Chapter 2

THEORY
About 80% of the world's primary copper comes from ores
in which copper is present as a sulfide mineral, for example,
chalcopyrite (CuFeS2) (the most abundant copper ore), bornite
(Cu5FeS4) and chalcocite (Cu2S). These ores contain typically
only about 0.5-2% copper.

The process of extracting copper from copper ore varies

according to the type of ore and the desired purity of the final
product. The conversion of copper consists of a series of
chemical, physical, and electrochemical processes. Methods
have evolved and vary with country depending on the ore
source, local environmental regulations, and other factors.

the steps used to process the cooper sulfide ores commonly

found in the western United States.

As in all mining operations, the ore must usually be beneficiated

(concentrated) to work this, the ore is crushed. Then it must be
roasted to convert sulfides to oxides, which are smelted to
produce matte. Finally, it undergoes various refining processes,
the final one being electrolysis.

1. COPPER SULFIDE ORES

a. COMMINUTION AND SEPARATION
Most copper ores contain a small percentage of copper
metal bound up within valuable ore minerals, with the remainder
of the ore being unwanted rock or gangue minerals, typically
silicate minerals or oxide minerals.

The first step of copper separating from other minerals in ore

mined by underground or open pit methods is commination of
the ore chunks essentially from rocks to grains of sand. (Mining
is actually the first stage of size reduction, accomplished with
explosives).
Primary, secondary, and tertiary crushing reduces the ore size to
about 25 mm, and grinding accomplishes finer reductions.
Separators (e.g., screens, cyclones) are used between stages to
control the size of particles going on to the next stage.

1. Crushing
Crushing often is accomplished in jaw, gyratory, and cone
crushers, which fracture rocks by compression (see figure 6-1
5). Jaw or gyratory crushers are usually used for the first stage
(primary crushing), and cone crushers for secondary and tertiary
crushing. The choice is determined by feed size (jaw crushers
handle larger pieces), the crushed ore is transported, usually on
conveyer belts, to the grinding mills.

1. Grinding
 In the copper ore grinding process, rod mill, ball mill and
regrind ball mill are used. Ball mill is the most common copper
ore grinding mill in copper ore concentrator.

b. concentration:

The next step in separating copper from other minerals in

mined ore is beneficiation, or concentration. The purpose of
concentration is to eliminate as much of the valueless material
as possible to avoid further expense in materials handling,
transportation, and smelting.

The ore is enriched by froth flotation (Figure 2). The powdered

ore is mixed with oil and agitated with water in a large tank to
which detergent has been added.

Compressed air is forced through the mixture, and the

lightweight particles of copper sulfide are carried to the top and
float on the froth. Heavier clays and other silicates settle to the
bottom of the tank. This residue is known as 'gangue'. The
copper-laden froth is skimmed off.

Froth flotation is the prevalent concentration method in the

copper industry; it separates the pulverized ore (containing
around 0.2 to 2.0 percent copper) into concentrates (with 20 to
30 percent copper) plus tailings (wastes of 0.05 to 0.1 percent
copper).
A flotation cell resembles a large washing machine (Figure 2)
that keeps all particles in suspension through agitation. The ore
is first conditioned with chemicals that make the copper
minerals water repellent (hydrophobic) without affecting the
other minerals. Then air is bubbled up through the pulp; with
agitation, the hydrophobic copper minerals collide with and
attach to the air bubbles and float to the top of the cell. As they
reach the surface, the bubbles form a froth that overflows into a
trough for collection. The other minerals sink to the bottom of
the cell for removal.

Figure 2 Concentration of copper ore by froth flotation.

c. ROASTING
 The roasting process is generally undertaken in
combination with reverberatory furnaces[12]. In the roaster, the
copper concentrate is partially oxidised to produce "calcine"[23]
and sulfur dioxide gas. The stoichiometry of the reaction which
occurs is:

CuFeS2 (s) + 3/2O2 (g) → CuO(s) + FeS(s) + SO2(g)

We do this by heating the concentrated ore from froth floatation.

It is heated at temperatures between (500-700°C), much of the
sulphur content remaining is burned off as sulphide gas,
resulting a calcine mix of copper oxides and sulfides.

2. SMELTING
 The initial melting of the material to be smelted is usually
referred to as the smelting or matte smelting stage.It can be
undertaken in a variety of furnaces, including the largely
obsolete blast furnaces, reverberatory furnaces, flash furnaces,
Isa smelt furnaces, etc. The product of this smelting stage is a
mixture of copper, iron and sulfur that is enriched in copper, and
which is called matte or copper matte.

In smelting, concentrates are processed at high temperatures to

produce a liquid copper-rich matte for converting, plus slag and
sulfur dioxide (S02). The purpose of the matte smelting stage is
to eliminate as much of the unwanted iron, sulfur and gangue
minerals (such as silica, magnesia, alumina and limestone) as
possible, while minimizing the loss of copper.

This step carried out in an oxygen flash furnace is heated using

natural gas to a high temperature. Next is added limestone, sand,
and fresh copper ore concentrate (chalcopyrite) is blown into the
furnace with oxygen. It is heated to 1200 K.

The oxygen in the air selectively reacts with the iron to form the
iron oxide, FeO, and leaves copper in the form the sulfide
(CuS). Sulfur dioxide is a byproduct and pollutant unless
captured and converted to sulfuric acid .The silicon dioxide in
the sand reacts with the limestone and the iron oxide to form
slag, FeSiO3 and CaSiO3. At the same time the excess sulfur in
the ore reduces copper(II) sulfide, CuS, to copper (I) sulfide,
Cu2S, which melts and flows out of the bottom of the furnace.
The slag is less dense and floats on the top.

The molten copper(I) sulfide, called copper matte, is run into a

converter furnace .

The matte forming reaction is:

CuO(s) + FeS(l) → CuS(l) + FeO(s)

Figure 4 (Smelting furnace)

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3. CONVERTING
The molten copper(I) sulfide, called copper matte, is run
into a converter furnace, where air containing oxygen is blown
through the copper matte convert to oxidize the sulfide ions
convert to sulfur dioxide. At the same time some of the sulfide
ions reduce the copper (I) ions to impure blister copper metal. A
final heating in an anode furnace is used to burn off the
remaining oxygen, the purity of this product is 98.5% .The
temperature in Converting stage is about (1373.15 K).

The overall reaction is:

CuS(l) + O2(g) → Cu(l) + SO2(g)

Figure 5 (Converting furnace)

4. ELECTROREFINING
 The copper is refined by electrolysis. The anodes cast from
processed blister copper are placed into an aqueous solution of
3–4% copper sulfate and 10–16% sulfuric acid. Cathodes are
thin rolled sheets of highly pure copper or, more commonly
these days, reusable stainless steel starting sheets.

A potential of only 0.2–0.4 volts is required for the process to

commence. At the anode, copper and less noble metals dissolve.
More noble metals such as silver and gold as well as selenium
and tellurium settle to the bottom of the cell as anode slime,
which forms a saleable byproduct.

Copper(II) ions migrate through the electrolyte to the cathode.

At the cathode, copper metal plates out but less noble
constituents such as arsenic and zinc remain in solution. The
reactions are:

At the anode : Cu(s) → Cu2+(aq) + 2e–

At the cathode : Cu2+(aq) + 2e– → Cu(s)

 Figure 6 (Electro refining cell)

Figure 7 (Pure copper cathodes)

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