Extractive Metallurgy

The process of extracting metals from their natural sources (ore) and preparing
them for practical use is known as metallurgy.
Principles of extraction
The extraction of pure metal from its ore involves several physical and chemical
methods. The suitability of method depends upon the nature of ore, the
properties of metals and local conditions. The extractive metallurgy of a metal
involves following operations :
1.
2.
3.
4.
5.

Crushing and grinding of the ore/pulverization.

Concentration or dressing of ore/ i.e ore benefaction.
Extraction of crude metal from concentrated ore
Reduction of ore to the metallic form and
Purification of metal/refining.

Crushing of Ores:
Larger pieces of ores obtained from earth's crust are broken up into
smaller pieces. This process is known as Pulverization.
Concentration of Ores:
Presence of earthy matter, rock matter, sand, limestone etc. in ore are known as
Gangue or Matrix. Removal of these impurities from ore is called concentration.
Following methods are employed for concentration of ore.
Gravity separation: This method of separation is based on the difference
in specific gravities of the gangue particles and ore particles.
The powdered ore is agitated with water or washed with a running stream
of water. Lighter impurities are washed away wuth floating water leaving
behind heavier ores.
Generally, oxide and carbonate ores are concentrated by this method.
For this, either wilfley table or Hydraulic classifier is used.

Magnetic separation: This method is used when either ore or gangue has
strong ferromagnetic nature.

Example: Wolframite (FeWO4) a

magnetic ore is separated from the
non-magnetic ore cassiterite
(SnO2)by this method.
Similarly, rutile TiO2 (magnetic) can
be separated from chlorapatite,
3Ca3(PO4)2. CaCl2 by magnetic
separation.

Froth Floatation process:

This method is used for
concentration of sulphide ores.
The process is based on the
difference in wetting characteristics
of the gangue and the ore with water
and oil. The gaunge surface being
preferentially wetted by water and
the ore by the oil.

The powdered ore is added to water containing pine oil (frothing agent).
A vigorous stream of air is now passed through, which thoroughly agitates the
mixture which disposes the oil into colloidal sized particles. As a result of this
the sulphide particles of the ore stick to the oil droplets ,becomes lighter and
rise to the surface in the form of froth. Water wets the gangue particles which
sink to the bottom.
The additives added are usually of three types.
Frothers : Frothers increase froth stability within desired limit. For example,
pine oil, soaps, resins etc.
Froth stabilisers (e. g., cresols, aniline) stabilise the froth before it is separated.
Collectors : enhance non-wettability of the mineral particles. The most
common among them are xanthates, carboxylic acids and their salts.

Sometimes, it is possible to separate two sulphide ores by adjusting proportion

of oil to water or by using depressants. For example, in case of an ore
containing ZnS and PbS, the depressant used is NaCN. It selectively prevents
ZnS from coming to the froth but allows PbS to come with the froth.
ILLUSTRATION 1

How does NaCN act as a depressant in preventing ZnS from forming the froth?
Solution :
NaCn forms a layer of zinc complex, Na2[Zn(CN)4] on the surface of ZnS and
thus prevents it from the formation of froth.
Leaching: It involves the treatment of the ore with a suitable reagent so as to
make it soluble while impurities remain insoluble . The ore is then recovered
from the solution by suitable method.
Leaching is often used if the ore is soluble in some suitable solvent.
The following examples illustrate the procedure:
(a) Leaching of alumina from bauxite
The principal ore of aluminium, bauxite, usually contains SiO2,
iron oxides and titanium oxide (TiO2) as impurities.
Concentration is carried out by digesting the powdered ore with a concentrated
solution of NaOH at 473 523 K and 35 36 bar pressure.
This way, Al2O3 is leached out as sodium aluminate (and SiO2 too as
sodium silicate) leaving the impurities behind:
Al2O3(s) + 2NaOH(aq) + 3H2O(l) 2Na[Al(OH) 4](aq)
The aluminate in solution is neutralised by passing CO2 gas and hydrated
Al2O3 is precipitated. At this stage, the solution is seeded with freshly
prepared samples of hydrated Al2O3 which induces the precipitation:
2Na[Al(OH)4](aq) + CO2(g) Al2O3.xH2O(s) + 2NaHCO3 (aq)
The sodium silicate remains in the solution and hydrated alumina
is filtered, dried and heated to give back pure Al2O3:
Al2O3.xH2O(s) 1470 K Al2O3(s) + xH2O(g)

(b) Other examples

In the metallurgy of silver and that of gold, the respective metal is
leached with a dilute solution of NaCN or KCN in the presence of air (for O2)
from which the metal is obtained later by replacement:
4M(s) + 8CN(aq)+ 2H2O(aq) + O2(g) 4[M(CN)2] (aq) +4OH(aq)
(M= Ag or Au)

Extraction of crude metal from concentrated ore

Calcination: It involves heating of the ore below its fusion temperature in
absence of air to produce a new compound having higher % metal .It also
removes the moisture, organic matter and volatile impurities it makes ore
porous.
CaCO3 CaO + CO2 (Calcined ore is
left)
(Lime stone)
AI2O3.2H2O AI2O3 + 2H2O
(Bauxite)
CuCO3.Cu(OH)2 2CuO + H2O +
CO2
(Malachite)

MgCO3 MgO + CO2

(Magnesite)

2Fe2O3.3H2O 2Fe2O3 + 3H2O

(Limonite)

Roasting: It involves heating of an ore in excess supply of air below its melting
point, to reduce other chemical changes.
4FeS2 + 11O2 2Fe2O3 + 8SO2

2ZnS + 3O2 2ZnO + 2SO2

2PbS + 3O2 2PbO + 2SO2

2Cu2S + 3O2 2Cu2O + 2SO2

HgS + O2 Hg + SO2
Roasting is usually done in reverberatory furnace or blast furnace.

Reduction to free Metal

Some of the methods commonly used to get free metal from ore are given
below:
Smelting : Reduction of the ore to the molten metals at a high temperature
using powerful reducing agent such as C, H2, CO, water gas, Na, K, Mg, Al is
called smelting.
Carbon reduction process: The oxides of less electropositive metals are
reduced by strongly heating them with coal or coke(the cheapest available
reducing agent).

ZnO + C Zn + CO
ZnO + CO Zn + CO2

PbO + C Pb + CO
PbO + CO Pb + CO2

MnO2 + 2C Mn + 2CO
Mn2O3 + 3C 2Mn + 3C

SnO + C Sn + CO
SnO + CO Sn + CO2

Fe2O3 + 3C 2Fe + 3CO

Fe2O3 + 3CO 2Fe + 3CO2

Calcium cannot be extracted from CaO by carbon reduction process.

Explain why?

During reduction, additional substance called flux is also added to the ore. It
combined with impurities to form easily fusible product known as slag.
Impurities + Flux Fusible product (slag)
Flux is a substance that is added to the ore during smelting (a) to decrease the
melting point (b) to make the ore conducting and (c) to remove all the
impurities (basic and acidic).
FeO
Impurity

SiO2
acidic flux

FeSIO3 (fusible slag)

SiO2
Impurity

CaO
basic flux

CaSIO3 (fusible slag)

Alumina is a bad conductor of electricity but when cryolite (flux) is added, it

becomes a good conductor and the melting point is decreased. Hence, CaF2, KF,
cryolite etc are neutral flux.
If FeO is present in the ore as impurity, then what type of flux is added to
remove it?
Reduction of aluminium (Gold Schmidt alumino thermite): This method is
employed in the case of those metals which have very high melting points and
their reduction with carbon is not satisfactory.
A mixture of concentrated ore and aluminium powder, commonly called as
Thermite, is taken in a steel crucible. The reaction is started by the use of an
ignition mixture of containing magnesium powder and barium peroxide.

3Mn3O4 + 8AI

9Mn + 4AI2O3

3MnO2 + 4AI

3Mn + 2AI2O3

B2O3 + 2AI

2B + AI2O3

Cr2O3 + 2AI

2Cr + AI2O3

During the reaction, aluminium gets oxidized to AI2O3while metal oxides

releases metals.
This reaction is highly exothermic. So, metal is obtained in molten state.
2Al + 3O2 ---> Al2O3 + 1670 kJ

Magnesium is used in a similar way to reduce oxides. In certain cases where the
oxide is too stable to reduce, electropositive metals are used to reduce metal
halides. Titanium (for supersonic aircrafts) zirconium (used in atomic reactors)
are obtained by the reduction of their tetrachlorides with metallic sodium or
magnesium.
TiCI4 + 2Mg

Ti + 2MgCI2 ;

TiCI4 + 4Na Ti + 4NaCI

Self reduction process: The cations of the less electropositive metals like Pb,
Hg, Sb and Cu may be reduced without the use of any additional reducing
agent.
The sulphide ores of less electropositive metals are heated in air to convert part
of sulphide ore into oxide, which then reacts with the remaining sulphide to give
the metal and sulphur dioxide.
For example, in the extraction of mercury, the sulphide ore (cinnabar) is heated
in a current of air when the following reactions take place.
2HgS + 3O2 2HgO + 2SO2
2HgO + HgS 3Hg + SO2 (self reduction reaction)
Similarly, in the extraction of copper, the sulphide and the oxide interact at an
elevated temperature to give the metal.
Cu2S + O2 SO2 + Cu2O
Cu2S + 2Cu2O SO2+ 6CU

(self reduction reaction)

Similar reactions take place in the self-reduction process for the extraction of
lead.
2PbS + 3O2 2PbO + 2SO2
PbS + 2PbO 3Pb + SO2

(self reduction reaction)

Reduction of oxides with hydrogen

Certain metallic oxides can be reduced using molecular hydrogen. Because of
inflammable nature of hydrogen, it is used in very few cases. Molybdenum and
tungsten are obtained by reducing their oxides by hydrogen at elevated
temperatures.

Co3O4 + 4H2 3Co + 4H2O

GeO2 + 2H2 Ge + 2H2O
2NH4[MoO4] + 7H2 2Mo + 8H2O + 2NH3
2NH3[WO4] + 7H2 2W + 8H2O + 2NH3

This method is not widely used because many metals react with hydrogen
at elevated temperature, forming hydrides. There is also a risk of
explosion from hydrogen and oxygen present in the air.

ILLUSTRATION 2
Why is it advantageous to roast a sulphide ore to the oxide before reduction?
Solution :

2MS + C CS2 + 2M

MS + H2 H2S + M

The free energies of formation of most sulphides are greater than

those for CS2 and H2S. So, the net reactions have unfavorable free
energy of formations. Thus, neither carbon nor hydrogen is a suitable
reducing agent for metal sulphides. Aluminium cannot be used, as
reaction with metal sulphide would produce aluminum sulphide,
which is not so exothermic. So, sulphide ores are preferentially
converted to oxide ores as any reduction method (reduction by C, H2,
AI etc.) could then be conveniently used.

ELECTROLYTIC REDUCTION
The strongest possible reducing agent is an electron. Any ionic material may be
electrolysed and reduction occurs at the cathode. This is excellent method and
gives very pure products but electricity is quite expensive. Electrolysis may be
performed in aqueous solution provided that the products do not react with
water.

This process is mainly used in the extraction of alkali and alkaline earth metals.
In the case of highly electropositive metals, isolation by chemical agents is
extremely difficult,as the oxides cannot be reduced by carbon at moderate
temperature. In such cases, the metal is obtained by electrolysis of fused salts,
oxides, hydroxides or chlorides. Under such conditions, the ions readily move to
the oppositely charged electrodes and are distinguished and discharged over
there. Sometimes, a small amount of some other salt is added to lower the
fusion temperature or to increase the conductivity or both. The metal is
deposited at cathode.

manufacture of sodium by
electrolysis of a fused mixture of
sodium and calcium chlorides
(Downs process).
The cell and electrodes used should
not be effected by the electrolyte or
the products. Hence a steel cell, a
graphite anode an iron cathode are
employed. The various reactions
that take place are;
An example of this is the
On fusion, NaCI Na+ + CI (ions become mobile)
On electrolysis,
(i) At the cathode (negative electrode): Na+ + e Na (reduction)
(ii) At the anode (positive electrode) : CI CI + e (oxidation);
CI + CI CI2
The products obtained react readily, hence a suitable arrangement has to be
made to keep them separate.

Refining or Purification
The metal obtained after reduction process still contains some impurities which
can be removed by applying following method.
a. Liquation process: This method is employed when impurities have
higher MP than metal. The impure metal is placed on the sloping hearth
of a furnace and gently heated. The metal melts and flows down leaving
behind the impurities.
Readily fusible metals like Sn, Pb Hg and Bi are refined by this method.
b. Distillation method: Volatile metals (Hg, Zn, Cd and arsenic As) are
easily purified by distillation. The impure metals is heated in a retort and

vapours of volatile metals are collected and condensed in a receiver

leaving behind non volatile impurities in the retort.
c. Pyrometallurgical oxidation process: This process is used when
impurities have greater affinity for oxygen than the metals itself. The
oxidation is done by
i.
ii.

Cupellation
Bessemerisation

d. Poling: This process is used to purify the metal from its oxide. In this
process, molten metal containing oxide of its impurity is stirred by logos
of green wood to reduce oxide to metal eg Cu from CuO.
e. Electrolytic refining: The impure metal is made anode while a thin sheet
of pure metal acts as cathode. The electrolytic solution consists of an
aqueous solution of salt or a complex of the metal. On passing the
current, pure metal is deposited on cathode and equivalent amount of
metal gets dissolved from anode. The soluble impurities pass into the
solution and insoluble impurities collect below the anode as anode mud.

f. Zone refining of fractional crystallization: The method is employed to

get metals of very high purity. (Ge, Si, B, Ga, In). This method is based
on the difference in solubility of impurities of molten and solid state
of the metal. A movable heater is allowed to move across the impure
metals rod from one end to the other end, The3 pure metal crystrallises
while the impurities pass on to the adjacent melted zone.

e) Vapour phase refining

In this method, the metal is converted into its volatile compound and collected
elsewhere. It is then decomposed to give pure metal. So, the two requirements
are:
(i) the metal should form a volatile compound with an available reagent,
(ii) the volatile compound should be easily decomposable, so that the recovery
is easy.
Mond Process for Refining Nickel: In this process, nickel is heated in a
stream of carbon monoxide forming a volatile complex, nickel tetracarbonyl:
The carbonyl is subjected to higher temperature so that it is decomposed giving
the pure metal:
van Arkel Method for Refining Zirconium or Titanium: This method is very
useful for removing all the oxygen and nitrogen present in the form of impurity
in certain metals like Zr and Ti. The crude metal is heated in an evacuated
vessel with iodine. The metal iodide being more covalent, volatilises:
Ti(s) + 2I2(g)
Ti I4(g)
The metal iodide is decomposed on a tungsten filament, electrically
heated to about 1800K. The pure metal is thus deposited on the filament.
TiI4(g)

Ti(s) + 2I2(g)

Other metals those can be purified this method are Zr, V, W, Hf etc.