PYROMETALLURGICAL PROCESSES

Wahidur Rahman Sajal

Lecturer, Dept. of MSE
Khulna University of Engineering and Technology
PYROMETALLURGY
 Extraction of metals… a process of reduction.
 Some energy is required to reduce (i.e. release) the metal and collect
it in elemental form.
 A pyrometallurgical process may be defined as one involving the
application of heat energy.
 Some reactions that are not thermodynamically possible at low
temperatures become so at elevated temperatures.

 There is greater ease of physical separation of the product metal from

gangue if the products can be melted or vaporized at high
temperatures.

 Example: Metal-slag separation

 Drying

 Calcination

 Roasting

 Smelting
DRYING
 Drying usually means the removal of small amounts of water or
moisture from concentrate ore, flux or other solid materials by using hot
gases.

 Water has a high heat of vaporization and, therefore, drying is a

comparatively expensive operation.

 Wet charging may impose some additional burden

1. Heat will be absorbed in evaporating the water
2. Lower the furnace temperature
3. Increase the required time for fusion of the charge
4. Mechanical difficulties in handling or charging may result from
wet, sticky material
PROBLEM 1: AMOUNT OF SOLID DRIED
Ore is dried by passing hot flue gases upward through a drying furnace
which is so designed that the ore enters the top and is discharged at the
bottom. The entering gases which pass upward through the furnace amount
to 10000 cu m per hour and contain 15% water vapor and the remainder
CO2 , N2 and O2 . The wet ore carries 13% moisture, all of which is removed.
The gases enter at 500˚C and are discharged at 100˚C and on leaving are
28% saturated with water vapor. Barometric pressure is 740 mm.

Determine the weight of ore dried per day(24 hours).

CALCINATION
 Calcination is the thermal treatment of an ore that brings about its
decomposition and eliminates the volatile products- usually CO2 , water
and organic matters.

 In calcination, the hot gases do not participate in any reaction but serve
merely to provide necessary heat for decomposition.

The temperature required for calcinations can be calculated from the free
energy temperature relationship.
CaCO3 CaO + CO2 ; Δ G 𝑇 = 42300 – 27.7 T cal
At 1123k or 850˚C , free energy becomes zero. Thus a temperature of 1000
˚C would be sufficient.
CALCINATION
 High temperature calcinations may also change in crystalline structure,
examples-

1. Periclase(MgO) is formed by calcining magnesite(Mg CO3 ) at about

1000˚C and convert the MgO to a stable crystalline structure.
Quicklime(CaO) is not widely used as a refractory because it is not
stable and combine with water and CO2 in air.

2. In refining of bauxites, a precipitate of aluminum trihydrate(2Al(OH)3 )

is filtered and calcined. The high temperature calcinations produce a
crystalline modification of alumina which will not rehydrate when
comes in contact with moisture.
ROASTING
 Very few ores and concentrates in their native form are suitable for direct
conversion to metal. For example, metals often occur as sulfides.

 The free energy change for the reduction of sulfides by carbon is often
positive and, therefore, carbon cannot reduce the sulfides.
2 ZnS + C = 2 Zn + C𝑆2 ; Δ G0 = + 105 kcal at 0˚C and = + 60 kcal at 900˚C

Sulfide minerals are also not soluble in water. This makes leaching
difficult.
ROASTING
 An oxide is more easily reduced to metal than a sulfide and leaching
becomes easier if the metal were present as a sulfate or an oxide.

 Therefore, an ore must be converted into a form suitable for subsequent

treatment. Such a conversion can be brought about by roasting

Heating an ore below the fusion point in excess of air to bring

about chemical conversion to a form that is more suitable for
subsequent treatment (reduction or leaching) for ultimate
extraction of metal
CLASSIFICATION OF ROASTING
 Oxidizing roasting
 Volatilizing roasting

 Chloridizing roasting

 Reducing roasting
OXIDIZING ROASTING
 In most cases its primary purpose is to oxidize sulphide minerals, as in
the reaction
MS + O2 = MO + SO2

 Air is usually used as the oxidizing agent in roasting process.

 May involve other reactions, leading to formation of sulphates or the
release of the metal itself in the elemental form.

 Reactions occurring may include

MS + 2O2 = MSO4 and MS + O2 = M + SO2 and
 When a sulphide ore is roasted to a point where almost the entire sulphur
content is eliminated, the residue is called a dead roast.
VOLATILIZING ROASTING
 This is done to eliminate volatile oxides such as As2 O3 , Sb2 O3 and
ZnO.

 In volatilizing roasting the flow of O2 should be controlled carefully

as excessive oxidation may lead to formation of non-volatile oxides.

 Example: To remove antimony as its oxide from a sulphide ore, it is

necessary to maintain an O2 -pressure high enough to oxidize the
antimony to Sb2 O3 , which is volatile but not so high as to form
Sb2 O4 , which is not so volatile.
CHLORIDIZING ROASTING
Converts certain metal compounds to chlorides from which the metal may
be subsequently reduced.

2NaCl(s) + PbS(s) + 2 O2 (g) = Na2 SO4 (s) + PbCl2 (g)

REDUCING ROASTING
 Reducing roasting consists of the heating an ore or concentrate in contact
with a reducing agent so as to effect the reduction of certain compounds.

 An example is the magnetization roast of hematite to magnetite.

3Fe2 O3 + CO = 2 Fe3 O4 + CO2

 If CO concentration is more than 3.5 per cent in furnace atmosphere at

1000˚C will lead to formation of wustite (FeO).
3 Fe3 O4 + CO = 3 FeO + CO2
CHEMISTRY OF ROASTING
 All the sulfide ore minerals are combustible.
 Some high-sulfide products (rich ores and concentrates) may often
be roasted autogenously
 If heat is not sufficient.. some fuel must be used with the roasting
furnace to maintain the required temperature.

Whether or not a material will roast autogenously depends upon

three factors:
(1) the type of sulfide present,
(2) the percentage of sulfide minerals in the ore or concentrate,
(3) the type of roasting furnace used.
CHEMISTRY OF ROASTING
 The principal object of most roasting operations is to oxidize the sulfide particles
to oxides or sulfates.

 The oxidation must be carried out without fusing the charge. Other reasons for
roasting are to volatilize certain impurities and/or to convert the roaster charge
into a porous sinter.

 Whatever the type of roaster used, the sulfide particles must be exposed to a
current of air and ignited.
 As the air strikes the heated particles, they begin to burn with some such
reaction as
4FeS2 + 11 O2 → 2 Fe2 O3 + 8 SO2 ;
4 C𝑢2 S + 3 O2 → 2 C𝑢2 O + 2SO2 ; and the current of air carries the SO2
away.
CHEMISTRY OF ROASTING
 As oxygen interacts with a sulphide, solid and
strong film of oxides is formed.

 For the reaction to continue, the oxygen and

SO2 gases must pass through the layer of oxide
to get to or from the interior of the particle.

Oxidation of Sulfide Mineral

Particles
CHEMISTRY OF ROASTING
 As roasting progresses, the film grows thicker and
its permeability to gases decreases. ..the oxidation of
the sulphide slows down.
 Even the roasting reaction tends to reverse because
the concentration of O2 decreases and the
concentration of SO2 increases.
 As a result, the removal of the last of the sulfur is
quite difficult.

Oxidation of Sulfide Mineral

Particles
CHEMISTRY OF ROASTING
 Another important chemical reaction that takes place in many
roasting operations is sulphatising or the formation of metallic
sulphates rather than oxides.
2 SO2 + O2 → 2 SO3 ;
 The SO3 in turn reacts with metallic oxides to form sulfates:

FeO + SO3 → FeSO4

CuO + SO3 → CuSO4
ZnO + SO3 → ZnSO4
CHEMISTRY OF ROASTING
 Whether or not sulphates will be formed depends upon
1. the partial pressure of SO3 in the roaster gases and
2. the temperature that determines the dissociation pressure of the
sulphates.

 Any particular sulfate will form only when the partial pressure of
SO3 is greater than the dissociation pressure of the sulfate. Low
roasting temperatures and high SO3 concentrations promote the
formation of sulphates.

 In general, high roasting temperatures will decompose sulphates

into oxides and SO3
INDUSTRIAL ROASTING METHODS

 Multiple hearth roasting

 Flash or suspension roasting

 Fluidized bed roasting

 Sinter roasting (blast roasting)

FLASH OR SUSPENSION ROASTING

 Preheated ore particles are made to fall

through a body of hot air, resulting in almost
instantaneous oxidation or ‘flashing’ of the
combustible constituents of the ore (mainly
sulphur).
 Flash roasting requires that the ore or the
concentrate be ground to a fine size, and the
dust loss in the roaster is likely to be high. This
method roasts very rapidly

Flash Roaster
FLUIDIZED BED ROASTING
 In fluidized bed roasting, the ore particles
are roasted while suspended in an
upward stream of gas.

 When the gas flow rate is very low the

gas permeates the bed (the bed is porous)
without disturbing the ore particles.

 In this stage, the pressure drop across the

bed is proportional to the flow rate.
FLUIDIZED BED ROASTING
 As the gas velocity increases, the bed expands
upwards
 In this stage, the pressure drop across the bed
depends on the gas velocity (segment AB).
 When the gas velocity is further increased, the
pressure drop across the bed approaches the lifting
points[segment BC].
 Finally, a stage is reached when the expansion of the
bed becomes independent of the gas velocity (point C).
 In this condition, the bed is said to be fluidized. This
fluidised bed, is capable of flowing like a liquid.
PREDOMINANCE AREA DIAGRAMS
 A large number of reactions are theoretically possible when a
sulphide is roasted.

 The temperature at which roasting is carried out is a important

factor in determining the nature of the product obtained.

 Predominance area diagrams provide data that help to control

roasting conditions so that desired products can be obtained.
PREDOMINANCE AREA DIAGRAMS
 The predominance area
diagrams are plotted from
thermodynamic data.
 Ni-S-O system

 At 1000 K, the condensed phase

is made up of Ni, NiO, Ni3S2
and NiSO4 .
 The gas phase normally contains
SO2 and O2 but some SO3 may
also be present.
Predominance Area Diagram for Ni-
S-O System at 1000K
PROBLEM 2:CALCULATION OF YIELD
A concentrate has the following composition, %; Cu-14; Fe-32; S-38;
SiO2 -4; CaO-1; Zn-4; undetermined-6: moisture content 3. A
desulphurization of 65 per cent is to be achieved. Assume that a
small excess of air is used and all of the iron is bound as Fe3 O4 .

Determine the composition of the yield.

SOLUTION
SOLUTION
SMELTING

 Smelting is a process of applying heat to ore in order to melt out

a metal.
 It is used to extract many metals from their ores, including
silver, iron, copper etc.
 Smelting uses heat and a chemical reducing agent to decompose
the ore, driving off other elements as gases or slag and leaving
the metal behind.
 The reducing agent is commonly a source of carbon, such as coke.
GENERAL EXPRESSION OF A SMELTING PROCESS

Mineral + Gangue + Flux + Reducing agent Metal + Slag + Gas

General characteristics of a Smelting Process

 the materials to be smelted are usually charged in the solid state

 the products of smelting are in the liquid state
 the heat required for smelting is generally supplied by external
sources
FLUXES
 It is desirable to have a liquid slag so that the metal can be easily
separated from the gangue. The formation of a liquid slag is facilitated
by the addition of a flux.

 Flux reacts with the oxidized portion of the charge and form a fluid slag.
 Limestone, lime and iron oxide….cheap enough for practical use

Criteria for choice of a flux

The chemical nature of the gangue
Siliceous gangue a basic oxide (lime)
Limey gangue an acidic oxide (silica)
SLAGS
Slags primarily consist of oxides.

Functions of a Slag
 to provide a medium in which the impurities in a
metal can collect in a refining process
 to act as a physical barrier to protect the metal
beneath from harmful effects of the atmosphere
 to act as a barrier to minimize heat loss from the
molten bath
PROPERTIES REQUIRED OF A SLAG

 Forease of separation, the difference between the specific

gravities of the slag and the metal should be sufficiently
high.

 The slag must be fluid enough to permit easy separation

from the metal and also to bring about a faster mass
transfer

(A viscous slag causes greater loss of metal by entrapment in

the slag)
METAL LOSSES IN SLAGS

 Serious
complication could arise during smelting if the reactant
and product oxides themselves form compounds

Example: Blast furnace smelting of lead ore, a significant

quantity of PbO may combine with silica
PbO + SiO2 = PbO. SiO2 (slag)

Fe-scrap is added to minimize this loss

PbO + Fe = FeO + Pb
PbO.SiO2 + Fe = FeO.SiO2 + Pb
REDUCTION SMELTING USING CARBON
Carbon is a unique reducing agent ….
Readily available and cheap, forms 2 volatile oxides (CO,
CO2 ) at the same time carbon also acts as a source of heat

Theoretically speaking
Carbon can reduce any metal oxide provided the
temperature is sufficiently high.
The Standard Free Energy
of Formation of a Number
of Oxides as a Function of
Temperature (Ellingham
Diagram)
REDUCTION SMELTING USING CARBON
The reduction of a metal oxide by carbon can be represented
MO (c) + CO (g) = M (c) + CO2 (g)
CO2 (g) + C (c) = 2 CO (g)

Combining the above reactions, we get the overall reaction as

MO (c) + C (c) = CO (g) + M (c)
REDUCTION SMELTING USING CARBON
 In a number of cases the temperatures required for reduction by carbon
is beyond practical limits. For example, ΔGo for the reduction of stable
oxides like MgO and Al2 O3 by carbon becomes negative at 1840 and
2000˚C respectively.

 To operate smelting processes above these high temperatures would be

expensive because of the fuel requirements and the difficulty of
producing refractory containers which would last for economic periods.

 At too high a temperature C may dissolve and form stable carbides

Example: Fe3 C is formed during BF reduction of iron oxides
METALLOTHERMIC REDUCTION
A compound can also be reduced by a metal that forms
more stable oxides.
 the principle is similar to that of carbon reduction

 metallothermic reduction is usually carried out on a

small scale and is rarely referred to as smelting.

The principle of metallothermic reduction can be

understood by referring again to the free energy
diagram for oxides.
METALLOTHERMIC REDUCTION
At 1200C, ΔG for the formation of Cr2 O3
is approximately – 120 kcal and that for
the formation of Al2 O3 is approximately –
190 kcal
The distance between the two lines at
1200˚C is –70 kcal, which is the difference
between these two standard free energies
of formation and, therefore, for the
reduction of Cr2 O3 by Al.
Cr2 O3 = Cr + O2 , ΔGo = +120 kcal
Al + O2 = Al2 O3 , ΔGo = - 190 kcal
ADD Cr2 O3 + Al = Cr + Al2 O3 , ΔGo = - 190
+120 = - 70 kcal
SOLID STATE REDUCTION
 Generally reduction smelting refers to an operation involving a reducing
agent and a slag to obtain liquid metal.
 This is not applicable where the melting point of the metal is very high or
where the ore is of very poor grade.

 For example, W has a very high melting point. Moreover, W ores generally
contain only about 2 per cent WO3 , the rest constituting the gangue. It
would be uneconomical to remove this gangue using a flux. In this case it is
advantageous to produce pure WO3 , using extensive ore dressing and
hydrometallurgical operations. WO3 is subsequently reduced to tungsten
powder by hydrogen at about 800 – 1000˚C. The reaction is
WO3 (s ) + 3 H2 = W (s) + 3 H2 O (g)
 The metal powder so obtained is processed to the desired shape through
powder metallurgy route.
MATTE SMELTING
 In the extraction of a metal from a sulphide ore, an important method
used involves the production of a liquid matte from the ore and its
subsequent conversion to the metal.
 In matte smelting, the sulphide ore is fused with a flux to produce a
molten mixture of sulphides known as a matte.
 The gangue materials pass off into the slag, which is immiscible with
the matte, i.e., it forms a separate layer. Some sulphur is lost in the
furnace gases as SO2 or SO3 .
 Matte smelting is usually carried out in a furnace and follows a roasting
operation.
 Roasting reduces the sulphide content of an ore in such a manner that
subsequent smelting with a suitable flux produces a matte of the
required grade. It should be noted that roasting brings about only the
partial oxidation mainly of FeS and FeS2 to FeO, which would pass off
into the slag .
EXTRACTION OF COPPER
 In principle it is possible to roast the sulphide ore of copper to oxide and
then reduce it by carbon. But since the concentrate also contain FeS, iron
oxides will also form.

 In fact oxidation of copper sulphide does not occur until Fe is fully

oxidized yielding Fe3 O4 . This Fe3 O4 is difficult to remove by slagging.

 The principal ore mineral of copper is chalcopyrite (CuFeS2) with a

usual copper content of less than 2 per cent. Usually the ores are
upgraded by floatation, the concentrates containing up to 55 percent
copper (generally, however, 11 – 35 percent copper).
EXTRACTION OF COPPER
 The concentrates are then roasted under controlled conditions.
During roasting, iron sulphide is partly converted into FeO for
subsequent removal by slagging.
2 CuFeS2 (s ) + O2 (g) = Cu2S (s ) + 2 FeS (s ) + SO2 (g)
FeS + O2 (g) = FeO (s ) + SO2 (g)

 The last reaction is not allowed to go to completion to ensure the

absence of higher oxides of iron.

 The roasted solids (consisting of copper sulphides, iron

sulphides and gangue minerals) are charged into a furnace
together with sufficient quartz (SiO2) to form a suitable slag.
EXTRACTION OF COPPER
 The charge is heated to 1200 – 1300oC. The smelting action is
essentially a simple melting operation and very little chemical
reaction takes place.

 Iron oxide is removed as a slag (FeO.SiO2).

 The remaining sulphides melt and collect as matte.

 These two liquids are immiscible and form two liquid layers. The
specific gravity of matte is twice that of slag and therefore, collects
beneath the slag with good matte/slag separation.
EXTRACTION OF COPPER
Cu is recovered from matte by blowing air through molten matte-
2 FeS + 3 O2 = 2 FeO + 2 SO2
 As the ferrous oxide forms, it reacts with silica to form a slag.
FeO + SiO2 = FeO.SiO2
 When the iron has been slagged from the matte, the blast is stopped
and the slag is poured off. The blowing is then resumed. Now the
copper sulphide is oxidised.
2 Cu2S + 3 O2 = 2 Cu2O + 2 SO2
 The copper oxide formed reacts with the unchanged sulphide to yield
metallic copper.
2 Cu2O + Cu2S = 6 Cu + SO2
 The yield of copper is about 99 percent pure and is subsequently
refined.