Pyrometallurgy
1. Introduction
Fathi Habashi
Department of Mining, Metallurgical, and Materials Engineering
Laval University, Quebec City, Canada
[Link]@[Link]
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Extractive Metallurgy
Pyrometallurgy is an ancient art
Melting Blowpipes
Bellows
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Water Wheel
The water wheel became an important part of a smelter.
Waterpower became more important than the availability
of ore when choosing the location for smelters. Thus,
the preferred smelter location changed from the
mountains, with proximity to ore and wood, to the river
valleys, with their availability of flowing water.
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The use of coke
In 1607 coal was first
converted into coke. This
simple step revolutionized
the iron industry, for coke
being hard and porous is
able to withstand a far
greater burden without
crushing, thereby making
possible the construction
of much larger furnaces
with resultant increase in
output.
Roasting
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Berzelius Bessemer
1779-1848 1818-1898
Formation of immiscible molten layers
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Fluxes
To facilitate the
melting process, a
flux is usually added
to combine with the
high-melting point
components and form
the slag having a low
melting point
Slags
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Silica
Slag
solid
solid
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Engineering Aspects
Unit Operations
Unit operation Application
Heat transfer All processes
Solid–
Solid–gas separation Accessory to all furnaces
Compaction of powders Feed to shaft and fluidized-
fluidized-bed furnaces
Oxidation of a solid phase Sulfide ores
Oxidation in molten phase Steelmaking, copper, and nickel
industries
Metallothermic reactions Preparation of reactive metals by
reduction of their oxides and halides
by other metals
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Steelmaking
Copper Smelting
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Chemical Aspects
Classification Process Application
Preliminary treatment Thermal pretreatment
• Phase transformation Li
• Selective melting Bi
• Melting and quenching Be
• Dehydration and Mg
dehydroxylation
• Calcination Mg
• Oxidation U, Au
Alkali fusion Nb,Ta, Zr
Sulfation of oxides Cu, Ni
Oxidation of sulfides Cu, Ni, Co, Zn, Pb
Matte formation Cu, Ni
Chlorination Ti, Zr, Nb
Fluorination Be, U
Metal separation Reduction Fe, Zn, Pb, U, Th, Nb
Conversion Cu, Ni, Pb
Thermal decomposition Pt, Pd
Refining Chemical Fe, Cu, Pb, Ni
Physico-chemical Pb
Physical Cd, Zn, Hg, Fe
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Metal separation
Form of metal Properties of metals separated
Examples
separated
Boiling point Melting point
Gas Below the Low Mg, Zn, Cd, Hg
temperature of
reduction
Liquid Above the Low Sn, Pb, Cu, Fe,
temperature of Ni
reaction
Solid Above the High Mo, W
temperature of
reduction
Reduction
► M2+ + e– → M+
► M2+ + 2e– → M
For example
2Fe2O3 + 3C → 4Fe + 3CO2
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► However, in some cases when an oxide is heated
with carbon, a carbide is formed instead of a
metal. In this case, other reducing agents have to
be used, e.g., hydrogen:
WO3 + 3H2 → W + 3H2O
► When hydrogen is not effective, metals such as
Al, Ca, Mg, and Na are used as reducing agents.
For example:
3Nb2O5 + 10Al → 6Nb + 5Al2O3
► When oxides do not yield metals by reduction,
they are usually halogenated, then reduced.
Reduction of halides is usually effected by metals,
e.g.:
UF4 + 2Mg → U + 2MgF2
Conversion
MS+ 3/2O2 → MO + SO2
2MO + MS → 3M + SO2
--------------------------------------------------------
MS + O2 → M + SO2
For example
Cu2S + O2 → 2Cu + SO2
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Other processes
z The liberation of mercury during the
oxidation of its sulfide is a special case
when a metal is formed by oxidation since
HgO decomposes at the temperature of
reaction.
z Also, the thermal decomposition of
platinum and palladium complex chlorides
is used as an industrial method for the
preparation of these metals
Refining
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Refining
Chemical methods, e.g., selective oxidation
applied for many metals and chemical transport
applied for nickel, zirconium, and few other
metals.
Physico-chemical methods, e.g., precipitation of
impurities from a molten metal. This is applied
mainly for the refining of lead.
Physical methods, e.g., distillation (applied for
mercury and zinc), vacuum melting (applied for
steel), zone melting (applied for germanium),
etc. The highest refining is only achieved by
physical methods.
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