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Use of Waste Copper Slag, A Sustainable Material
Use of Waste Copper Slag, A Sustainable Material
DOI 10.1007/s10163-014-0254-x
REVIEW
Received: 18 February 2013 / Accepted: 30 March 2014 / Published online: 3 May 2014
Ó Springer Japan 2014
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Management in India: options and opportunities’ calcu- cities out of twenty-nine passed the statutory guidelines by
lated the amount of land that was occupied by waste dis- European countries (except the Netherlands) for high
posed post-independence, until 1997. The study estimated quality composts. The study also found that incidence of
the land occupied in multiples of the size of a football field heavy metals in solid waste compost from cities (population
and arrived at 71000 football fields of solid waste, stacked \1 million) is less than half of that from bigger cities, but
9 m high. Based on a business as usual (BAU) scenario of the compost still does not clear the quality control stan-
91 % land filling, the study estimated that the waste gen- dards in all instances. If all solid waste generated in India
erated by 2001 would have occupied 240 sq.km or an area in the next decade is composted as mixed waste and used
half the size of Mumbai; waste generated by 2011 would for agriculture, it would introduce 73000 tons of heavy
have occupied 380 sq.km or about 220000 football fields or metals into agricultural soils as shown in Table 1. Heavy
90 % of Chennai, the fourth biggest Indian city area-wise; metals concentration in mixed solid waste compost in
and waste generated by 2021 would need 590 sq.km which comparison with quality control standards as shown in
is greater than the area of Hyderabad (583 sq.km), the Fig. 4 can cause harm to public health and environment
largest Indian city, area-wise [4]. A lot of effort is given to and is the major concern leading to its restricted agricul-
utilize the coal combustion waste, ceramic industry waste, tural use [11]. Mixed waste composting is therefore not an
foundry sand, etc. It is also essential to give a fair focus on option for sustainable waste management. In countries like
the initial waste from aluminum, zinc, copper, and other India where more than 91 % of solid waste is land filled
metal industry waste for their proper economic and sus- and there are no other alternatives available, mixed waste
tainable utilization. composting is widely practiced and considered better (if
There are solutions for proper utilization of industrial not the best) than land filling [8]. If all solid waste gen-
wastes viz. fly ash (from thermal power plants), blast fur- erated in India from 2011 to 2021 is treated in mechanical
nace slag and steel slag (from iron and steel industries), biological treatment (MBT) facilities and the compost was
phospho-gypsum (from fertilizer plants), red mud (from used for agriculture, it would introduce 73000 tons of
aluminum industries), lime sludges (from sugar, paper, heavy metals into agricultural soils.
calcium carbide industries), lead–zinc slag (from zinc
industries), and kimberlite (from mining) for manufacture
of cement and related building materials. A study con- Industrial waste generated in India and their utilization
ducted by the Indian Institute of Soil Science (IISS),
Bhopal, found that compost produced from solid waste in Industrial and mineral wastes from mineral processing
India is low grade, with high heavy metal concentrations industries, such as metallurgy, petrochemicals, chemicals,
and low nutrient value. Figure 3 shows the range of con- paper, and pulp account for nearly 150 million tonnes per
centration of heavy metals zinc (Zn), copper (Cu), cad- annum. The more important wastes from these industries
mium (Cd), lead (Pb), nickel (Ni), and chromium (Cr) in from the view point of building materials are fly ash from
MSW composts from 29 cities. Compost from only two thermal power plants, slag from steel industry, press mud
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from sugar industry, paper sludge from pulp and paper areas of utilization are given in report of central pollution
industry, phospho- chalk and phospho-gypsum from fer- control board, India.
tilizer industry, carbide sludge from the acetylene industry,
calcium carbonate sludge from soda ash and chrome sludge Types of slag
from sodium chromate industry, red mud from aluminum
industry, and metallurgical slags from nonferrous industry SLAG is a broad term covering all nonmetallic coproducts
[21, 22]. Data on the availability of these wastes and their resulting from the separation of a metal from its ore. Its
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chemistry and morphology depend on the metal being pro- aggregate, rail ballast, asphaltic concrete aggregate, soil
duced and the solidification process used. Slags can be conditioner, hard stand areas, and unconfined construc-
broadly categorized as ferrous (iron/steel) and nonferrous tion fill.
(copper, lead/zinc) depending on the industry from which
they come. Figure 5 presents a general schematic diagram Electric arc furnace slag (EAF or steel furnace slag)
for the slag production process for copper, nickel, and lead–
zinc slags. Nonferrous slags, which are only 12 % of the Produced when scrap metal and fluxes are oxidized by the
total annual production and their types and uses, are use of an electric current, molten slag is generally placed
described below: into ground bays for cooling. Both BOS and EAF slags are
somewhat heavier than blast furnace slag and most quar-
Ferrous slag products iron blast furnace slag (BFS) ried rock material. Uses include (a) blending with many
other products such as granulated slag, fly ash, and lime to
This is the by-product from the reduction of iron ores to form pavement material, skid resistant asphalt aggregate,
produce molten iron and molten slag. and unconfined construction fill.
1. When allowed to cool slowly to a crystalline rock
Copper/lead/zinc slag (CLZS)
form, it becomes a light gray vesicular rock known as
air-cooled blast furnace slag. Principle uses include
Formed from the smelting of ores, it is generally granulated
(a) uncrushed—fill and embankments (particularly
to form a sand size product with a top size of about 5 mm,
areas subject to severe loading such as mainline rail
with only a small quantity of material below 1 mm. It is
systems), working platforms on difficult sites, pave-
dark in color and has attracted the name of black sand.
ments, where binding fines are produced by rolling to
Mostly spherical in nature, it has been used as concrete
break the slag down to fill the voids. (b) Graded road
sand.
base—on its own or blended with other slags and/or
with other natural rocks and sands. (c) Crushed and
Utilization of copper: historical prospective,
graded—for concrete aggregates, concrete sand, glass
availability, and use
insulation wool, filter medium, and use under concrete
slabs as a platform.
Copper is one of the basic chemical elements. In its nearly
2. By passing the molten slag through high volume high
pure state, copper is a reddish-orange metal known for its
pressure water sprays, a glassy, sand-type (granulated)
high thermal and electrical conductivity. It is commonly
material is formed, known as granulated blast furnace
used to produce a wide variety of products, including
slag. The color of this product is very similar to normal
electrical wire, cooking pots and pans, pipes and tubes,
beach sand. (a) The principal use is as cement
automobile radiators, and many others. Copper is also used
replacement (when ground), replacing 30–50 % of
as a pigment and preservative for paper, paint, textiles, and
portland cement in ‘normal’ concrete, but can replace
wood. It is combined with zinc to produce brass and with
up to 70 % in specialist applications such as marine
tin to produce bronze. It is a ductile metal with excellent
concrete. (b) Other uses include glassmaking, trace
electrical conductivity and find extensive use as an elec-
elements in agriculture, concrete block manufacture,
trical conductor, as a heat conductor, as a building material,
sporting field sub-base (for drainage), filtration med-
and as a component of various alloys. Copper has played a
ium, reinforced earth embankments, and mine back-
significant part in the history of mankind, which has used
filling and grit-blasting medium requiring fine etching.
the easily accessible uncompounded metal for nearly
10000 years. A copper pendant from about 8700 B.C. was
Basic oxygen steelmaking slag (BOS or steel furnace found in what is now northern Iraq. There is evidence that
slag) by about 6400 B.C., copper was being melted and cast into
objects in the area now known as Turkey. By 4500 B.C.,
This slag is formed when molten iron, scrap metals, and this technology was being practiced in Egypt as well. Most
various fluxes, such as lime, are oxidized by injecting of the copper used before 4000 B.C. came from the random
large amounts of pure oxygen into the molten iron mix to discovery of isolated outcroppings of native copper or from
create molten steel and molten slag. Slow cooling of the meteorites that had impacted Earth. The first mention of the
molten slag produces a dense rock material. Principal systematic extraction of copper ore comes from about 3800
uses include a. blending with many other products such as B.C. when an Egyptian reference describes mining opera-
granulated slag, fly ash, and lime to form pavement tions on the Sinai Peninsula. During the Roman Empire,
material, and b. other uses include, skid resistant asphalt copper was principally mined on Cyprus, hence the origin
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Table 2 Typical physical properties of copper slag Table 3 Chemical analysis of copper slag
Property Typical value Constituent % Weight
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Table 4 Different abrasive Abrasive Composition Mohr’s hardness Density Dusting Recycling
media along with their (g/cu.cm)
properties
Silica sand Crystalline silica 7.0 1.6 Low No
Best quality
Average quality same 6.5 1.6 High No
Staurolite/zircon Iron aluminum silicate 7.5 2.0 Mod No
Garnet Iron aluminum silicate 7.5 2.0 Low Yes
Almandite
Andradite Calcium silicate 6.5 1.8 High No
Olivine Iron silicate 6.5 1.9 High No
Spec. hematite Iron oxide 6.0 2.3 Mod No
Copper slag Iron silicate glass 6.0 1.6 Mod No
Nickel slag Nickel iron glass 6.0 1.6 High No
Iron slag Iron silicate glass 6.0 1.6 High No
Coal boiler slag Ca iron silicate glass 6.0 1.4 High No
Steel grit/short Iron (steel) 6.0 2.2? Low Yes
Baking soda Sodium carbonate 2.0–3.0 1.1 High/Low No
Crushed glass Alkaline silicate GLASS 6.0 1.6 High No
Organic media Various 2–3 0–1.0 N/A No
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and slag. Since slags are almost always associated with certain pozzolanic materials produce a very compact
copper mines, the general term ‘copper slag’ has come to cement paste that limits the space available for hydration
be used even for slags that might be more accurately be products, a determining factor in the formation of hydrated
called ‘lead slags’, ‘zinc slags,’ or even ‘arsenic slags’. calcium aluminates. SEM was found to be a useful ana-
Copper slags carry small amounts of the metals that were lytical technique when aluminates are formed and can be
present in the original ores and smelter concentrates [14]. clearly detected by XRD.
The purpose of the slag was to act as a collection mecha- Land filling is not a desirable option for the disposal of
nism of these undesirable contaminates during the recovery solid hazardous and nonhazardous waste materials. It is not
of the metal of interest. Copper slags are common substi- a liable method because of future environmental costs and
tutes for silica sand in countries where mines and smelters problems associated with land filling regulations. This
are abundant. The different materials used for the abrasive method increases load of toxic metals and other contami-
media is given in the Table 4. nants in the landfill, potentially increasing the threat to
groundwater contamination. Increasing economic and
Use of cooper slag in pavement industry financial factors also dictates that industry should look
forward to recycling and reuse of waste material as a better
In India, there is great demand of aggregates mainly from option to land filling. Wastes and by-products can be used in
civil engineering industry for road and concrete construc- addition to concrete without the need for large changes in its
tions. The construction of highways and development of preparation. For all waste and by-product contents, the
several expressways for high-speed corridors exert tremen- strengths increase as the curing time of the concrete
dous pressure on natural resources. Many highway agencies, increases. In general, it would be suitable for any applica-
private organizations, and individuals are in the process of tion that does not require high strengths, especially not in
completing a wide variety of studies and research projects the short term [14, 17]. The porosity and the absorption
concerning the feasibility, environmental suitability, and coefficient increase with an increase in waste content and
performance of using waste industrial products in highway decrease as the curing time increased [15, 18, 19]. The
construction [1, 2]. These studies try to match society’s need deformability of concrete also increases with the increase in
for safe and economic disposal of waste materials with the waste contents [8, 9, 20]. The density of the concrete
highway industry’s need for better and more cost-effective decreases with an increase in waste content and increases as
construction materials. Various studies explore the potential the curing time increases. In previous study on concrete
use of copper slag as fine aggregate (up to 30 %) in the design M15 and geopolymer, the mixed concrete is a desirable
of bituminous mixes like bituminous macadam, dense bitu- option to utilize or reuse of solid hazardous waste materials
minous macadam, bituminous concrete, and semi-dense shown in Figs. 8 and 9. Solidified materials are weak and
bituminous concrete, which enhance the property of the contain significantly less cementitious materials and more
bituminous mixes. Nonferrous slags are produced during the water, for example concrete. Due to waste addition, CSH
recovery and processing of nonferrous metal from natural hydration is poisoned. In these situations, ettringite plays an
ores. The slags are molten by-products of high temperature important role—it increases strength and durability char-
processes that are primarily used to separate the metal and acteristics. UCS increases with a decrease in crystalline
nonmetal constituents contained in the bulk ore. phases. Aggregate, which makes up 70 % of the concrete
volume, is one of the main constituent materials in concrete
Use of cooper slag in cement and concrete production. However, due to the high cost of natural sand
used as a fine aggregate and the rising emphasis on sus-
The copper slag obtained may exhibit pozzolanic activity tainable construction, there is a need for the construction
and may therefore be used in the manufacture of addition- industry to search for alternative materials as fine aggre-
containing cements. Blends of copper slag with portland gates in concrete production. Copper slag, which is the
cement generally possess properties equivalent to portland waste material produced in the extraction process of copper
cement containing fly ash, but very different to the silica metal in refinery plants, has low cost, and its application as a
fume incorporation. Copper slag and fly ash reduce the heat fine aggregate in concrete production reaps many environ-
of hydration more effectively than silica fume in mortars. mental benefits such as waste recycling and solves disposal
The replacement of 30 % cement by copper slag reduces problems. Currently in Singapore, the Building Construc-
the flexural and compressive strength in a similar way to fly tion Authority limits the replacement of sand by copper slag
ash; however, after 28 days, the reduction is less than the to a maximum of 10 % by mass in construction engineering
percentage of substitution. The pozzolanic activity of with additional precautionary measures in place.
copper slag is similar to that of fly ash and higher than Hwang and Laiw in 1989 make an attempt to find out the
silica fume. In the presence of low water/cement ratios, usability of copper used as a fine aggregate. The physical and
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solid wastes, effort has been made and mathematical construction industry and for infrastructural development
models were also established universally and as a conse- made with waste copper slag also affects the cost of con-
quence, considerable quantity of wastes is now being struction comparable to pure concrete. This concrete is safe
recycled and used to achieve environmentally sound enough to be used in environmental applications in roadbeds
management. Studies on potential use of different mining and as filling material. Thus, due to the beneficial use of the
tailings in bricks have revealed that this waste along with immobilized material, this type of industrial wastes and by-
clay can be effectively utilized for making better quality products usability appears to offer a promising way to
fired bricks and use of copper has resulted in achieving improve sustainable environment in developing countries.
high strength. The user of copper slag in cement can be assured of the
The potential environmental risk by the geotechnical nonleachability of copper and other elements. This further
utilization of wastes needs to be avoided. Many waste ensured the performance of cement and using copper slag
materials might be contaminated by toxic and hazardous in different cement types shall also help the manufacturers
substances and require treatment for safe disposal. Waste to reduce the cost of production.
utilization can serve not only to prevent the negative envi-
ronmental impact but also to preserve and protect nature. In
this study, we are put steps in such a waste called copper slag References
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