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FINAL TERM (NOTES)

EXTRACTIVE METALLURGY

ALUMINUM
 Aluminium is a chemical element with the symbol Al and atomic number
13.
 Aluminum is the most abundant metal in Earth.
 It occurs in the nature in form of aluminum oxide and other combined forms.
 It has a Orthorhombic crystal system.

Ores of aluminium:
 Bauxite, Al2O3.2H2O.
 Cryolite. Na3.Al.F6
 and Corundum. Al2O3

Alloys of aluminium:
 Alclad: aluminum sheet made by bonding high-purity aluminum to a high
strength core material.
 Al-Li (lithium, sometimes mercury)
 Alnico (aluminum, nickel, copper)
 Birmabright (aluminum, magnesium)
 Duralumin (copper, aluminum)

Uses of aluminum
Aluminum is usually alloyed with other elements such as silicon, copper or
magnesium. Pure aluminum isn't very strong, and alloying it adds to it strength.
Aluminum is especially useful because it

 has a low density;

 is strong when alloyed;
 is a good conductor of electricity;
 has a good appearance; resists corrosion.
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Extractive metallurgy of Aluminium:

I. Ore dressing– cleaning ore by means of separation of the metal

containing mineral from the waste (gangue).

II. Bayer process- Chemical treatment of bauxite for converting the

hydrated aluminum oxide to pure aluminum oxide (Al2O3).
At this stage crushed and ground bauxite is mixed with hot sodium hydroxide
solution, which dissolves the aluminum hydroxide, forming solution of sodium
aluminate.

The residual impurities (oxides of silicon, iron and titanium), which called “red
mud”, are separated from the sodium aluminate solution.

The solution is then treated in precipitator tanks, where aluminum trihydrate

precipitates from the solution.

The aluminum trihydrate after separation from the sodium hydroxide is converted
into pure aluminum oxide by heating to 1800F (1000ºC)

Al2O3+2NaOH+3H2O⟶2NaAl(OH)4

NaAl(OH)4⟶Al(OH)3+NaOH

2Al(OH)3⟶Al2O3+3H2O (1000 C)

III. Reduction of aluminum from aluminum oxide by the electrolytic

process.
As aluminum oxide is a very poor electricity conductor its electrolysis is carried
out in a bath of molten cryolite (mineral, containing sodium aluminum fluoride –
Na3AlF6).
The technology is called Hall-Heroult process.
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Schematically the process is presented in the picture:

The electrolytic cell for aluminum production consists of a pot with carbon lining,
serving as negative electrode (cathode) and positive electrodes (anodes), connected
to the current conductor (bus bar).
The anodes are immersed into the bath of molten cryolite.
The aluminum oxide is added to the cryolite and dissolved in it. When electric
current passes between the anodes and the cathode through the cryolite, aluminum
oxide decomposes to metallic aluminum deposited at the cathode and oxygen
liberated at the anode.

The molten aluminum is periodically tapped from the furnace into a crucible and
cast into ingots.

Al3++3e−⟶Al (Cathode)

2O2−⟶O2+4e− (Anode)

Aluminium deposits in pakistan:

 Muzaffarabad-Kotli.
 Bandi Kapla-Khanpur Hazara.
 Margalla Hills.
 Attock Surge area.
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ZINC
 Zinc (Zn) is a metallic element of hexagonal crystal structure
 Have density of 7.13 grams per cubic centimetre.
 It has only moderate hardness.
 In solid form it is grayish white.
 but when freshly cast or cut it has a bright, silvery appearance.

Ores of zinc:
 smithstone (ZnCO3)
 calamine [Zn2(OH)2SiO3]
 sphalerite (ZnS)
 zincite (ZnO)

Zinc ores normally contain 5–15% zinc.

Alloys of zinc:
 Nickel Silver (nickle-zinc)
 Brass-copper-zinc alloy
 Zamak-zamak 3 (copper,zinc, aluminium, manganese)

Uses of zinc:

With good calenderability, abrasive resistance, corrosion resistance, castability,

and room temperature mechanical properties, zinc can be made into various alloys
with many other metals. Mainly in the form of galvanization, zinc-based alloys and
zinc oxide, it has applications in the automobile, construction and shipbuilding
industries, light industry, machinery, household electrical appliances, batteries and
other industries. Currently, its consumption among non-ferrous metals is second
only to aluminum and copper.
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Extractive metallurgy of zinc:

Concentration of Ore:

Froth Flotation Process

Froth Flotation process is mainly used to remove gangue from sulphide ores. The
ore is powdered and a suspension is created in water. The main ingredients of the
froth flotation are the Collectors and Froth Stabilizers. Collectors (pine oils, fatty
acids etc) increase the wettability of the metal part of the ore and allows it to form
a froth and Froth Stabilizers (cresols, aniline etc) sustain the froth. The oil wets the
metal and the water wets the gangue. Paddles and air constantly stir up the
suspension to create the froth. This frothy metal is skimmed off the top and dried
to recover the metal.

Metal from Concentrated Ore

The next step in the extraction of zinc is called Roasting. The concentrated ore is
finely ground into small pieces and then suspended in a rising stream of air. The
sulphur content can be reduced hugely with this process. This also converts the
Zinc Blende to ZnO which is way more reactive. The reaction occurring here is

Zinc Oxide is then mixed with Coke and ground into fine pieces and heated at
1673 K in fire clay containers in a process which is also known as the Belgian
Process. Here the Zinc Oxide gets reduced to metallic Zinc. The carbon from coke
acts as the reducing agent in this reaction. The reaction of the final step of
extraction of zinc is

Since, the boiling point of Zinc is way back at 1180 K, the zinc formed
immediately vaporizes and distills over leaving behind non-volatile impurities such
as Cadmium, Lead and Iron. This gas containing zinc vapours is collected and
cooled to yield solid zinc. This crude metal is called Spelter. It can be further
purified by fractional distillation.
Zinc alloys with many other metals: Nickel silver, bronze, brass and soft electrical
solder all contain zinc. A lot of the zinc manufactured is used to galvanize iron to
prevent corrosion.
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Zinc deposits in pakistan:

Duddar mine:
The Duddar mine is one of the largest lead and zinc mines in Pakistan. The mine
is located in western Pakistan in Balochistan. The mine has reserves amounting to
50 million tonnes of ore grading 3.2% lead and 7% zinc thus resulting 1.6 million
tonnes of lead and 3.5 million tonnes of zinc.
Zinc deposits are also found in surmai and gunga which are estimated over 160
million tons.

LEAD
 Lead is a chemical element with the symbol Pb
 atomic number 82
 Lead is soft and malleable, and also has a relatively low melting poin
 When freshly cut, lead is silvery with a hint of blue; it tarnishes to a dull
gray color when exposed to air
 Having density of11.29 gram/cm3
 face-centered cubic (fcc).

Ores of lead:
 Galena PbS
 Cerrusite PbCO3
 Anglesite PbSO4
 Lead ochre PbO
Uses of lead:
i. For making lead pipes,
ii. For making telegraph and telephone wires,
iii. In making bullets and lead accumulators,
iv. In lead chambers, for the manufacture of sulphuric acid,
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v. For making alloys like solder, pewter and type metal,

vi. For preparing tetraethyl lead (Pb(C2H5)4) which is used as an additive
to petrol to prevent knocking

Other applications
 As lead has radiation resistance, it can be used by hospital personnel and
some other workers who work in high radiation environments to protect
them from its effects. In addition, it can also be used in the post and
telecommunications industries, metallurgy, chemical industry, railways,
transportation, construction, weapons, aerospace, aviation, oil and other
industries.

Extracrive metallurgy of zinc:

Lead is mainly extracted from the sulphide ore galena. Galena contains lead sulphide
and small quantities of silver.
1. Concentration: The ore is concentrated by froth floatation process.
2. Smelting in a Reverberatory furnace: The concentrated ore is roasted in a
reverberatory furnace at a moderate temperature. The temperature of furnace is controlled
by regulating the air supply. During roasting, galena is partly oxidized to lead monoxide and
partly to lead sulphate.
2PbS + 3O2 � 2 PbO + 2SO2
PbS + 2O2 � PbSO4
More of galena is then added. The temperature is raised and simultaneously the air
supply is reduced. Lead sulphide reacts with the two oxidised products giving lead.
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PbS+2PbO � 3Pb+SO2
PbS+PbSO4 � 2Pb+2SO2
Thus in this process roasting and smelting are carried out in the same furnace,
at two different temperatures.
About 90% of lead is obtained as metal, the rest passes into slag. Lead is
recovered from the slag by heating with lime and powdered coke.

Purification of Lead
Lead extracted by the above method contains impurities such as silver, copper, tin,
bismuth, gold and iron. It is refined by the following processes.
a. Liquation
The impure metal is heated on a sloping hearth. Lead melts and flows down the slope.
The infusible impurities remain on the hearth.
b. Desilverisation
Silver is removed by either Pattinson's process or Park's process.
c. Electrolytic refining
Very pure lead is obtained by this process.
Anode - Impure lead
Cathode - Very pure lead
Electrolyte - Lead fluosilicate + Hydrofluosilicic Acid
(PbSiF6) (H2SiF6)
The metallic impurities which are more electropositive than lead, such as iron and tin, go
into the solution while the rest of the impurities are thrown down as anode mud.
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Lead deposits in pakistan:

Duddar mine:
The Duddar mine is one of the largest lead and zinc mines in Pakistan. The mine
is located in western Pakistan in Balochistan. The mine has reserves amounting to
50 million tonnes of ore grading 3.2% lead and 7% zinc thus resulting 1.6 million
tonnes of lead and 3.5 million tonnes of zinc.
Zinc deposits are also found in surmai and gunga which are estimated over 160
million tons.

URANIUM:
 uranium (U), radioactive chemical element of the actinoid series of
the periodic table,
 atomic number 92.
 It is an important nuclear fuel.
 19 gram/cm3
 Crystal structure of orthorhombic
 Highest atomic weight.

Ores of uranium:
 uraninite (UO2
 carnotite,
 tyuyamunite,
 torbernite
 autunite.

Alloys of uranium:

Quaternary System

Uranium-Aluminum-Manganese-Iron Uranium-Carbon-Nitrogen-Oxygen

Uranium-Carbon-Chromium-Iron Uranium-Carbon-Titanium-Plutonium
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Uranium-Carbon-Iron-Nickel Uranium-Carbon-Zirconium-Cerium

Uranium-Carbon-Molybdenum-Plutonium Uranium-Carbon-Zirconium-Thorium
Uses of uranium:

Uranium is now used to power commercial nuclear reactors that produce electricity
and to produce isotopes used for medical, industrial, and defense purposes around
the world.

Extractive metallurgy of uranium:

 Acid Leaching

Acid leaching is commonly performed by agitating an ore-leach mixture for 4 to as

long as 48 hours at ambient temperature. Except in special circumstances, sulfuric
acid is the leachant used; it is supplied in amounts sufficient to obtain a final leach
liquor at about pH 1.5. Sulfuric acid leaching circuits commonly employ either
manganese dioxide or chlorate ion to oxidize the tetravalent uranium ion (U 4+) to
the hexavalent uranyl ion (UO22+). Typically, about 5 kilograms (11 pounds) of
manganese dioxide or 1.5 kilograms of sodium chlorate per ton suffice to oxidize
tetravalent uranium. In any case, the oxidized uranium reacts with the sulfuric acid
to form a uranyl sulfate complex anion, [UO2(SO4)3]4-.

 Alkaline leaching:

Uranium was selectively leached by the mixture of sodium carbonate, sodium

hydroxide and hydrogen peroxide from hydrous oxide

Uranium ores that contain significant amounts of basic minerals such as calcite or
dolomite are leached with 0.5 to 1 molar sodium carbonate solutions. Although a
variety of reagents has been studied and tested, oxygen is the uranium oxidant of
choice. Typically, candidate ores are leached in air at atmospheric pressure and at
75° to 80° C (167° to 175° F) for periods that vary with the particular ore.
The alkaline leachant reacts with uranium to form a readily soluble uranyl
carbonate complex ion, [UO2(CO3)3]4-.
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Deposits of uranium in pakistan:

Bannu Basin, Sulaiman Range, Dera Ghazi Khan, Issa Khel, Mianwali District and
Kirther Range. Qabul khel, Baghal Chur,

SILVER
 Silver is a chemical element with the symbol Ag
 atomic number 47
 A soft, white, lustrous transition metal, it exhibits the highest electrical
conductivity, thermal conductivity, and reflectivity of any metal.
 Having density of 10.49 g/cm³
 Having crystal structure, face-centered cubic (fcc).
Ores of silver:
 Silver is found generally in lead ores, copper ores, and cobalt arsenide
ores and is also frequently associated with gold in nature.
 The most important ore mineral of silver is argentite.
 The major silver ores are considered to be argentite (Ag2S), proustite
(Ag3AsS3), and polybasite [(Ag,Cu)16Sb2S11].
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Silver alloys:
 Argentium sterling silver (silver, copper, germanium)
 Britannia silver (silver, copper)
 Electrum (silver, gold)
 Goloid (silver, copper, gold)
 Platinum sterling (silver, platinum)

Uses of silver:
 It is used in making ornaments, coins, decorative articles etc.
 It is used in electroplating of silver, making silver mirror etc.
 Silver halides are used in conventional x-ray film as an image receptor.
 Silver sulfadiazine is used as a topical cream to treat burns, which is an anti-
infective medicine.
 Silver is used in bandages and dressings to prevent the spread of infections,
as well as in gels and ointments for minor scrapes and cuts.
 Silver nitrate is used from a long time as drops for newborn babies to
prevent pink eye.
 Colloidal silver is used to treat ceramic water filters to aid in killing bacteria
and pathogens and also to help bring clean water to developing nations.
 Silver Coat technology is used in Foley catheters in urology to prevent
urinary tract infections from catheter use.

Extractive metallurgy of silver:

The chief ore of silver is argentite and silver is extracted from argentite by the
hydrometallurgy process. The different steps involved in the extraction of silver are:

a. Ore – Concentration:

Argentite being sulphide ore and is concentrated by froth flotation process. The
pulverized ore is kept in a large tank containing water and pine oil. The mixture is
disturbed by passing compressed air where ore forms froth with pine oil & comes
to the surface while impurities are left in water.
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b. Treatment with sodium cyanide:

The concentrated ore is treated with 0.4% to 0.7% aqueous solution of sodium
cyanide and the current of air pass through it. The argentite ore dissolves in sodium
cyanide forming sodium argento cyanide.

Ag2S + GNaCN → 2Na [Ag(CN)2] + NO2S

Sod argento cyanide

The reaction is reversible so it is passed to oxidize Na2S to Na2SO4 such that the
equilibrium shifts towards product.

Na2S + O2 → Na2SO4

The solution is filtered and the filtrate containing sodium argento cyanide is used
to recover silver metal.

c. Precipitation of Silver:

The solution obtained is treated with Zn scrap where Xn displaces silver from its
complex.

Zn + 2Na [Ag (CN)2] → NO2[Zn (CN)4] | 2Ag

Sod Zincyanide

The ppt is collected, washed and fused to get compact mass of silver.
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d. Refining:

The impure silver is purified by the electrolytic method. A block of impure metal is
the anode while a thin strip of pure silver is the cathode. A mixture of AgNO3
solution is an electrolyte. On passing current impure silver dissolves and an
equivalent amount of pure silver is deposited at the cathode.

AgNO3(aq) → Ag+ + NO–3

At cathode: Ag+ + e → Ag

At anode: Ag → Ag+ +e

Deposits of silver in pakistan:

Pakistan on Wednesday said it has discovered major reserves of iron ore as well as
copper, silver and gold in Punjab. The reserves were found in Chiniot city in the
Punjab, around 160 kilometres (around 100 miles) north-west of Lahore, by
Chinese group the Metallurgical Co-operation of China.
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GOLD
 Gold is a chemical element with the symbol Au
 Highest atomic number of 79
 It is a bright, slightly orange-yellow, dense, soft, malleable,
and ductile metal in a pure form.
 Having density of 19.3 g/cm³
 Having crystal structure, close-packed,face-centered cubic (fcc).
Ore of gold:
 calaverite, (AuTe2)
 sylvanite, (Ag,Au)Te 2,
 petzite (Ag3AuTe2)
Alloys of gold:
Color of Gold Alloy Composition

Yellow Gold (22K) Gold 91.67% Silver 5% Copper 2% Zinc 1.33%

Red Gold (18K) Gold 75% Copper 25%

Rose Gold (18K) Gold 75% Copper 22.25% Silver 2.75%

Pink Gold (18K) Gold 75% Copper 20% Silver 5%

Uses of gold:
Of all the minerals mined from the Earth, none is more useful than gold. Its
usefulness is derived from a diversity of special properties.
 Gold conducts electricity,
 does not tarnish,
 is very easy to work,
 can be drawn into wire,
 can be hammered into thin sheets,
 alloys with many other metals,
 can be melted and cast into highly detailed shapes,
 has a wonderful color and a brilliant luster.
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 Decoration, jewellery and medals

 Electronics
 Space exploration
 Medicine and dentistry
Extractive metallurgy of gold
 Extraction of Gold by Cyanide Leaching (Heap leaching):

In this process the gold-bearing rock is crushed to sand and dust. Subsequently, the
rock dust – piled in heaps, columns or stored in tanks – is combined with a sodium
cyanide solution (sodium salt of hydrogen cyanide acid HCN). The acid detaches
the gold from the rock dust and transports it in the acid seepage fluid in a
chemically bound form. Subsequently, the gold is filtered out of the leach solution
by adding zinc dust., then washed out of the muddy substrate and finally dried. The
recovered raw gold is later refined into fine gold. The slurry formed is treated with
activated zinc or carbon for the extraction of gold. Cementation is the next process
which involves the use of zinc electrode with a paste of carbon immersed in the
solution containing the gold cyanide.
Major reservations exist against this method of extraction due to the release of
highly poisonous, easily flammable hydrogen cyanide acid, which presents
significant risks for human beings and the environment.
4 Au + 8 NaCN + O2 + 2 H2O → 4 Na[Au(CN)2] + 4 NaOH

At Cathode –

 Extraction of Gold by the Amalgam Process

The amalgam process is the oldest technical method of extracting gold and was
used in antiquity. With the amalgam process the gold bearing rock is likewise
crushed to fine sand. Afterwards mercury is added to the rock dust. Gold has the
property that enables it to join to the surface of the mercury. The gold enriched
mercury forms a silvery shining alloy solution, the so-called amalgam. The
amalgam collects at the bottom of the mixing container and is easily separated
from the other minerals. Subsequently, the amalgam is heated until the mercury
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evaporates leaving the pure raw gold. This method also involves dangers to health
and the environment experienced when vaporizing highly poisonous mercury.
 Extraction of Gold using the Electrowinning Process
This method uses an electrochemical approach. Here advantage is taken during the
extraction of other precious metals such as f.e. copper or zinc where also small
quantities of gold are found in the extracted rock. In the process of the electrolytic
cleaning of the rock sludge the anode activates the precious metal bearing rock
sludge. The cathode is made of a piece of pure metal. During electrolysis, the gold
in the raw rock material is not dissolved and collects as a sludge under the anode.
Together with gold other precious metals (f.e. Silver, copper, lead, tin) concentrate
in this anode-sludge and can be easily skimmed off. Then using a suitable process
the individual precious metals can be separated from each other.
Deposits of gold in pakistan:
 Reko Diq mine:
Located in the Chaghi District of Balochistan in Pakistan. It is one of the largest
copper and gold mines in the world located in the south west part of Pakistan in
Balochistan province. Reko Diq represents one of the largest copper and gold
reserves in the world having approximately 12.3 million tons of copper and ore
grading of 0.41% copper and gold reserves amounting to 41.5 million ounces.
 Saindak Copper Gold Project:
is located near Saindak town in Chagai District of Balochistan, Pakistan. The
discovery of gold, copper & silver deposits at Saindak was made in the 1970s in
collaboration with ahe Saindak Copper-Gold Project was set up by Saindak Metals
Ltd, a company fully owned by the Government of Pakistan, by the end of 1995 at
a cost of PKR 13.5 billion. Currently Metallurgical Corporation of China is
operating two mechanized hard rock underground Copper-Gold mines with current
production of 7.25T per annum of copper-gold from smelting process
Pakistan and China signed a formal contract worth $350 million for development
of Saindak Copper-Gold mine project. The mines were leased for a 10-year period
to Metallurgical Corporation of China Ltd. (MCC), a subsidiary of the China
Metallurgical Group Corporation.

Which raw materials is used in smelter?

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Smelters are organizations that purchase raw materials from mines, recyclers and scrap
suppliers and melt them down to produce metals intended for use in production.
Manufacturers that use tin, tungsten, tantalum or gold (3TGs) at some point within
their supply chain must purchase metals from a smelter.

w hat is the us

what is the use of air in smelter furnace

Roasting the carbonate and sulfide minerals in air converts them to oxides. The oxides, in
turn, are smelted into the metal. Carbon monoxide was (and is) the reducing agent of choice for
smelting. It is easily produced during the heating process, and as a gas comes into intimate
contact with the ore.

Casting process in smelter

Hot forming processes, such as die-casting, investment casting, plaster casting, and sand
casting, each provide their own unique manufacturing benefits. Comparing both the
advantages and disadvantages of the common types of casting processes can help in selecting
the method best suited for a given production run.
Bessemerization in copper
Bessemerisation is a method in which the air is blown into the molten copper mat that is
deposited in a Bessemer converter. In the final stage of smelting, the other products that
remain, including FeS, are oxidized and removed as slag(FeSiO3).
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