibank Ergani Copper Plant, Elazig-Turkey (Kiyak et al., 1999).
(3) Caletone Smelter Chile (Imris et al., 2000). (4 /7) Indian Copper Plants (Agrawal et al., 2000). (8) Kure Copper Slag (Yucel et al., 1992). (9 /10) Copper
Queen, Prince, USA (Mobasher et al., 1996).
Table 3
Typical chemical compositions of the slag
303
304
4. Chemical composition
Chemical analysis of various copper slags are shown in Table 3. Copper content is
limited to 0.5 /2%. Major constituents are iron, silica, alumina and calcium oxide.
5. Slag characterisation
Microscopic observations indicate most of the copper slags are well crystallised. In
addition to iron oxides, other oxides such as silica, alumina, lime and magnesia
constitute 95% or more of the total oxides. Composition of some of the slag phases
obtained by Quantitative Electron Microprobe analyses (Imris et al., 2000) is given
in Table 4. The X-ray diffraction pattern shown in Fig. 1 revealed 2FeO /SiO2, Fe3O4
and Ca (Fe, Mg) (SiO3)2 as the main phases present in the slag (Kiyak et al., 1999).
As the metals are most stable in oxide and silicate forms, construction material
produced from copper slag have least possibility of corroding.
The TG/DTA tests on copper slag (Fig. 2) showed the transformation of fayalite
to hematite and amorphous silica (Eq. (5)), magnetite to maghemite and hematite
(Eq. (6)) and emission of SO2 due to oxidation. Marked weight gain in the 374 /
989 8C range followed by a weight loss from 989 to 1040 8C was observed. The
weight gain in the 374 to 989 8C indicated the oxidation of fayalite (Eq. (5)). The
weight loss above 989 8C was due to the oxidation of copper and iron sulphides
present in minor amounts in copper slag.
2FeOSiO2 1=2 O2 0 aFe2 O3 SiO2
Fe3 O4 0 gFe2 O3 0 aFe2 O3
(5)
(6)
The exothermic peaks at 516 and 767 8C in DTA was related to the magnetite to
maghemite and maghemite to hematite transformation, respectively (Eq. (6)). The
endothermic dip at 1040 8C was associated with the slag melting.
Slag
Slag phase
Cu, %
Fe, %
S, %
Si, %
Ca, %
Al, %
Mg, %
66.0
11.5
B/0.2
1.0
1.5
6.5
45.9
98.3
63.9
56.2
17.3
3.7
/
0.5
0.6
/
26.3
0.2
27.8
29.5
/
/
/
1.2
1.8
/
/
1.0
2.9
6.0
/
/
/
1.1
/
Table 4
Quantitative electron microprobe analyses of copper slag
305
306
et al., 1992). Earlier, ancient copper slag of Kure in Turkey was subjected to
carbothermic reduction to produce a Fe /Co /Cu alloy by Topkaya (1990). It was
found that with the addition of 4% coke powder, an alloy containing 1.72% Co and
4.41% Cu could be obtained at 1400 8C in 1 h with Co and Cu recoveries of 97.7 and
86.7%, respectively. Yucel et al. (1999) reported the treatment of ancient Kure
copper slag by carbothermal reduction process in a DC arc furnace of open top type
by adding coke. In 1-h reduction time at a temperature between 1430 and 1480 8C
maximum metal recovery was obtained. Similar conditions in closed type furnace
resulted in higher cobalt and copper contents of the matte and also the higher
recoveries. In closed system recovery of cobalt and copper were 95.7 and 90%,
respectively. Fluxing materials such as CaO and Al2O3 caused an increase in iron
reduction but no appreciable influence on cobalt and copper recovery was noticed.
Granulated slag of Sterlite Industries India Limited was used to recover iron values
(Premchand et al., 2000) in a 50 KVA furnace. Eighty five percent iron recovery was
obtained from a charge of 10 kg granulated copper slag mixed with 2.5 kg lime and
600 gm graphite powder smelted for 1 h duration using 45 kW h power.
307
308
309
loads or their geometry are comparable with those of the traditional abrasive
material, their micro-hardness being however, lower. As a result, slag abrasive
materials can be applied in abrasive tools for machining non-ferrous metals, wood or
plastics. In these cases, the specific machining output approaches that of the tools
containing silicon carbide or alundum which is the striking features of the slag based
abrasive.
Copper slag was used (Wyzsza Szkola Inynierska, 1987) as a binder in preparation
of grinding wheel. The service properties of these grinding wheels, the ultimate
strength, its cutting characteristics, service life and the condition of the working
surface showed the advantage of using slag based binder instead of ceramics binder.
With these wheels lower porosity of the ground surface, higher grinding efficiency
and reduced energy consumption were attained.
A comparative studies on the application of grinding wheels made of copper slag
and those made of polyurethane resins was carried out by Pluta (1989). The studies
have been performed for the machining of corrosion-resisting 1H18N9T steel, 55
plain carbon steel in the heat-treated condition, and 59 lead brass. The results
obtained are better than those relating to alundum grinding wheels. The highest
machining ability was found in the case of heat-treated steel, the lowest in the case of
brass.
The freely solidifying copper slag obtained as a waste material from a high
temperature copper process was investigated for its use as abrasive (Andrzej et al.,
1992). When disintegrated its billets yield grains which may be used as a substitute
abrasive of micro-hardness about 7 GPa and mechanical strength equivalent to that
of electro-corundum. Slag softening temperature at 1190 8C makes it unsuitable for
use as a ceramic bonded abrasive. Heat treatment at 800/1000 8C can significantly
improve the mechanical properties of slag and the abrasive. The product has
properties comparable with those of corundum.
The possibility of utilisation of freely solidifying copper slag as an abrasive was
indicated by Grot and Oleska (1989). The investigations were carried out using liquid
and solid compounds of various compositions and polishing were done on steel,
brass, aluminium and Zn /Al alloys. For some compositions of abrasive-buffing
composites satisfactory results were obtained.
Minerals Research and Recovery, Arizona, USA manufactured a loose grained
abrasive (sharpshot) from an air-cooled slag from a plant of Ajo, Arizona. These
abrasives are very consistent in its composition and physical properties and are
reported to be environmentally safe (B/0.1% free silica).
7.2. Pavement
The use of copper slag aggregates in hot mix asphalt pavements was investigated
by Transportation Research Board, Washington (Collins and Cielieski, 1994). Fine
copper slag has reportedly been used in hot mix asphalt pavements in California and
granulated copper slag has been incorporated into asphalt mixes in Georgia to
improve stability. Although it is rarely used, Michigan Department of Transporta-
310
311
fired at 1025 8C for 1 h gives the standard floor tiles with bend strength 57 MN/m2,
water absorption of 2 wt.%, hardness of 750 VH and very good acid resistance.
In firing mutual diffusion of atoms between touching particles takes place, which
is also known as sintering. As a result of sintering the particles become fewer and
larger and pores are eliminated. Strength in fired body is due to interlocking of
crystal. The principle behind fast-firing is that one can promote densification by
bypassing the coarsening regime with rapid heating. It enables the material to obtain
the mechanical characteristics required for the different uses and the properties of
chemical inertia (Yet-Ming Chiang et al., 1997).
Copper slags was utilised for the manufacturing of coloured glasses by Dongping
et al. (1997). A mixture of slag 12/43, SiO2 35/52, lime 5/18 and soda 15/25% was
melted at 1300 8C to obtain coloured glass containing SiO2 52 /61, Fe2O3 9 /23,
CaO 6 /19, Na2O 6/15, and Al2O3 0.5 /1.5%. The colour of glass changes
sequentially from light green, yellow green, brown green to black green with
increasing Fe2O3 content in the glasses.
8. Conclusion
Favourable physico-mechanical and chemical characteristics of copper slag lead to
its utilisation to prepare various value added products such as cement, fill, ballast,
abrasive, cutting tools, aggregate, roofing granules, glass, tiles etc. These materials
have been found to be possessing superior mechanical properties and they may be of
cheaper varieties than the similar conventional materials. The utilisation of copper
slag in such manners may reduce the cost of disposal. This may also leads to less
environmental problems. Improvement in plant economics may also be expected.
Metals and alloys can also be produced from the copper slag by various pyro, hydro
and pyro-hydrometallurgical routes. Therefore, it is evident that judicial utilisation
of different types of copper slag is of prime importance in the present days industrial
waste management.
312
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