Pyrometallurgy 2

Smelting process

Smelting

Smelting is essentially a melting operation in which the constituents of

the charge, in the molten condition, partition into two or more phases
which may be slag, matte, speiss or metal.
the charge often contains fluxes to facilitate formation of a low-melting

slag phase
All the oxides obtained by concentration of oxide ores/minerals or
by roasting of
sulfide concentrates are reduced by means of a suitable reducing
agent.
Physical characteristics like melting and boiling points, vapor

pressure and so on of the metal as well as the relative stability of its
oxide as compared to the oxides of impurity metals and gangue
mineral oxides are major factors in the selection of reducing
agents.
In general, carbon, carbon monoxide, and hydrogen are the

reducing agents of commercial and industrial importance.
In special cases, as in the production of highly reactive metals such

as uranium, thorium, beryllium, zirconium, titanium and so on,
metals having high affinity for oxygen, such as magnesium,
calcium may be employed as reducing agents.
The different types of smelting are:
(i) Reduction smelting

(ii) Matte smelting;
(iii) Flash smelting.
Electric arc furnace smelting: Ferroalloys are manufactured by smelting of ores in
electric arc furnaces in the presence of carbon, for example, ferro-manganese from
pyrolucite (MnO2), ferro-silicon from silica sand (SiO2) and ferro-chrome from chromite
(FeO∙Cr2O3).
Reverberatory smelting: Tin is produced by smelting cassiterite concentrate (SnO2) in a
reverberatory smelting furnace in the presence of carbon.
Reduction in retort: In Pidgeon process, calcined dolomite (CaO∙MgO) is reduced with
ferrosilicon at 1200 C under a reduced pressure of 10-4 mmHg and magnesium vapor is collected
at the cooler end of the retort. In the old and obsolete retort process, after dead roasting of
sphaterite, zinc oxide was reduced with carbon at 1100 C.
Metallothermic reduction: Ferro-columbium is manufactured by reduction of Cb-rich
concentrate (mineral: columbite-tantalite (FeMn)(CbTa)5O6) with aluminum in a thermit process
in which some preheat is necessary. Welding and repair of railway tracks by thermit process, in
which high grade hematite is reduced with aluminum, is well known.
The Kroll process is very popular for the production of titanium sponge by reduction of vapors of
TiCl4 with liquid magnesium.
Uranium, thorium, zirconium, and beryllium are obtained by reduction of their respective
fluorides by magnesium and/or calcium.
REDUCTION SMELTING
The reduction smelting process involves the reduction of oxidic

sources of metals with carbon in the presence of a flux. The
process can generally be represented as:
mineral + reducing agent + flux = metal + slag + gases
number of metals are produced from oxide minerals.
Iron, manganese, chromium, and tin are exclusively obtained from oxide ores.
Rich ores, for example, hematite, chromite can be directly reduced
Lean ores are first concentrated by communication, classification, jigging, and
tabling. Sulfide ores, such as galena and sphalerite concentrates are first
roasted to oxides for subsequent reduction to metals.
Carbonate minerals such as dolomite is calcined prior to reduction to
magnesium
The blast furnace is the most popular of the furnaces used for carrying out
reduction smelting operations
Metal, M can be obtained by reducing the metal oxide, MO2
with a reducing agent R according to the reaction:
MO2 (s,l) + R (s,l) = M (s,l) + RO2 (s)

For the above reaction to proceed in the forward direction,
RO2 must be more stable than MO2; that is, the free energy of formation of RO2 should be more
negative as compared to that of MO2.
The change in free energy of the reaction should be negative enough to get a large value of the
equilibrium constant that is related to the free energy change, ΔG (ΔG = −RT ln K).
A large equilibrium constant will generate a high proportion of M and RO2 when the reaction
reaches equilibrium.
Ellingham diagram for oxides
The application of the Ellingham diagram in the selection of a
reducing agent may be understood by analyzing Figure
for reduction of Cr2O3 with Al. At 1200 C, ΔG for the formation
of 2/3 Cr2O3 is approximately -520 kJ and for the formation of
2/3Al2O3 is approximately -840 kJ.
The difference between the two lines at 1200 C is -320 kJ, which
represents the difference between the two standard free energies
of formation of Cr2O3 and Al2O3 and also the free energy change
for the reduction of Cr2O3 by Al. This can be explained by the
reactions as follows:
Subtraction
ΔG = -840 - (-520) = -320 kJ.
Since reduction of Cr2O3 by Al, having a large negative standard free

energy change gives a large value of K = 2.5 × 1011 at 1200 C, there will
be a large proportion of chromium metal at equilibrium.
This is the fundamental background of the aluminothermic reduction of
chrome ore. The reaction proceeds rapidly once the charge (Cr2O3 + Al)
is ignited. Due to its strongly exothermic nature, the reaction produces
its own high reaction temperature.
The matte smelting process
The matte smelting process involves the fusion of sulfidic sources of metals
with a flux without the use of any reducing agent. This results in the production
of a molten mixture of sulfides, known as the matte, the gangue associated with
the starting sources passing into the slag. The reaction can generally be
represented as
sulfidic source concentrate + flux = matte + slag + gases
The term matte smelting has come being almost synonymous with the pyro way of extraction of copper.
Matte smelting of chalcopyrite
Metal sulfides are low melting compared to metal oxides, lower temperatures are
required for matte smelting.
The primary objective of matte smelting is to produce a liquid matte (mixture or
solution of Cu2S and FeS) containing almost all the copper present in the charge and a
slag with least copper.
The charge, roasted chalcopyrite concentrate contains sulfides and oxides of iron and
copper as the major components and some sulfates with other gangue mineral as well
as Al2O3, CaO, MgO, and SiO2. Silica is also added as a flux to produce a low-melting
(~1150 C) slag but smelting is carried out at 1250 C to produce a fluid slag.
The flash smelting process
Mostly for sulphide type of ore or mineral, combines into one the flash roasting and the
smelting operations.
The sulfide concentrate fines react with oxygen at high temperatures. The oxidation
process itself generates sufficient heat for the smelting process to occur simultaneously.
The combustion rate in the furnace is conducive for rendering the gases that come out
enriched with sulfur dioxide (a gaseous output of good quality that can be economically
processed to sulfuric acid).
The principal advantages of flash smelting include low energy cost compared to reverberatory
and electric furnace smelting, high SO2 in the effluent gases, and high rate of production of
high-grade liquid matte containing 60–65% Cu.
However, there is high loss of copper in the slag. Currently, more than 50% of the total world
production of copper matte is produced by flash smelting. In flash smelting, a mixture of dry
fine particulate chalcopyrite concentrate (100 μ), quartzite flux, and recycle material is blown
into a smelting unit through burners with oxygen or hot air or a mixture of both.
Fluxes
catalyzing the desired reactions and chemically binding to unwanted
impurities or reaction products. Calcium oxide, in the form of lime, was
often used for this purpose, since it could react with the carbon dioxide
and sulfur dioxide produced during roasting and smelting to keep them
out of the working environment.
Slag

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Smelting process

Smelting is essentially a melting operation in which the constituents of

the charge often contains fluxes to facilitate formation of a low-melting

Physical characteristics like melting and boiling points, vapor

In general, carbon, carbon monoxide, and hydrogen are the

In special cases, as in the production of highly reactive metals such

(i) Reduction smelting

The reduction smelting process involves the reduction of oxidic

MO2 (s,l) + R (s,l) = M (s,l) + RO2 (s)

ΔG = -840 - (-520) = -320 kJ.

Since reduction of Cr2O3 by Al, having a large negative standard free

sulfidic source concentrate + flux = matte + slag + gases

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