Methods of Extraction

1
 Introduction
• In an extraction process, the bulk of the metal is separated from the
impurities present in the ore by using a system, which invariably
comprises more than one phase.
• Metal enters the metallic phase while the impurities enter the non-
metallic phase or phases.
• Driving force for the reactions involved in metal extraction depends on
the differences in the chemical potentials of the chemical elements.
• During a chemical reaction, an element tends to move from a high to low
chemical potential state. The basic aim of the extraction process is to
create conditions conducive to such a transfer which facilitates the
extraction of a metal or its compound.

2
 Types of extraction processes
• Pyro metallurgy: A vast majority of metallurgical reactions are made to
take place at elevated temperatures when the ore compounds become
relatively unstable, facilitating the release of the metal.
• Electrometallurgy: It is a process in which the dissociation or
decomposition of a compound in solution(i.e. reduction of an ion)is
brought about by employing electrical forces.
• Hydrometallurgy: The reduction process depends on the judicious
manipulation of the chemical reactions taking place in an aqueous
solution.

3
 Pyro Metallurgy - advantages
It remains the principal means of metal extraction in terms of number of
applications and in the tonnage of metal produced.
It is based on chemical changes occurring at high temperatures i.e. 500 –
20000C. Pyro Metallurgy is often cheaper and more versatile than other two
methods because of
•At high temperature, reaction rate is accelerated and higher productivity
(higher the temperature, the smaller is the activation energy barrier that
opposes the progress of the chemical reaction.
•Ability to use inexpensive reducing agents or raw materials
•Ability to shift the reaction equilibrium with temperature. For example at
250C, the equilibrium position of the reaction. ZnO + C - Zn + CO is far to
the left, but at 12000C, it shifts to the right. In other words, ‘C’ cannot reduce
ZnO except at high temperatures.

4
 Pyro Metallurgy - advantages
• Physical separation of a product metal from waste is facilitated when the
products are liquefied or vaporized at high temperatures. At these
temperatures, the liquid metal and liquid slag that are formed separate
out, facilitating metal extraction. Some examples are
a. Some of the common metals such as Fe, Pb, Cu, Al, Mg, Na and Sb are
produced by the processes where the metal is reduced to either the liquid
or the gaseous state permitting its separation from the residue.
b. Refractory metals such as Ti, Zr, Mo, Ta and Nb are expensive because
they are directly reduced to solid metal, necessitating another expensive
process either to separate the metal from the residue or to pre-purify the
metal compound so that no residue remains after reduction.

5
 Pyro Metallurgy - advantages
• Pyro metallurgy process can bring about the reduction of a compound,
which cannot take place in the presence of water. Reactive metals cannot
be extracted from the aqueous solution.
• As a result, only pyro metallurgy or fused salt electrolysis is used to
extract the highly reactive metals namely the alkaline earth metals,
zirconium and Titanium.
• A high temperature process has the inherent ability to treat large
tonnages of ores in a compact space, which leads to a saving in the capital
cost.

6
 Pyro Metallurgy

• There are three main steps in pyro metallurgy

a. Calcination
b. Roasting
c. Smelting

7
 Calcination

• It is a thermal treatment of an ore, which brings about its decomposition

and eliminates the volatile product – usually carbon dioxide or water
• Reaction for the decomposition of calcium carbonate in a kiln is
CaCO3 = CaO + CO2 ΔGT0(cal) = 42300 – 37.7T
• When the CO2 pressure is 1 atm, ΔGT0 becomes equal to zero and ‘T’ is
1123 K or 8500C. If the kiln temperature is 10000C, decomposition
happens rapidly. The reaction is endothermic and the rate of
decomposition is probably controlled by the rate of heat transfer to the
particle.
• Since the solid residual product is porous and permeable, the gaseous
product can escape easily.

8
 Calcination

• The decomposition temperature of a carbonate is the temperature at

which the partial pressure of CO2 equals 1 atm. Most carbonates actually
decompose at temperatures lower than the decomposition temperature
of calcium carbonate (MgCO3 = 4170C, MnCO3 = 3770C, FeCO3=4000C).
• This can be used for differential calcination. For example, a magnesium
ore that contains both Mg and Ca can be beneficiated by calcining the ore
at temperature around the decomposition temperature of MgCO3 . Water
is used to leach MgO and the undecomposed CaCO3 is left behind.

9
 Roasting

• It is a process, which precedes smelting in pyro metallurgy and leaching in

hydrometallurgy. Only very few ores and concentrates in their native form
are suitable for the direct conversion to the metal.
• An oxide is more readily reduced to the metal than a sulphide and
leaching becomes easier if the metal is present as a sulphate, chloride or
oxide. Mineral constituent of an ore is converted into another chemical
form through roasting, using oxygen or some other element.
• Roasting traditionally was used to remove ‘S’ or other elements such as
‘As’ and ‘Te’ in the form of volatile oxide from the ore.
• Nowadays roasting encompasses a wide variety of operations including
reduction, sulphation and chloridization. The product, thus obtained
becomes amenable to subsequent treatment for the extraction of metal.

10
 Oxidizing Roasting

• This burns out the ‘S’ from a sulphide ore and replaces it in whole or in
part by an oxide. The general reaction is
MS + 3/2 O2 (g)  MO + SO2 (g) For example, ZnS + 3/2 O2 (g)  ZnO + SO2 (g)
• Reaction above gives an overall picture of roasting. In reality, a
complicated series of reversible reactions occur. During roasting, metal
sulphates may also be formed. High temperature breaks up the sulphates,
especially zinc sulphate.
• When a sulphide ore is roasted to a point, where almost the entire
sulphur content is eliminated , the residue is called ‘dead roast’.
• A catalytic agent often speeds up the roasting process. Quartz and other
gangue materials often act as catalysts during roasting.

11
 Oxidizing Roasting

• Roasting depends upon factors such as time, temperature, availability of

oxygen or air, physical condition of the ore and nature of the physical
condition of the ore.
• Durations of the roasting processes vary greatly. Blast roasting is done in
a flash of time. Hearth roasting takes hours, Heap roasting months and
weather roasting years.

12
 Volatilizing Roasting

• It eliminates volatile oxides such as As2O3, Sb2O3 and ZnO from the ore. In
this process, the flow of oxygen is to be carefully controlled as excessive
oxidation may cause the formation of non-volatile higher oxides.

13
 Chloridizing Roasting

• It is done to convert certain metal compounds to chlorides under oxidizing

or reducing conditions. Metals such as U, Be, Nb, Zr and Ti are extracted
from their chlorides. Chloridizing reactions are
2NaCl + MS +2O2 = Na2SO4 + MCl2 --- reaction 1
4 NaCl + 2 MO + S2 + 3O2 = 2 Na2SO4 + 2 MCl2 ---- reaction 2
• Reaction 1 is suitable for the roasting sulphide ore and the reaction is
exothermic. Reaction 2 is for the oxide ore and the addition of ‘S’
facilitates the chlorination. Carbonates decompose on heating giving rise
to oxide and the reaction 2 is valid.
• Sulphates and Silicates react with a Chloride by a direct interchange of the
elements and radicals without the addition of ‘S’.

14
 Other kinds of Roasting

These include
a.Sulphating Roasting: converts certain sulphide ores to sulphates prior to
leaching.
b.Magnetic Roasting: is the partial reduction of an oxide prior to actual
reduction smelting.
c.Blast Roasting or Sinter Roasting: modifies the physical condition of an ore
(eg. Agglomeration), but also helps in partial oxidation.

15
 Chemistry of Roasting

Many reactions are possible, when a sulphide is roasted. When ‘M’ is a

divalent metal, some of the possible reactions are
MS2 = MS + ½ S2 (g) -----1
½ S2 (g) + O2 (g) = SO2 (g) ----- 2
MS(s) + 3/2 O2 (g) = MO(s) + SO2 (g) ----- 3
SO2 (g) + 1/2O2 (g) = SO3 (g) ----- 4
MO(s) + SO3 (g) = MSO4 (s) ------ 5
MSO4 (s) = MO ySO3 (s) + (1-y) SO3 (g) ---- 6
MO. ySO3 (c) = MO(c) + ySO3 ----- 7
•Examples of MO.ySO3 are PbSO4.PbO (y=1/2) and PbSO4. 2PbO (y=1/3). At
the temperatures commonly used for roasting, reactions 2 and 3 have large
negative free energy changes.

16
 Predominance Area Diagram
• The temperature at which roasting is carried out decides the nature of the
product obtained. To get the desired product, we can determine the best
operating temperature by knowing both the composition of the gas used
and the equilibrium relationship in an M-S-O system.
• Isothermal behaviour of some M-S-O systems with respect to their
stabilities can be represented by Predominance Area Diagrams.
• They indicate for a specified temperature, those solids, which are in
equilibrium with a gas having specified partial pressures of oxygen and
sulphur dioxide.

17
 Predominance Area Diagram
• Even in the case of partial roasting, where equilibrium conditions do not
prevail, the diagrams can be used to identify the type of product formed
as the reaction proceeds towards equilibrium.
• These diagrams are plotted from the available thermodynamic data and
they are helpful to determine the best operating conditions to obtain the
desired end products.

18
 Use of Predominance Area Diagram

DG: NiS(s) + 2 O2(g) = NiSO4 (s) ---- reaction 1

DH: 2 NiO(s) + 2 SO2(g) + O2(g) = 2NiSO4 ---- reaction 2
FC: 3 NiS(s) + O2 (g) = Ni3S2(s) + SO2 (g) ----- reaction 3
EB: Ni3S2 + 2O2(g) = 3 Ni (s) + 2SO2(g) --- reaction 4

•At 1000 K, if the roaster gas phase contains 10% SO2

and 10% O2, it is seen from the diagram that NiSO4 is
thermodynamically stable. On the other hand, if the
gas phase contains only 1% SO2 and 1% O2 the final
product is NiO.
•Nickel Sulphate is formed under oxidizing conditions
at a high partial pressure of SO2. Although NiS can be
converted to NiSO4 at high partial pressure of SO2, in
practice, it is more convenient to do so through the
intermediate formation of Ni3S2 and NiO.

19
 Roasting Practice
• Roasting is a preliminary step in many extraction processes. It is necessary
to choose a roasting method which would facilitate subsequent
operations.
• Generally a roasting process is chosen based on two major criteria
a. Required physical condition: If the ore is to be smelted in BF, the product
should be coarse and cellular. For a reverberatory furnace or for a retort,
the product should be fine. For leaching, the product should be porous in
nature and the formation of insoluble compound should be avoided.
b. Required chemical composition: If ‘Pb’ is the prime metal, it is desirable to
eliminate the entire ‘S’ before subsequent BF smelting. For ‘Cu’, entire ‘S’
need not be eliminated. For ‘Zn’, entire ‘S’ is to be removed. However the
formation of zinc ferrite should be avoided if zinc is extracted by leaching
since leaching the ferrite is difficult.

20
 Roasting Practice
Several other factors need to be considered while doing the roasting
•The chemical composition of an ore and of the minerals present in it may be
an important consideration for the selection of the particular roasting
process.
•In the manufacture of sulphuric acid from sulphurous gases that are evolved
during roasting, the process should ensure the availability of gas rich SO 2i.e.
fluidized bed roasting. It eliminates atmospheric pollution.

21
 Roasting Practice

•If precious metals or other valuable metals which may be lost at excessively
high temperatures, we may adopt low temperature operation.
•Most desirable combination of roasting operations is one that is
commercially the most satisfactory in the long run.
•Utilization of sulphurous gases is recommended not only because it results
in economic gain, but also it prevents atmospheric pollution.

22
 Roasting Practice

Multiple Hearth Roasting (Macdougall type

roaster)
•It consists of several circular brick hearths
superimposed on each other. The entire structure
is enclosed in a cylindrical brick-lined steel shell.
•Mechanical rabbles attached to arms move over
the surface the surface of each hearth to
continuously shift the ore. Arms are attached to a
rotating central shaft that passes through the
centre of the roaster.
•Ore is discharged at the top hearth and it moves
downwards through alternate passages around
the shaft and the periphery and finally emerges at
the bottom. Oxidizing gases flow upwards.

23
 Roasting Practice
Multiple Hearth Roasting (Macdougall type roaster)
•In a well-insulated roaster, external heating is unnecessary except when the
charge is highly moist. The hearths at the top of the roaster dry and heat the
charge.
•Ignition and oxidation of the charge occur lower down. In this type of
roaster, the process is effectively controlled, but there are certain drawbacks
such as
a.Process is slow
b.Sulphurous gases are lean and hence not suitable for the production of
sulphuric acid.

24
 Roasting Practice – recent techniques

Flash Roasting
•Preheated ore particles are made to fall through a body
of hot air, resulting in the almost instantaneous
oxidation or flashing of the combustible constituents of
the ore, mainly ‘S’.
•A flash roaster is specifically designed to ensure a large
combustion zone

Fluosolid Roasting (Fluidized Bed Roasting)

•In this process, the particles are roasted while
suspended in an upward stream of gas. When a gas is
passed upwards through a bed of solids – small and
preferably regular in size over the range 0.005-0.05cm in
diameter – the behaviour of the bed depends on the
velocity of the gas.
•With the increase in velocity, a stage is reached when
the expansion of the bed becomes independent of the
gas velocity. The bed looks like a well stirred boiling
liquid. In this condition, the bed is said to be fluidized.

25
 Roasting Practice – recent techniques
Ignition temperature and autogenous roasting
•The fluidized bed roasting is ideal for sulphide ores because the oxidizing
reactions that take place during roasting are highly exothermic. There is a
minimum temperature above which the reaction is sustained by the heat
liberated.
•When the ore particle is initially maintained at this minimum temperature in
a stream of air and the roasting initiated by an ignition device, then the
reaction continues to proceed even in the absence of any external heat.
•In a fluidized bed roaster, the minimum temperature required depends on
the characteristics of the ore as well as the process conditions of ignition
(geometry of the reactor and fluid flow)
•A fluidized bed roaster has a high energy efficiency because it can be
autogenously operated. Further it is useful in the recovery of ‘S’ because the
gas that it produces has a high SO2 content.

26
 Sinter Roasting

• Fine ores and concentrates are to be

agglomerated before they can be charged in BF,
otherwise heavy dust losses result.
• Sinter roasting is the treatment of a sulphide ore
in a sintering machine where roasting and
agglomeration take place simultaneously. This is a
standard practice for lead sulphide ores in which
the fine flotation concentrates are agglomerated.
• Sinter roasting is carried out in a Dwight-Lloyd
sintering machine. The fine concentrate is charged
as a layer of 15-50 cm thick on to an endlessly
revolving belt of grates or pallets which moves
over wind boxes at a regulated speed.
• A burner under the ignition hood is used to start
the combustion of the bed surface. The
combustion is propagated through the mass of
charge by a current of air drawn through the
charge into the wind box which is connected to
the suction fan.
27
 Sinter Roasting

• High temperatures are developed in the material to cause partial or

incipient fusion, which produces a porous material called ‘sinter’.
• A certain amount of moisture is necessary to render the sinter porous.
When the sinter reaches the end of the machine, it is discharged and
cooled. The cooled sinter is sized to give a uniform product.
• Sinter roasting of a sulphide ore does not require the addition of any fuel.
In the case of oxide ore, addition of fuel to achieve sintering is essential.
• In the case of zinc ore, multiple hearth roaster or sinter roasting is used. In
the case of copper ores, reverberatory furnace is more often used.

28
 Smelting
• It is a heating process of a metal or matte. Generally the process is one of
the reduction of oxide of the metal with carbon / sulphur / sulphide / in a
suitable furnace (reverberatory furnace / BF / Electric furnace)
• During smelting, it should be remembered that since the gangue in the
ore is less fusible than the metal, the flux must be added to form a slag
that is easily fusible.
• The smelting process for metal may be written as
mineral + gangue + reducing agent + flux -- metal / matte + slag + gas
• Some of the general characteristics of smelting are
a. Materials to be smelted are usually in the solid state
b. Products are in the liquid state. Solid material that escapes is the dust
which is carried away by the furnace gases.
c. Heat required for smelting is supplied by external sources.

29
Reduction Smelting

• Reduction smelting is carried out

in BF. Matte Smelting is done in
reverberatory furnace or flash
smelter. Both reduction smelting
and matte smelting can be done in
an electric furnace.
• In reduction smelting, the ore is
reduced by carbon in the presence
of flux to produce the molten
metal and the slag. Sometimes,
reduction is brought about by
another metal, whose oxides are
much more stable than those of
the metal being extracted.
• In matte melting, reducing agent is
not used. Sulphide itself acts as a
reducing agent. In this operation,
products are molten matte and
molten slag ------- metal is not
produced.

30
 Fluxes
• In smelting, a flux is used to lower both the liquidus temperature and the
viscosity of the slag. For a siliceous gangue, a basic oxide such as lime is
used as a flux and vice versa for the basic gangue.
• When the flux is acting as a cover, either potassium carbonate or sodium
carbonate is used as flux. Oxidizing fluxes such as Na2O2 / NaNO3 /KNO3
and reducing fluxes such as NaCN are employed in case of precious
metals.
• A neutral flux such CaF2 / Na2SO4 finds application in fused salt electrolytic
bath.

31
 Slags
• There are two main functions of slag
a. To collect the unreduced gangue minerals so as to form a separate layer
b. To provide a medium in which the impurities in the metal can collect
during the refining process (often the impurities get partitioned between
the metal and slag)
• To fulfil these functions, the slag must possess the following properties
a. Difference between the specific gravities of the slag and the metal should
be sufficiently high so that one can be easily separated from each other.
b. Slag should be sufficiently fluid enough to permit its easy separation from
the metal and also to bring about the mass transfer faster.
c. Slag must have a chemical composition which ensures that the activities
of the impurities and of the dissolved gangue minerals are low.

32
 Reduction Smelting using Carbon
• Carbon as a reductant is easily available and is also not expensive. All the
metal oxides can be reduced by carbon provided the temperature is high
enough.
• The reduction reaction is represented as
MO(s) + C(s) = CO(g) + M(s)
2MO(s) + C(s) = 2M(s) + CO2(g)
• The above reactions are between two solids and since the reactions are
controlled by solid state diffusion across a small area of contact, they
proceed at slow rate.
• If the reduction takes place in more than one step i.e. intermediate
reaction between a gas and a solid, the reaction will proceed faster
MO(s) + CO(g) = M(s) + CO2(g) (at temperature below 7000C, the reduction is represented by
this reaction)
CO2(g) + C(s) = 2CO(g)

33
Reduction Smelting using Carbon (refer Ellingham
diagram)

•
Electrode Reaction Standard Potential, E 0 (V vs. SHE)

Temperatures required for reduction by O3(g)+2H++2e−→O2(g)+H2O

H2O2+2H++2e−→2H2O
2.070
1.776

carbon in a number of cases are beyond Au3++3e−→Au

Cl2(g)+2e−→2Cl−
1.500
1.358

practical limits. It is possible to produce Mn Pt2++2e−→Pt

O2+4H++4e−→2H2O (pH=0)
1.200
1.229

or alloy of manganese in a BF. Pd2++2e−→Pd

H2O2+2e−→2OH−
0.987
0.880

• Metals lying above Mn in the emf series form Hg2++2e−→Hg

O2+2H2O+4e−→4OH− (pH=7) (a)
0.854
0.820

oxides having higher negative free energies of Ag++e−→Ag

Cu++e−→Pd
0.800
0.521

formation and may be reduced by carbon but O2+2H2O+4e−→4OH− (pH=14)

Cu2++2e−→Cu
0.401
0.337

not in a BF. Electric furnace which can obtain 2H++2e−→H2

Fe3++3e−→Fe
0.000
–0.036

higher temperature may be suitable for the Pb2++2e−→Pb

Sn2++2e−→Sn
–0.126
–0.136

purpose. Ni2++2e−→Ni
Co2++2e−→Co
–0.250
–0.277

• During cooling from the reaction In3++3e−→In

Cd2++2e−→Cd
–0.342
–0.403

temperature, a reverse reaction may occur if 2H2O+2e−→H2(g)+2OH− (pH=7) (a)

Fe2++2e−→Fe
–0.413
–0.440

the reduced metal is in the form of a vapour Ga3++3e−→Ga

Cr3++3e−→Cr
–0.530
–0.740

(as in the case of Mg). Some metals such as Zn2++2e−→Zn

2H2O+2e−→H2(g)+2OH− (pH=14)
–0.763
–0.828

Zn can be condensed in the presence of ‘CO’ Mn2++2e−→Mn

Zr4++4e−→Zr
–1.180
–1.530

where the reverse reaction is limited to a Al3++3e−→Al

Mg2++2e−→Mg
–1.660
–2.370

great extent. Na2++2e−→Na

Ca2++2e−→Ca
–2.710
–2.870
K2++2e−→K –2.930
Li2++2e−→Li –3.050

34
Reduction Smelting using Carbon (refer Ellingham
diagram)

• Some reactive metals may react with ‘CO’

when the gas mixture is cooled. For example,
reverse reaction of ‘Mg’ is to be restrained by
shock cooling.
• At high temperatures, fresh problems may
arise . For instance, a new stable phase
namely metallic carbide may appear, when
the metal reacts with the carbon itself. The
formation of carbide can be suppressed if the
metal is produced in the presence of another
solvent metal.
• Production of ferro-alloys also makes use of
the advantage gained by alloying. FeV, FeTi,
FeSi, FeNb etc are produced by the reduction
of the corresponding oxide by carbon in the
presence of iron. Even alloying does not
always ensure a carbide-free product

35
 Metallothermic Reduction of Oxides

• An oxide is reduced by a metal that

forms stabler oxides. Such a
metallothermic reaction carried out in
an open container or a closed container
(bomb) completely avoids carbon
contamination.
• Metallothermic reduction is carried out
on a small scale and is rarely referred to
as smelting. In practice, the reduction
would depend on factors such as the
reaction rate and the physical properties
of the reactants and products.
• Fe2O3 (l)+ 2 Al(l) = Al2O3(l) + 2 Fe(l) (thermit
reduction) - All the products are liquid
state and alumina can be slagged off as
liquid using another oxide as flux.

36
 Smelting furnaces
1. Blast Furnace
• Fe and Pb are produced in the BF. Imperial smelting process was developed in
England for the simultaneous production of Pb and Zn. When ‘Pb’ is tapped,
zinc is recovered by dissolving the out coming zinc vapours in a running stream
of hot molten lead. Zinc separates from lead on cooling.
2. Reverberatory Furnace
• In BF smelting reducing conditions are created . If such conditions are not
needed or undesirable, a simpler furnace such as ‘reverberatory furnace’
furnace is used. For example, in smelting of tin, reverberatory furnace is used
to minimize the reduction of more stable oxide impurities such as iron oxide.
3. Electric arc smelting
• When high temperature is required for reduction and fusion, electric arc
smelting is employed. A temperature around 20000C is easily attained in it.
Ferroalloys which need high temperatures for reduction use electric furnace.
4. Metallothermic reduction
• No special furnace is required for the metallothermic reduction of an oxide.
Need for external heat is limited because the reactions are mostly exothermic

37
 Flash smelting

• It is a process which combines the

operations of flash roasting and
smelting. It burns the concentrate
(falling through the combustion
chamber of a flash smelter) with
oxygen or preheated air blown in with
concentrate.
• Sufficient heat is generated to form a
matte and slag which settle in the
hearth. In flash smelting, enriched
preheated air or pure oxygen is used
to increase the combustion rate and to
maintain the autogeneous smelting.
• The gases coming out of the furnace
are rich in SO2 (due to the high
combustion rate) and can be used for
the manufacture of sulphuric acid.

38
 Matte smelting

• In the extraction of a metal from the sulphide ore, an important

method used involves the production of a liquid matte from the ore
and its subsequent conversion to the metal.
• Sulphide ore is fused with a flux to provide 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 as SO2or SO3. For a sulphide ore, matte smelting is
a thermal concentrating process.

39
 Matte smelting
• Matte is a metallic sulphide solution that contains minor amounts of
oxygen and sometimes some metal too. Matte exhibits a high electrical
conductivity (comparable with that of a metal) and has a density between
that of a metal and slag.
• It is insoluble in the metal and slag phases. Thus three distinct layers
namely slag, matte and metal are produced. Matte is an excellent solvent
for some impurity metals, especially for valuable traces of precious
metals.
• Matte smelting which is usually done in a reverberatory furnace follows a
roasting operation. Roasting first reduces the sulphide content of an iron
ore in such a manner that subsequent smelting with a suitable flux
produces a matte of the required grade.
• For example, roasting brings about the partial oxidation mainly of FeS and
FeS2 to FeO, which would pass off to the slag phase.

40
 Matte smelting
• Matte smelting is adopted in the extraction of copper, nickel and
sometimes antimony. The common ores of these metals contain sulphide
minerals including FeS. During roasting prior to matte smelting the
sulphides of iron are oxidized more easily than those of copper and nickel.
• Oxidation of Cu2S or Ni3S2 can be avoided by controlling the oxidation of
the ore so as to produce only FeO and not Fe2O3 / Fe3O4. This is necessary
because higher oxides of iron do not pass off into slag easily.
• Copper is recovered from the matte by a process, known as ‘smelting’ in
which air is blown through a side blown converter.
• Initially the residual FeS is oxidized and slagged out. Subsequently the
sulphides of copper are converted into metallic copper.

41
 Reduction of halide by another element
• A number of rare and reactive metals are
produced by the reduction of a halide by
another metal. The basic reaction is: MXn
+ M’ = M’Xn + M where M and M’ are two
different metals and X is a halide (fluorine
or chlorine).
• Earlier this reaction was used extensively
for the extraction of reactive metals. Now
a days, this method is used for a few
metals such as ‘Ti’ and ‘Zr’.
• Kroll’s process employed for the reduction
of a halide using ‘Mg’ is an example of this
process. The reaction is: TiCl4 + 2Mg =
2MgCl2 + Ti
• Sodium can be used in stead of Mg.
• Principle of halide reduction can be
understood from a chloride free energy
diagram. It is drawn for the formation of
chlorides from 1gm mole of chlorine for
each of the reactions represented.

42
 Reduction of Halide by another element
• Elements such as Na, K, Li, Ca and Mg appear at the bottom because their
halides are very stable. These metals are excellent reducing agents.
• Melting, boiling and sublimation points of the chloride are designated as
M, B and S respectively and those of the metals as M’, B’ and S’
• Position of the line for CCl4 clearly shows that carbon is not a suitable
reducing agent for chlorides.
• Lines for most of the chlorides have an upward slope, but HCl has a slight
downward slope. It means that hydrogen becomes a slightly better
reducing agent at higher temperatures.

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 Reduction of Halide by another element
• Halides usually have low melting and boiling points. If the metal produced
at the reduction temperature is itself in a liquid state, then a clean liquid-
liquid separation of the metal and slag is easily obtained. UF4 + 2 Ca =
CaF2 + U
• Melting points of reactive metals are high and these metals may be
obtained in the form of a solid entrapped in the mass of slag. Sometimes
it is done by incorporating booster reactions during bomb reductions so as
to provide exothermic heat to melt the whole charge and thereby obtain
a clean separation.

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 Halide metallurgy and Halogenation
• Halides are seldom found as natural ore deposits on land, they are
produced from naturally occurring minerals by halogenation. Most
commonly used halides are chlorides and fluorides.
• Chloride is preferred to fluoride because it is less corrosive and is easily
handled. On the other hand, many chlorides are hygroscopic where as
fluorides or not. In fused salt electrolysis, fluorides are preferred to
chlorides.

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 Halide metallurgy and Halogenation
• Halogenation is carried out to achieve some of the following objectives
a. Opening up of relatively complex minerals and the recovery of the
metallic values.
b. Beneficiation of low grade ores to yield the metallic halide either in the
vapour state or in the condensed state. Many metallurgical wastes can be
chlorinated for the subsequent metal recovery.
c. Production of pure halides of reactive metals from which oxygen-free
metal can be obtained. Reactive metals such as U, Th, Ti, Be and Zr , if
produced from oxides may contain appreciable quantities of oxygen
which is detrimental to their properties.
d. Refining of crude metals

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 Chlorinization processes
• They are categorized into three types
a. Chloridizing roasting
b. Chloridizing vaporization
c. Chlorination in fused salts

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 Chloridizing Roasting
Ore is roasted with common salt and the solid chloride is recovered by
leaching. This method is ideal for a sulphide ore where the roasting
reaction is autogenous.
• For an oxide ore, the roasting reaction is facilitated by the addition of
elemental sulphur.
• Reactions are:
2 NaCl + MS + 2O2 = Na2SO4 + MCl2
4 NaCl + 2 MO + S2 + 3 O2 = 2 Na2SO4 + 2 MCl2
• Reaction is valid for carbonates which decompose on heating. Sulphates
and Silicates may decompose sodium chloride by the direct interchange
of the elements and radicals without the addition of Sulphur.

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 Chloridizing vaporization
• It is done at higher temperatures than in chloridizing roasting and the
product chloride is recovered by volatilization. Elimination of the
reaction products is easy in the case of volatile chlorides such as those of
Zr, Ti and Be.
• Specific problems are encountered if the metal has a variable valency.
For example chlorination of chromium produces both CrCl2 (boiling point:
13020C) and CrCl3 (boiling point: 9430C ).
• Former may plug up the chlorinator, if the chlorination is not done at
sufficiently high temperature. Problem is resolved by using a slight excess
of chlorine at 10000C so that only CrCl3 is produced.
• During chloridizing vaporization, oxidizing conditions usually prevail due
to the presence of O2, CO2 and H2O in the combustion gases and only the
stable chlorides can be prevented from oxidation.

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 Chlorination in a fused salt
• This is useful, if the metal chloride is highly hygroscopic and cannot be
introduced in an electrolytic cell without contamination due to water.
• In situ chlorination of a dry oxide in the electrolytic cell renders the feed
water-free and avoids undesirable current losses.
• In some electrolytic processes, a metal chloride is produced by bubbling
chlorine through a fused salt bath in which pellets of oxide or carbonate
along with carbon are suspended.

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 Direct and Indirect chlorination
There are mainly two types of chlorination.
a. Direct chlorination: it is brought about by chlorine alone. MO (s) + Cl2 (g) =
MCl2(g) + ½ O2(g)
b. Indirect or reduction chlorination: This involves some reducing agents as
well. MO(s) + C(s) + Cl2 (g) = MCl2(g) + CO(g)
• Using the available free energy data in the literature, we can show that the
chlorination of all the commercially important metal oxides proceeds almost
to completion under normal operating conditions and in most cases,
temperature is between 500 and 10000C.
• If we consider the use of HCl and other metal chlorides as chloridizing agents,
the reactions are:
MO(s) + 2 HCl(g) = MCl2(g) + H2O(g)
MO(s) + M’Cl2(g) = MCl2 (g) + M’O
• All these reactions are governed by the differences between the standard
free energies of formation of the oxide / chloride pairs.

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 Direct and Indirect chlorination
• Direct chlorination of stable oxides such as MgO, Cr2O3 and Al2O3 is not
thermodynamically feasible unless reduced pressures are continuously
used to remove the chloride vapors as they are formed at high
temperatures.
• A sulphide is directly chlorinated more easily than an oxide as the former
reacts at very low temperatures. Vapors generated generally contain
S2Cl3 which may condense along with metal chloride vapors and may
result in the contamination of the product. This is avoided if the metal
chloride is in the solid state.
• When direct chlorination is not feasible under 1 atm ( example TiO2 and
ZrO2), reduction chlorination is resorted to. In reduction chlorination,
carbon is the most effective reducing agent. Other reducing agents such
as S, CO, and H2 have been tried.

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 Direct and Indirect chlorination
• Reduction chlorination can also be done using higher valency chloride
compounds such as FeCl3 , CrCl3 , CuCl2, VCl4 , TiCl4 etc in association with
reducing agents such as H2S and CO. Lower chlorides are formed and
chlorine is released.
• Presence of a reducing agent normally enhances the chlorination rate.
Many sulphide ores are amenable to selective chlorination.

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Beneficiation of low-grade ores by halogenation

• Treatment of a low-grade ores by chlorination aims at

a. Removal of undesirable constituents in the form of volatile chlorides by
selective chlorination
b. Recovery of the metallic values in the form of volatile chlorides.
• Upgrading of minerals such as ilmenite and chromite is brought about by
the selective chlorination and volatilization of the iron oxide impurity.
• Beneficiation by chlorination is necessary because, in these minerals,
iron is present in chemical combination with the desired metals and
cannot be eliminated by the conventional ore dressing methods.

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Beneficiation of low-grade ores by halogenation

• During the chlorination process and subsequent elimination of iron

oxide, our aim is to produce only FeCl3 which has a low boiling point
(3190C). During this process, less volatile FeCl2 is to be avoided (boiling
point: 10260C) by using an excess of chlorine.
• For example, during the chlorination of ilmenite with HCl gas, formation
of FeCl2 is drastically reduced by introducing a small amount of air along
with HCl gas.
• Selective or differential chlorination is used for recovering useful metals
from low-grade ores such as those of Sn, Mn, Fe, V, Ni, and W.
Differential chlorination is successfully employed for recovering from
monazite, rare earth metals, Th and P.

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 Metallothermic reduction of oxides and halides

• During metallothermic reduction, vacuum would aid the reaction only if

there is an increase in the number of gaseous molecules.
a. TiCl4(g) + 2 Mg(l) = Ti(s) + 2MgCl2 (l) : vacuum would have an adverse effect
• Some metals have been successfully produced by the metallothermic
reduction of the metal oxide, when the reactants are in the condensed
state.
b. 2(MgO.CaO) + 1/6 (FeSi6) -----2 Mg(g) +1/6 Fe + 2CaO.SiO2 : Magnesium
Extraction (Pidgeon Process)
• Under vacuum, it is also possible to reduce the oxides of Pb, Zn, Mn, and
Bi with Silicon.

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 Refining of metals by chlorination
• Selective chlorination is effectively used for refining many crude metals.
For example, Betterson process for refining lead (Pb) uses either chlorine
or PbCl2 for the preferential chlorination of the main impurity zinc at
about 350-4000C.
• Goldschmidt process for deleading tin, uses fused SnCl2 and lead which is
an impurity forms a more stable lead chloride and metallic tin at around
250-2600C by its reaction with SnCl2. Any excess SnCl2 is recovered as
volatile SnCl4 by chlorination.
• Gold bullion can be refined by chlorination. During this, gold remains
unaffected while Ag, Pb, Cu, Sb, and other impurities are chlorinated and
removed.

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 Pyrometallurgical processes using vacuum
• Reactions that are favourable by the use of vacuum are represented as
below:
a. Thermal reduction
R(s, l) + MA(s, l) = RA(s, l)+ M(g)
b. Thermal dissociation
MA(s, l) = M(g) + A(s, l)
MA(s, l) = M(s, l)+ A(g) where A is acid radical such as ‘s’, ‘o’ and R is a reducing
agent.
• Use of vacuum helps in eliminating the reaction product, which is volatile
and hence the reaction becomes feasible.
• Thermal decomposition of oxide under vacuum does not offer any
possibility for metal extraction. This is because most of the oxides require
a very high degree of vacuum and high temperatures.

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