Module 2B

Methods of extraction: Pyrometallurgy Techniques (Stage 2)

Reduction processes
Extraction of metals at the bottom of the reactivity series
Hydrometallurgical treatment
Extraction of iron and aluminium
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Pyrometallurgy techniques
• Stage 2: Reduction to metallic state
• Smelting is employed in converting concentrated ore or calcinated or
the roasted ore to metallic state

Mixture of ore and reducing agent is heated in the presence of flux(es)

to a high temperature sufficient enough to turn the whole mass into
molten form.

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Flux
• Flux is any substance that is introduced in the smelting of ores to
promote fluidity and remove objectionable impurities in form of slag.
• Acidic and Basic fluxes
• Acidic: Used when gangue (impurity) is basic. Examples are silica,
borax
• SiO2 + CaO → CaSiO3

• Basic: Employed to remove acidic gangue (silica, silicates) etc.

Examples include CaCO3, MgCO3
• CaCO3 + SiO2 → CaSiO3 + CO2

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What reductant?
• The nature of metal determines which reductants would be used.
• (i) Carbon and Carbon (II)oxide: Used for Fe, Cu, Pb, Sn, Co and
Zn
• Fe2O3 + 3C → 2Fe + 3CO
• Fe2O3 + 3CO → 2Fe + 3CO2
• Co3O4 + 4C → 3Co + 4CO
o
•
140 C
• Co3O4 + 4CO → 3Co + 4CO2

PbO + C → Pb + CO
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Reduction process contd.
• Reduction with Aluminium, Sodium, magnesium or hydrogen:
Used for Cr, Ti, Mo and W
• Titanium chloride is heated to 850°C with Mg or Na in an atmosphere
of Argon, to produce titanium.
• TiCl4 + 2Mg → Ti + 2MgCl2

• Cr2O3 + 2Al → 2Cr + Al2O3 + heat

• 3Mn3O4 + 8Al → 9Mn + 4Al2O3 + heat

• Reduction with aluminium is termed Goldschmidt’s Alumino –
thermite reduction
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Reduction process contd.

• Smelting with water gas (CO + H2)

• Nickel oxide obtained from roasting of Nickel sulphide (NiS) is heated

carefully in a tower at 350 °C in which a current of water gas is passed.
• Roasting of NiS
• NiS + O2 → NiO + SO2

• Reduction of NiO
•

• 2NiO + CO + H2 → 2Ni + H2O + CO2

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Reduction process contd.
• Auto /Self reduction:
• The ore is heated in a supply of air at moderate temperatures (500-700 °
C) for partial conversion
• 2PbS + 3O2 → 2PbO + 2SO2
• PbS + 2O2 → PbSO4
• Air is cut off and a little lime is added (to remove impurities) and the
mixture is heated at 800 °C
• PbS + 2PbO → 3Pb + SO2
• PbS + PbSO4 → 2Pb + 2SO2

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Self reduction of sulphide ores
• Example: extraction of copper from its sulphide.
• Most Cu are obtained from ores e.g. Copper pyrites CuFeS2, Copper
glance Cu2S.
• Part of the sulphide is converted to Cu (I) oxide by roasting in air.
• (1) 2 Cu2S + 3O2 → 2Cu2O + 2SO2
• Copper (I) oxide
• When supply of air is cut off (absence of air) and temperature is
increased, the rest of sulphide (unchanged) reacts with the oxide to
form the metal and sulphur dioxide.
• Cu2S + 2Cu2O → 6Cu + SO2

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Self reduction of sulphide ores contd.
• 2) 2 CuFeS2 + 4O2 → Cu2S + 2FeO + 3SO2
• Product roasted with silica
• FeO + SiO2 → FeSiO3 (slag)
• Iron silicate
• Molten slag floats on the molten Cu2S and tapped off separately.

• Impure Cu2S is heated in air to form Cu (I) oxide as shown in

example 1
• Copper produced is known as blister copper

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Extraction of metals at the bottom of the
reactivity series
• Metals at the bottom of the reactivity series include Hg, Ag etc. They
can be extracted by heating the ore alone or displacement from aqueous
solution
• Heating the ore: Hg and Ag compounds are unstable and decompose
to the metal on heating
• HgS + O2 → Hg + SO2
(currambar)

• The mercury distills over at the temperature of the furnace and

condensed in water in cooled receiver.

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Extraction of metals at the bottom of the
reactivity series contd.
• Displacement from aqueous solution. The metal is precipitated
from a solution of its ion using a metal higher in the activity series e.g.
extraction of Ag.

• Insoluble Ag2S ore is dissolved in a solution of cyanide ions to form

cyano argentate (I) ions.
• Ag2S(s) + 4CN- → 2[Ag(CN)2]-(aq) + S2-

• Ag is precipitated from the solution by adding powdered zinc dust

• 2[Ag(CN2 ]‑(aq) + Zn(s) → [Zn(CN)4]2-(aq) + 2Ag(s)
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Hydrometallurgical treatment
• Involves leaching , separation of leached products (solid and liquid),
purification of solution obtained (by solvent extraction or ion
exchange chromatography, isolation of desired metal (precipitation and
electrolysis)

• Leaching: Crushed or ground ore is treated with water or other agents

e.g. H2SO4, HCl, NaOH, NaCO3, FeCl3 etc to obtain preferential
dissolution of valuable or undesirable constituents

• Recovery of metals from leaching solution: precipitation or electrolysis

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Purification of the metal
• Purification of the metal
• Metal obtained from the reduction of ore is usually contaminated with
impurities e.g. unchanged ore, other metals in the ore and non metals
(C, Si, P,S) from the anions of the ore, slag or flux. e.g. blister copper
contains small amount of Cu2S, Fe and S. It is purified by electrolysis
of CuSO4

• Other methods include, oxidative refining, distillation etc

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Extraction of Iron
• Occurrence: Iron is about 6.2% of the earth crusted rock. 4th most
abundant element and 2nd most abundant metal.

• occurs in silicates, sands and clays and all living matter.

• essential for haemoglobin production in blood and chlorophyll in

plants.

• Compounds of Fe: Iron pyrites- FeS2, haematite (Fe2O3), ignetite

(Fe3O4), Fe2O3.XH2O (rust).
• Major raw materials are haematite and rust.
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Extraction of Fe contd.
• Fe rarely occurs pure. It is used in variety of steels
• Steps involved in the extraction of iron
• (i) Preparation of ore for reduction in a blast furnace.
Crushing the ore to obtain lumps of uniform size.

Preheating of lumps by hot gas from furnace to drive off H2O and
other volatile materials (impurities).

• Prepared iron ore contains 30-95% Fe oxides with main impurities

like silica, Al2O3.

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The blast furnace
production of iron
(ii) Reduction of the iron oxide using
carbon in the presence of limestone in a
blast furnace.

The furnace is fed mechanically that no air

escapes during the charging.
Mixture of iron ore, coke and limestone is
added at the top of the furnace and blasts
of air are driven into the furnace through
small holes called ‘tuyere’ near the base.

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Extraction of Fe contd.
• C + O2 → CO2, ∆ H = – ve

• CO2 + C → 2CO

• Fe2O3 + 3CO → 2Fe + 3CO2 (CO reduces oxide in the

upper parts of the furnace.

• As the Fe falls towards the base it is melted, flows to the hearth where
it is collected and tapped off every few hours.

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Extraction of Fe contd.
• Limestone helps in the extraction of impurities from the iron.

• At high temp in the furnace, the limestone decomposes into CaO and
CO2. CaO reacts with impurities in the iron.
• CaCO3 → CaO + CO2

• CaO + SiO2 → CaSiO3

(calcium silicate)
• CaO + Al2O3 → CaAl2O4
• (calcium aluminate)
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Extraction of Fe contd.
• The mixture of CaSiO3 and CaAl2O4 remaining molten at furnace
temperature is called ‘slag’.

• Slag flows to the bottom of the furnace where it floats on the molten
iron and tapped off at a different level separately from the iron.
• Slag is used for road making materials, cement and light weight building
materials.
• Iron obtained is not pure and it is called Pig iron. It is hard but brittle
and melts at 1500 K.
• Cast iron is formed when Pig iron is re-melted, mixed with scrap steel
and cooled in moulds.

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Extraction of Fe contd.

• Pig iron obtained from blast furnace contains 8% impurities e.g. C

(3-5%), Si (1-2%), S (0.05-0.1%), P (0.05-0.1%) and Mn (0.5- 1%).

• Pure iron is obtained on a small scale by (i)the reduction of pure oxide

or hydroxide with hydrogen .
• Fe2O3 + 3H2 → 2Fe + 3H2O
• (ii)carbonyl process in which iron is heated with carbon monoxide
under pressure and the Fe(CO)5 formed is decomposed at 250 oC to
generate iron metal.

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Extraction of Aluminium
• Aluminium occurs majorly as bauxite(Al2O3.2H2O)
• Purification of bauxite:
• Impurities (e.g. SiO2, FeO) can impair the quality of Al, therefore must
be removed.
• Removed by heating ore with NaOH solution
SiO2(s) + 2OH-(aq) → SiO32-(aq) + H2O
Al2O3(s) + 2OH-(aq) → 2AlO2- (aq) + H2O
Al(OH)3 is precipitated out of solution by treating mixture of aluminate
and silica with acid
AlO2- + H3O+ → Al(OH)3(s)
• 2Al(OH)3 Δ→ Al2O3 + 3H2O
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Extraction of Aluminium contd.
Electrolysis of Al2O3
• Al2O3 is mixed with molten cryolite (NaAlF6) (lowers melting point of
Al2O3 and acts as solvent).

• Cathode: 4Al3+ + 12e- → 4Al(l)

• Anode: 6O2- → 3O2 + 12e-
• 3C(s) + 3O2 → 3CO2

• Overall reaction: 4Al3+ + 6O2- + 3C → 4Al +3CO2

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