Minia University Faculty of Engineering

Chemical Eng. Department Second Year

Metallurgy and Materials Science

Course Code CHE

Part I

Extractive Metallurgy

Prepared By
Prof. Dr. Eng.
A.M. Bastaweesy
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 Principals of Extractive Metallurgy

Chapter (1) Ore Dressing (ore Beneficiation)

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 Figure 1: Process flow chain of extractive metallurgy
Rocks- A rock is made up of 2 or more minerals. You need minerals to make rocks, but
you don't need rocks to make minerals. All rocks are made of minerals.
For example, granite is a mixture of the minerals quartz, feldspar, and biotite.
Some rocks made of only one mineral like Limestone made of calcite
Minerals- A mineral is composed of the same substance throughout. There are more
than 3000 different minerals in the world. Minerals are made of chemicals - either a single
chemical element or a combination of chemical elements.
Difference between rock and mineral- A rock is made up of 2 or more minerals, whereas
a mineral is composed of the same substance throughout.
Aluminium is the most abundant metallic element but iron has played a much greater role
in human history and is an essential part of everybody, literally! Iron is one of 94 naturally
occurring elements. It is a metallic material with a silver-grey colour and metallic lustre.
Its Atomic Number is 26 and its symbol is Fe. Iron is found in all parts of the planet. It
comprises about 5% of the Earth’s crust but is thought to make up perhaps as much as
80% of the planets core. There are four naturally occurring stable isotopes of iron with at
least four unstable isotopes also known to exist.
Characteristics of a mineral
It must occur naturally. It must be inorganic It must be a solid
It must possess an orderly internal structure, that is, its atoms must be arranged in a
definite pattern.
It must have a definite chemical composition that may vary within specified limits."
Ores
Ores are those minerals from which metal are extracted conveniently and profitably.
Types of Ores
There are mainly four types of ores such as Oxides; Carbonate Ores; Sulphide; Halides
Ores.
Types of Ores Element Name of Ores
Oxides Aluminium Bauxite (Al2O3.2H2O)
Copper Cuprites (Cu2O)
Iron Hematite (Fe2O3)
Tin Casseterite (SnO2)

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 Carbonate Ores Calcium Limestone (CACO3)
Zinc Calamine (ZnCO3)
Iron Siderite (FeCO3)
Sulphide Zinc Zinc blende (ZnS)
Copper Copper glance (Cu2S)
Lead Galena (PbS)
Mercury Cinnabar (HgS)
Halide Ores Sodium Rock Salt (NaCl)
Fluoride Fluorspar (CaF2)
Silver Horn silver (AgCl)
Ores and Methods of Extraction of some Common Metals
Metals Occurrence Extraction method
1. Lithium Spodumeme LiAl(SiO3)2 Lipidolite Electrolysis of fused LiCl/ KCl
2. Sodium Rock salt (NaCl) Electrolysis of fused NaCl /
CaCl2
3. Magnesium Carnallite (KCl.MgCl2.6H2O) Electrolysis of fused MgO or
Magnesium (MgCO3) MgCl2 / KCl carbon reduction of
MgO
4. Calcium Limestone (CACO3) Electrolysis of fused CaCl2/
Dolomite (MgCO3.CaCO3) CaF2
Gypsum (CaSO4)
5. Copper Cuprites (Cu2O) Roasting of sulphide partially
Copper glance (Cu2S) and reduction
2Cu2O + Cu2S → 6Cu+SO2
6. Aluminum Bauxite (Al2O3.2H2O) Electrolysis of Al2O3 dissolved in
Cryolite (Na2AlF6) molten Cryolite or in Na2AlF6

7. Zinc Zinc blende (ZnS) Roasting and then reduction

Zencite (ZnO) with C
Calamine (ZnCO3)
8. Lead Galena (PbS) Roasting of sulphide ore then
reduction of the oxide
9. Iron Hematite (Fe2O3) Reduction with the help of CO
Magnetite (Fe2O4) and Coke in blast furnace,
Siderite (FeCO3) chemical reduction with CO,
Iron pyrite (FeS2) Calcination followed by
Limonite (Fe2O3.3H2O) reduction with CO. Roasting
followed by reduction with CO.
Ore- A mineral occurring in sufficient quantity and containing enough metal to permit its
recovery and extraction at a profit. Or, a mineral or naturally occurring aggregate of
minerals from which a valuable constituent, especially a metal, can be profitably mined or
extracted is an ore.

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MINERAL: It is a naturally occurring inorganic compound of one or more metals in
association with nonmetals such as oxygen, Sulphur and the halogens. A mineral has
fixed composition and well defined physical and chemical properties.
Many factors determine whether a rock is an ore, including supply and demand, and the
location of the material.
Simple ores are ores that yield a single metal.
Complex ores are ores that yield more than one metal.
By-products are the minor metals that are recovered from an ore. Co-products are the
major metals obtained from an ore (if > 1)
Ore Minerals
The ore minerals are those that contain the desired metals. A list of the common ore
minerals is given below.
The gangue minerals are the worthless minerals that have to be mined and then
separated from the ore minerals. They are usually the common rock-forming minerals.
FERROUS METALS
magnetite, Fe3O4; hematite, Fe203; goethite, FeO(OH);
iron
siderite. FeCO3; chamosite, Fe2AI2SiO5(OH)4
manganese pyrolusite, MnO2
nickel pentlandite (Ni,Fe)9S8
chromium chromite, FeCr2O4.
molybdenum molybdenite, MoS2
tungsten wolframite, FeWO4; scheelite, CaWO4
Metal- An alloy of two or more metallic elements.
Therefore, Rocks have minerals, which in large concentration are called ores and these
are mined for metals!

A mineral is a solid formation that occurs naturally in the earth while a rock is a solid
combination of more than one mineral formations, which is also occurring naturally.
A mineral has a unique chemical composition and is necessarily defined by its crystalline
structure and shape. On the other hand, since a rock can be composed of several
minerals it is classified according to the process of its formation. A rock can also contain

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organic remains and mineraloids apart from regular mineral formations. Some rocks may
include just one mineral formation though.
The commercial value of minerals is immense and rocks are mined to extract these
minerals. Such rocks are known as ores and the residue of the rock after the mineral has
been extracted is called tailing.
The classification of rocks also depends on their mineral and chemical composition,
texture and the process of formation. Rocks are therefore classified as igneous,
sedimentary and metamorphic. A rock cycle defines how one rock form changes to
another. For example, a sedimentary rock form is limestone that is composed only of the
mineral calcite.
Minerals and Ores: Natural materials
The Earth is the main source of minerals and ores. Most of the elements do not found in
Free State because of their reactive tendencies. Potassium, sodium, calcium,
magnesium, aluminium, zinc, iron, lead etc are the metals found in combined state.
Minerals are the natural materials in which the metals and their compounds are found in
earth. Ores are those minerals from which metal are extracted conveniently and
profitably. These ores contain good percentage of metal.
The Earth’s is the main source of minerals and ores. Most of the elements do not found
Free State because of their reactive tendencies. Potassium, sodium, calcium,
magnesium, aluminium, zinc, iron, lead etc are the metals found in combined state.
Minerals are the natural materials in which the metals and their compounds are found in
earth.
These ores contain good percentage of metal. Hence, we can say all minerals are not
ores but all ores are the minerals.
Abundances of the metals in the Earth's Crust

A common classification of metals is given below. Note that iron is the only element that
is both abundant and has useful metallic properties. Some other elements are important
primarily because they alloy with iron to form various steels. The non-ferrous metals are
in high demand in their own right. Precious metals are important because of their value,
fissionable metals because of their radioactive properties. Minor metals are produced in
small quantity but all have important, specialist uses.
Subdivision of metals used by the metals industries. –

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Group Typical metals
Iron and ferroalloy iron, manganese, nickel, chromium, molybdenum, tungsten,
(ferrous) metals vanadium, cobalt
non-ferrous metals copper, lead*, zinc*, tin, aluminium
precious metals gold, silver, platinum group
fissionable metals uranium, thorium
Minor metals antimony, arsenic, beryllium, bismuth, cadmium, mercury,
niobium, selenium, tantalum, tellurium, titanium, zirconium
NON-FERROUS
METALS
chalcopyrite, CuFeS2; bornite, Cu5FeS4; covellite, CuS; chalcocite,
copper Cu2S; malachite, CuCO3.Cu(OH)2; azurite, 2CuCO3.Cu(OH)2; cuprite,
Cu2O; chrysocolla, CuSiO3.2H2O

zinc sphalerite, ZnS

lead galena, PbS

tin cassiterite, SnO2;stannite, Cu2FeSnS4

aluminium gibbsile, Al(OH)3; boehmite, AIO(OH)

Primary and Secondary Ores

Primary ore minerals are those associated with the original episode of ore deposition.
Secondary ore minerals are those deposited during subsequent weathering at or near
the surface.
The effect of weathering is to leach many metals from the ore to leave a leached capping
or gossan. These metals may then enrich the underlying ore in a process known as
secondary enrichment.
The Grade of an Ore
The grade of an ore is the fraction by mass of the valuable material it contains. If:
The mass of the ore = M
The mass of valuable material contained = m
Then the grade (in %) = m/M * 100
Sometimes, the ore is described in terms of its ore mineral content. It can then be
converted to metals grade using the appropriate relative atomic masses.
For example, a rock containing 1% of chalcopyrite (CuFeS2) would have a grade of:
(1 x 63.5) / (63.5+ 56 +2x32) = 0.34% Cu
where the atomic masses of Cu, Fe and S are 63.5, 56 and 32 respectively.
The grade above which a given deposit is not economic to mine is known as the cut-
off grade. Ores well above this value are termed high-grade; those close to this value
are termed low-grade.
The multiplication factor needed to reach the cut-off grade from the average crustal
abundance is known as the concentration factor. As shown below, this can vary greatly

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from metal to metal. In general, the greater the concentration factor, the more expensive
the metal.
Ave. crust Ave. cut-off (%) (%)Conc. factor
Aluminium (AI) 8 30 3.75
Iron (Fe) 5 25 5
Copper (Cu) 0.005 0.5 100
Tin (Sn) 0.0002 0.2 1000
Gold (Au) 0.0000004 0.0008 500
Mercury (Hg) 0.000008 0.2 25000
General Principles & Processes of Isolation of Metals

Types of Ores:
Ores may be divided into four groups
Native Ores: These ores contain the metal in free state eg. Silver gold etc. These are
usually formed in the company of rock or alluvial impurities like clay, sand etc.
Oxidized Ores: These ores consist of oxides or oxysalts (eg. carbonates, phosphate)
and silicate of metal. Important oxide ore includes, Fe2O3, Al2O3.2H2O etc. and important
cabonate ores are limestone (CaCO3), Calamine (ZnCO3) etc.
Sulphurised Ores: These ores consist of sulfides of metals like iron, lead, mercury etc.
Examples are iron pyrites (FeS2). galena (PbS), Cinnabar (HgS)
Halide ores: Metallic halides are very few in nature. Chlorides are most common
examples include horn silver (AgCl) carnallite KCl. MgCl2.6H2O and fluorspar (CaF2) etc.
Metallurgy:
It is the process of extracting a metal from its ores. The following operations are carried
out for obtaining the metal in the pure form.
Crushing of the ore Dressing or concentration of the ore.
Reduction of metal. Purification or refining of the metal

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 Size-Grade Characteristics
Grade-tonnage plots usefully depict the metal available in a given deposit for different
cut-off grades. There are two extreme deposit types: dispersed and confined. The grade-
tonnage plots demonstrate how a small reduction in cut-off grade for the dispersed
deposit can generate a significant increase in metals. Secondary enrichment also
converts rock to ore.
The term “Size reduction” is applied to all the ways in which particles of solids are broken
or cut to smaller pieces. Commercial products must sometimes meet very specific
requirements as to the size and sometimes the shape of the product. On the other hand,
particles are ground to increase the reactivity of solids in some industrial reactions. Also,
this permits separation of unwanted large impurities by mechanical methods. Finally, it
reduces the bulk of fibrous materials for easier handling.
Solids are broken in four different ways: by (1) compression, (2) impact, (3) attrition and
(4) cutting. In general, compression is the main mode for coarse reduction, giving off only
few fines, whereas impact can yield coarse or fine particles and attrition gives extremely
fine particles. Cutting is only used whenever the product is to be of some definite shape
with little or no fines.

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10
 Crushers and grinders are used for size reduction (also known as comminution). An ideal
crusher or grinder should have a large capacity, consume as little energy as possible and
the product particles should practically have the same size. In practice all these criteria
are hardly met. As a matter of fact, the actual capacity of any crusher or grinder is always
several times less than its ideal capacity, also the power required for crushing or grinding
is much higher than the calculated theoretical power. Finally, it is not uncommon to have
products having a very large particle size distribution. Sometimes, a screen can be put at
the outlet of the crusher or grinder so as to remove the coarsest particles in the product
but this provision cannot eliminate the too fine particles produced.
Industrial Size Reduction Equipment
Size reduction equipment is divided into Crushers, Grinders, Ultrafine grinders and
Cutting machines. Crushers do the heavy work of breaking large pieces of solids into
smaller lumps. Primary crushers are run on materials out of mine the size of which may
reach more than one meter and breaking it into 150 – 300 mm lumps. A secondary
crusher reduces those lumps to particles in the size range of 5 – 10 mm. Grinders reduce
crushed feed to powder. The product from an intermediate grinder will usually pass a 40
mesh screen (about 0.35 mm) while most of the product of a fine grinder will pass 200
mesh screen (0.074 mm). Ultrafine grinders will accept a feed of a few mm in size and
reduce it to a product of sizes in the range 1 – 50 µm. Cutters will deliver particles of
definite shape and size, typically a few mm in length.
The principal types of size reduction machines are:
1- Crushers:
a- Jaw crusher b- Impact crushers c- Gyratory crushers d- Crushing rolls
2-Grinders:
a- Hammer mills and other impact types b- Ball mills, Tube mills and Rod mills.
c- Roller mills and bowl mills d- Attrition mills
3-Ultrafine grinders:
a- Hammer mills with internal classification b- Fluid energy mills c- Agitated mills.
4-Cutting machines:
a- Knife cutters.
n the following, some of these of machines will be considered in details:
The jaw crusher
In a jaw crusher, feed is admitted between two jaws, a stationary jaw or anvil and a
movable jaw, which reciprocates in a horizontal plane. It makes an angle of 20 - 30o with
the stationary jaw. It is driven by an eccentric so that it applies great compressive force
on the lumps caught between the jaws. Large lumps caught between the upper parts of
the jaws are broken, drop in the narrower space below and are re-crushed the next time
the jaws close. After sufficient reduction they drop out of the bottom of the machine. The
jaws open and close from 250 to 400 times per minute. “Blake crusher” it is possible to
regulate the maximum size of product by adjusting the maximum clearance between the
two jaws at their lower parts using a spring. In this type, the pivot at which the movable
jaw is fixed is located at the top of this jaw. This decreases the possibility of choking at
the outlet of the crusher. Size reduction in jaw crushers occurs mainly by a compression
mechanism and to lower extent by impact.
Crushers and grinders are used for size reduction (also known as comminution). An ideal
crusher or grinder should have a large capacity, consume as little energy as possible and

11
the product particles should practically have the same size. In practice all these criteria
are hardly met. As a matter of fact, the actual capacity of any crusher or grinder is always
several times less than its ideal capacity, also the power required for crushing or grinding
is much higher than the calculated theoretical power. Finally, it is not uncommon to have
products having a very large particle size distribution. Sometimes, a screen can be put at
the outlet of the crusher or grinder so as to remove the coarsest particles in the product
but this provision cannot eliminate the too fine particles produced.

A Blake Type Jaw Crusher

Gyratory cone crusher

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Mill (grinding) grinding of solid materials occurs through mechanical forces that break
up The structure by overcoming the interior bonding forces. After the grinding, the state
of the solid is changed: the grain size, the grain size disposition and the grain shape.
Milling also refers to the process of breaking down, separating, sizing, or classifying
aggregate material. For instance, rock crushing or grinding to produce uniform aggregate
size for construction purposes, or separation of rock, soil or aggregate material for the
purposes of structural fill or land reclamation activities. Aggregate milling processes are
also used to remove or separate contamination or moisture from aggregate or soil and to
produce "dry fills" prior to transport or structural filling.
Grinding may serve the following purposes in engineering:
Increase of the surface area of a solid fracturing of a solid with a desired grain size
Pulping of resources Grinding machines
In materials processing a grinder is a machine for producing fine particle size reduction
through attrition and compressive forces at the grain size level. See also crusher for
mechanisms producing larger particles. In general, grinding processes require a relatively
large amount of energy; for this reason, an experimental method to measure the energy
used locally during milling with different machines was recently proposed.

Ball mill
A typical type of fine grinder is the ball mill. A slightly inclined or horizontal rotating cylinder
is partially filled with balls, usually stone or metal, which grind material to the necessary
fineness by friction and impact with the tumbling balls. Ball mills normally operate with an
approximate ball charge of 30%. Ball mills are characterized by their smaller
(comparatively) diameter and longer length, and often have a length 1.5 to 2.5 times the
diameter. The feed is at one end of the cylinder and the discharge is at the other. Ball
mills are commonly used in the manufacture of Portland cement and finer grinding stages
of mineral processing, one example being the Sepro tyre drive Grinding Mill. Industrial
ball mills can be as large as 8.5 m (28 ft) in diameter with a 22 MW motor,[4] drawing
approximately 0.0011% of the total world's power (see List of countries by electricity
consumption). However, small versions of ball mills can be found in laboratories where
they are used for grinding sample material for quality assurance

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Ball mills fall in the tumbling mills class of mills. As a principal of operation, the ball mill
grinds material based on the falling action of steel balls caused by the cylindrical rotation
of the mill. In general, the larger the diameter of the mill, the slower the rotation. Ball mills
have a ball charge of 30 - 40% by volume and a total charge of 35 – 45% with limitations
mainly hinged on inlet, and outlet openings as well as on the balance between a
cascading grind producing attrition breakage leading to fine grinding and a cataracting
grind producing impact breakage leading to coarse particle grinding. As ore particles
become smaller from the impact breaking, they become less susceptible to it and instead
succumb to attrition grinding. The charge is also in such a way that the dead zone
(Stagnant zone) is to be kept as small as possible.
SAG mill

Principle of SAG Mill operation

SAG is an acronym for semi-autogenous grinding. SAG mills are autogenous mills that
also use grinding balls like a ball mill. A SAG mill is usually a primary or first stage grinder.
SAG mills use a ball charge of 8 to 21%.[6][7] The largest SAG mill is 42' (12.8m) in
diameter, powered by a 28 MW (38,000 HP) motor.[8] A SAG mill with a 44' (13.4m)
diameter and a power of 35 MW (47,000 HP) has been designed.
Attrition between grinding balls and ore particles causes grinding of finer particles. SAG
mills are characterized by their large diameter and short length as compared to ball mills.
The inside of the mill is lined with lifting plates to lift the material inside the mill, where it
then falls off the plates onto the rest of the ore charge. SAG mills are primarily used at
gold, copper and platinum mines with applications also in the lead, zinc, silver, alumina
and nickel industries.
Vertical shaft impactor mill (VSI mill)
A VSI mill throws rock or ore particles against a wear plate by slinging them from a
spinning center that rotates on a vertical shaft. This type of mill uses the same principle
as a VSI crusher.
Tower mill
Tower mills, often called vertical mills, stirred mills or regrind mills, are a more efficient
means of grinding material at smaller particle sizes, and can be used after ball mills in a
grinding process. Like ball mills, grinding (steel) balls or pebbles are often added to stirred
mills to help grind ore, however these mills contain a large screw mounted vertically to lift

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and grind material. In tower mills, there is no cascading action as in standard grinding
mills. Stirred mills are also common for mixing quicklime (CaO) into a lime slurry. There
are several advantages to the tower mill: low noise, efficient energy usage, and low
operating costs. Huller (also called a rice mill, or rice husker) is used to hull rice

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Concentration
Physical Method
Gravity separation: The powdered ores is agitated with water or washed with a running
stream of water. The heavy ore particles of sand, clay etc. are washed away.
Gravity separation uses different densities of individual ore components. A stream of
water together with a mash flow in a thin layer across a longitudinally vibrating slightly
tilted sluice plate (Fig. 1.3). Since gravity also applies during this separation process, the
lightest grains are washed off the sluice in the shortest way, while heavy grains are
transported to the end of the sluice via the vibrational movement.

Principle of gravity separation on sluices

Froth Floatation Process: The finely divided ore is introduced into water containing
small quantity of oil (e.g. Pine Oil). The mixture is agitated violently with air a froth is
formed which carries away along with it the metallic particles on account of the surface
tension forces. The froth is transferred to another bath where gangue-free ore settles
down.

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Flotation process includes these steps:
1. Grinding to liberate the mineral particles.
2. Reagent conditioning to achieve hydrophobic surface charges on the desired particles.
3. Collection and upward transport by bubbles in an intimate contact with air or nitrogen.
4. Formation of a stable froth on the surface of the flotation cell.
5. Separation of the mineral laden froth from the bath (flotation cell).
Chemicals used for the flotation play an important role in this process, because they have
an influence on the different flotation (surface) properties of minerals. They can be divided
into these groups:
1) Collectors – are used to alter the surface properties of the particles and facilitate the
attachment of air bubbles.
2) Frothers – the reagents that must modify the surface tension of the minerals to be
floated, i.e. permit transportation of valuable mineral to the froth phase.
3) Regulators – control the interaction of collectors between individual minerals, i.e. they
can increase or decrease the selective adsorption of collectors on specific minerals for
achieving the separation of individual minerals. Modifying reagents can change the pH of
the pulp.
a) Modifier - change the pH of the pulp.
b) Depressant – adsorption of modifying reagents on mineral surfaces create a
hydrophilic mineral surface that cannot react with collectors.
c) Activators - remove collector coatings from the mineral surface, causing depression of
the mineral.

Illustration of two different particles subjected to a contact angle test

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 Foam flotation principle
2) Magnetic separation
Magnetic separation is a technique for separating iron ore from impurities on the basis of
the difference in their magnetic properties. This type of separation is widely used for the
beneficiation of magnetite ore. A drum with a permanent magnet is rotated in slurry and
the result is that magnetite ore, which is magnetic, becomes attached to the surface of
the drum and is separated from the slurry, while non-magnetic impurities remain in the
slurry, thus accomplishing the separation. The separation of hematite ore, which is weakly
magnetic, employs an apparatus with an electromagnet that can generate a stronger
magnetic force. Recently, such an apparatus is also being used commercially to collect
hematite ore from the tailings. Magnetic force separation is applied to relatively fine ore
with diameters of approximately 0.05mm to 1mm.
Magnetic separation uses different magnetic properties of minerals contained in the ore,
especially magnetic susceptibility and permeability. The basis of magnetic separation lies
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in a separation of the ore to magnetic and non-magnetic products. Grains which resist the
effects of mechanic forces (gravity, friction, adhesion, viscosity of the environment and
hydraulic resistance during wet magnetic separation) due to the application of a magnetic
force are separated into the magnetic product. The main types of equipment for magnetic
separation are drum and belt magnetic separators (Fig. 1.4).

Principle of magnetic separation of ore minerals belt mag. separator

Electrostatic separation
The feed is presented uniformly to the rotating roll surface by a velocity feed system. Both
conductor and nonconductor particles are sprayed with ions. Conductor particles rapidly
lose their charge to the grounded roll surface and are thrown off by centrifugal force.
Nonconductor particles are pinned to the rolled surface and are brushed off that surface.
Both conductor and nonconductor particles are collected in a partitioned product hopper
at the bottom of the unit. The operating variables—roll speed, applied voltage, feed rate,
splitter position, and the electrode combination and position—are adjusted to achieve
effective separation.

Principle of electrostatic ore minerals separation

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 Operating principle of a roll-type electrostatic separator
Electrostatic separation is one of those important unit operations where electrical
conductivity property of mineral surface is used selectively to separate out desirable
mineral from other undesirable minerals.
Electrostatic forces are generated by the action of an electric field on a charged particle.
Consequently, in any electrostatic separation process one needs a source of electrical
potential to generate the electric field and a process by which the individual particles are
charged electrically. It is found that the following factors have significant effect on the
process:
1. Intensity of electric field
2. Particle size
3 . Relative humidity
4. Temperature of the particle/bed
5. Inter-electrode distance
Electrostatic separation has the following advantages over any other processes:
1. The electrostatic forces work on the particles to be separated only; they do not affect
the medium in which the particles are located
2. The trajectories of the particles under the influence of the electric field follow the electric
field lines. The electric field lines may be shaped to suit the particular application
3. The direction of electrostatic forces may be reversed by either changing the polarity of
the charge or the direction of the external electrostatic field
4. The electrostatic forces may be arranged to work in combination with other forces such
as gravitational or centrifugal forces
5. The electrostatic separation forces are independent of the substrate of the material on
which the surface electric charge is generated. They are determined solely by the product
of electric field and charge. In magnetic separators the forces are considerably greater,
yet such forces work on magnetic materials only. The electrostatic forces do not
differentiate between magnetic and non-magnetic materials. The charged magnetic
particle placed in an electric field will be subjected to forces practically equal to those

20
acting on a similar particle made out of nonmagnetic material and charged with the same
charge.
Chemical Methods
Drying and calcination
Drying
Drying is the removal of water from the ore, using a moderate amount of heat
temperatures on the order of 100°C). Only the mechanically bound water is removed
(water filling pores and cracks, or that is adhering to the particle surfaces). Chemically-
bound water, such as water of hydration in the ore crystal structure, is not removed by
drying processes.

Calcination
The term calcination is used to denote thermal decomposition of solids and is expressed
by the general reaction
Solid 1 = Solid 2 + Gas
Calcination is a widely used unit operation in process metallurgy, and the compound
represented as solid 1 is usually a carbonate and solid 2, an oxide. The decomposition of
hydroxides, besides being termed as drying as indicated in the previous section, is also
called calcination.
For example, consider decomposition of a carbonate, which can be shown chemically as:
MCO3 (s) = MO (s) + CO2 (g)
it may be mentioned that while the temperature required in the case of ferrous carbonate
(FeCO3) is only 200 °C, those required for magnesium carbonate (MgCO3) and calcium
carbonate (CaCO3) are 400°C and 900°C respectively; the temperature requirements for
strontium carbonate (SrCO3), whilst some others (not shown) such as barium carbonate
(BaCO3) and sodium carbonate (Na2CO3) are even higher. In air, the dissociation of a
carbonate can be considered to begin at the temperature at which the dissociation
pressure (equilibrium pressure of carbon dioxide) of the carbonate exceeds the partial
pressure of carbon dioxide in air (about 0.03%). However, vigorous decomposition of
carbonates occurs at temperatures at which the dissociation pressure exceeds the
atmospheric pressure.

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Three different types of furnaces are generally in use for calcination. The shaft furnace is
considered to be the most suited for calcining coarse limestone. Furnaces of the rotary
kiln type are used for handling materials of mixed particle sizes and lumps which
disintegrate during the process. Calcination can be carried out in a fluidized bed-reactor
for materials of small and uniform particle size. These furnaces are usually fired with gas,
oil or coke; in some cases electric heating is resorted to.
Originally, calcination referred to the heating of limestone above 900°C to drive off the
CO2 and produce lime:
CaCO3(s) ===> CaO(s) + CO2(g)
In current practice, calcination refers to any process where the material is heated to
drive off volatile organics, CO2, chemically bound water, or similar compounds. For
example:
2 Al(OH)3(s) ===> Al2O3(s) + 3 H2O(g)
2FeO•OH(s) ===> Fe2O3(s) + H2O(g)
Drying means removal of free water – moisture – or other solvents from the processed
materials (ores, concentrates) and their conversion into a gas phase. Sources of moisture
can be e.g. mining and preparation processes, transportation, hydrometallurgical
processes… The product of drying is a dry mass – material dried to a constant weight,
usually at 150°C and at certain air humidity. Drying is performed in rotary drum furnaces,
tunnel furnaces, or fluid furnaces, in which drying is performed by particles floating in a
drying medium.
Calcination is a pyrometallurgical process, during which chemically bound water, e.g.
hydrate and crystal water, is removed from the processed materials. Disintegration of
some hydrates, carbonates, halides, sulphates and other compounds occurs as well.
a) Calcination as a dehydration process – e.g. fluid dehydration of FeSO4.7H2O (iron
vitriol):
FeSO4.7H2O → FeSO4.H2O + 6 H2O
or calcination of aluminum hydroxide Al2O3.3H2O: Pyrometallurgy
b) Calcination as a dissociation of carbonates – calcination can also denote other
pyrometallurgical processes, which proceed with (or also without) access of air. An
example can be dissociation of carbonates to oxides: MeCO3 → MeO + CO2
Some carbonates release CO2 easily, others require quite high temperatures for the
dissociation process. Each carbonate features certain dissociation temperature, at which
pressure of the released gas reaches the value of atmospheric pressure p CO2 = 1.
Approximate dissociation temperatures of selected carbonates: ZnCO 3 = 135°C; FeCO3
= 158°C; MnCO3 = 210°C; PbCO3 = 300°C; MgCO3 = 410°C; CaCO3 = 910°C.
Calcination: Carbonate or hydrated oxide ores are subjected to the action of heat in
order of expel water from hydrated oxide and carbon dioxide from a carbonate.
ZnCO3 --> ZnO + CO2 CaCO3 --> CaO + CO2
Al2O3×2H2O --> Al2O3 + 2H2O 2Fe2O3×3H2O --> 2Fe2O3 + 3H2O

22
23
Roasting:
Roasting is a method of preparation of ores and concentrates before further
pyrometallurgical or hydrometallurgical processing. The aim of roasting is to produce a
calcine with suitable chemical and physical properties required for further processing.
Roasting is performed at elevated and high temperatures, although still under melting
temperatures to prevent a phase change of the processed material.
Roasting involves chemical changes other than those of thermal decomposition (usually
included under calcination). A roast may sometimes effect drying and calcination or
thermal decomposition in passing.
For example, the first stages in the roasting of covellite (CuS) is really a calcination step
to Cu2S with the elimination of sulfur which escapes as a gas to the surface of each
particle and burns there to SO2. The last stages in the oxidative roasting of covellite or
chalcocite involve the thermal decomposition of CuSO4 to cuprite CuO. Hence, roasting
depends on the diffusion of chemical species through the products to the reaction front in
each particle. Thus, in the roasting of chalcocite (Cu2S) or the second-stage roasting of
covellite (CuS) oxygen must diffuse into the particle and SO2 out of it. In order to assist
diffusion a draft must be maintained to keep the partial pressure of the gaseous products
low outside the particles.
Magnetizing and chloridizing roasts are usually reducing in character and require good
control of furnace atmosphere with respect to CO/CO2 and H2/C12 ratio, respectively.
Sintering is in general an oxidizing process that is used to eliminate carbonate and sulfide
as well as to produce agglomerated products.
Basic Steps in Roasting:
• Particles are heated.
• Reactive gas (air, oxygen, chlorine, etc.) contacts the particles.
• Particles react with the gas.
• Gaseous reaction product are carried away.
Since the particles do not melt, the reaction starts on the particle surface and gradually
works in to the particle core, as shown in the Shrinking-Core reaction model (Figure 5)

The Shrinking-Core model. As the shell of oxidized ore becomes thicker, it becomes more
difficult for fresh gas to reach the unreacted ore, and so the roasting rate slows down. It
is often difficult to react the last bit of material in the center of the particles.

24
Basic Roasting Terms:
• Dead Roast: the ore is completely reacted, and leaves the process cold.
• Sweet Roast: the ore is completely reacted, but leaves the furnace still hot.
• Sour Roast: the roasting reaction is not run to completion.
Types of Metallurgical Roastings
Not only does roasting involve oxidation, but it can accomplish any of the following
objectives:
1. Oxidation roasting to burn out sulfur from sulfides and replace it in whole or in part with
lattice oxygen.
2. Magnetization roasting accomplishes controlled reduction of hematite to magnetite,
thus enabling concentration of the ore by magnetic separation.
3. Sulfation roasting to convert metal sulfides or oxides to sulfates, usually prior to
leaching. This is especially valuable for manganese and uranIum ores.
4. Chloridation roasting to convert certain metals to their volatile chlorides.
5. Carburization roasting to prepare calcine or refractory metals for chlorination as with
titanium and zirconium ores.
6. Carbonate or soda ash roasting to extract refractory elements such as chromium from
their ores by forming leachable soluble compounds as sodium chromate.
7. Segregation roasting or chlorometallization to isolate metallic particles from the ore
matrix onto a reducing surface. This is particularly useful for beneficiating copper and
copper nickel oxidized ores through volatilization of their chlorides by Hel, followed by
deposition in a metallic state on a carbonaceous substrate. Hydrogen chloride gas is
generated by the action of hot water vapor (700-900° C) on sodium chloride in presence
of quartz, a common constituent of most minerals, according to
2NaCl + SiO2 + H2O → Na2SiO3 + 2HCl (4.1-1)
Ores of metals such as antimony, bismuth, cobalt, gold, lead, palladium, silver, and tin,
which form volatile chlorides or oxychlorides,(2) may respond to the segregation roasting.
8. Volatilizing roast to eliminate other metals with volatile oxides such as AS2O3, Sb2O3,
or ZnO which can be condensed in the colder parts of the roaster. A volatilizing roast at
carefully controlled temperature is sometimes used in the ore dressing of bismuth to
remove arsenic and antimony as oxides.
9. Reducing roast to convert oxide to metal in a complex matrix prior to leaching or
smelting.
10. Sintering or blast roasting to modify the physical characteristics of the ore or
concentrate. This usually covers agglomeration and pelletization as in the iron ore
industry.
Examples:
2PbS + 3O2 --> 2PbO + 2SO2 PbS + 2O2 --> PbSO4
2ZnS + 3O2 --> 2ZnO + 2SO2 ZnS + 2O2 --> ZnSO4
CuS + 2O2 --> CuSO4 2Cu2S + 3O2 --> 2Cu2O + 2SO2
Chemical composition of a roasted material changes during roasting. Chemical bonds
between individual elements are modified, new bonds occur, valences of elements
change, some elements are removed in forms of various compounds and gasses.
Since heterogeneous reactions occur (gas-condensed phase), the main factor during
roasting is the atmosphere in a roasting furnace. According to the character of the main
roasting reaction (i.e. character of the gaseous atmosphere), possibly according to the

25
composition of final roasting products, the following basic types of roasting can be
distinguished:
1. Oxidizing roasting 2. Sulphate roasting
3. Reaction roasting
a) chloride roasting b) segregation roasting c) chlorination and fluorination
4. Reduction roasting
Roasting furnaces
Roasting furnaces provide perfect contact of all particles of a roasted material with the air
or a gaseous atmosphere. For roasting of ores and concentrates, the following types of
aggregates are mostly used:
a) Multi-rack furnaces
b) Rotational drum furnaces
c) Convection furnaces
d) Fluidization furnace

Multiple-hearth roasting furnace

The wedge multiple-hearth roaster, shown in Figure 4.1-1. In this furnace both heat and
mass are transferred counter-currently as the ore progresses down the shaft and across
each of a series of hearths, being continuously turned over by rotating rakes which also
advances the ore across the hearths.

26
Despite the poor accessibility of furnace gases to the surface of the finely ground ore
particles, a high proportion of the reactions takes place only as the ore falls from one
hearth to the next one below.
Important parameters during roasting are above all temperature, amount of air or gas,
roasting furnace power output and raw materials input humidities. Calcine quality, i.e.
degree of desulphurization, presence of sulphidic sulphur, development of ferrites and
silicates, metallic compounds, physical properties etc., have to be regularly controlled.
Equilibrium equations

Fig. 2 General Kellogg’s diagram and equations of phase equilibria.

• PREDOMINANCE AREA DIAGRAMS:
❖ The isothermal behavior of some M-S-O systems with respect to their relative stability
can be represented by predominance area diagram.
❖ These diagrams indicate those solids which are in equilibrium with the gas having
certain partial pressure of oxygen and Sulphur dioxide.
❖ Hence this diagram helps to predict the type of solid present that would be in
equilibrium with the roaster gas of a known composition.

27
❖ Sulphur dioxide gas is taken into account because during roasting of sulphide ore SO2
gas obtains.
Rate and development of the sulphide roasting process are influenced by these factors:
a) physical and chemical properties of sulphides,
b) grinding degree,
c) process temperature,
d) amount of air for mixing of a roasted material.
WHAT ARE THE ADVANTAGES OF HIGH TEMPERATURE?
as at high temperature, the reaction rate is accelerated which leads to more metal
production.
Also at high temperature the inexpensive reducing agent can be used and cheaper raw
material can be used.
as we know that the reaction rate doubles in each 10ºC rise of temperature which
requires small activation energy. It helps in fast reaction.
• Shift of reaction is possible.
• Brings about a reduction which cannot takes place in presence of water.
• Only pyrometallurgy and fused salt electrolysis can extract reactive metals namely the
alkaline earth metals zirconium and titanium.
• Ability to treat a large tonnage of ore in a compact space, which leads to a saving in
capital cost.
There are 4 processes that are included in pyrometallurgical treatment. i.e.
1. Calcination 2. Roasting 3. Smelting 4. Refining

28
Smelting is a process of applying heat to ore in order to extract a base metal. It is a form
of extractive metallurgy. It is used to extract many metals from their ores,
including silver, iron, copper, and other base metals. Smelting uses heat and a
chemical reducing agent to decompose the ore, driving off other elements as gases
or slag and leaving the metal base behind. The reducing agent is commonly a source
of carbon, such as coke—or, in earlier times, charcoal.[1]
The carbon (or carbon monoxide derived from it) removes oxygen from the ore, leaving
the elemental metal. The carbon thus oxidizes in two stages, producing first carbon
monoxide and then carbon dioxide. As most ores are impure, it is often necessary to
use flux, such as limestone, to remove the accompanying rock gangue as slag.
Plants for the electrolytic reduction of aluminium are also generally referred to
as aluminium smelters.
Leaching
The theory and practice of leaching, the removal of materials by dissolving them away
from solids, is well developed and will be discussed in more detail in the following section.
Nature of leaching
Leaching is a primary extractive operation in hydrometallurgical processing, by which a
metal of interest is transferred from naturally occurring minerals into an aqueous solution.
In essence, it involves the selective dissolution of valuable minerals, where the ore,
concentrate or matte is brought into contact with an active chemical solution known as a
leach solution.
The transfer of a metal from the ore to the leach solution constitutes a transfer from a
solid to a liquid phase. Because the dissolution is selective, most of the unwanted
components in the ore are unaffected by the leaching process and remain in the solid
state. Consequently, the metal is separated when the solids are separated from the
solution after the leaching process has been completed, and the solution that is produced
is termed a pregnant solution or leach liquor. The solid product is termed the residue or
tailings. Furthermore, it is important that in the solution the waste minerals and
compounds being rejected by the leaching reaction should have a solubility low enough
to yield an acceptable separation of valuable and waste minerals during the leach, and to
obtain a leach solution of acceptable purity for subsequent metal recovery.
For the efficient leaching of metal from the metal-bearing species in an ore, use has to be
made of an appropriate water-based chemical reaction that will yield a water-soluble
metallic species. The thermodynamic characteristics of the reaction system will indicate
the maximum possible extent to which the value-bearing mineral can be converted to a
soluble species, as well as the solubility of that species in the aqueous solution. The
degree to which such a transfer can be achieved is determined by the rate at which the
reaction proceeds.
The following mechanisms, determining the overall leaching rate, are involved in a single
stage leaching process:
> The reagents must diffuse to the mineral surface.
> Reagents must adsorb on the surface.
> Chemical reaction must take place on the surface.
> Reaction products must desorb from the surface.
> Reaction products must diffuse from the surface vicinity to the bulk of the solution.

29
The rate of the slowest of these mechanisms controls the overall rate of the leaching
process. Therefore, any effort to increase the rate at which one of these mechanisms
occurs will be successful only if that step is rate-controlling.

Schematic diagram of a single stage leaching process

In a leaching process, attention is focused on the chemical reactions that result in the
dissolution of the metallic species. The following three important factors influence the
viability of a leaching operation:
~ The degree of dissolution that can be achieved.
~ The selectivity of the leaching reactions.
~ The cost of the leach solution.
~ The capital cost of the leach equipment
The degree of dissolution. For a high degree of metal extraction from an ore, the
dissolution of the value metals must be as complete as possible, which is the primary
consideration in the implementation of any leaching operation. Any valuable metal that
remains unreacted in the ore, after leaching, constitutes a loss of the metal.
Selectivity of leaching. The second factor that affects the viability of leaching is the
selectivity of the dissolution reactions. This factor is important because all ores contain a
variety of minerals, other than those in which the metal of interest occurs. Inevitably, some
of these will be attacked by the leach solution with the result that unwanted species are
taken up in the leach liquor. The selectivity of the leaching reactions determines the
degree to which this happens and, consequently, the purity of the metal-bearing solution
that is produced by the leach.
The following parameters in a leaching process are of importance.
> Particle size. The ore or concentrate particles must be small enough for the valuable
metals they contain, to be exposed physically to the leach solution, and it does not matter
if the mineral is not completely liberated. What is of importance is the degree of exposure
of the mineral to ensure complete leaching of a mineral grain in an ore.
The degree of exposure influences the rate at which leaching proceeds. Generally the
> Diffusion rates. The rate of diffusion of reactants or products can control the rate of a
leaching process. When the diffusion of a species in the solution phase to and from the
mineral surface is slow, an increase in the degree of agitation of the solution will increase
the rate at which the species diffuse. If the rate-controlling mechanism is the diffusion of
some species through a porous layer around the mineral particles, or through fissures in
the particles, the degree of agitation does not influence the rate of leaching very much. In
such cases, the options available for increasing the leaching rate are either to decrease

30
the size of the particles or to increase either the temperature or the concentration of the
reagents in the leach solution. On the other hand if it is chemically-controlled then it will
not be influenced by agitation; provided that enough agitation is done to prevent the solids
from settling.
> The rate of chemical reaction. In some situations, the rate at which the leaching
reactions proceed at the mineral surface determines the kinetics of leaching. To increase
the chemical reaction rate, the degree of exposure of the valuable metal can be increased,
the temperature or pressure of the leaching system can be increased, or a catalyst can
be employed. For a diffusion-controlled process the increase in the leaching rate due to
an increase in temperature is much less remarkable than for a chemically controlled
process.
> Leach agent concentration. The rate of leaching increases with increasing
concentration of the leaching agent.

Extraction (leaching from ore)

31
> Pulp ‫ اللب‬density. The rate of leaching increases with decreasing pulp density. In the
case of high pulp densities, low quantities of solution and high concentrations exist, this
will cause the equilibrium to shift and reaction rates will decrease.
Insoluble products. If an insoluble reaction product is formed during leaching, then the
rate will depend on the nature of this product. If it forms a non-porous layer, the rate of
leaching will greatly decrease. If, however, the solid product is porous, it will slightly or
not at all affect the rate.
Reactions for leaching copper minerals and pyrite
Minerals Reaction(s)
Copper sulphides
Chalcocite
Cu2S +1/2O2 + H2SO4 → CuS + CuSO4 + H2O (1)
Cu2S +Fe2(SO4)3 → CuS + CuSO4 + 2FeSO4 (2)
Covellite
CuS + 2O2 → CuSO4 (3)
CuS +Fe2(SO4)3→ CuSO4 + 2FeSO4 + S (4)
Chalcopyrite
CuFeS2 + O2 + 2H2SO4→CuSO4 + FeSO4 + 2S +2H2O (5)
CuFeS2 +2 Fe2(SO4)3→CuSO4 + FeSO4 + 2S + 2H2O (6)
Copper carbonates, oxides and silicates:
Malachite
Cu2 (OH)2CO3+ 2H2SO4+ 2CuSO4 + 3H2O+ CO2 (7)
Azurite
Cu3(OH)2(CO3)2+ 3H2SO4→ 3CuSO4 + 4H2O+ 2CO2 (8)
Cuprite
Cu2O +1/2O2 + 2H2SO4→2CuSO4 +2H2O (9)
Chrysocolla
CuSiO3+2H2O + H2SO4→CuSO4 + SiO2+3H2O (10)
Pyrite
FeS2 + 3.5 O2 + H2O → FeSO4 + H2SO4 (11)
2 FeSO4+ H2SO4 + 0.5 O2 → Fe2(SO4)3 + H2O (12)
FeS2 + 7Fe2(SO4)3 + 8H2O → 15 FeSO4 + 8H2SO4

32
Chapter (2) Iron and Steel Making

33
 Types of iron ore
The major rock types mined for the production of metallic iron are massive hematite, pisolitic
goethite/limonite, which provide a 'high-grade' ore, and banded metasedimentary ironstone,
magnetite-rich metasomatite, to a much lesser degree, rocks rich in siderite, rocks rich in
chamosite which provide a 'low-grade' ore.
Elemental iron (Fe) is ranked fourth in abundance in the earth's crust and is the major constituent
of the earth's core. It rarely occurs in nature as the native metal.
The pure metal is silvery white, very ductile, strongly magnetic and melts at 1528° C.
Iron accounts for approximately 95% of all metals used by modern industrial society.
Metallic iron is most commonly produced from the smelting of iron ore to produce pig iron.
Major iron Ores
Name Formula % Fe

Hematite Fe2O3 69.9

Magnetite Fe3O4 74.2

Geothite / Limonite HFeO2 ~ 63

Siderite FeCO3 48.2

Chamosite (Mg,Fe,Al)6(Si,Al)414(OH)8 29.61

Pyrite FeS 46.6

Ilmenite FeTiO3 36.81

WHATEVER material we are to manufacture cast iron, wrought iron, or steel or for whatever
purpose the metal is to be used, the first step in the operation is smelting iron ore in a blast furnace
with fuel and flux, and obtaining pig iron The pig iron thus produced is an impure grade of iron,
containing usually 3 to 4 per cent, of carbon, up to 4 per cent, of silicon, up to 1 per cent, of
manganese, and a few hundredths of 1 per cent, each of Sulphur and phosphorus.
The amount of pig iron made exceeds that of any other product manufactured by man.

Magnetite Haematite

34
 Goethite
Limonite
FUELS AND FLUXES
Fuels are impure forms of carbon. By their union with oxygen they furnish heat:
C+ O =CO (generates 29,160 calories).
3 CO+ O =CO2 (68,040). C+O2 =CO2 (97,200).
Charcoal. The purer the carbon the better it serves the purposes mentioned. For this
reason charcoal, which has the least amount of objectionable impurities, was once the
great metallurgical fuel. Even to-day blast furnaces use charcoal for the production of
pure pig relatively free from sulphur. Except in favored localities, charcoal is costly.
Furthermore, its weakness permits it .to crush easily; so charcoal furnaces are restricted
to small sizes, and 'charcoal iron' is higher in price.
Anthracite. Anthracite is purer than coke, but its denseness makes it offer a large
resistance to the blast in furnaces having much height.
Coke. Coke is the great blast-furnace fuel, and a near-by supply of this material makes
Pittsburg, Chicago, Alabama, and Colorado the great smelting centers that they are. In
the United States practically 94 per cent, of the pig iron is made with coke as fuel, 5 per
cent, with anthracite as fuel, and 1 per cent, with charcoal.
A bituminous coking coke contains about 30 per cent, by weight of volatile matter. When
this coal is heated, or ' coked/ the volatile matter is driven off, leaving a porous, spongy
mass of a silvery gray color and good strength. This is coke, and an analysis of a
specimen from the famous Connellsville region near Pittsburg is: Volatile matter =0.67
per cent.; fixed carbon =87.05 percent; ash = 10.60 per cent.; sulphur =0.74 per cent.;
phosphorus =0.016 per cent.
Metallurgical coke must be hard and porous while still being physically strong. Its four
main functions in a blast furnace are:
·as a fuel;
·to supply carbon for the reducing reactions which convert iron oxide to metallic iron;
·to provide a permeable support for the feed materials charged into the furnace so that
the reducing gases derived from the 'air' blast can pass up the furnace; and to provide
the carbon which is dissolved in pig iron.

35
 coke

Fluxes
Iron ore, coal and air are the main raw materials for iron and steelmaking but many other
substances are used. Apart from energy sources, such as natural gas and electrical
power, the majority of these supplementary materials can be broadly classified as fluxes,
alloys and refractories. Some of the most common are listed together with their main
functions and sources in Table 4, below.
Fluxes are the materials used in metallurgical processing to react with impurities to form
a liquid slag at the process temperature. This allows the metal to be easily separated from
the impurities.
The impurities are mainly oxides, either as they occur in the feed (gangue and ash) or
generated in refining, so the fluxes are also generally oxides.
Some supplementary raw materials for fluxes, refractories alloying
Material Process Function
Limestone Flux in ironmaking and steelmaking
Dolomite Flux in ironmaking and steelmaking
Quartzite Flux in ironmaking
Serpentine Flux in ironmaking
Fluorspar Slag fluidity in steelmaking
Magnesite Refractory brick linings
Manganese Ore Ferromanganese, silicomanganese manufacture for alloying steel
Composition
Fluxes have 'acidic' or 'basic' properties. Silicon dioxide, SiO2, forms an acid slag, while
calcium oxide, CaO, forms a basic slag.
This is analogous to acids and bases in aqueous chemistry, such that acid and basic
oxides tend to react together. Physically, this means that high melting point oxides can
form lower melting point mixtures. Chemically, if there is a surplus of one type of oxide,
then the mixture will more strongly hold (dissolve) an oxide of the other type in the slag.
Therefore a very basic slag (high in CaO, low in SiO2) is more efficient for removing
phosphorus during refining because phosphorus pentoxide P2O5 is an acid oxide. On the
other hand, a basic slag will not dissolve basic oxides so readily, which enables high
melting point oxides to be used as container materials for slags providing they are the
same type as the slag. Thus "basic" oxygen steelmaking employs basic slags (high in
CaO and often saturated in magnesium oxide MgO) in a vessel lined with high melting
point basic oxide refractory bricks (mainly MgO), referred to as magnesia bricks.
Limestone, the most used flux, is a sedimentary rock, usually white, varying from hard
and compact to soft and friable.

36
Limestone for use in a Bas furnace must be burnt (calcined) in kilns before charging. A
fine grained lump limestone is needed to produce a sufficiently hard lime.
Dolomite is becoming increasingly important as a flux material. It is a combined calcium
magnesium carbonate, geologically similar to limestone, reacting chemically in the same
way.
Lump material is calcined along with limestone as a BOS flux, and fines may be added to
the sinter plant to modify the blast furnace slag composition.
Fluxes. The ash of fuels will not melt readily. By adding the correct amount of lime to
them they are transformed into a fusible mass, which remains in a liquid form in the
furnace and is easily removed by opening a hole in the side. This fusible ma-terial is
known as slag or cinder, and the added lime is known as flux. The flux is usually added
in the form of limestone (CaCO3), but the heat in the upper layers of the furnace drives
off the carbonic acid, leaving lime (CaO).
The gangue of our iron ores consists usually of silica, alumina, etc., and, like the fuel ash,
requires the addition of the correct amount of limestone flux to make it into a fusible slag.
In the Pittsburg district we charge about 1200 Ib. of limestone, 2200 Ib. of coke, and 4000
Ib. of ore for every long ton of pig iron made.

Agglomeration of iron Ores

37
Pelletizing

38
The amount of each is increasing, however, from time to time, as the higher-grade ores
are becoming exhausted and there are more impurities to be fluxed and melted.
The iron ores used for smelting consist of chemical compounds of iron and oxygen
containing more or less water, either in the form of moisture or chemically combined as
water of crystallization.
Hematite (Fe2O3). The best known of these ores is hematite, containing when pure 70
per cent, of iron. The red or brown hematites are the richer varieties (Lake Superior
deposits, containing, in some cases, as much as 68 per cent, of iron), while the hydrated
hematites, or limonites, usually contain a good deal of water of crystallization and are
consequently poorer in iron, not often yielding much more than 50 per cent iron.
Oolitic hematite is a variety that exists in the form of spherical grains or nodules. It is
important because it sometimes contains limestone and is, therefore, valuable not only
for the iron but for the fluxing quality of the lime. The Minette ore of Lothringen (formerly
Lorraine), Luxemburg, and France is an enormous deposit of this oolitic hematite, running
from 30 to 35 per cent, iron and giving a pig iron containing about 2 per cent, of
phosphorus. This ore is the basis of the iron industry of Germany, France, and Belgium,
and, upon judicious mixing of varieties, when necessary, is self-fluxing Magnetite (Fe3O4).
Magnetite contains, when pure, enough iron (72.4 per cent.) to attract the magnet. In the
United States it is often mixed with other impurities, such as silica, titanium, and
phosphorus, so much so as to render the ore either too poor in iron to be smelted
profitably, or too high in phosphorus to make good steel, or so high in titanium as to

39
interfere with the blast-furnace smelting by producing sticky slags which are not easily
handled.
The magnetite ores of Sweden are, however, the purest ores that exist in large quantities
anywhere, and form one of the sources of the Swedish iron and steel, which is famous all
over the world for its purity, that is, for its freedom from the objectionable elements sulphur
and phosphorus. It is these Swedish products which supply the steel industry of Sheffield
with pure material for its tool steel and cutlery.
Siderite (FeCO3). Another variety of iron ore is the so called 'spathic' iron ore, or siderite,
which is, however, without any importance in the United States. This forms the famous
*clay ironstone ' of the Cleveland district in England. It is poor in iron and is therefore no
longer smelted in any quantity in the United States in competition with the rich hematites.
This ore is almost always calcined before smelting to expel the carbonic acid, in order to
save the blast furnace the extra work of this expulsion in its upper levels.

As an additional example, reference is drawn to oxide systems in which one of the peer
examples is shown in Figure 4.4 (A), which depicts the predominance ‫ هيمنه‬diagram for
oxides of iron in contact with CO/CO2 mixture. It can be well used to obtain the answer
of: (i) consequence of contacting Fe2O3 with a gas mixture such that the composition and
temperature correspond to the point of X; (ii) the minimum temperature required at which
reduction of Fe3O4 with CO/CO2 mixtures causes wustite (FeO) to form; and (iii) the
reaction product expected to form first as a result of oxidation of iron with CO2 at 1200 K.
The Figure 4.4 (A) is very often studied with a line superimposed to indicate the
equilibrium in reaction
C + O2 = 2 CO

40
at 1 atm., as is carried out in Figure 4.4 (B) by a dashed line. This particular line provides
the gas composition in equilibrium with solid carbon at the temperature in question. So,
any point away from the dashed line will represent a composition that is not in equilibrium,
and the reaction,

Figure 4.4 (A) Predominance diagram of iron and its oxides in contact with carbon
monoxide/dioxide mixtures; (B) predominance diagram of (A) with the equilibrium line for
carbon in contact with its oxides superimposed.

41
Sintering

Principle of ore raw materials agglomeration

42
Sintering is a thermal process (1300–1400ºC) by which a mixture of iron ore, return fines,
recycled products of the iron and steel industry (mill scale, blast furnace dusts, etc.), slag
forming elements, fluxes and coke are agglomerated in a sinter plant with the purpose of
manufacturing a sintered product of a suitable chemical composition, quality (physically)
and granulometry to be fed into the blast furnace, ensuring a homogenous and stable
operation in the blast furnace. This definition proposed in, describes the sintering process,
but prior to sintering there is an important process called granulation.
Granulation is the homogenization of the iron ore mixture in a rotatory drum with 7–8%
water having as objective the obtaining of a pre-agglomerated product, which is then
delivered as a layer over a continuously moving grate or “strand” (Dwight-Lloyd machine)
to obtain the sintered product. This process that takes between 30 and 60 min. (including
the addition of moisture, granulation and feeding to the sintering machine) has a
fundamental role as it ensures an adequate sinter bed permeability and hence good
productivity.
Dwight-Lloyd technology is the main iron ore sintering technology. Basically, this
equipment consists in a sintering grate that is a continuous chain of large length and
width, which is formed by the union of a series of pallet cars making the sintering strand.
The process in the Dwight-Lloyd machine begins with each pallet car passing below the
charging hopper. Feeding is carried out in two layers: the hearth layer that protects steel
grates from over-heating during the sintering process, which is formed by sinter of coarse
granulometry (10–20 mm, with a granulometry not enough to be sent to the blast furnace)
in a layer of 3–6 cm; and the layer of fine material (0–8 mm) granulated to be sintered
(fine material, return fines, fluxes, and coke). Once charged, the pallet car passes below
an initializing furnace, causing the combustible ignition on the surface of the mixture, and
being at the same time the mixture subjected to downdraught suction through the load.
The combustion of the coke breeze (or alternative combustible in the corresponding case)
does not take place in the whole thickness of the bed instantaneously, on the contrary,
combustion happens as a horizontal layer that moves vertically through the bed. In this
way, permeability is important, and for that reason granulation is a fundamental step. This
movement of the combustion zone defines several zones in the sinter bed (from the lower
to the upper zone): cold and wet zone, is the zone of the sinter mix to be sintered at a
temperature lower than 100ºC; drying zone, zone at temperatures between 100 and
500ºC where the vaporization of moisture and dehydration of hydroxides take place;
reaction zone, where the maximum temperatures are reached during the combustion of
coke (exothermic), decomposition of carbonates (endothermic), solid phase reactions,
reduction and re-oxidation of iron oxides and reactions of formation of the sintered mass
take place; and finally, cooling zone, is the zone where the cooling and re-crystallization
of the sintered product take place. The high thermal efficiency is consequence of the heat
accumulation in a partial layer called sintering zone or flame front (which progresses at
10–30 mm/min) toward the sintering grate, and in this way a 500–600 mm bed height
would be sintered in around 25 min. Finally, the flame front reaches the bottom of the
layer at the end of the strand, where the sintered product is discharged and subjected to
cooling, crushing, and screening, being three kinds of product finally obtained: 0–5 mm
(or 0–10 mm, called return fines and sent back to the beginning of the sintering process;
5–20 mm (or 10–20 mm or 10–15 mm, used as hearth layer in the sinter strand with the

43
functions previously mentioned; and, > 20 mm (or >15 mm, sent to the blast furnace
directly. Maximum sizes around 50 mm.
As we mentioned, flame front is the region limited by the moment where the coke begins
to combust and the moment where the coke burned [19]. There are other definitions that
can be
·coke breeze (small particles of coke from the screening plant);
·fine fluxes such as fine limestone, dolomite, quartzite, and serpentine;
·mill scale (small flakes of iron oxide from the rolling mills); and
·flue dust and precipitator dust (fine ore bearing particles) collected from the blast furnace
and BOS furnace exhaust gases.
This moistened mixture is coarsened by a granulation process and is then spread as a
layer up to 550 mm thick on a moving grate which travels like an endless belt. The grate
carries the mixture through a furnace, in which gas burners ignite the coke. The coke
burns in horizontal layers which proceed vertically downward as the air for combustion is
continuously drawn down through the mixture as it travels along the moving grate.

Sinter
During this process the layers reach temperatures of approximately 1300°C, fusing the
pre-blended fine ore mix together forming a solid clinker mass.
This fused mix is broken down into lumps, cooled and screened, forming a sinter product
with a mean size of 23-26 mm which is sent to the blast furnace on conveyors.
Granulated mix Roll feeder Ignited mixture

44
In modern practice, the combined iron plus coke burden is self-fluxing and virtually no
limestone is required at the blast furnace. When the flux is added at the sinter plant, the
limestone is pre-calcined, the sinter strength and chemical reactivity are improved and
the sinter can be prepared at a lower temperature. Consequently the fuel rates
(consumptions) and productivities of both processes improve.
Slag Basicity
It is very useful when relating the properties of a multi-component system to its
composition to develop an index based upon the composition. The problem in developing
an index is how to reflect the significance of each component of the system in the index.
The different nature of the acid and basic oxides has been used in the development of
slag composition indices, generally termed basicities. Examples of basicity indices that
have been developed are given below in equations 1 to 4.
Excess Bases = r [(CaO)+ (MgO)] - r [(SiO2) + (Al2O3)] (1)
Basicity = r [(CaO)+ (MgO)] / r [(SiO2) + (AlO3)] (2)
Bell's Ratioi, = r [(CaO) + 0.7*(MgO)] / r [0.94*(SiO2) + 0.18*(AlO3)] (3)

(4)
Basicity indices can be grouped into general categories:
a) Differences between the amount of bases and acids, equation 1;
b) Bases to acids ratios based upon the weight percentages, equation 2;
c) Bases to acids ratios based upon the molar concentrations, equation 3; and
d) Sum of the basicity of each component and its molar concentration, equation 4.
As would be expected based on the previous description of slag structure, those indices
which reflect the molecular nature of the slag composition, equations 3 and 4, tend to be
better predictors of slag properties. However, as the index defined by Equation 2 is;
C + O2 = 2 CO
would occur, in the forward or backward direction. In a closed reactor vessel and with no
other reactions occurring, the composition of the gas would go down (or up) toward the
dashed line. However, if iron and its oxides are present, there are a number of other
reactions that can accompany:
C + O2 = 2 CO
A gas of composition and temperature corresponding to the point Y in Figure 4.4 (B) is
considered to have established a contact with carbon in a reactor containing Fe 3O4 inside.
It is clear that the stable oxide at this point Y is FeO and the reaction
Fe3O4 + CO = 3 FeO + CO2
occurs using CO and propelling the gas composition down from point Y. Simultaneously,
reaction,
C + O2 = 2 CO
takes place, producing CO and propelling to move the gas composition upwards from the
point Y. In actuality, some change of the composition will occur and that, of course,
depends on the rates of the different reactions, and reactions,
Fe3O4 + CO = 3 FeO + CO2
And C + O2 = 2 CO

45
occur until consumption of either all the Fe3O4 or all the carbon. Considerations such as
this point to the conclusion that only at the two points identified by intersection of solid
and dashed lines is carbon in equilibrium with more than one solid phase. The situations
are: below the lower temperature intersection, carbon is in equilibrium with Fe 3O4, above
the higher temperature one, it is in equilibrium with Fe (this statement for the time being
ignores the solubility of carbon in iron), and between the two intersections it is in
equilibrium with FeO. The lower intersection therefore provides the minimum temperature
for reduction of Fe3O4 to FeO by C (at 1 atm.), and the upper one the minimum
temperature for reduction of FeO to Fe.
The roasting process mostly applied to sulfidic sources is carried out in appliances of
different types with different design features. Without describing their features and
constructional details, it may simply be mentioned here that some of the widely acclaimed
roasting units are traveling grate furnaces, multiple hearth furnace, rotary kilns, and
fluidized-bed roasters.
FUNDAMENTALS OF SMELTING REDUCTION
As the name implies, smelting reduction involves both reduction and smelting, i.e. melting
accompanied by chemical reaction(s). The unit operations that take place in any smelting
reduction process are summarized below. In an ideal SR reactor, in the strictest sense,
all the reduction reactions should take place together in the liquid state in a single-step.
In actual practice, for effective process control, most SR processes utilise two reactors
and at least two, if not three, process steps that include: the removal of oxygen from the
oxide in the solid-state to varying extents in stage one, followed by the removal of the
remaining oxygen via liquid phase reduction reactions in stage two. Sometimes, the latter
is completed in two steps rather than one, i.e. SR then becomes a three-stage operation.
The initial reduction of iron oxide begins in the temperature range of 850°C to 1050°C.
The basic reactions involved are as follows:
3Fe2O3 + CO = 2Fe3O4 + CO2 (1)
Fe3O4 + CO = 3FeO + CO2 (2)
FeO + CO = Fe + CO2 (3)
The carbon monoxide required for reduction, is generated by the well-known Boudard
reaction:
C + CO2 = 2CO (4)
Up to this stage, SR is similar to solid-state DR. Beyond solid-state reduction of
haematite/magnetite to wustite, smelting reduction, essentially involves reduction of
molten FeO by CO.
This gives rise to far higher transport rates owing to convection, and a remarkable
increase in the conversion rate because of enlargement in the specific phase contact
area. The latter is a direct consequence of the dispersed nature of the phases. These two
major advantages of SR accrue because of the formation of liquid phases, which does
not happen in DR.
From studies on the oxidation and reduction behaviour of pure molten iron oxide by
CO/CO2 mixtures at 1500°C, it has been concluded that the rate controlling step for both
oxidation and reduction is the inter-diffusion of iron and oxygen atoms within the melt. It
has also been found that mass transport plays an important role in the reduction kinetics.

46
The overall reaction rate is proportional to the square root of the gas flow rate. Therefore,
all out efforts are made to increase the amount of gas that is available for reduction.
To generate sufficient amount of reducing gas, all SR processes consume fairly large
quantities of reductant (normally coal). Having generated the large volume of gas that is
required, its effective utilisation becomes extremely important. However, this gives rise to
one of the inherent deficiencies of SR, i.e. with most SR reactor configurations given the
productivity requirements, the entire gas cannot be fully utilised in the process, and rich
gas at a high temperature leaves the SR reactor. It is for this reason that the use of the
export gas in any SR process has a marked influence on the cost of the hot metal made.
In fact, in many cases, unless the net export gas from the SR reactor is gainfully utilised,
ironmaking itself becomes totally uneconomical. Without sufficient credit for the off-gas,
the cost of hot metal made by smelting reduction can be as much as 40–50% higher than
that of blast furnace hot metal, despite starting with less expensive and inferior grade raw
materials. The reverse is the case if adequate credit can be obtained from the utilisation
of the off-gases. The most convenient way to utilise the exit gas is to cogenerate electrical
power. Alternatively, the exit gas can be fed to a shaft furnace direct reduction unit,
located adjacent to the smelting reduction reactor.
Iron making - the reduction of Iron ores
Blast Furnace Method

47
Iron is present in most natural ferrous ores as an oxide, together with some impurities.
Production of iron in the blast furnace is a thermochemical process, during which the
metal is reduced from its oxides by a series of chemical reactions and carburized to
reduce its melting temperature.
The majority of impurities present in the ore and fuel are removed as a separate liquid
product called slag.
The modem coke-burning blast furnace is a massive structure, towering up to 100 metres
high.
The furnace shell consists of a truncated cone-shaped steel casing 30 to 40 metres high,
lined with up to a metre of refractory brickwork. The furnace works continuously and
usually operates for up to 15 years before new cooling staves and refractory lining are
required.
Hearth dimensions of blast furnaces vary widely. The largest blast furnaces in the world,
with diameters up to 16 metres, produce over 10,000 tonnes of hot metal per day.
Process
Raw materials are continuously fed into the furnace top, producing the iron and slag which
are removed at the base periodically. A hot air blast, together with auxiliary fuels, is
injected into the furnace through the tuyeres. It takes about eight hours for a piece of
solid-feed material to pass through the furnace. Names of the various main parts of a
blast furnace are shown in Figure 4.
Ø Charging
The raw materials charged into a blast furnace are:
·iron ore (Fe2O3 + gangue) as lump, sinter and/or pellets, according to availability;
· coke (C + ash) to provide the reducing agent (CO) and the heat necessary to melt the
iron;
·minor amounts of limestone, dolomite and quartzite fluxes to control slag chemistry; and
·air (O2 + N2) to burn the coke (the air is preheated to about 1150°C).
The fluxes are added, mainly as part of the sinter or pellets, to control slag chemistry, i.e.,
to make slag containing typically, 34% SiO2, 41 % CaO, 15% Al2O3 and 7% MgO. The
gangue and ash are mainly acidic SiO2 and Al2O3 so the fluxes are primarily basic CaO
and MgO.
The increased availability of natural gas has resulted in it being injected with the air blast
as a supplementary fuel. In some circumstances coke ovens gas is a cost effective
alternative, while in countries with high energy costs, injection of pulverized ‫ المسحوق‬coal
is common. Productivity is increased by enriching the pre-heated blast air with oxygen.
Humidification of the blast air by adding steam is used to control furnace temperature. A
scale car or a weigh hopper normally weighs all the solid raw materials charged to the
furnace top. The flow rate of injected fuels is measured along with the blast air.
The proportions of the charges depend upon the nature of the raw materials being used.
The order in which they are charged is important, because their distribution in the furnace
affects efficiency

48
Progress of the reduction reactions and temperature of the burden
49
 The basic oxygen furnace and blast furnace as counterparts
(Rectangular brackets indicate that the element is dissolved in hot metal)

50
Example 1:
An iron blast furnace is to smelt an ore mixture having the following composition:
60% Fe, 10% SiO2, and 4% CaO. The available flux contains 92% CaCO3 and 8% SiO2.
The coke contains 90% C, 7% SiO2, and 3% CaO. Determine the weight of ore, flux, and
coke to be charged to yield 1000 kg of pig iron containing 95% Fe, 4% C, and 1% Si, and
a slag having the ratio SiO2: CaO = 1:2, assuming that the furnace requires 950 kg of
coke per tonne of pig iron.

51
Solution:

Let x equal the weight in Kg of flux required: then

Blast Furnace Direct Reduction Smelting Reduction

Ironmaking Process Ironmaking Process Ironmaking Process
Large-scale production Small-scale production Small-scale production
capacity capacity capacity
High maturity Low maturity Low maturity
Low requirements of raw High requirements of raw Higher requirements of raw
Materials materials materials
Use Coke Do not use coke Use a small amount of coke
Do not use natural gas use natural gas Do not use natural gas
Large pollutants generated Small pollutant generated Small pollutant generated

52
 Figure 2. Partially reduced Fe2O3 particle
Dolomite is an anhydrous carbonate mineral composed of calcium magnesium carbonate,
ideally CaMg(CO3)2. The term is also used for a sedimentary carbonate rock composed mostly of
the mineral dolomite. An alternative name sometimes used for the dolomitic rock type
is dolostone.
53
Formation of reaction product layers in the gaseous reduction of hematite pellets.

Sketch of a partially reduced sphere of FeO showing layers and kinetic steps.
SMELTING PRACTICE AND PRODUCTS
The furnace is filled with alternate layers of fuel, flux, and ore, down to the top of the
smelting zone. The exact location of this zone will be dependent upon the volume and
pressure of blast, size of furnace, character of slag made, etc., but will extend from the

54
level of the tuyeres to a few feet above them, or about to the top of the bosh. It will require
perhaps 15 hours for the material to descend from the top of the furnace to the smelting
zone. During this descent, it is upheld partly by the resistance of the upwardrushing
column of hot gases, partly by its friction on the walls of the furnace, and partly by the
loose column of coke which extends through the smelting zone and to the bottom of the
furnace, and which alone resists melting in the intense heat of this zone. The blast,
entering the furnace through the tuyeres, consists of 23 per cent, by weight of oxygen
and 77 per cent, by weight of nitrogen, together with varying amounts of water vapor from
moisture in the air (see page 38). The nitrogen is practically inert chemically and performs
no -function other than that of absorbing heat in the 1 There is a great fall in the pressure
of the blast between the tuyeres and the throat, which represents the work done by the
air in helping to support the stock smelting zone and giving it out at higher levels. The
oxygen attacks all the coke in the smelting zone and as much of it below the level of the
tuyeres as is not covered by accumulations of iron
in addition, slag in the hearth, producing a large volume of carbon monoxide gas (CO)
and a temperature of about 1510 C. (2750 F.).
It is of minor importance whether the CO gas is formed directly or as a result of the two
following reactions:
C +O2 =CO2
CO2 + C =2CO
The CO and nitrogen pass up between the particles of solid material, to which they give
up the greater part of their heat. The former also performs certain chemical reactions, and
thus in both ways the rising column of gases prepares the charge for its final reduction in
the smelting zone.
Chemical Reactions in the Upper Levels. As soon as the iron ore enters the top of the
furnace, two reactions begin to take place between it and the gases:
(1) 2Fe2O3+8CO=7CO2+4Fe+C;
(2) 2 Fe2O3+ CO =2 FeO+Fe2O3+CO2;
moreover, this continues with increasing rapidity as the material becomes hotter. The
carbon formed by reaction No. 1 deposits in a form similar to that of lampblack on the
outside and in the interstices of the ore. This reaction, however, is opposed by two
reactions with carbon dioxide gas:
(3) Fe+CO2 = FeO + CO; (4) C+CO2 =2CO.
Reaction No. 3 begins at a temperature of about 300 C. (575 F.), which is met with about
3 or 4 ft. below the top level of the stock; and No. 4 begins at about 535 C. (1000 F.), or
20 ft. below the stock line. Reaction No. 4 is so rapid that the deposition of carbon ceases
at a temperature of 590 C. (1100 F.). All the way down the ore is constantly losing a
proportion of its oxygen to the gases. At higher temperatures than 590 C., FeO is stable,
and practically all of the Fe2O3 (or Fe304 if magnetite is being smelted) has been reduced:
(5) Fe3O4+CO =3 FeO+CO2.
The reaction between iron oxide and solid carbon begins at 400 C. (750 F.).
(6) Fe2O3 + 3C =2 Fe+ 3 CO.
At 700 C. (1300 F.) solid carbon begins to reduce even FeO:
(7) FeO + C= Fe + CO.

55
Practically all the iron is reduced to a spongy metallic form by the time the temperature of
800 C. (1475 F) is reached. This is about 45 ft. from the stock line and less than 30 ft.
above the tuyeres. At 800 C. the limestone begins to be decomposed by the heat, and
only CaO comes to the smelting zone:
(8) CaCO3 =CaO + CO2.
The foregoing facts are summarized in Fig. 22, which is adapted from H. H. Campbell,
with certain changes. 1 It is not supposed that these figures are exactly correct for the
different levels, and it is probable that they change from day to day and from furnace to
furnace, but a general idea may be obtained from this sketch. It will be seen that the upper
15 or 20 ft. of the stock is a region of Fe2O3 and Fe3O4, gradually being converted to FeO
by CO gas, and forming quantities of CO2 gas. If these reactions were the only ones, the
top gases would contain no CO and would have no calorific power, but reaction No. 1
produces both metallic iron and carbon, both of which reduce CO2 and waste much
energy, as far as the blast furnace is concerned:
Reaction No. 3, Fe+CO2 =FeO+CO, absorbs 2340 calories, but wastes 68,040 calories.
Reaction No. 4, C+CO2 =2 CO, absorbs 38,880 calories.
From 20 to 35 ft. below the stock line is the region of FeO, gradually being converted to
metallic iron sponge by carbon. On the lower level of this zone the limestone loses its
CO2 , which joins the other furnace gases. From 35 ft. down to the smelting zone is the
region of metallic iron. This spongy iron is impregnated with deposited carbon which
probably to some extent soaks into it and dissolves, in a manner like in nature but not in
degree to the way ink soaks into blotting-paper. This carburization of the iron reduces its
melting-point and causes it to become liquid at a higher point above the tuyeres than it
otherwise would.
On reaching the smelting zone the iron melts and trickles quickly down over the column
of coke, from which it completes its saturation with carbon. At a corresponding point the
lime unites with the coke ash and impurities in the iron ore, forming a fusible slag which
also trickles down and collects in the hearth. It is during this transit that the different
impurities are reduced by the carbon, and the extent of this reduction determines the
characteristics of the pig iron, for in this operation, as in all smelting, reduced elements
are dissolved by the metal, while those in the oxidized form are dissolved by the slag.
Only one exception occurs, namely, that iron will dissolve its own sulphide (FeS) and, to
a less extent, that of manganese (MnS), but not that of other metals, as, for instance,
CaS.
Chemical Reactions in the Smelting Zone. There is always a large amount of silica
present in the coke ash, and some of this is reduced according to the reaction :
(9) SiO2+2C=Si+2CO.
The extent of this reaction will depend on the length of time the iron takes to drop through
the smelting zone, the relative intensity of the reducing influence, and the avidity with
which the slag takes.
Carbon monoxide, carbon and hydrogen are the basic reductants in a blast furnace; they are
oxidized to carbon dioxide, carbon monoxide and water vapour during the reduction
a) Pig Iron shall have the highest possible temperature for the optimum heat balance of
melting, ensuring increased throughput of steel scrap and thus reducing costs of melting
- e.g. from 1350 to 1400°C.

56
Pig Iron
Pig iron is an alloy of iron with carbon (about 4.5 %), silicon, manganese, sulphur, phosphorus
and other elements. It is produced by reduction of iron oxides, in the liquid state, in blast furnaces.
This term usually also refers to a liquid product produced by smelting reduction (SRI; Translator’s
Note: Smelting Reduction Iron), manufactured without a blast furnace and without coke.
Pig iron is divided into steel-making pig iron, which is intended for further processing to steel by
various refining processes, and foundry pig iron, from which cast iron is produced by re-melting.
Chemical Composition of Pig Iron
Silicon 0.5 – 0.7 wt. % Silicon, on the one hand improves heat balance during its oxidation to
SiO2, on the other hand increased content of Si results in larger amount of emerging (SiO2) and,
to ensure required basicity of slag, also more charged lime and hence higher weight of slag -
which worsens heat balance of melting.
Manganese 0.5 – 0.7 wt. % Manganese is during refining oxidized to MnO which is after
completion of the process transferred as waste together with slag to a slag heap. Mn is not
involved in the process of desulfurization due to high temperatures and its low content in metal.
In the end of melting, it may affect lower content of oxygen in metal (it appears in a bottom blown
OBM converter).
Carbon 4.2 – 4.5 wt. % Due to high content of C in pig iron, carbon significantly contributes to
heat balance, i.e. to heating of a charge during refining to the tapping temperature of steel

57
(oxidation of carbon covers approx. 50% of total heat of exothermic reactions). During its
oxidation, CO bubbles are formed and ensure homogenization of bath and course of reactions
between metal and slag.
Phosphorus 0.12 – 0.17 wt. % (in the Czech Republic) Content of P in pig iron is limited
(literature states max. 0.3 wt. % of P), since only oxidizing environment of a converter can provide
its transition into slag and higher contents of phosphorus would require the double-slag melting
technology.
Phosphorus content in pig iron is given by content of P in a charge of a blast furnace, particularly
in iron ore, from which it is completely eliminated during the blast furnace process into metal.
Sulfur 0.020 – 0.025 wt. % Content of sulfur in pig iron is associated with melting process in a
blast furnace - the lower content of sulfur, the higher manufacturing costs of pig iron. Oxidizing
environment of a converter is not suitable environment for metal desulfurization. Production of
steel with minimal contents of sulfur can be provided by the ladle metallurgy or by desulfurization
of pig iron in a pouring ladle between a blast furnace and a converter. When producing steels with
controlled sulfur content (SBQ: 0.03 to 0.06 wt. %; cutting steels: 0.1 to 0.2 wt. % of S), pig iron
with increased sulfur content is used.

58
2) Slag-forming Materials (Fluxes)
Quicklime is the main component of fluxes. Optimal lumpiness of lime is 3 to 5 cm, sometimes it
is also used as lime powder pressed into “pellets”. Content of CaO in lime dedicated for steelworks
should be min. 95.0 wt. %, MgO content max. 2 wt. %., SiO2 content max. 1 wt. %, content of
higher oxides R2O3 max. 1 wt. %, content of sulfur max. 0.05 wt. % and loss on ignition (CO2
content + humidity) max. 3 - 4 wt. %.
The specific surface area of grains is an important property of lime. Soft burnt lime has final firing
low content in metal. In the end of melting, it may affect lower content of oxygen in metal (it
appears in a bottom blown OBM converter).
Carbon 4.2 – 4.5 wt. % Due to high content of C in pig iron, carbon significantly contributes to
heat balance, i.e. to heating of a charge during refining to the tapping temperature of steel
(oxidation of carbon covers approx. 50% of total heat of exothermic reactions). During its
oxidation, CO bubbles are formed and ensure homogenization of bath and course of reactions
between metal and slag.
Phosphorus 0.12 – 0.17 wt. % (in the Czech Republic) Content of P in pig iron is limited
(literature states max. 0.3 wt. % of P), since only oxidizing environment of a converter can provide
its transition into slag and higher contents of phosphorus would require the double-slag melting
technology.
Phosphorus content in pig iron is given by content of P in a charge of a blast furnace, particularly
in iron ore, from which it is completely eliminated during the blast furnace process into metal.
Sulfur 0.020 – 0.025 wt. % Content of sulfur in pig iron is associated with melting process in a
blast furnace - the lower content of sulfur, the higher manufacturing costs of pig iron. Oxidizing
environment of a converter is not suitable environment for metal desulfurization. Production of
steel with minimal contents of sulfur can be provided by the ladle metallurgy or by desulfurization
of pig iron in a pouring ladle between a blast furnace and a converter. When producing steels with
controlled sulfur content (SBQ: 0.03 to 0.06 wt. %; cutting steels: 0.1 to 0.2 wt. % of S), pig iron
with increased sulfur content is used.

59
60
Reusable Material
Many wastes from industrial processes can serve as a substitute for iron ores or fluxes
due to their chemical composition and properties.
We rank steel scrap, iron scales, metallurgical dusts and sludges, steel-making slag, etc.
among the most frequently used reusable materials. Proportion of reusable material in a
blast furnace charge depends on the content of detrimental substances in this material.
Most of fine-grained materials, especially waste in the form of dusts and sludges, are not
only ineligible for direct processing in a metallurgical production unit but they are also a
big Production of pig iron in a blast furnace.
Accordingly, the reactions take place:
Above 570ºC:
3 Fe2O3 + CO = 2 Fe3O4 +CO2 (∆Hº298 = 2667 kJ) (22)
Fe3O4 + mCO = 3FeO + CO2 + (m–1)CO (∆Hº298 = 2667 kJ) (23)
FeO + nCO = Fe + CO2 + (n-1)CO (∆Hº298 = -13942 kJ) (24)
Below 570ºC:
Fe3O4 + pCO = 3Fe + 4CO2 + (p-4) CO (∆Hº298 = -15156 kJ) (25)
The coefficients m, n and p represent the volumes of CO necessary for the formation of
the corresponding volume of CO2 in the respective equilibrium gaseous mixture (CO
+CO2).
From the known dependences of Gibbs energy change
∆Gº = -RT lnKp (26) ∆Gº = a + bT (27)
It is possible to derive the dependence of the equilibrium composition of gas on a
temperature. For example for the reduction of magnetite, the relation can be derived:
log Kp = log (pCO2/pCO) = - 1834/T +2,17 (28)
Graphical representation of the dependences calculated for individual reactions is shown
in following Figure. Balances between iron, wüstite, magnetite, (CO + CO2) mixture and
carbon

61
Balances between iron, wüstite, magnetite, (CO + CO2) mixture and carbon
The diagram includes also the equilibrium curve of Boudouard reaction which is
particularly important for the FeO - C system. The graph is known as the Baur-Glässner-
Boudouard diagram.
From the thermodynamic point of view, the intersections of Boudouard equilibrium curves
with the equilibrium curves of reduction reactions represent beginnings of direct

Basic technical-economical indicators

The production, consumption and cost indicators count among the basic technical-
economical indicators of pig iron production. However, since the price of pig iron produced
is governed by its quality, evenness of the chemical composition and temperature of the
iron counts among the technical-economical indicators.
Specific consumption of coke is coke consumption recalculated per unit of produced
pig iron.
Specific fuel consumption is coke and substitute fuels consumption recalculated per
unit of produced pig iron.
Measuring occurrence of slag is slag resulting amount recalculated per unit of produced
pig iron
Chemical composition of steel slags is given by number of factors, e.g. whether it is
refining by blowing oxygen, deoxidation or secondary refining of steel; whether it is an
basic or acidic process or what aggregate or technological stage is melting process in.
In terms of tasks, which steel slag serves, especially in terms of reactions between metal
and slag, respectively metal and lining, we define two terms – the basicity and the
oxidizing ability of the slag.
The basicity according to molecular theory of slags can be put both as a ratio of weight
contents of basic and acidic oxides, e.g.
Sponge iron
Iron produced as a solid by the reduction of iron oxide is popularly known as sponge iron.
The ancient iron makers were in effect making sponge iron, since molten metal
temperatures could not be attained. Sponge iron made was used to manufacture wrought

62
iron products directly; even today, sponge iron is a feed for electric furnaces. Therefore,
in technical literature, sponge iron is also referred to as Direct Reduced Iron (DRI). DRI
is often compacted to reduce its porosity—this product is called Hot Briquetted Iron (HBI).
_ Once electric arc furnace steelmaking started growing, metallic feed in the form of steel
scrap became scarce. DRI was used to supplement scrap as auxiliary feed material in
EAFs.
_ Blast furnace-based steel plants require relatively large capital investment and depend
on metallurgical coking coal, which is not available everywhere. On the other hand, the
DRI manufacturing units are small in size, the total capital investment is limited, and the
reductant can be non-coking coal or gaseous reductants like natural gas. Consequently,
the alternative processes are especially attractive for the developing countries.
Definition of Direct Reduced Iron
DRI or sponge iron refers to porous iron produced by the DR process. The DR process
is a solid-state reaction process (i.e., solid–solid or solid–gas reaction) in which
removable oxygen is removed from the iron oxide, using coal or reformed natural gas as
reductants, below the melting and fusion point of the lump ore or agglomerates of fine
ore. The external shape of the ore remains unchanged.
Due to removal of oxygen (about 27–30% reduction in weight occurs), a honeycombed
microstructure develops suggesting the name Sponge Iron (i.e., solid porous iron;
lumps/pellets with many voids filled with air).
DRI is obtained when iron oxide (generally lump iron ore or pellets) is reduced to metallic
form in solid state.
Since there is no melting, the external shape is retained.
Color changes from red to black. The true density ranges from about 3.5 · 103 to 4.4 · 103
kg/m3. The true density of pure iron is 7.8 · 103 kg/m3. Thus, there is about 45–56%
reduction in true volume and this is manifested in the formation of pores throughout the
interior of sponge iron pieces.
Direct Reduction Processes
Based on the types of reductant used, the DR processes can be broadly classified into
two groups:
1. Using solid reductant, that is, coal-based DR process
2. Using gaseous reductant, that is, gas-based DR process
Coal-based processes
In coal-based DR processes, non-coking coal is used as reducing agent. In solid
reduction processes, iron oxides together with solid reductant (non-coking coal) are
charged into the reactor. The generation of reducing gas (mainly CO) takes place in the
reduction reactor, and the product has to be separated from excess reductant, ash, and/or
sulfur absorbing materials (lime, dolomite) by magnetic separation after discharge at low
temperature, which makes product handling more complicated. Because of the presence
of these substances in DRI, hot briquetting and hot feeding are not possible for coal-
based process. Magnetic separator also does not work at high temperatures to separate
the DRI.
Coal-based DR processes like SL/RN (1970), ACCAR (1973), KRUPP (1973), CODIR,
and TDR (1975), using rotary kiln as a reactor and coal as a reductant, have been
developed worldwide. India, due to its large reserve of non-coking coal, has shown keen
interest in pursuing these technologies using such coal as a cheap energy source for

63
highest DRI production[4] in the world. These processes are highly sensitive to the types
of raw materials used.
The following are coal-based processes:
1. Rotary kiln–based processes
SL/RN, CODIR, ACCAR, DRC, TDR, SIIL, OSIL, Jindal
2. Shaft furnace–based processes Kinglor, Metor, NML, Vertical Retort
3. Rotary hearth furnace (RHF)-based processes INMETCO, FASTMET, Comet
The main advantages of coal-based processes are as follows:
(i) They do not require high-grade coal that is scarcely available.
(ii) They use noncoking coal.
(iii) They can be installed at lower capacity.
(iv) They can be easily installed at places where small reserves of coal and iron ore are
available.
(v) Modules of small-scale operation are available.
Disadvantages of coal-based processes are as follows:
(i) Lower economy of scale.
(ii) High energy consumption (16.0–21.0 GJ/t).

Advantage of DRI
• It allows steel making to dilute metallic residuals in scrap
• Since it is manufactured it has a uniform composition
• It has a uniform size
• DRI has low sulphur and phosphorus content as compared to scrap
• It allows improvement in BF productivity

64
Midrex Process flow sheet

Oxygen injection flow

65
Direct Reduction
The term 'Direct Reduction' applies broadly to processes which remove oxygen from
iron ores to produce a high metallic solid iron product without going through a molten
stage. Three primary products are made by direct reduction:
· DRI (direct reduced iron) or sponge iron as it is also called;
· HBI (hot briquetted iron) which is DRI in the briquetted form for ease of transport and
storage. The HBI has an approximate 93% iron content; and
· Iron Carbide (Fe3C).
The term Direct Reduction is somewhat misleading, suggesting a process that converts
iron ore to steel directly, which is not the case. DRI, HBI and iron carbide are solid forms
of iron which require further processing through melting and refining to produce the final
steel product, this further processing generally being carried out in an electric arc furnace
(EAF).
The characteristics of DRI material vary from plant to plant. Important variables include:
· the iron content;
· the oxide content;
· the carbon content; and
· physical properties.
The iron is also used for feed in blast furnaces and BOF's when economics allow.
Reformed natural gas (a mixture of H2 and CO) is generally used as the reducing agent
for Direct
Reduction plants although some processes use coal.
In recent years, increasing world EAF steelmaking capacity, coupled with a growing
shortage of high quality scrap, has led to strong growth in the number of DRI/HBI plants
around the world.
Global DRI/HBI capacity has grown from approximately 20Mt/a in 1990 to around 34Mt/a
in 1996. Further growth in DRI/HBI production is foreseen as growth in EAF steelmaking
continues.
Ø Gas Based Direct Reduction
Total gas based world DRI and HBI production for 1996 was approximately 30Mt/a which
was produced by four commercial processes: MIDREX, HYL, FIOR, and the iron carbide
process.
When the direct reduction process was commercialised in the 1960's and 70's, the first
operations to prove viable were those of HYL and MIDREX. These processes were based
on the gaseous reduction of ore in lump or pellet form, and these are still by far the most
widely used technologies. The MIDREX process produces around 21Mt/a of HBI and DRI
while 8Mt/a is currently produced by the HYL process. Both processes use natural
reformed gas in a shaft furnace.
More recently, development effort has been focussed on processes which can use ore in
a fines form using a fluidised bed reactor. This type of process potentially has an
economic advantage because it avoids the need for a separate process, such as sintering
or pelletising, to agglomerate raw materials.
Either lump ore, or pellets prepared for direct reduction ironmaking, are charged as raw
material from the top of a shaft furnace. The ore is reduced inside the furnace and the
reduced iron is discharged from the bottom of the furnace. Reductant gas blown in from
about the middle of the shaft furnace reduces the raw material above the nozzle and

66
escapes from the top of the furnace. The cooling gas, which circulates in the lower portion
of the furnace, cools the DRI. Both the charging and discharging ports are dynamically
sealed by a sealing gas, allowing the continuous charging of raw material and discharging
of DRI.
The reaction occurring in the shaft furnace is the well-known reduction reaction of iron,
described as follows:
Fe2O3 + 3CO → 2Fe + 3CO2 Fe2O3 + 3H2 → 2Fe + 3H2O
The exhaust gas (top gas) emitted from the top of the shaft furnace is cleaned and cooled
by a wet scrubber (top gas scrubber) and recirculated for reuse. The top gas containing
CO2 and H2O is pressurized by a compressor, mixed with natural gas, preheated and fed
into a reformer furnace. The reformer furnace is provided with several hundreds of
reformer tubes filled with nickel catalyst. Passing through these tubes, the mixture of top
gas and natural gas is reformed to produce reductant gas consisting of carbon monoxide
and hydrogen. The reaction that occurs in the reformer tubes is as follows:
CH4 + CO2 → 2CO + 2H2 CH4 + H2O → CO + 3H2
2CH4 + O2 → 2CO + 4H2 CO + H2O → CO2 + H2
CH4 → C(S) + 2H2

Definition of Direct Reduced Iron

DRI or sponge iron refers to porous iron produced by the DR process. The DR process
is a solid-state reaction process (i.e., solid–solid or solid–gas reaction) in which
removable oxygen is removed from the iron oxide, using coal or reformed natural gas as

67
reductants, below the melting and fusion point of the lump ore or agglomerates of fine
ore. The external shape of the ore remains unchanged.
Due to removal of oxygen (about 27–30% reduction in weight occurs), a honeycombed
microstructure develops suggesting the name Sponge Iron.[1] (i.e., solid porous iron;
lumps/pellets with many voids filled with air).
DRI is obtained when iron oxide (generally lump iron ore or pellets) is reduced to metallic
form in solid state.
Since there is no melting, the external shape is retained.
Color changes from red to black. The true density ranges from about 3.5·103 to 4.4·103
kg/m3. The true density of pure iron is 7.8 · 103 kg/m3. Thus, there is about 45–56%
reduction in true volume and this is manifested in the formation of pores throughout the
interior of sponge iron pieces.
REACTIONS OF DIRECT REDUCTION PROCESSES
Reduction Reaction for Solid Reductant
The reduction of iron ore occurs at 900–1000_C (1173–1273 K) in the presence of coal.
Although it is a solid–solid reaction, it takes place via a gas–solid reaction:
3Fe2O3s + COg → 2Fe3O4 s + CO2g (2)
Fe3O4s + COg → 3FeOs + CO2g (3)
FeOs + COg → Fes + CO2g (4)
CO2g + Cs → 2COg (5)
Hence, the overall reaction is
Fe2O3s + Cs → Fes + 3COg (6)
Carburization
3Fes + 2COg → Fe3Cs + CO2g (7)
3Fes + Cs → Fe3Cs (8)
Where the reduction is carried out below approximately 1000_C (1273 K), the reducing
agents is CO and the DRI produced is porous and have roughly the same size and shape
as the original iron ore or pellets. The metallic iron also absorbs carbon according to
reactions (7) and (8) to form iron carbide (Fe3C) from iron oxide is removed by a gaseous
reducing agent (CO and H2) that takes part in the reduction of iron oxide.
Methane (CH4) is not used directly for the reduction of iron ore because
_ The rate of the reaction is very slow
_ Due to high temperatures, decomposition of methane takes place and carbon soot is
formed
CH4g → Cs + 2H2g (9)
Hence, methane (CH4) has to be reformed into CO and H2 in the presence of a catalyst
(Ni or Al2O3) at 950_C (1223 K). There are four types of reformations:
_ Steam reformation
CH4g + H2Og → COg + 3H2g (10)
_ Oxygen reformation
CH4g + 1/2O2g → COg + 2H2g (11)
_ Carbon dioxide reformation

68
CH4g + CO2g → 2COg + 2H2g (12)
_ Combination of steam and oxygen reformation
2CH4g + H2Og → 1/2 O2g + 2COg + 5H2g (13)
Reduction reaction for gaseous reductant
Apart from reactions (2) to (4), a considerable part of reduction occurs due to H2 gas:
3Fe2O3s + H2g → 2Fe3O4s + H2Og (14)
Fe3O4s + H2g → 3FeOs + H2Og (15)
FeOs + H2g → Fes + H2Og (16)
In gas-based DR process, the reducing agent is a mixture of CO and H2. The
interconversion reaction between
CO and H2O takes place according to the following reaction:
COg + H2Og → CO2g + H2g (17)
This reaction is popularly known as water–gas displacement reaction and occurs at a
temperature below 1000_C, due to the unstability of CO gas. The water–gas
displacement reaction becomes less important above 1000_C because any water formed
from the reduction of iron ore is rapidly reduced by carbon:
H2Og + Cs → COg + H2g (18)
As per the thermodynamic requirements, when a system is in equilibrium, all parts of the
system must be in equilibrium.
Therefore, whatever (pCO2/pCO) ratio is in equilibrium with a solid phase must also be in
equilibrium with the gaseous phase [water vapor and hydrogen gas in reaction (17)].
Carburization
3Fes + COg + H2g → Fe3Cs + H2Og (19)
3Fes + CH4g → Fe3Cs + 2H2g (20)
Most of the previously mentioned reactions are endothermic and hence heat must be
provided for these reactions to occur. So heat transfer plays a very dominant role in the
DRI production processes.
The important point to be noted is that even after reduction to the FeO stage, over 22%
oxygen (starting oxygen 30%) still remains, which is removed only in the final stage of
reduction of wustite to metallic iron.
The most common reducing agents used in iron oxide reduction process are carbon
monoxide, hydrogen, and mixtures of these two gases. The thermodynamics of iron oxide
reduction deals primarily with the equilibrium between its oxides and these reducing
agents. Thermodynamic calculation shows the feasibility of the reaction, whether the
reaction moves in forward direction or not.
The feasibility of the reaction is indicated by a decrease in free energy. The term standard
state generally considers one atmospheric pressure and a temperature of 25_C (298 K).

69
 Fig. 1 Free energy vs. temperature diagram for main oxides.
Iron Oxide Form Fe2O3 Fe3O4 FeO Fe
Oxygen content 30:1% 27:7% 22:3% 0%
(21)
Fig. 1 is a representation of the Ellingham diagram of a few key oxides that are of major
interest in iron oxide reduction. The lines of oxides lying on the higher sides represent a
less stable oxide as compared to the lines on the lower sides. It can be seen that above
727_C (1000 K) the line of CO2 formation from CO and O2 lies slightly above the line of
FeO formation from Fe and O2. This means that under standard state the following
reaction cannot proceed in the forward direction:
Fig. 1 Free energy vs. temperature diagram for main oxides.
FeOs + COg ⇄ Fes + CO2g (4)
Reaction (4) is the key reaction in DRI making and the reaction is made to move in the
forward direction by keeping a large excess of CO over CO2; the CO/CO2 ratio is required
to be over 2.52 at 1000_C (1273 K) for the reaction to proceed,[16] that is, by decreasing
the activity of CO2.
Compared with BFs, the reduction potential of DR is considerably lower and the reduction
takes place at a much lower temperature. The net result is that while in BF ironmaking,
70
FeO is completely reduced to iron (there is no FeO even in the slag phase in BF), the DR
process is incapable of reducing FeO completely, and some FeO is always present in
DRI. Gas-based DRI contains less FeO than coal-based DRI because of the presence of
hydrogen gas in reformed natural gas.
Reduction by carbon monoxide
The three reduction reactions by carbon monoxide gas with their heats of reaction at 25_C
(298 K) are as follows:
3Fe2O3s + COg → 2Fe3O4s + CO2g ΔHo298 =-52:43 kJ/mol of Co (2)
Fe3O4s + COg → 3FeOs + CO2g ΔHo298 = 40:46 kJ/mol of C0 (3)
0
FeOs + COg → Fes + CO2g ΔHo298 = -18:54 kJ/mol of C (4)
The heat of reactions at 25_C (298 K) were calculated by the data taken from the standard
reference book.[17] It is worth noting that for reactions (2) and (4), the heat of reactions
are negative, which means that the reactions are exothermic, whereas for reaction (3), it
is positive, that is, the intermediate stage of reduction of magnetite to wustite is
endothermic and requires a considerable amount of heat.
Since wustite (FeO) is metastable below 567_C (840 K), iron oxide reduction takes place
in two stages:
Fe2O3  Fe3O4  Fe (22)
1/4 Fe3O4s + COg → 3/4 Fes + CO2g, ΔH 298 = -3:778 kJ/mol of C0 (23)
o

This reaction is also exothermic. However, most DR processes operate at temperatures

more than 600ºC (873 K) so that reduction reaction (23) is only of minor interest.

Fig. 2 Fe–O–C system.

71
 Steel Making

The ion theory of slags uses Lewis electron theory of acids and basics to express the
basicity. According to this theory, activity of free oxygen ions (aO2-) is used as a measure
of basicity in oxide melts. Sources of these ions are basic oxides with ionic bond in the
lattice (CaO, MgO, MnO, FeO etc.), which is easily dissociated. Acidic oxides (SiO2, P2O5
etc.) characterized by a stable covalent bond in the molecules are, however, in molten
slag able to bond free oxygen ions to create complex anions (e.g. etc.) and thus reduce
the activity of O2- ions.
Theoretical fundamentals of steelmaking

72
Oxidation ability of slags shows their ability to dissolve oxygen in the metal. Since iron
oxide is the main source of oxygen in the steel, the oxidation ability of the slag is described
by the activity of FeO (Molecular theory), or by the product of activities of ferrous and
oxygen ions (Ionic theory).
Reactions occuring during production and refining of steel
Refining oxidation reactions in the steelmaking furnaces take place predominantly due
to the oxygen gas injection. In the area of direct contact of gaseous oxygen with the liquid
metal occur following reactions
2 Fe(l) + O2(g) = 2 (FeO) (1)
[Si] + O2(g) = (SiO2) (2)
2 [Mn] + O2(g) = 2 (MnO) (3)
2 [C] + O2(g)= 2 CO(g) (4)
The bulk of gaseous oxygen is consumed by reaction (101). Emerging FeO partially
passes into the slag and partially is the source of oxygen in metal by reaction
(FeO) = Fe(l) + [O] (5)
Reaction (105) creates conditions for the oxidation of other elements directly in the metal
bath
[Si] + 2 [O] = (SiO2) (6)
[Mn] + [O] = (MnO) (7)
[C] + [O] = CO(g) (8)
With the emergence ‫ ظهور‬of the slag containing FeO are also created conditions for the
oxidation of other elements at slag/metal interface.
2 (FeO) + [Si] = (SiO2) + 2 Fe(l) (9)
(FeO) + [Mn] = (MnO) + Fe(l) (10)
(FeO) + [C] = CO(g) + Fe(l) (11)
5 (FeO) + 2 [P] = (P2O5) + Fe(l) (12)
Emerging oxides create the liquid slag. In acidic processes resulting slag is composed of
oxides FeO, MnO, SiO2 and their compounds (FeSiO3, Fe2SiO4, MnSiO3, Mn2SiO4).
Dephosphorization in acidic processes does not occur, because equilibrium of the
strongly exothermic reaction (12) is at high temperatures moved entirely to the left. That
is because in acidic slag is all MnO bound to SiO2, reaction (7), (10) are completely shifted
to the right and produced „acidic“ steel contains hardly any manganese (0.02 - 0.03 %
Mn). On the contrary, high SiO2 content in the slag (in the end of melting process as high
as 65%) causes, that even produced steel contains silicon before deoxidation.
In basic processes the added lime is dissolving and strongly basic CaO displaces
manganese oxide and iron oxide from silicates.
(Fe2SiO4) + 2 (CaO) = (Ca2SiO4) + 2 (FeO) (13)
(Mn2SiO4) + 2 (CaO) = (Ca2SiO4) + 2 (MnO) (14)
In alkaline slags is therefore all SiO2 bound to Mono-, Di-, and Tricalcium silicate and
therefore even the silicon content in the refined steel is zero. On the contrary in
consideration of the reaction (14) elevated content of free MnO in the slag shifts the
equilibrium of the reaction 10) to the left and therefore the refined „basic“ steel contains
0.15 to 0.2 % manganese.

73
Dephosphorization of steel by reaction (12) ensures the oxidizing and basic slag, and
the activity of emerging P2O5 is reduced by the reaction with calcium oxide
4 (CaO) + (P2O5) = (Ca4 P2O5) (15)
Regarding dephosphorization, the optimal content of CaO in the slag is 40 to 45 % and
15 to 20 % of FeO. Too high content of CaO in the slag, as well as the metal temperature
below 1500°C negatively affect the rate of dephosphorization because the slag is too
viscous.
The significance of high content of CaO in the slag increases especially at the end of
melting, where the high temperature shifts the equilibrium of strongly exothermic reaction
(12) to the left, and only reduced activity of P2O5 can compensate this negative effect. In
certain steel technologies, „slag off“ methods and creation of new slag are used for
reduction of the content and therefore the activity of P2O5.
The most important refining reaction is the oxidation of carbon – decarburization
reaction. This reaction due to emerging bubbles of CO stirs the bath, ensures the course
of reactions between the slag and metal, creates conditions for reduction of hydrogen and
nitrogen content in the steel, for flotation and separation of inclusions and also the thermal
effect involved in the heating of steel is important. Oxidation of carbon is accompanied by
the formation of gas phase – CO bubbles, to whose nucleation is necessary to provide
energy, which is at least equal to the surface energy of these bubbles. Therefore, so-
called “Homogenous” carbon reaction (104) requires significant oxygen supersaturation
of the bath. These kinetic difficulties associated with the nucleation of bubbles are also
the reasons of course delay of the carbon reaction in the process of refining pig iron (after
complete oxidation of silicon), even if the corresponding balanced activities of oxygen
with regard to silicon and carbon in the molten pig iron are almost identical.
Other curiosity of carbon oxidation while forming carbon monoxide, affinity of carbon to
oxygen with increasing temperature is growing, see the Figure above. This
decarburization process curiosity is used in vacuum processes in the manufacture of
stainless steel.
Transmission and distribution of sulphur between the molten metal and the slag
show reactions
Fe(l) + [S] = (FeS) (16)
(FeS) + (CaO) = (CaS) + (FeO) (17)
Fe(l) +[S] + (CaO) = (CaS) + (FeO) (18)
[S] + (CaO) = (CaS) + [O] (19)
The largest share of sulphur is removed from the metal by its absorption in the slag. Only
in the oxygen converter (LD and OBM) is 10 to 15 % of the removed sulphur oxidized to
SO2. Equations (18) and (19) are equal when it comes to expression of desulphurisation
of steel. The relation between them is given by equation (5) describing the distribution of
oxygen between the slag and the metal. From the equations for the balanced constants
of the equations (18) and (19) can be derived conditions ensuring low sulphur content in
the metal.
These are:
o The high activity of (CaO) in the slag (basic slag)
o The low activity of (FeO) in the slag (reducing slag)

74
 Steel production in top-blown converters (LD)
LD converters replaced the production in Siemens-Martin furnaces in the world and their
application meant a rapid increase of steel production.
The first oxygen converter was developed and industrially applied in 1952 in Linz and
Donawitz, Austria. The process is therefore referred to as LD. Currently this is the most
used type of oxygen converter, although already many variations have been developed,
in particular bottom-blown converters and converters with combined blowing.
Charge of a Converter
1) Metal Charge. Metal charge of a converter consists of liquid pig iron and steel scrap.
a) Pig Iron shall have the highest possible temperature for the optimum heat balance of
melting, ensuring increased throughput of steel scrap and thus reducing costs of melting
- e.g. from 1350 to 1400°C.
Chemical Composition of Pig Iron
Silicon 0.5 – 0.7 wt. % Silicon, on the one hand improves heat balance during its
oxidation to SiO2, on the other hand increased content of Si results in larger amount of
emerging (SiO2) and, to ensure required basicity of slag, also more charged lime and
hence higher weight of slag - which worsens heat balance of melting.
Manganese 0.5 – 0.7 wt. % Manganese is during refining oxidized to MnO which is after
completion of the process transferred as waste together with slag to a slag heap. Mn is
not involved in the process of desulfurization due to high temperatures and its
low content in metal. In the end of melting, it may affect lower content of oxygen in metal
(it appears in a bottom blown OBM converter).
Carbon 4.2 – 4.5 wt. % Due to high content of C in pig iron, carbon significantly
contributes to heat balance, i.e. to heating of a charge during refining to the tapping
temperature of steel (oxidation of carbon covers approx. 50% of total heat of exothermic
reactions). During its oxidation, CO bubbles are formed and ensure homogenization of
bath and course of reactions between metal and slag.
Phosphorus 0.12 – 0.17 wt. % (in the Czech Republic) Content of P in pig iron is limited
(literature states max. 0.3 wt. % of P), since only oxidizing environment of a converter can
provide its transition into slag and higher contents of phosphorus would require the
double-slag melting technology.
Phosphorus content in pig iron is given by content of P in a charge of a blast furnace,
particularly in iron ore, from which it is completely eliminated during the blast furnace
process into metal.
Sulfur 0.020 – 0.025 wt. % Content of sulfur in pig iron is associated with melting process
in a blast furnace - the lower content of sulfur, the higher manufacturing costs of pig iron.
Oxidizing environment of a converter is not suitable environment for metal desulfurization.
Production of steel with minimal contents of sulfur can be provided by the ladle metallurgy
or by desulfurization of pig iron in a pouring ladle between a blast furnace and a converter.
When producing steels with controlled sulfur content (SBQ: 0.03 to 0.06 wt. %; cutting
steels: 0.1 to 0.2 wt. % of S), pig iron with increased sulfur content is used.
b) Steel Scrap
For oxygen converters unalloyed steel scrap is used, because alloyants (e.g. Cr, Ti, Mo,
etc.) would deteriorate quality of slags. Lumpiness of waste should not damage lining of
a converter during charging (heavy scrap) nor should increase duration of charging (too
lightweight scrap).

75
2) Slag-forming Materials (Fluxes)
Quicklime is the main component of fluxes. Optimal lumpiness of lime is 3 to 5 cm,
sometimes it is also used as lime powder pressed into “pellets”. Content of CaO in lime
dedicated for steelworks should be min. 95.0 wt. %, MgO content max. 2 wt. %., SiO2
content max. 1 wt. %, content of higher oxides R2O3 max. 1 wt. %, content of sulfur max.
0.05 wt. % and loss on ignition (CO2 content + humidity) max. 3 - 4 wt. %.
The specific surface area of grains is an important property of lime. Soft burnt lime has
final firing temperature of limestone approx. 1150°C. It is characterized by large specific
surface area and higher rate of dissolution in slag, but also higher loss on ignition (higher
content of CO2). Hard burnt lime has final firing temperature approx. 1300°C, has smaller
specific surface area and dissolves more slowly in slag. It is characterized by lower loss
on ignition below 2 wt. %.
low content in metal. In the end of melting, it may affect lower content of oxygen in metal
(it appears in a bottom blown OBM converter).
Reactivity of lime - lime quality test. It represents consumption of 4 molar HCl (in ml) used
for neutralization of a defined sample of lime in aqueous solution at 40°C and that in the
2nd and 10th minute of the process. HCl is titrated with an indicator phenolphthalein.
Consumption of HCl in the 2nd minute characterizes rate of dissolution (assimilation) of
lime and consumption of HCl in the 10th minute characterizes content of CaO in lime.
Dolomitic lime (CaMg(CO3)2)obtained by firing dolomite comprises about 12 wt. % of
MgO and 83 wt. % of CaO, and other components as normal lime. This lime increases
MgO content in slag and reduces wear of magnesite linings. Content of MgO in slag
should not exceed 7 wt. %, higher content of MgO increases density of slag and slows
down processes between slag and steel.
Lime consumption per a melt varies between 33 to 40 kg of lime per 1 ton of pig iron. It is
calculated from weight of pig iron, content of silicon and phosphorus and required basicity
of slag.
Fluxes - their target is to adjust chemical composition of slag and hence its properties
such as fluidity (viscosity), oxidation ability, to reduce wear of lining etc. Among fluxes we
include dolomite and magnesite (MgO source), agglomerate (source of iron oxides), iron
scales (source of FeO), sometimes bauxite (source of Al2O3), formerly also fluorspar
(CaF2 source).
Chemical composition of slag is affected also by carbon materials, added to a charge to
improve heat balance of a converter, such as anthracite, coke, coal. These materials
should not contain sulfur and phosphorus and minimum of ash - components that
negatively affect the converter process.
4.2 Sequence of Charging a Converter
1) As first, steel scrap is charged by means of charging boxes (gutter).
2) Lime is charged in batches so as it is assimilated by emerging slag as fast as possible.
First batch of lime is dropped onto scrap, second after beginning of oxygen blowing. Along
with lime also agglomerate and carbon materials (anthracite, coal) are charged.
3) Molten pig iron is poured directly onto a solid charge, a converter is then rotated into
operational (vertical) position, an oxygen lance is lowered into a converter and oxygen
blowing begins.

76
4) When oxidation of carbon is finished, approximately in 13th minute of blowing a sample
of metal is collected (by means of “sublance” at lowered intensity of blowing) and to finish
dephosphorization, raw dolomite, magnesite or other lime is charged onto a charge.
Oxygen blowing continues another 2 or 3 minutes.
5) On the bottom there is sometimes added so called steelworks agglomerate with a high
content of MgO (≈ 20 wt. %), which protects lining resp. prolongs its lifetime.
6) Preheating of scrap is often carried out to improve heat balance of melting. Anthracite,
coal, coke are dropped onto steel scrap and oxygen is blown before pig iron pouring,
carbon materials are burnt and so preheat the solid part of a charge.
Reactivity of lime - lime quality test. It represents consumption of 4 molar HCl (in ml) used
for neutralization of a defined sample of lime in aqueous solution at 40°C and that in the
2nd and 10th minute of the process. HCl is titrated with an indicator phenolphthalein.
Consumption of HCl in the 2nd minute characterizes rate of dissolution (assimilation) of
lime and consumption of HCl in the 10th minute characterizes content of CaO in lime.
The basis of LD process is refining pig iron with oxygen which is top-blown into the bath
of liquid metal by water-cooled copper nozzle, placed in the axis of the basic-lined
converter. Purity of oxygen must be min. 99.5%.
Scheme of top-blown oxygen converter and the overall layout are shown in the following
Figures.

77
Oxygen converter is lined with basic refractories. It consists essentially of its own body,
tilting mechanism, nozzle and dedusting equipment.
The heat weight for the first LD converters was 30 to 35 tons; currently the largest number
of oxygen converters operate with heat weight from 150 to 250 tons and the biggest
converters operate with heat weight up to 400 tons.
The following Figure shows dimensions and shapes of converters for different heat
weight.
Basic metal charge is formed by molten pig iron (about 72%) and steel scrap (about 28%),
further fluxes are added (slag-forming additives, e.g. lime, diluent, magnesite, etc.),
furthermore it is also possible to add iron ore, sinter, return slag, etc., especially for the
bath cooling and treatment of slag.
This process is mainly used for the production of medium and low carbon steels. The
duration of the heat, including repair times, charging, pouring pig iron, finishing and
tapping takes about 50 minutes, the time of oxygen blowing takes 18 minutes from this
time. The intensity of the blowing is about 2.5 to 3.5 m3.t-1.min-1.
The entire process has the following stages:
o Repair of linings
o Charging of fluxes, additives and charging of steel scrap
o Charging (pouring) of pig iron
o Oxygen blowing (finishing)
o Tapping coupled with the deoxidation and alloying
Repair of the linings is currently performed so that during tapping of steel the slag, to
which granulated MgO is added, is left in the converter. It is followed either by tilting of
the converter on sides or splash of the slag using oxygen blowing. This will spray a slag
(coat) on the walls and it will harden them.
Charging of steel scrap together with lime and diluents is performed by charging boxes
using crane so that the entire operation is carried out during one time interval.
Pouring pig iron is performed immediately after attaching charge from the ladle using a
crane.
It´s followed by oxygen blowing using an oxygen, water-cooled copper nozzle,
examples of which are shown in the following Figure.
Repair of the linings is currently performed so that during tapping of steel the slag, to
which granulated MgO is added, is left in the converter. It is followed either by tilting of
the converter on sides or splash of the slag using oxygen blowing. This will spray a slag
(coat) on the walls and it will harden them.
Charging of steel scrap together with lime and diluents is performed by charging boxes
using crane so that the entire operation is carried out during one time interval.
Pouring pig iron is performed immediately after attaching charge from the ladle using a
crane.
It´s followed by oxygen blowing using an oxygen, water-cooled copper nozzle,
examples of which are shown in the following Figure.
Combined ways of blowing
Converters with combined blowing join the advantages of LD and OBM – higher
productivity and simplicity of LD with technological advantages of bottom-blowing. They
make it possible to run the oxidation process in the vicinity of the equilibrium state and
thus improve the conditions for dephosphorization and desulphurization of the steel. Top-

78
blown converters are therefore complemented by alternative bottom-blowing of Ar, N2,
O2, CO2, CmHn, together with solid slag forming additives using nozzles or porous blocks.
Development focuses on specially modified bottom-blown converters into which, together
with oxygen, fuel – oil, gas or dust coal is additionally brought. Thus blown converters
enable processing of higher amounts of steel scrap. KMS process is known for example,
where oxygen and coal is blown into the bath along with dust lime.
All new oxygen converter processes assume the maximum utilization rate of reaction
vessel followed by the completion of the cast by secondary metallurgy methods in the
vessel outside the convertor.
Possible options are shown in the following Figures.

Oxidation
The oxidation process removes impurities such as silicon, manganese, and carbon as
oxides. These oxides either escape as gas or form a solid slag. The refractory lining of
the converter also plays a role in the conversion—the clay lining is used in the acid
Bessemer, in which there is low phosphorus in the raw material. Dolomite is used when
the phosphorus content is high in the basic Bessemer (limestone or magnesite linings are
also sometimes used instead of dolomite).
In order to give the steel the desired properties, other substances could be added to the
molten steel when conversion was complete, such as spiegeleisen (an ironcarbon-
manganese alloy).
Following are the disadvantages of this process:
(i) An oxygen plant to prepare oxygen is required.
(ii) It cannot treat pig-iron of all grades and varieties.

79
(iii) It is not possible to control temperature precisely.

The change of the the chemical composition of the metal bath in T - furnace
80
 The Bessemer Process Bessemer Converter
Bessemer converter is a pear-shaped furnace, 20 feet high and 10 feet in diameter. It is
made of steel plates and is lined inside with brick to resist heat. There are number of
holes at the base, called tuyeres, for air circulation. The converter can be rotated on a
horizontal central axis.

Process
The Bessemer converter is turned into a horizontal position and molten pig iron is poured
into it. A blast of hot air is sent through the tuyeres.
The converter is rotated so that it is vertical and hot air is blown continuously. In its upward
travel through the converter, the air oxidises the impurities in pig iron.
Manganese and silicon are oxidised to the respective oxides during the first 5 to 10
minutes. Carbon monoxide is liberated at a later stage and it burns with a blue flame at
the mouth of the converter. When all the carbon is oxidised, the blue flame dies out. To
convert pig iron to steel, the required amount of carbon is then added. This is in the form
of an alloy of iron called spiegeleisen. It contains carbon and manganese besides iron.
The resulting product is manganese steel, which is removed by tilting the converter.
Note:
>Adding a little aluminium or silicon-iron alloy to molten steel helps in removing dissolved
carbon monoxide or nitrogen from the molten metals.
>Gas must not be left behind as an impurity. The presence of carbon monoxide or
nitrogen can cause defects like blowholes in castings.
Slag Formation
The impurities like manganese oxide and silicon dioxide formed during the initial stages
of the Bessemer process are removed when they react with each to form a slag.
The Bessemer process was the first inexpensive industrial process for the mass-
production of steel from molten pig iron. The process is named after its inventor, Henry
Bessemer, who took out a patent on the process in 1855. The key principle is removal of
impurities from the iron by oxidation with air being blown through the molten iron. The
oxidation also raises the temperature of the iron mass and keeps it molten.
81
The process is carried on in a large ovoid steel container lined with clay or dolomite called
the Bessemer converter.
The capacity of a converter was from 8 to 30 tons of molten iron with a usual charge being
around 15 tons. At the top of the converter is an opening, usually tilted to the side relative
to the body of the vessel, through which the iron is introduced and the finished product
removed. The bottom is perforated with a number of channels called tuyères through
which air is forced into the converter. The converter is pivoted on trunnions so that it can
be rotated to receive the charge, turned upright during conversion, and then rotated again
for pouring out the molten steel at the end.
Oxidation
The oxidation process removes impurities such as silicon, manganese, and carbon as
oxides. These oxides either escape as gas or form a solid slag. The refractory lining of
the converter also plays a role in the conversion—the clay lining is used in the acid
Bessemer, in which there is low phosphorus in the raw material. Dolomite is used when
the phosphorus content is high in the basic Bessemer (Thomas limestone or magnesite
linings are also sometimes used instead of dolomite).
In order to give the steel the desired properties, other substances could be added to the
molten steel when conversion was complete, such as spiegeleisen (an iron-carbon-
manganese alloy).
1. Bessemer Process:
This process was invented by British engineer who patented more than 100 inventions
over his lifetime. He is most famous for inventing this process. He was knighted in 1879.
Depending upon the nature of lining material of converter, this process may be acidic or
basic. In acidic process, the lining material is acidic in nature such as clay, quartz, etc. It
is adopted when iron ores are free from or when they contain very small amount of sulphur
and phosphorus. In basic process, the lining material is basic in nature such as lime,
magnesia, etc. It is adopted for pig-iron containing impurities of any type. The basic
process is commonly adopted.
The Bessemer converter is wide at bottom and narrow at top as shown in fig. 11-1. It is
mounted on two horizontal trunnions so that it can be tilted or rotated at suitable angle.
The tuyeres are provided at the bottom to allow passage of air from the air duct to the pig
–iron.
The working of converter is as follows:
(i) The converter is tilted and it is charged with molten pig-iron from cupola furnace or
sometimes even directly from the blast furnace.
(ii) The converter is brought in an upright position and a blast of hot air is forced through
the tuyeres.
(iii) The air passes through the molten pig-iron. It oxidizes impurities of pig-iron and a
brilliant reddish-yellow flame is seen at the nose of converter.
(iv) The flame is accompanied by a loud roaring sound and within 10 to 15 minutes or so,
all the impurities of pig-iron are oxidized. The order of oxidation of various impurities is
silicon, carbon, manganese, sulphur and phosphorus.
(v) When the intensity of flame has considerably reduced, the blast is shut off and the
required amount of suitable material such as ferro-manganese, spiege-leisen, etc. is
added to make steel of desired quality.

82
(vi) The blast of air is started for a few minutes. The converter is then tilted in discharge
position and the molten metal is carried into ladles or containers.
(vii) The molten metal is poured into large rectangular moulds for solidification. Such
solidified mass is known as the ingot. These ingots are then further treated to form steel
of commercial pattern

.
2. Cementation Process:
This process was formerly used to manufacture steel. It is costly and it is now therefore
practically not adopted. It consists in converting pig-iron to almost pure wrought-iron and
then preparing steel by adjusting carbon content.
This process is carried out as follows:
(i) The bars of pure wrought-iron are taken and they are placed between the layers of
powdered charcoal. The dome-shaped furnace known as the cementation furnace is
generally used for this purpose.
(ii) The furnace is heated and the bars are subjected to an intense heat for a period of 5
to 15 days as per quality of steel required.
(iii) The wrought-iron combines with carbon and steel of desired composition is formed.
This steel is covered with blisters or thin bubbles and it is therefore known as the blister
steel. Its structure is not homogeneous and it is full of cavities and fissures. The blister

83
steel cannot be used for making edge tools. It can only be used for machine parts and
facing hammers.
Open-Hearth Process:
This is also sometimes referred to as the Siemens- Martin process as Siemens of
Germany first invented this process by about the year 1862 and Martin made some
improvements in the process. The open-hearth process may either be acidic or basic as
in case of Bessemer process. The basic open-hearth process is more commonly adopted.

This process is carried out in open-hearth furnace as shown above. This furnace
resembles the reverberatory furnace which is used in the manufacturing process of
wrought-iron.
The working of furnace is as follows:
(i) The hearth is filled with molten pig-iron from cupola furnace or sometimes even directly
from the blast furnace.
(ii) A mixture of pre-heated air and coal gas is allowed to pass over the hearth. This
mixture catches fire and because of the peculiar shape of the roof, it attacks the molten
metal. This produces intense heat and impurities of metal are oxidized.
(iii) When impurities of metal are removed to the desired extent, suitable material such as
ferro-manganese, spiege-leisen, etc. is added to make steel of required quality.
(iv) The molten metal is then poured into moulds for forming ingots. These are then further
treated to form steel of commercial pattern.
This process is extensively used in the manufacturing process of steel as it possesses
the following advantages:

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(i) The basic slag obtained from the open-hearth process contains phosphorus. This slag
in powder form can therefore be used as good fertilizer.
(ii) The great economy can be achieved by providing regenerative chambers on either
side of the hearth as shown in fig. 11-2. These chambers make use of the waste heat of
hot gases of combustion. The hot gases are allowed to pass through brick gratings of
regenerative chamber before they escape through chimney.
The directions of entering and leaving for air and gas are reversed at regular short
intervals. The heated brick gratings pass on heat preserved by them to the entering air
and gas.
(iii) The operations involved in the process are simple.
(iv) This process makes it possible to utilize a high percentage of scrap and this scrap is
converted into new useful steel by this process.
(v) The time required to remove the impurities is short.
(vi) The steel manufactured by this process is homogeneous in character.
Advantages:
1-The great advantage of the open hearth was its flexibility: the charge could be all molten
pig iron, all cold scrap, or any combination of pig iron and scrap.
2-Basic open hearth furnaces are capable of processing iron of almost any chemical
composition.
3-The process is suited to handle any amount of low cost steel scrap.
4-Open hearth furnaces can operate on any kind of fuel.
5-The quality of open hearth furnace is the highest among commercial steel making
processes ( Bessemer, Thomas and oxygen converter techniques ).
6-Adequate temperature control.
7-Adequate Chemical composition control.
Disadvantages:
1-High initial cost.
2-Large floor space requirements.
3- The open hearth process is a batch type.
4-Low productivity as compared with oxygen converter process.
5-The necessity of providing fluxes and regenerators ( such as alloying elements) raises
the costs of construction and running of open hearth furnaces.
6-Precious control of melt temperature cannot be made.
7-Accurate control of chemical composition cannot be satisfied.
8-Limited control of furnace atmosphere.
Advantages of Open Hearth Process over Bessemer Process
Open-hearth process has the following advantages over Bessemer process.
(1) Scrap Iron, low grade pig and cast iron and the iron ore (haematite) can he directly
converted to steel.
(2) The temperature can be controlled more effectively since external source of heat Is
used.
(3) The composition of steel is uniform and accurate and can be controlled easily as the
product is analysed from time to time.
(4) Iron is not lost as slag since blast of hot air is not passed through the molten mass.
(5) Steel obtained is of high grade and good quality.

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Electric Arc Furnaces

The Electric Arc Furnace (EAF) has been in use for nearly 100 years as a method for
making steel. In the early years of the 20th century, its use was restricted to small scale
(several tonnes) operations, producing special types of steel. In more recent years the
EAF has grown in popularity as technical problems have been solved and the availability
of low cost, reliable electrical power supplies have become widespread.
In the last 20 or so years, the EAF has experienced something of a renaissance as
technical innovations have led to very significant improvements in productivity, steel
quality and operating cost. These developments have proceeded to the point where the
EAF is generally preferred as a low capital, flexible route for producing a large proportion
of flat products and almost exclusively, long products
Process
The modem EAF consists of a refractory lined steel shell or hearth that holds the scrap
charge while it is being melted and retains the liquid steel until it is ready to tap. The upper
walls of the hearth (above the metal level) are typically water cooled copper panels. The
furnace has a water cooled roof that can be swung aside as necessary for scrap charging.
In most cases, scrap is added to the EAF via steel buckets or baskets that are positioned
over the hearth. The buckets have doors in the bottom that open in a clam shell fashion
to release the scrap.
All types of scrap and scrap substitutes can be added this way. Charge carbon and fluxes
(lime and dolomite) are sometimes added via the scrap bucket. For regular sized
materials such as DRI/HBI, these are preferably added via conveyor belt to a "fifth hole"
opening in the roof. This is known as continuous charging. It is normal to charge at least
two buckets and as many as five per heat. The density of the scrap charge determines
the number of buckets required to reach the tap weight.
EAFs can be either AC (3 electrodes, each with its own phase) or DC (single or twin
electrode).

86
In an AC furnace, the roof has at least five openings, one for each of the three electrodes,
one for fume evacuation and the above mentioned additions hole. In AC, the current path
is from the electrode tip to the bath and back to the next electrode (in the phase rotation).
In DC, the current passes from the electrode through the bath to a return electrode in the
furnace hearth.
The electrodes are made of graphite that has been manufactured to have special
properties of conductivity and strength at high temperature.
The electrodes are consumed in the process and need to be continually replaced. This is
done by "slipping" the electrode down lower in the holder arm and adding a new section
to the top.
Electrode sections are screwed together. The melting energy is supplied from the
resistive heat generated when an arc is struck in air.
Electrical power is supplied from a grid to a substation, then to a step-down transformer.
The furnace also has its own transformer that serves to alter the furnace electrode's
voltage value.
These voltage "taps" are usually automatically selected but can be manually selected by
the furnace operators. The electrode voltage determines the maximum arc length and
therefore the melting energy that is supplied. The EAF electrode position is regulated so
that the desired arc current and power is maintained at the chosen setting. This is usually
achieved by constantly measuring the impedance (voltage divided by current) and feeding
it back to a control system that raises or lowers the electrode arms, as conditions inside
the furnace change during melting.
Oxygen is used to assist in refining the steel and removing impurities such as phosphorus.
A lime rich slag is used to collect such unwanted elements and provide a base material
to be foamed by CO evolution. This foamy slag helps improve energy efficiency during
heating by preventing direct radiation of the unshielded arc to the furnace roof. The
foaming action causes the slag to be continuously flushed from the EAF up until tap time.
When the appropriate steel chemistry and temperature has been achieved, the steel is
tapped through either a spout (i.e. like a teapot) or a submerged taphole, into a ladle and
then on to a ladle furnace for secondary treatment.
The construction of the electric arc furnace
Electric arc furnaces were used as the main steel aggregates for the prodution of alloyed
and high-grade steel for a long time. In the last twenty years, however, the look at their
usage has started to change completely and today they are also used as a device to quick
melt of the steel scrap and production of crude steel. Further processing of crude steel –
part of refining, deoxidation as well as alloying shifts are made in secondary metallurgy.
The goal is to maximize the significant electic power, which has increased in modern UHP
(Ultra High Productivity) compared to conventional EOP furnaces from the usual 100 to
200 kW.t-1 of steel maximum power to 300 to 600 kW.t-1 and in the future possibly even
more.
EOP are mostly built as a three-phase folding AC (alternating current) furnaces adapted
for top charging with automatic movement of electrodes. The heat source is an electric
arc which burns between graphite electrodes and conductive batch. In recent years
several furnaces working with DC (direct current) were built worldwide. The aim was to
reduce the consumption of graphite electrodes and to improve the working environment.

87
The electric arc furnace consists of the actual furnace, motion mechanisms and electrical
equipment. The outer part of the furnace (the door and the shell) are made of the steel
sheet of welded or riveted construction. In the front part of the furnace there is a handling
area, in the back part of the furnace there is a tapping hole. The construction of the arc is
formed by a circular frame equipped with the water cooling. In the arc there are apertures
for the passage of electrodes.
The furnace is lined in several layers with refractory bricks based on magnesite. The last
working layer of the hearth lining is made by tamping down the ground dolomite or
magnesite. The lining of the roof is made of shaped bricks, silica or chromium-magnesite.
Charging of the batch for these furnaces is performed either by charge box or charge
bucket.
Electric Arc Furnaces
Electric arc furnaces may be categorized as direct arc and indirect arc. Both types of
units are suited for the melting of high melting point alloys such as steels. They may be
lined with acid or basic refractories. The main advantage of the Electric Arc Furnaces
over the Basic Oxygen Furnaces (BOF) is their capability to treat charges containing up
to 100% of scrap. About 33% of the crude steel in the world is made in the Electric Arc
Furnaces
Direct arc furnaces are very popular for the melting of alloy steels and range in size from
a few kilograms, for laboratory units, to about 400 tons per batch. Typical units found in
foundries are in the range of 1 to 10 tons. The furnace generally consists of steel shell

88
lined with acid or basic refractories. The roof which can normally swing away to facilitate
charging, generally contains three carbon electrodes operate on a high tension three-
phase power supply. These electrodes protrude vertically through the roof and an electric
current passes directly through them into the metal bath. The entire unit is capable of
being tilted for discharge of the melt through the pouring spout.
Indirect arc furnaces: generally consist of a horizontal barrel shape steel shell lined with
refractories. Melting is effected by the arcing between two horizontally opposed carbon
electrodes. Heating is via radiation from the arc to the charge. The barrel shaped shell is
designed to rotate and reverse through approximately 180° in order to avoid excessive
heating of the refractories above the melt level and to increase the melting efficiency of
the unit.
Indirect arc furnaces are suitable for melting a wide range of alloys but are particularly
popular for the production of copper base alloys. The units operate on a single-phase
power supply and hence the size is usually limited to relatively small units.

Advantages
1- High melt rates. 2- High pouring temperatures.
3- Excellent control of melt chemistry. 4- Accurate control of melt temperature.
5- Furnace atmosphere can be controlled.
6- Flexibility i.e. can be rapidly started and stopped, allowing the steel mill to vary
production according to demand.
Disadvantages
1- High initial cost.
2- High operation and maintenance costs.
3- The process is a batch type.

89
indirect arc furnace

90
 Chapter (3)
Copper Extraction

Copper is an unreactive metal, it reacts only slowly with the atmosphere. This means that
huge lumps of copper metal are found buried in the ground as nuggets. This is
called native copper. The largest nugget of native copper ever found came from
Minnesota, USA and weighed over 400 tonnes. Native copper isn’t mined because there
is so little of it. Therefore it is of little commercial importance.
Mining Metals

91
Metals are often found as compounds in ores. An ore is a rock or mineral that has enough
metal in it to make it worth extracting.
Mining copper
About 200 years ago the UK was an important world source of copper and tin and there
were mines in Cornwall and Devon. These mines have now closed and today the biggest
copper mines are in Chile (Escondida mine) and Indonesia (Grasberg mine). These
produce many millions of tonnes of copper ore per year.
The main ores of copper are sulfides and oxides. From their chemical formulas you can
calculate the percentage of copper in each mineral. However this is not the same as the
percentage of copper in the ore as that also contains unwanted silicates and other
minerals, called gangue, that will have to be separated.

Copper minerals and ore are found throughout the Earth’s crust. They occur in both
sedimentary and igneous rocks. The outer 10 km of the crust contains 33 g of copper for
every tonne of rock. This is not enough to make it commercially viable to extract the rock.
Copper mines are only set up where there is more than 5 kg of copper per tonne of rock
(0.5% by mass). Ideally, the figure should be closer to 2%.
The world’s largest copper ore deposits are found in Chile on the west coast of South
America. This is due to the volcanic activity that is part of the process that created the
Andes mountain chain.

92
93
 Processing Stages
Stage 1: Crushing and grinding
The ore from the mine contains about 2% copper. To get at the copper the first stage is
crushing in huge cylindrical ball mills.

Ball mills crush the ore into a fine powder.

Stage 2: Froth flotation
The powdered ore is mixed with a special paraffin oil which makes the copper mineral
particles water repellent. It is then fed into a bath of water containing a foaming agent
which produces a kind of bubble bath.
When jets of air are forced up through the bath, the water repellent copper mineral
particles are picked up by the bubbles of foam. They float to the surface making a froth.
The unwanted waste rock (gangue) falls to the bottom and is removed.
The froth is skimmed off the surface and the enriched ore (mainly the copper mineral) is
taken away for roasting. The mixture of water, foaming agent and paraffin is recycled.
After this stage the enriched ore now contains about 25% copper by mass and is
called copper concentrate. It is valuable enough to ship to other plants and other countries

94
for processing. For example China, Germany and Japan are major copper producers that
use concentrate from around the world.
Stage 3: Roasting
At this stage of the process, the chemical reactions begin. They convert the copper
minerals into copper metal.
We can illustrate the types of process using the example of chalcopyrite – CuFeS2. From
the formula, it is clear that iron and sulfur have to be removed in order to produce copper.
The roasting process:
Changes some of the CuFeS2 to copper oxide
Removes some of the sulfur as sulfur dioxide
This is done by heating the concentrated ore from froth flotation. It is heated to between
500 °C and 700 °C in air. The product from the roaster is called calcine. It is a solid mixture
of oxides, sulfides and sulfates. One reaction that takes place is:
2CuFeS2(s) + 3O2(g) → 2FeO(s) + 2CuS(s) + 2SO2(g)
As SO2 is hazardous, it has to be removed from the gases released into the environment.
One way of solving the problem is to convert it to sulfuric acid. This is either sold for
industrial use or used to extract oxide ores of copper by leaching.
Stage 4: Smelting with fluxes
The calcine is heated to over 1200 °C with fluxes such as silica and limestone. The calcine
melts and reacts with the fluxes. Some impurities form a slag (such as FeO.SiO 2), which
floats on the surface of the liquid (like oil on water) and is easily removed.
The smelter for sulfide ores produces sulfur dioxide gas. This is scrubbed from the flue
gases to make sulfuric acid for leaching copper from oxide ores. Scrubbing sulfur dioxide
also protects the environment.
For example:
FeO(s) + SiO2(s)→ FeO.SiO2 (slag)
This is very similar to the removal of impurities in the blast furnace. The liquid left is a
mixture of copper sulfides and iron sulfides. It is called a matte.
Smelting is a unit process for pyro metallurgical extraction of metal in which gangue
minerals are separated from the metal in liquid state. The components of the materials
are heated above the melting points so that they are separated in the liquid state. When
metal is separated as molten sulphides, the process is called matte smelting and when
metal is separated as liquid metal it is called reduction smelting. This lecture concerns
with the matte smelting and few other lectures will be devoted on materials and heat
balance in matte smelting. Brief description of matte smelting is given so that readers can
apply to solve materials and heat balance problems. For details consult any book on non‐
ferrous metals extraction.
Matte smelting
Matte is a molten mixture of sulphides. Of the greatest industrial importance is iron‐
copper matte which is an intermediate product in the extraction of copper from sulphide
ores. In production of nickel, matte of copper‐nickel is an intermediate product. Next is
copper‐ nickel matte.
One advantage of matte smelting is its low melting point which makes it possible to smelt
sulphide ores at lower temperatures than required for metals. Thus a matte with equal
amounts of copper and iron sulphide melts below 1000, whereas an alloy of Fe and Cu
would melt at around 1400. This leads to lower thermal energy requirements and gangue

95
minerals can be separated easily as slag. Thus matte smelting comprises of the following
inputs and outpust
Roast Copper Ore + Flux + Air + Fuel + Heat  Matt + Slag + Gas
Matt Grade = [(Amount of Copper in Matt) / (Amount of Cu2S + FeS)] x 100
Stage 5: Conversion of matte to copper blister
the liquid matte is oxidised with air to form blister copper in a converter.
Blister copper from the smelter is poured into the anode casting moulds. The anodes are
cast into slabs about 1 metre square with arms at the top corners for lifting.
The reactions are:
a) Elimination of iron sulfide by oxidation to iron oxide which forms a slag:
2FeS(l) + 3O2 + SiO2(l) → 2FeO.SiO2 + 2SO2 (g)
air flux slag gas
b) Formation of blister copper by reduction of copper sulfide:
Cu2S(l) + O2(g) → 2Cu(l) + SO2
air blister copper gas
An important objective of matte smelting is to produce a slag which contains as little Cu
as possible. This is done by:
(a) Including SiO2 flux in the furnace charge to promote matte-slag immiscibility
(b) Keeping the furnace hot so that the slag is molten and fluid.
Matte smelting is most often done in flash and submerged tuyere furnaces (Figs I .4 and
1.5). It is carried out to a lesser extent in top lance furnaces (Mitsubishi, Isasmelt,
Ausnielt), shaft furnaces, reverberatory furnaces, and electric furnaces.

Fig. 1.4. Flash furnaces are typically 20 m long and 7m wide. They smelt 1000 to 3000 tons
of concentrate/day. In two cases, concentrate is flash smelted directly to molten copper.

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Converting
Copper converting is oxygen enriched-air or air oxidation of the molten matte from
smelting. It removes Fe and S from the matte to produce crude (99% Cu) molten copper.
This copper is then sent to fire- and electrorefining. Converting is mostly carried out in the
cylindrical Peirce-Smith converter, Fig. 1.6.

Peirce-Smith converter for producing molten 'blister' copper from molten Cu-Fe-S matte..
Oxygen-enriched air or air 'blast' is blown into the matte through submerged tuyeres.
Silica flux is added through the converter mouth or by air gun through an end wall. Off
gas is collected by means of a hood above the converter mouth.
Liquid matte (1200°C) is transferred from the smelting furnace in large ladles and poured
into the converter through a large central mouth, Fig. 1.6b. The oxidizing 'blast' is then
started and the converter is rotated - forcing oxygen enriched-air or air into the matte
through a line of tuyeres along the length of the vessel. The heat generated in the
converter by Fe and S oxidation is sufficient to make the process autothermal.
The converting takes place in two sequential stages:

97
Positions of Peirce-Smith converter for charging, blowing and skimming. SO2 off gas
escapes the system unless the hooding is tight. A converter is typically 4 or 4.5 m
diameter. Hoboken converters are similar but with axial off gas removal,
Stage 6: Anode casting
The blister copper produced by this process is 99% pure copper. The name ‘blister’ copper comes
from the fact that this final process produces bubbles of sulfur dioxide on the surface of the copper.
The blister copper is cast into anodes ready for electrolytic refining.
The anode casting turntable moves slowly round. The anodes can be lifted out at the far side.
This huge wheel is used to cast the anodes. Molten copper is poured into a mould and the wheel
is turned for the next mould. Meanwhile, the molten copper cools and solidifies into anodes over
a metre tall. The mould includes short supporting arms used to lift and suspend the anodes.

Lifting the solidified anodes into cooling tanks

Stage 7: Electrolytic refining
The blister copper is already virtually pure (in excess of 99% copper). But for today’s market, this
is not really pure enough! It is purified further using electrolysis. This is known as electrolytic
refining. The blister copper is cast into large slabs which will be used as the anodes in the
electrolysis apparatus. The electrolytic refining of copper produces the high quality, high purity
copper required by industry.
Even the best chemical method cannot remove all the impurities from the copper, but with
electrolytic refining it is possible to produce 99.99% pure copper.

98
 Copper cathodes are hung between anodes.
Copper cathodes are hung between anodes. Can you recognise the shape of the suspension
arms on the anodes from the picture of anode casting? Copper atoms on the anode lose
electrons to become Cu2+ ions in the electrolyte. At the cathode the copper ions take back
two electrons to return to being copper atoms. It may seem that the whole process
achieves nothing: Cu → Cu2+ → Cu.
The purification happens because the other metals in the anode (impurities) will not dissolve in
the electrolyte solution. They fall to the bottom of the tank. The cathodes are 99.99% pure copper.
The blister copper anodes are immersed in an electrolyte containing copper sulfate and sulfuric
acid. Pure copper cathodes are arranged between the blister copper anodes and a current of over
200A passes through the solution. This is driven by a low voltage of about 1.3V and so the process
is safe.
What happens in electrolysis?
Under these conditions, copper atoms dissolve from the impure anode to form copper ions. These
migrate towards the cathodes where they are deposited back as pure copper atoms.
At the anode: Cu(s) → Cu2+(aq) + 2e-
At the cathode: Cu2+(aq) + 2e- → Cu(s)

In copper refining many anodes and cathodes are suspended alternately. All the cathodes are
connected to the negative terminal and all the anodes to the positive terminal.

99
Copper atoms on the anode surface lose two electrons becoming soluble Cu2+ ions.
Cu2+ ions have a positive charge. They find themselves in an electric field between the electrodes.
Being positive, they move to the negative cathode where they pick up two electrons and go back
to being metallic atoms with no charge.
In an electric circuit, electron flow goes from negative to positive so the process transports
electrons from the cathode to the anode.
Gradually, the anode is eroded and the cathode grows. Insoluble impurities in the anode fall to
the bottom as a sludge.
What happens to the impurities?
Gold, silver, platinum and tin are insoluble in this electrolyte and so do not deposit on the cathode.
They form a valuable ‘sludge’ that collects under the anodes.
Soluble impurities of iron and nickel dissolve in the electrolyte, which has to be continually purified
to prevent excessive deposition onto the cathodes, which would reduce the purity of the copper.
Recently, stainless steel cathodes have replaced copper cathodes. Identical chemical reactions
take place. Periodically, the cathodes are removed and pure copper is scraped off.

100
 Cathode copper is remelted and cast into billets ready for turning into copper products
What happens to the impurities?
Any metal in the impure anode which is below copper in the electrochemical series (reactivity
series) does not go into solution as ions. It stays as a metal and falls to the bottom of the cell as
an "anode sludge" together with any unreactive material left over from the ore. The anode sludge
will contain valuable metals such as silver and gold.
Metals above copper in the electrochemical series (like zinc) will form ions at the anode and go
into solution. However, they won't get discharged at the cathode provided their concentration does
not get too high. The concentration of ions like zinc will increase with time, and the concentration
of the copper(II) ions in the solution will fall. For every zinc ion going into solution there will
obviously be one fewer copper ion formed. (See the next note if you aren't sure about this.) The
copper(II) sulfate solution has to be continuously purified to make up for this.
Uses of copper
Amongst other things copper is used for:
1- Electrical wiring. It is a very good conductor of electricity and is easily drawn out into wires.
2- Domestic plumbing. It does not react with water, and is easily bent into shape.
3- Boilers and heat exchangers. It is a good conductor of heat and does not react with water.
4- Making brass. Brass is a copper-zinc alloy. Alloying produces a metal harder than either
copper or zinc individually. Bronze is another copper alloy, but with tin.
5- Coinage. In many countries, as well as the more obvious copper-colored coins, "silver"
coins are also copper alloys - this time with nickel; these are known as cupronickel alloys.
UK pound coins and the gold-colored bits of euro coins are copper-zinc-nickel alloys.

This flow diagram summarises the sulfide ore processing stages. Find the two
furnaces that send sulfur dioxide gas to the acid plant.
101
Exercise in matte smelting

Solution

102
103
 Chapter (4)
Refining of aluminium
Extraction of Aluminium:
Important Ores of Aluminium:
Bauxite : Al2O3×2H2OCryolite: Na3AlF6
Feldspar: K2OAl2O3×6SiO2 or KAlSi3O8
Mica: K2O×3Al2O3×6SiO2×2H2O
Corundum: Al2O3
Alumstone or Alunite: K2SO4×Al2(SO4)3×4Al(OH)3

Bauxite Ore Pure Alumina

Purification of Bauxite

Aluminum is found in varying amounts in nature as alumino-silicates (contains aluminum,

silicon, and oxygen) in various types of clay. As the minerals are weathered they gradually

104
breakdown into various forms of hydrated aluminum oxide, Al 2O3.xH2O, known as
bauxite.
Physical Properties of Bauxite
White, gray, sometimes stained yellow, orange, red, pink, or
Color
brown by iron or included iron minerals
Streak Usually white, but iron stain can discolor
Luster Dull, earthy
Diaphaneity Opaque
Cleavage None
Mohs Hardness 1 to 3
Specific Gravity 2 to 2.5
Diagnostic
Soft, low specific gravity, color. Often exhibits pisolitic habit.
Properties
Chemical Variable but always rich in aluminum oxides and aluminum
Composition hydroxides
Crystal System n/a
The primary ore of aluminum. Synthetic bauxite is used as an
Uses
abrasive and as a fracking proppant.
The chemical formula for aluminium oxide is Al2O3 and it is commonly referred to as
alumina. Alumina as produced in the Bayer process is a white, inert and odourless powder
and is mainly used as raw material for aluminium production
The bauxite is purified by the Bayer Process. First the ore is mixed with a hot concentrated
solution of sodium hydroxide. The NaOH will dissolve the oxides of aluminum and silicon
but no other impurities such as iron oxides, which remains insoluble. The insoluble
materials are removed by filtration. The solution which now contains the oxides of
aluminum and silicon are next treated by bubbling carbon dioxide gas through the
solution. Carbon dioxide forms a weak acid solution of carbonic acid which neutralizes
the sodium hydroxide from the first treatment. This neutralization selectively precipitates
the aluminum oxide, but leaves the silicates in solution. Again filtration is used for the
separation. After this stage the purified aluminum oxide is heated to evaporate the water.
Aluminum in the metal form is very difficult to obtain by using some of the traditional
chemical methods involving carbon or carbon monoxide as reducing agents to reduce the
aluminum ions to aluminum metal. One of the earliest and costly methods in 1850 was to
reduce aluminum chloride with sodium metal to obtain aluminum metal and sodium
chloride. (Sodium metal is not easy to obtain either). As a result some of the earliest
aluminum metal was made into jewelry.
Extraction of Aluminium
The aluminium oxide is very stable. The carbothermic reduction of aluminium oxide has
not been adopted because:
(1) It requires a very high temperature (above 2000°C),
(2) At that temperature, aluminium carbide is formed,
(3) The refractory required, for such high temperature, is readily available and very
expensive.

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Alumina is used for the production of aluminium metal, through the Hall–Héroult
electrochemical smelting process.
It is also used in applications such as industrial and medical ceramics, sandpapers,
pigments, cosmetics and pharmaceuticals.
The Bayer Process is the most economic means of obtaining alumina from bauxite. Other
processes for obtaining alumina from metal ores are also in use in some refineries,
particularly in China and Russia, although these make up a relatively small percentage of
global production.
The process stages are:
1. Milling
The bauxite is washed and crushed, reducing the particle size and increasing the
available surface area for the digestion stage. Lime and "spent liquor" (caustic soda
returned from the precipitation stage) are added at the mills to make a pumpable slurry.
2. Desilication
Bauxites that have high levels of silica (SiO2) go through a process to remove this
impurity. Silica can cause problems with scale formation and quality of the final product.
3. Digestion
A hot caustic soda (NaOH) solution is used to dissolve the aluminium-bearing minerals in
the bauxite (gibbsite, böhmite and diaspore) to form a sodium aluminate supersaturated
solution or “pregnant liquor”.
Gibbsite:
Al(OH)3 + Na+ + OH- → Al(OH)4- + Na+
Böhmite and Diaspore:
AlO(OH) + Na+ + OH- + H2O → Al(OH)- + Na+
Conditions within the digester (caustic concentration, temperature and pressure) are set
according to the properties of the bauxite ore. Ores with a high gibbsite content can be
processed at 140°C, while böhmitic bauxites require temperatures between 200 and
280°C. The pressure is not important for the process as such, but is defined by the steam
saturation pressure of the process. At 240°C the pressure is approximately 3.5 MPa.
The slurry is then cooled in a series of flash tanks to around 106°C at atmospheric
pressure and by flashing off steam. This steam is used to preheat spent liquor. In some
high temperature digestion refineries, higher quality bauxite (trihydrate) is injected into
the flash train to boost production. This "sweetening " process also reduces the energy
usage per tonne of production.
Although higher temperatures are often theoretically advantageous, there are several
potential disadvantages, including the possibility of oxides other than alumina dissolving
into the caustic liquor.
4. Clarification/Settling
The first stage of clarification is to separate the solids (bauxite residue) from the pregnant
liquor (sodium aluminate remains in solution) via sedimentation. Chemical additives
(flocculants) are added to assist the sedimentation process. The bauxite residue sinks to
the bottom of the settling tanks, then is transferred to the washing tanks, where it
undergoes a series of washing stages to recover the caustic soda (which is reused in the
digestion process).

106
Further separation of the pregnant liquor from the bauxite residue is performed utilising a
series of security filters. The purpose of the security filters is to ensure that the final
product is not contaminated with impurities present in the residue.
Depending on the requirements of the residue storage facility, further thickening, filtration
and/or neutralisation stages are employed prior to it being pumped to the bauxite residue
disposal area.
5. Precipitation
In this stage, the alumina is recovered by crystallisation from the pregnant liquor, which
is supersaturated in sodium aluminate.
The crystalisation process is driven by progressive cooling of the pregnant liquor,
resulting in the formation of small crystals of aluminium trihydroxite (Al(OH)3, commonly
known as “hydrate”), which then grow and agglomerate to form larger crystals. The
precipitation reaction is the reverse of the gibbsite dissolution reaction in the digestion
stage:
Al(OH)4- + Na+ → Al(OH)3 + Na+ + OH-
6. Evaporation
The spent liquor is heated through a series of heat exchangers and subsequently cooled
in a series of flash tanks. The condensate formed in the heaters is re-used in the process,
for instance as boiler feed water or for washing bauxite residue. The remaining caustic
soda is washed and recycled back into the digestion process.
7. Classification
The gibbsite crystals formed in precipitation are classified into size ranges. This is
normally done using cyclones or gravity classification tanks (a series of thickeners utilising
the same principles as settlers / washers on the clarification stage). The coarse size
crystals are destined for calcination after being separated from spent liquor utilising
vacuum filtration, where the solids are washed with hot water.
The fine crystals, after being washed to remove organic impurities, are returned to the
precipitation stage as fine seed to be agglomerated.
8. Calcination
The filter cake is fed into calciners where they are roasted at temperatures of up to 1100°C
to drive off free moisture and chemically-connected water, producing alumina solids.
There are different calcination technologies in use, including gas suspension calciners,
fluidised bed calciners and rotary kilns.
The following equation describes the calcination reaction:
2Al(OH)3 → Al2O3 + 3H2O
Alumina, a white powder, is the product of this step and the final product of the Bayer
Process, ready for shipment to aluminium smelters or the chemical industry.

107
108
109
110
The extraction of aluminium by the electrolysis of aluminium salts in an aqueous medium
is not feasible, due to decomposition of the aqueous solution which results in the evolution

111
of hydrogen at a much lower voltage than that needed for the electro-deposition of
aluminium ions.
Hence, the universally adopted process for the extraction of aluminium is the Hall-Heroult
process, in which alumina (Al2O3) dissolved in cryolite (3NaF.AlF3) is electrolyzed. The
alumina, obtained from the Bayer process, is a pure form to be used as the electrolyte in
the electrolytic cell. But this process consumes a large amount of electrical energy.

Block Diagram of Unit Operations

Bayer Process
In the Bayer process, high purity alumina is produced from bauxite (Fig. 8.1). The bauxite
is leached by sodium hydroxide under high pressure (25 atmospheres) and a temperature
at 220°C to form soluble sodium aluminate, from which Al(OH)3 is precipitated. The
alumina is obtained by calcinations of Al(OH)3.

112
Flow sheet of Bayer process
113
Initially, bauxite obtained from the mines is crushed and ground to a very fine size to
separate silica from bauxite, since silica is concentrated in the finer fractions.
By comminuting, alumina can be enriched in the coarser fractions. The coarser fractions
are further ground along with caustic soda in a ball mill to form slurry, which is fed into an
autoclave (at 220°C temperature and 25 atmospheres pressure).
The alumina, in the bauxite, is dissolved in caustic soda:
Al2O3:H2O + 2NaOH  2NaAlO2 + 2H2O (8:1)
Al2O3.3H2O + 2NaOH  2NaAlO2 + 4H2O ) 8:2)
The impurities, present in bauxite, leave as suspended solids in the solution. The
dissolution of the alumina monohydrate [reaction (8.1)] requires a temperature of 230°C
and a time of 3 h, whereas that for the alumina trihydrate [reaction (8.2)] requires a
temperature of 180°C and a time of 1 h. Since the bauxite is a mixture of the monohydrate
and the trihydrate, the temperature used is 180–220°C and the time allowed is 2.5 h.
Under these conditions, 86–88% alumina in the bauxite goes into the solution. At such
high temperatures, a sufficiently high pressure (5–25 atmospheres) must be applied in
order to retain water in the liquid state.
Then the liquid is cooled below 100°C, and the settling of red mud is speeded up by the
addition of starch. Any remaining red mud in the liquid is eliminated by washing with hot
water. Finally the liquid is filtered; the filtrate obtained is a clear solution of sodium
aluminate. The residue left behind after filtration consists mainly of ferric hydroxide, silica,
and non-dissolved alumina.
The heat of the hot liquid is extracted by heat exchanger for conservation and for cooling
the liquid below the critical temperature required for alumina precipitation.
Very fine, freshly prepared aluminium hydroxide is added to create nuclei in order to
accelerate the precipitation of Al(OH)3. The precipitate is separated from the liquid in the
thickener, and the product is calcined in a rotary kiln to produce anhydrous alumina.
Depending on calcinations temperature, resultant Al2O3 is either a loose hygroscopic
c-Al2O3 (800°C) or a denser a-Al2O3 (1200°C), but generally the product is a mixture of
both components due to flow rate of transformation.
2NaAlO2 + 4H2O  2Al)OH)3 + 2NaOH (8:3)

2Al(OH)3  Al2O3 + 3H2O (8:4)

The effect of various factors on the efficiency of the Bayer process is as follows:
(1) The finer the bauxite, the better dissolution of alumina in the leach liquid.
(2) Wet grinding is more efficient than dry grinding, and also cuts down the time required
for dissolution.
(3) Dissolution is accelerated by increasing temperatures; above 100°C water would be
evaporated, hence high pressures up to 25 atmospheres are applied to attain a
temperature up to 220°C.
(4) There is a lower limit to the temperatures. Below that limit, aluminium hydroxide may
precipitate, leading to a loss of alumina.
(5) The sensible heat, collected from hot liquid, is used for producing steam for
dissolution.

114
(6) The entire amount of alumina in solution is not allowed to precipitate because this may
lead to the simultaneous precipitation of dissolved silica. Therefore, the precipitation is
deliberately kept incomplete; the residual solution is recirculated to the dissolution stage.
(7) For the efficient calcinations of alumina, the rotary kiln should be able to attain a
temperature as high as 1400°C. The decomposition of Al(OH)3 produces Al2O3.H2O and
Al2O3.3H2O (water is chemically bound). The minimum temperatures required for the
dehydration of the monohydrate and the trihydrate are 1200°C and 800°C respectively.
Hall-Heroult Process
In 1886, Hall in the USA and Heroult in France independently patented a process for the
commercial production of aluminium. This process is based on the electrolytic
decomposition of alumina dissolved in a liquid bath of cryolite. A source of cheap electric
power is the primary requisite for the Hall-Heroult process, which also requires high purity
alumina, cryolite, and ashless carbon electrodes.
The electrolysis of aluminium from alumina is done in an electrolytic cell (Fig. 8.2). The cell
contains a rectangular refractory lined steel container which is 5 m long, 2 m wide and 1 m deep.
The bottom of the container is conducting and acts as cathode which consists of refractory bricks
of carbon bonded by tar binder.
Iron plate and iron bar are embedded in the carbon mixed for good conduction to form cathode.
Anodes are one of two forms: firstly, the anode may be prebaked carbon electrodes that are
replaced from time to time. Embedded in the anode is a copper bar for contact with the cell bus
bar. Up to 24 anodes form the complement of one cell. The average life is 8–10 days. Secondly,
the continuous electrodes by continuous feeding carbonaceous paste (hot mixture of 70%
petroleum or pitch coke and 30% pitch as binder) into the steel moulds. The carbonaceous
paste is baked in the cell itself during electrolysis by the heat resulting from the resistance
offered to the passage of the electric current, and acts as the anode. The baked carbon
anode and the lining cathode must be sufficiently strong (250–300 kg/cm2 of compressive
strength) and dense (< 25% porosity). Electrical contact is established by rows of iron
pins attached to the casing and to aluminium bus bars which also help to carry the weight
of the electrode. As the electrode is consumed and lowered into the electrolyte the sheet
aluminium casing melts joints the electrolyzed metal in the bottom of the cell.

Fig. 8.2 Hall-Heroult process for aluminium production

115
A tap hole for the collection of molten aluminium metal is located on the bottom of the
furnace. The density of the bath must be less than that of liquid aluminium, or else the
liberated metal will float and upset cell operation. Molten aluminium is collected at the
bottom, as its density (2340 kg/m3) is higher than that of the electrolyte (2030 kg/m3).
Since alumina is not an ionic compound, very few ionic melts are capable of dissolving it
to any appreciable extent. However, cryolite (3NaF.AlF3), a naturally occurring mineral,
can dissolve up to 15% alumina at 1000°C. Cryolite has been successfully synthesized
by passing hydrogen fluoride (HF) through sodium aluminate (Na6Al2O6) solution, the
hydrogen fluoride is produced from naturally occurring CaF2.
CaF2s + H2SO4aq  2HFaq + CaSO4s (8:5)
Na6Al2O6aq + 12HFaq  2Na3AlF6s + 6H2Oaq (8:6)
Small amounts of CaF2 and NaF are added to the cryolite bath to enhance its conductivity
and to improve the metal recovery. Cryolite melts at 990°C, at which temperature it will
take up to 10% of its weight of alumina. At 1000°C, the density of the molten cryolite is
approximately 2100 kg/m3 and that of Al2O3 is 3960 kg/m3, which sink at the bottom of
the cell. When the bath containing about 10% CaF2, 80% cryolite, 5% Al2O3, and a small
amount of NaF is electrolyzed, the aluminium (density 2340 kg/m3) is liberated which is
heavier than the bath and collected at the bottom of the bath. In this way, the aluminium
metal is protected against atmospheric oxidation. The density is one of the factors which
limit the concentration of Al2O3 in the bath; the higher the amount of Al2O3 in the bath,
the higher its density and consequently the sinking of aluminium is rendered more difficult.
Depth of electrolyte is maintained at about 0.25 m.
During operation, the cell is filled with cryolite and the anode is lowered into that. Current
is passed through the cell until the cryolite (melting point 990°C) melts. When the bath
attains the molten state, then only alumina is charged to the cell. The alumina
decomposes to alunimium and oxygen, which is an endothermic reaction, necessary heat
is supplied by the resistance offered by both the electrodes and the electrolyte.
2Al2O3  4Al + 3O2 ∆Hº= 838,683 J/mol of Al2O3 )8:7(
This oxygen reacts with carbon in anode to form CO and CO2 gases. The agitation of the
bath takes place due to evolution of CO and CO2 gases; as well as magnetic stirring due
to the current flowing through the bath from anode to cathode.
The agitation help maintain fresh additions of alumina in suspension long enough for
dissolution in the electrolyte. If the alumina content of the bath (normally 5–10%)
decreases below 2%, then normal contact between the anode and the bath is interrupted
by a gas film which increases the resistance which causes the voltage to rise from 5–6 V
to as much as 40–50 V. Fluorine gas is deposited at the anode surface where it forms a
gas film which is electrically insulating, occasioning a rise in the voltage. The current then
is carried by arcing between the carbon anode and the electrolyte. As a result, normal
operation is hampered. This effect is known as the anode effect. With addition of sufficient
alumina to the bath the voltage returns to its normal value.
When alumina is dissolved in molten cryolite, the ions are present as follows:
In solute: Al3+, O2−.
In solvent: Na+, Al3+, AlF63−, F−.

116
The oxygen ions (O2−) are the only ions foreign to the solvent and may react with Al3+ to
form AlO+ and AlO2− in the melt. Moreover, Al2O3 may go into solution in the form of AlO+
and AlO2−. During electrolysis, several reactions involving all the ions take place
simultaneously in the melt.
Na3AlF6  NaAlF4 + 2NaF (8:8)
NaAlF4  NaF + AlF3 (8:9)
The NaF produced initiates a number of reactions as indicated by the following two
theories.
Theory 1: The NaF is dissociated into Na and F:
6NaF  6Na + 6F (8:10)
6Na + 2AlF3  6NaF + 2Al (8:11)
6F + 2Al2O3  2AlF3 + 3O2 (8:12)
3O2 + 6C  6CO or 3O2 + 3C  3CO2 )8:13(
Theory 2: The NaF reacts with Al2O3 to form Na2O:
6NaF + Al2O3  2AlF3 + 3Na2O (8:14)
3Na2O  6Na + 3/2 O2 )8:15(
6Na + 2AlF3  6NaF + 2Al (8:16)
3/2O2 + 3C  3CO or 3/2O2 + 3/2C  3/2CO2 (8:17)

The foregoing two theories attribute the constant presence of sodium vapour and fluorine
above the cryolite bath to the decomposition of NaF. It is also observed that the depletion
of alumina or the lowering of its activity enhances the formation of fluorine [reaction (8.10)]

117
or NaF [reactions (8.9) and (8.11)]. An increased generation of fluorine causes the anode
effect, which prevents normal operation.
Decomposition Potential
To estimate the voltage required for the process, first decomposition reaction may be
written as:
1/2Al2O3 (solution inNa3AlF6)  All + 3/4O2g; ∆G8:18 )8:18(
This reaction (Eq 8.18) may be split up into a series of reactions, for which the standard
free energies are known, as follows:
All + 3/4O2g  1/2Al2O3s; ∆G8:19 )8:19(
1/2Al2O3s  1/2Al2O3l; ∆G8:20 (8:20)
1/2Al2O3l + Na3AlF6l  1/2Al2O3 (solution inNa3AlF6); ∆G8:21 (8:21)
At 1000°C, for the reaction:
4/3All + O2g  2/3Al2O3s; ∆G8:22 )8:22(
The free energy change of reaction (8.22), ∆G8.22 = − 861.9 kJ
Hence, ∆G8.19 is [(3/4) x (−861.9)] = − 646.43 kJ /mol of Al.
∆G8.20 can be calculated from the heat of fusion for Al2O3. ∆G8.19 is equivalent to
converting ½Al2O3, at 1000°C, to the molten state. ∆G8.20 can be obtained as 15,899.2
J. ∆G8.21 is the free energy change for the dissolution of Al2O3 into cryolite.
Therefore, for 1 mol of Al2O3,
∆G8:21 = - RTlnk = - RT ln[aAl2O3 in Cry/aAl2O3x aNa3AlF6] = - RT ln[aAl2O3 in Cry] (8:23)
Since aAl2O3 and aNa3AlF6 are unity for pure states.
If the bath contains 8 wt% alumina and rest cryolite, then the mole fraction of alumina can
be calculated as follows:
Mole fraction of
Al2O3 = [(wt%Al2O3/molwt of Al2O3)/{(wt%Al2O3/molwt of Al2O3(+(wt%cryolite/molwt of
cryolite)}] (8:24)
= [(8/102)/{( 8/102)+(92/210)}] = [0:078/(0.078 + 0.438)] = 0.15
Assuming that the solution is ideal and the activity of alumina is equal to its mole fraction.
Therefore, ∆G8.21 = − RT ln[aAl2O3 in Cry] = − [(8.314 x 1273) ln (0.15)] = 20,078.4 J
Since R = 8.314 J/mol.K and T = (1000 + 273) K = 1273 K
Now,

) 8:25(
We know,
∆G = Fz E (8:26)
where F is the Faraday’s constant = 96,500 J/v. g.equivalent; z is the valancy of
aluminium and E is the decomposition potential for reaction (8.18).
Hence
∆G8:18 = 610; 452:4 J = FzE = 96500 zE (8:27)
Therefore,

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E = [610452.4/)96500 x 3)] = 2.11v (8:28)
This theoretically calculated value compares well with the experimentally obtained values
between aluminium and electrodes, which lies between 2.1 and 2.15 v.
In practice, a consumable graphite electrode serves as the anode. To calculate the
decomposition potential of an aluminium (liquid) cathode and carbon (solid) anode, the
reaction (8.18) has to be combined with the carbon oxidation reactions:
3/4O2(g) + 3/4C(s) = 3/4 CO2(g); ∆G8:29 (8:29)
3/4O2(g) + 3/2C(s) = 3/2 CO (g); ∆G8:30 (8:30)
From standard book*, the thermodynamics values of ∆G8.29 and ∆G8.30 obtain as
−296,401.59 J and −334,936.87 J respectively, at 1000°C. Combining reaction (8.29) with
reaction (8.18):
1/2Al2O3(solution inNa3AlF6) + 3/4 C(s) = Al)l( + 3/4CO2)g( ∆G8.31 (8:31)
Therefore,

So, E = 1.08 v.
Now, Combining reaction (8.30) with reaction (8.18):
1/2Al2O3(solution inNa3AlF6) + 3/2 C(s) = Al(l( + 3/CO(g) ∆G8:32 (8:32)
Therefore,

So,
E = 0.95 v.
From the above calculation, it is evident that graphite aids the decomposition of alumina
because it reacts with the oxygen to form CO and CO2. Under normal operating
conditions, about 50% by volume of CO is produced; the amount may increase
considerably at a low current density. In general the values of E calculated from reactions
(8.31) and (8.32) are of equal importance. Hence, the average theoretical decomposition
potential is taken, i.e. [(1.08 + 0.95)/2] or 1.015 v.
Factors Affecting Electrolysis
The certain operating factors which affect the electrolysis of alumina are as follows:
(1) The bath temperature is an important factor. As a rule, an increase in temperature
decreases the current efficiency. For every 4°C rise in the bath temperature (above the
normal 970°C), the current efficiency falls by 1% because the higher the temperature, the
more the number of side reactions and the greater the dissolution of the metal in the bath.
(2) The higher the current density, the greater the current efficiency. Therefore, the
current density is maintained at a very high value.
(3) The lower the density of the bath, the higher the rate of separation of the metal
liberated from the bath. The density can be lowered by using a high AlF3/NaF ratio; a ratio
of slightly less than 3 is considered optimum. When the quantity of AlF3 is higher than
NaF; the conductivity of the bath is decreased, the solubility of alumina is reduced, and a
large volume of fluorine is produced. On the other hand, a high NaF content reduces the
current efficiency due to an increase in the concentration of sodium ions and the

119
deposition of sodium on the cathode. The sodium deposition directly lowers the current
efficiency.
(4) The current efficiency is also affected by the interpolar distance, which is the distance
from the bottom of the anode to the top of the molten bath. The current efficiency
increases along with the interpolar distance, reaching a maximum (about 90%) when the
distance is about 0.65 m.
(5) The cell efficiency can be improved by strictly controlling the addition of alumina. The
current efficiency is a minimum when the Al2O3 content in the bath is 4%. At values lower
and higher than 4%, the current efficiency increases.
The current efficiency (CE) has an empirical relationship with various operating variables
as follows:

)8:33)
2
where T is the temperature of the cell (°C), i is the anode current density (A/cm ),
D is the inter-electrode distance (cm), CAl2O3 is the wt% Al2O3, CCaF2 is the wt% of
CaF2, and XAlF3 is the mol fraction of AlF3.
Refining of Aluminium
The purity of aluminium metal produced by the Hall-Heroult process is about 99.5%, this
is sufficient for most alloying purposes. However, for electrical applications and for
canning, a higher degree of purity is required. To achieve this higher purity, an electrolytic
method is used which is also known as the three layer process (Fig. 8.3). The graphite
electrode is used as cathode and carbon bottom acts as anode. Electrolytic refining takes
place in a cell in which the anode is at the bottom, the current travelling up through the
bath and being collected at the top by graphite electrodes. This method depends for its
operation on the adjustment of the specific gravity of the electrolyte so that it is lighter
than an anodic copper-aluminium alloy, but heavier than pure aluminium. A dense
electrolyte (which consists of 36% aluminium fluoride, 30% cryolite, 18% barium fluoride,
and 16% calcium fluoride) forms the middle layer (density is 2800 kg/m 3). The impure
metal is alloyed with copper (28–30% Cu), and this heavy alloy (density is 4500 kg/m 3)
forms the bottom layer. The purified aluminium (99.99%, density is 2300 kg/m3) is floated
upward during electrolysis to form the top layer. The temperature of electrolysis is at about
950°C. Magnesite refractory acts as insulating wall.
Refining reactions involved as follows:
At anode: Al  Al3+ + 3e- (8:34)
At cathode: Al3+ + 3e-  Al (8:35)
Impure aluminium is dissolved at the anode to form Al3+ ions; then aluminium ions (i.e.
Al3+) are deposited at the cathode in the pure form
Commercial aluminium is poured in a molten condition into the well connected with the
anode alloy metal in the bottom of the cell. Current from this layer causes pure alunimium
to pass through the electrolyte and float on the top layer from where it is periodically taken
out. The impurities which are retained in the bottom alloy layer gradually build up and
having a relatively low solubility crystallize out in the later stage. These impurities consist
mainly of iron, silicon, zinc and copper entangled with aluminium. The consumption of the

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electrolyte and graphite electrode each is equivalent to about 6% of the aluminium metal
produced.
This method is also applicable for the refining of aluminium scrap without magnesium.
This process will be ineffective if the impure metal contains magnesium which may have
come from Al–Mg scrap; due to magnesium reacting with the electrolyte.

Fig. 8.3 Refining of aluminium

8.4 Properties
Atomic weight of aluminium is 26.97, melting point is 660°C and boiling point is 1800°C.
The main impurities of commercial aluminium (99.3–99.6% Al) are iron and silicon
together with traces of titanium and copper. At room temperature, aluminium has a
specific gravity of 2.7 as compared with 8.89 for copper and 7.8 for iron. Its high strength
to weight ratio is a distinct advantage in many structural applications. The metal exhibits
good corrosion resistance, electrical and thermal conductivity. The thermal conductivities
and electrical resistivities of Ag, Cu, Au, and Al (as shown in Table 7.1) are outstanding
when compared with those of other metals. The metal has high reflectivity of light and low
emissivity. Aluminium has strong affinity for oxygen, a film of oxide forms spontaneously
on any freshly cut surface. To this property aluminium owes its high resistance to chemical
and. atmospheric attack. Aluminium can be hot rolled, extruded, forged, cold rolled,
drawn, stamped and machined as readily. One of the primary characteristics of aluminium
is that it can be worked and formed by the usual fabricating processes.
The tensile strength of commercial aluminium is low, ranging from 6.3–14.2 kg/mm2
according to the amount of cold working. The modulus of elasticity of aluminium (and its
alloys) is approximately one-third of that of steel, which means that the elastic deflection
under load of aluminium is three times that of steel. Purer grades of aluminium are known
as super-purity aluminium, and contain not less than 99.99% Al. The super-pure
aluminium is softer, more ductile, heats more efficiently, and possesses higher thermal
and electrical conductivities and greater resistance to corrosion than the commercial
metal.

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The addition of other metals to aluminium affords the means of increasing the strength
and hardness. The small amount of impurities present in commercial alluminium is
sufficient to increase its strength up to 50%, as compared with the pure metal. The metals
most commonly used in the production of aluminium alloys are copper, silicon,
manganese, magnesium and zinc. These metals may be added singly or in combination
to produce a desired result.
Al–Cu (8%) contains 1% Fe, and 1.2% Si; and Al–Cu (Y alloy) contains 4% Cu, 2% Ni,
and 1.5% Mg. Y alloy is superior to first alloy due to addition of Ni. Y alloy was developed
to withstand stress at elevated temperatures and is largely used as piston material.
Duralumin has the composition 3.5–4.5% Cu, 0.5% Mg and 0.5% Mn; together with small
quantities of Si and Fe. It is the first heat treatable alloy to be discovered and age
hardening is done at ordinary room temperature for 4–5 days to increase in strength and
hardness spontaneously.
Al–Si alloy has high fluidity, possess good casting qualities and also has excellent
resistance to atmospheric corrosion, making it of value in the production of architectural
and ornamental castings. Alloys containing 5% Si are used for these purposes.
Al–Mg alloys have combined properties of high resistance to marine exposure, excellent
strength, ductility and good machining qualities. They are rather difficult to cast and
require special treatment to prevent oxidation while casting. Al–Mg (10%) alloy has the
highest combination of tensile strength, elongation and resistance to impact, after heat
treatment.
Applications
After copper, aluminium metal is considered the most important non-ferrous metal.
Since aluminium is a good conductor of heat and electricity, and it is also less expensive
than copper; nowadays it is replacing the copper in electrical applications.
In EGYPT, aluminium is gradually replacing the copper in the power transmission lines
and in other electrical applications. A composite conductor made of aluminium wires that
surround a core of steel wires with a high tensile strength is being extensively used as an
overhead conductor. The core compensates for the low strength of aluminium. For
transformer winding, aluminium strips or foils interleaved with insulators are used. Due to
very good ductility and flow properties of aluminium, it is used for extrusion of vessels and
containers. For kitchenware, chemical and food processing industries, pure grade
aluminium is used due to its corrosion resistance and non-toxic properties. High
reflectivity and low emissivity of aluminium explains its use as roofing and thermal
insulation either as metal foil or aluminium paint. In steelmaking, aluminium acts as
deoxidizing agent to remove oxygen in liquid steel.
USES OF ALUMINIUM
Aluminium is a soft metal with a density of 2.7 g cm -3 Aluminium can be easily extruded
through dies to form various shapes.
1. It is used for making angles used in windows.
2. It is a good conductor of electricity. Since it is not as good conductor as copper, thicker
cables of aluminium are used for transmission of electricity.
3. Aluminium forms many useful alloys e.g., magnalium (AI and Mg), duralumin (AI, Cu,
Mg and Mn). Aluminium alloys are used in aircraft and other transportation vehicles.
4. In the form of finely-divided powder, aluminium is used in antirust paints.
5.Aluminium foil is used for wrapping cigarettes, confectionery, etc.

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6.Aluminium is used to produce metals such as chromium and manganese from their
ores (aluminothermic process)
Cr2O3 + 2Al → Al2O3 + 2Cr
3MnO2 + 4Al → 2Al2O3 + 3Mn
7. Aluminium utensils are extensively used for household purposes.

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 Chapter (5)
Zinc Extraction
Details about of Zn:
Name: Zinc
Symbol: Zn
Atomic number: 30
Valency: 2
Electronic configuration: 1s2, 2s2, 2p6, 3s2, 3p6, 3d10, 4s2
Atomic Weight: 65.38 amu
3
Density: 7.13 gm/cm
0
Melting Point: 419.5 C
0
Boiling Point: 910 C
Physical Properties
i. It is a blueish white lusticous metal.
ii. zinc is brittle at ordinary temperature but it becomes malleable from 100-150 c
then again it becomes brittle.
iii. It melts at 420. c and boils at 900. c and has sp. Gravity 7.13.
Chemical Properties
1. Action of air:-
Dry air has effect on zinc but in moist air, zinc forms a protective layer of basic zinc
carbonate.
Zn + O2 + H2O + CO2 → ZnCO3.Zn (OH)2
When heated in air, zinc burns greenish blue flame forming clouds of light, white
power of zinc oxide which is commonly known as ‘philosopher’s wool. Beside this
name, other common names are ‘Zinc white and china white.
2Zn + O2 → 2ZnO
2. Action of water:-
Pure zinc does not react with water but impure zinc displaces hydrogen gas. Zn-
inc reacts with hno3 in four different concentrations giving different reduced
product.
Zn + H2O → ZnO + H2
3. Action with acids:
Dilute H2SO4 and dil. HCl gives H2 gas with zinc
Zn + dil. H2SO4 → ZnCl2 + H2
Zn + dil. HCl → ZnSO4 + H2
With hot and conc. H2SO4 zinc gives SO2 gas
Zn + 2H2SO4 → ZnSO4 + SO2 + 2H2O
Zinc reacts with HNO3 in four different conditions giving different product:
i. with very dil. HNO3
With very dil. HNO3, Zn gives ammonium nitrate
4Zn + 10HNO3 → 4Zn(NO3)2 + NH4NO2 +3H2O
ii. with dil. HNO3
Zinc reduces dil. HNO3 to nitrous oxide (N2O)
4Zn + 10HNO3 → 4Zn(NO3)2 + N2O +5H2O
iii. With modrately conc. HNO3

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 Zinc reduces moderately conc. HNO3 to NO (nitric oxide)
3Zn + 8HNO3 → 3Zn(NO3)2 + 2NO2 +4H2O
iv. With conc. HNO3
Zinc reduces conc. HNO3 to NO2 (nitrogen dioxide)
Zn + 4HNO3 → Zn(NO3)2 +2 NO2 +2H2O
4. Reaction with Alkalies:-
Zinc readily dissolve in hot and conc. solution of caustic bases like NaOH , KOH, etc
giving hydrogen gas.
Zn + NaOH → Na2ZnO2 + H2
Zn + KOH → K2ZnO2 + H2
5. Displacement Reaction:-
Zinc can displace less electropositive metals from their salt solution
Zn + CuSO4 → ZnSO4 + Cu
Zn + 2Na[Au(CN)2] → NA2[Zn(CN)4] + 2Au
Zinc Mining
80% of zinc mines are underground, 8% are of the open pit type and the remainder is a
combination of both. However, in terms of production volume, open pit mines account for
as much as 15%, underground mines produce 64% and 21% of mine production comes
from the combined underground and open pit mining.
Zinc is found in the earth’s crust primarily as zinc sulfide (ZnS). Rarely is the ore, as
mined, rich enough to be used directly by smelters; it needs to be concentrated. Zinc ores
contain 5-15% zinc. To concentrate the ore, it is first crushed and then ground to enable
optimal separation from the other minerals. Typically, a zinc concentrate contains about
55% of zinc with some copper, lead and iron. Zinc concentration is usually done at the
mine site to keep transport costs to smelters as low as possible.
Occurrence:

SPHALERITE
Sphalerite ((Zn,Fe)S) is a mineral that is the chief ore of zinc. It consists largely of zinc
sulfide in crystalline form but almost always contains variable iron. When iron content is
high it is an opaque black variety, marmatite. It is usually found in association with galena,
pyrite, and other sulfides along with calcite, dolomite, and fluorite. Miners have also been
known to refer to sphalerite as zinc blende and black-jack.
Zinc occurs in nature only in combined state. The main ores of zinc are:

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Zinc blende – ZnS
Calamino – ZnCO3
Zincite – ZnO
Franklinite – ZnO. Fe2O3
Willimite – 2ZnO. SiO2
Common Minerals of Zn: Zinc Oxides Zinc Sulphides
Occurance: Zincite (ZnO), Zinc blende (ZnS), Calamine, Zinc Carbonate (ZNCO3) etc.

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9.3 Extraction of Zinc
There are two routes of extraction of zinc: pyrometallurgical process, and
hydrometallurgical process followed by electrometallurgical process.
9.3.1 Pyrometallurgical Process
The techniques of smelting and converting are applied for Cu2S in copper metallurgy.
But for ZnS, they are not possible due to high melting point of ZnS even at
1500 °C. Hence, a different method is applied in zinc extraction.
Flow sheet for pyrometallurgical process is shown in Fig. 9.1. After grinding of
ore, separation of sulphides of lead and copper is done; and concentration of zinc
(50–60% Zn) is produced.
a. Crushing and Pulverization:
The big lumps of ore is first crushed by a jaw crusher and powered in ball mills.
b. Concentration:
Froth flotation process
The crushed and pulverized ore is concentrated by froth flotation process. This process
is used for the concentration of sulphide ore. The powered ore is suspended in water and
after adding pine one, it is stirred by passing the compressed air. The particles of the
sulphide ore which are wetted by the oil comes to the surface along the froth (fizzy
substance) which is taken out and the gangue particles remains at the bottom which are
then removed.
Zinc blende is concentrated by floath floatation process. The pulverized ore is kept in
large tank containing water and pine oil. The mixture is agitated by passing compressed
air. Ore forms froth and comes to the surface while impurities are left in water.

Roasting:
Oxidation of zinc concentrate (ZnS) is necessary for the subsequent reduction and
recovery of zinc metal. Oxidation is carried out by roasting, either a partial roast followed
by sintering or in one operation as a dead roast. Complete elimination of sulphur is
desirable as any remaining after roasting ties up twice its weight of zinc, which is lost in
subsequent operation. The zinc sulphide concentrate always contains some lead sulphide
which is eliminated during initial stages of roasting, i.e. by volatilization; hence, the
multiple hearth roaster is used. The roaster has eight hearths and a top drier hearth. The

127
remaining lead sulphide is removed during sintering at high temperature. Heating is
unnecessary when a partial roast is done, for the blende contains sufficient sulphur to
support combustion down to 7–8% sulphur; but for dead roasting, external heating is
necessary to drive off the last few per cent of sulphur; this is provided by a firebox on the
bottom hearth, either oil or gas is used as fuel.
Roasting is a process of oxidizing zinc sulfide concentrates at high temperatures into an
impure zinc oxide, called "Zinc Calcine". The chemical reactions taking place during the
process are:
The process of roasting varies based on the type of roaster used. There are three types
of roasters: multiple-hearth, suspension, and fluidized-bed.
Partial roasting of zinc concentration (ZnS) is done at 700–800 °C to zinc calcine
(ZnO, which contain 1–4% S). For a dead roasting a higher temperature (1000 °C)
is required.
2ZnS + 3O2 → 2ZnO2 + SO2 9:1
Presently, roasting is carried out in a suspension roaster or fluidized bed roaster instead
of earlier in a conventional hearth roaster, because the former has certain advantages:
(a) it is autogenous; (b) good control over the temperature; and (c) high roasting rate.
Then sintering of zinc calcine (ZnO) is done at 1200–1400 °C in a Dwight-Lloyd sintering
machine to provide lump feed for retort distillation and to eliminate residual sulphur,
cadmium and lead.
Zincor uses the conventional roast-leach-electro-winning process to produce zinc metal.
The roasting process of ZnS concentrate makes use of four Lurgi fluidized bed roasters
to produce calcine (which contains ZnO and ZnFe2O4 as zinc products) and SO2 gas.
The roasting plant consists of two small roasters and two big roasters, with cross-
sectional areas of 18 m2 and 35 m2 respectively. A typical Zincor roaster is shown
schematically in Figure below.
In an attempt to increase production, O2 enrichment was first tested and then introduced
into the fluidizing air. The ability of O2-enriched air to increase the rate of the ZnS
oxidation reaction allowed higher feed rates to the roasters, without increasing the flow
rate of fluidizing air. This was very successful and O2 enrichment up to 26% (21% O2 in
air and 5% O2 from a 99.5% O2 source) was implemented on all four roasters1.
The concentrated are is heated in excess supply of air above 9000c on the hearth of
reberveratory furnace. During roasting. Zinc sulphide is converted to Zinc Oxide.
2ZnS + 3O2 → 2ZnO + 2SO2
The concentrated ore is roasted in the excess of air at a temperature of 900 degree
celsius in the reverbatory furnace.
So the ore reacts with oxygen to form Zinc Sulphide (ZnS) and Sulphur dioxide (SO 2)
which is given by the reaction below.
2ZnS+3O2 → heat
2ZnO+SO2
Small amount of ZnS may be oxidized to ZnSO4 but above 9000c , ZnSO4 decompose
forming Zinc Oxide (ZnO)
ZnS + 2O2 → ZnSO4
ZnSO4 above 900 → 2ZnO + 2SO2 + O2

128
Reverbatory furnace
During this process, some ore of the ZnS is also converted into zinc sulphate.
ZnS+2O2⟶ZnSO4
Above 900 degree celsius, this zinc sulphate decomposes to give Zinc Oxide.
ZnSO4 → 900°C
2ZnO+SO2+O2
In this roasting process, the volatile impurities are also removed as their oxides.
C+O2⟶CO2 S+O2⟶SO2

129
4P+5O2⟶2P2O5 4As+3O2⟶2As2O3

Flow diagram for extraction of zinc by pyrometallurgical process

130
d. Reduction:
The roasted ore is mixed with coke and heated strongly so that the zinc and oxides get
converted into Zinc. For reduction, either Belgian process or vertical retort process is
used. But vertical retort is the modern and continuous method.
Vertical retort process:
Retort Distillation
In horizontal retort process, 2 m long retorts, each having a diameter of 25 cm and a
thickness of 5–6 cm, are lined up in a gas fired furnace in batches of several numbers at
a time. Retorts cannot make of metals because most of metals produce alloy with zinc
when heated at high temperature. The retorts are generally made of fireclay. The retorts
are first charged with mixture of fine size ZnO and an excess of coal (30–40% by weight),
then heated to a maximum temperature to volatilize zinc which is subsequently
condensed. Theoretically, one part of carbon will reduce seven parts of zinc oxide, but in
practice it has been found necessary to use four to five times this amount, principally to
keep the carbon dioxide concentration as low as possible (C + CO2 = 2CO), and also to
protect the retorts by holding up the molten slag. This large excess of carbon, over that
the theoretically required, is necessary to insure complete reduction and to maintain a
reducing atmosphere in the retort by reducing any carbon dioxide that may be formed.
The furnace is gradually heated up to 1400 °C, distillation start around 1100 °C.

The first gas to come off is coal gas, burning with a luminous flame; as the reduction
proceeds, and carbon monoxide is given off, the luminosity diminishes and the flame
becomes purple. The beginning of zinc distillation is marked by the flame of bluish-white
colour and generally at this stage the prolongs are fitted to the condensers. Finally, when
all the distillable zinc has been expelled, the flame loses its bluish tinge and becomes
purple again, indicating that the cycle has been completed. Temperature of condenser is
important: if it becomes too low (below 400 °C) excessive blue powder forms, and if too
high, zinc vapour will pass off uncondensed. A temperature of 1400 °C is generally
maintained in the furnace, and retorts temperature being 100–200 °C lower.
Reduction of zinc oxide by carbon is a strongly endothermic reaction, which requires
temperature in the range of 1200–1400 °C.

131
ZnOs + Cs → Zng + COg ∆H = - 238.49 kJ 9:2
The liberated zinc vapour is extremely sensitive to oxidation and it is necessary to carry
out the distillation in a closed system. The carbon monoxide forms in reaction (9.2), then
further reduces to zinc oxide:
ZnOs + COg → Zng + CO2g ∆H = - 75.31 kJ 9:3
At high temperature the carbon dioxide is unstable, so it reacts with more carbon present
in the system to form carbon monoxide:
Cs + CO2g → 2CO 9:4
Zinc boils at 907 °C, and carbon does not reduce zinc oxide until 1120 °C, so zinc is
liberated in the vapour form. In this state it is not only susceptible to oxidation by the
ordinary oxidizing agents such as air and water vapour, but it is capable of oxidizing by
carbon dioxide. Reactions (9.3 and 9.4) are reversible reactions, but the concentration
must be very high before the backward reactions take place. With zinc vapour [reaction
(9.3)], however, the backward reaction occurs with small concentrations of carbon
dioxide. In general, condition of reduction is (pco /pco2)gas phase > (pco
/pco2)equilibrium, so pco should be maintained at a high level in order to prevent the
oxidation of zinc vapour to zinc oxide due to presence of CO2 gas. If the zinc vapour is
much diluted with other gases, it condenses not to liquid zinc but to a mixture of solid zinc
encrusted with zinc oxide, which is known as blue powder.
Vertical Retorts

Vertical retorts are made of carborundum, as refractory by mixing with 6–12% of clay.
Carborundum is nothing but silicon carbide (SiC), which has a melting point above 2700 °C. The

132
conductivity of silicon carbide is about five times higher than that of fireclay. Vertical retort is a
shaft of rectangular cross-section. The height of the heating zone is about 7.5 m, and inside
dimensions of retort cross-section average 300 _ 1500 mm.
Generally, gas is used to heat the retort by burning of gases in chambers. Modern vertical retort
is heated by electrical energy. The graphite electrodes are introduced through the silicon carbide
walls near the bottom of the retort. The electrical energy provides the heat to the system. The
charge is introduced as briquettes from the top and slag is discharged continuously from the
bottom. Modern vertical retorts are provided with automatic charging and discharging systems
which help the handling of raw materials as well as products.
The roasted zinc concentrate, coking coal and coal tar (as binder), after a through mixing, the
charge is passed through a briquetting machine. The briquettes are heated to 750–900 °C to
strengthen briquettes and make them adequately porous.
Distillation in vertical retorts is no different in chemistry than the standard horizontal retort
technique. Since the conductivity of silicon carbide is higher and therefore zinc is removed more
completely, zinc content in slag is generally less than 5%.
A condenser is lined with refractory brick and provided with internal partitions that lengthen the
path of gases. The zinc vapour is condensed very fast in order to avoid the formation of blue
powder (ZnO + Zn). 3–4% zinc, all iron, gangue, copper, and precious metals are contained in
the residues of the retort processes.
Zinc recovery is about 95%. The comparisons between horizontal and vertical retorts are shown
in Table 9.1.
Zinc vapours are condensed to metal and some are oxidized. Besides zinc, retort slag always
carries lead, copper and noble metals; therefore they require additional treatment. A top layer of
zinc containing some lead (about 0.8%) and an intermediate layer of zinc and iron (15–20%) is
called hard metal, which is recycled to the retorts. Bottom lead layer is further smelted to recover
the lead. The zinc layer is refined by fractional distillation due to wide difference in the boiling
points of zinc (907 °C), cadmium (780 °C) and lead (1620 °C); therefore, easy separation of one
metal from the other.
Physical Chemistry of Zinc Smelting
The reaction taking place in a retort may be written as (in general):
x2yZnOs + xy Cs‫→ ق‬ x2yZng + xCOg + yCO2g 9:5
When zinc oxide and carbson are heated together, variable amounts of zinc, carbon
monoxide and carbon dioxide are produced. This reaction (9.5) is the sum of the following
reactions:
xZnOs + xCs → xZng + xCOg 9:6
2yZn + yC → 2yZng + yCO2g 9:7
It is significant that the so-called temperature of reduction of zinc oxide had been reported by
investigators over the range of 780 to 1310 °C. These divergences had been attributed in the past
to differences in the physical form of zinc oxide and carbon, to differences in the gas pressure,
and to allotropic modifications. It is certain that no amount of continued heating at a definite
pressure will cause gas-free carbon to reduce zinc oxide continuously below a certain
temperature. It is also obvious that attempts to measure the temperature at which reduction takes
place have measured only the temperature at which the rate of reaction becomes measurable.
At higher temperatures, where the reaction takes place at any definite temperature, either zinc
oxide or carbon, or both, disappear from the system. In other words, if a system containing zinc
oxide and carbon is vented at a definite pressure, a condition of equilibrium can exist at only one
temperature. Below this temperature, reduction by carbon does not take place, and above it
continuous reaction takes place. This is the system which is unstable as far as chemical
equilibrium is concerned.

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Reactions within the charge in a retort produce water vapour, hydrocarbons, carbon monoxide
and carbon dioxide; but only the last two (CO and CO2) are the important factors in the production
of blue powder, which is a mixture of zinc and zinc oxide.
Zinc is a moderately strong basic metal and may be used to reduce carbon monoxide:
Zng + COg → ZnOs + Cs 9:8
This would necessarily involve the reversal of the producer gas reaction:
2COg → CO2g + Cs 9:9
CO2g + Zng → ZnOs + COg 9:10
The reaction (9.8) is the combination of the reactions (9.10) and (9.9).
It has been shown that reaction (9.9) is slow below 1100 °C but reaction (9.10) is perceptible
above 300 °C and very fast above 550 °C, so that the rate at which zinc is oxidized is determined
by the slowest step. Large amounts of carbon dioxide would be present in the equilibrium mixture
at temperature below 850 °C, but at this temperature the rate of the reaction is so slow that
equilibrium would be obtained only in week or month. Catalysts are known that would increase
this rate, but they are not present in the charge. Therefore, the reaction with carbon monoxide
probably accounts for the formation of only a part of the blue powder
The important ore of Zinc is Zinc blende (ZnS). So it is extracted from zinc blende by carbon
reduction process. The following are the steps involved for the extraction process of zinc.
It is one of the most important, continuous and commercial technique for the reduction of zinc.
Here, zinc ore is mixed with the coke in the ratio of 2:1. It is passed through the charging door.
The retort is heated by the producer gas (CO + N2). Zinc vapour along with the carbon monoxide
is led to the condenser by applying a suction and forcing producer gas from below. Following
reaction takes place during reduction.
ZnO + C ⟶ Zn + CO
Molten Zinc is taken out from the condenser time to time. The crude metal obtained is
called zinc spelter which contains about 3% of other impurities.
e. Purification: The spelter zinc contains Fe, Pb, As, Sb, Cd as impurities. It is further
purified by electrolysis process.
Reduction (Smelting):-
ZnO obtained during roasting is mixed with coke and heated strongly where ZnO is
reduced to Zn by carbon.
ZnO + C → Zn + CO
The reduction is done in vertical refort. In this process roasted are mixed with coke in the ration
of 2:1 and small briquets are made. These briquets are fed into vertical report furnance, from the
charging door. The report is heated externally by burning produce gas (w+N2) to about 14000c.
The vapour of zn is camed to condenser where it condenses to give molten zinc called spelter
zinc.
Zinc smelting is the process of converting zinc concentrates (ores that contain zinc) into pure zinc.
The most common zinc concentrate processed is zinc sulfide, which is obtained by concentrating
sphalerite using the froth flotation method. Secondary (recycled) zinc material, such as zinc oxide,
is also processed with the zinc sulfide. Approximately 30% of all zinc produced is from recycled
sources.
There are two methods of smelting zinc: the pyrometallurgical process and the hydrometallurgical
process (over 90% of hydrometallurgical process is in electrolytic plants using electrolysis
process). Both methods are still used. Both of these processes have the same first step: roasting.
Blast furnace process (Imperial Smelting Process)
This process was developed by the National Smelting Company at Avonmouth Docks, England,
in order to increase production, increase efficiency, and decrease labour and maintenance costs.

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L. J. Derham proposed using a spray of molten lead droplets to rapidly chill and absorb the zinc
vapour, despite the high concentration of carbon dioxide. The mixture is then cooled, where the
zinc separates from the lead. The first plant using this design opened up in 1950. One of the
advantages of this process is that it can co-produce lead bullion and copper dross. In 1990, it
accounted for 12% of the world's zinc production.
The process starts by charging solid sinter and heated coke into the top of the blast furnace.
Preheated air at 190 to 1,050 °C (370 to 1,920 °F) is blown into the bottom of the furnace. Zinc
vapour and sulfides leave through the top and enter the condenser. Slag and lead collect at the
bottom of the furnace and are tapped off regularly. The zinc is scrubbed from the vapour in the
condenser via liquid lead. The liquid zinc is separated from the lead in the cooling circuit.
Approximately 5,000 metric tons (5,500 short tons) of lead are required each year for this process,
however this process recovers 25% more lead from the starting ores than other processes.
The IS process is an energy-intensive process and thus became very expensive following the rise
of energy prices. Today, Imperial Smelting furnaces are only in operation in China, India, Japan
and Poland.

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5. Imperial Smelting Process (ISP):
The process inside the furnace based on reaction i. e. reduction of ZnO by C in the
imperial blast furnace gives rise to Zn in vapour form which gets condensed by using
molten lead.
Principle: The process is carried out by using counter current principle, where the blast
and preheated air given to the furnace through the tuyere and the preheated coke get
charged from the top.
• ISP furnace is of square cross section consists of water jacket brick lined shaft.
• Feed is given from the top of the furnace at positive pressure where we introduced
preheated coke and sinter through a double bell charging system.
• ISP consists of two condensers.
Function of Condenser: These are used mainly for two purposes as
• Cooling of furnace gases resulting due to condensation of Zn
• Dissolving condensed Zn in molten Pb

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The smelting reactions takes place in ISP are
Reaction 2.29: 𝐶+1/2𝑂2→𝐶𝑂
Reaction 2.30: 𝐶+𝑂2→𝐶𝑂2
Reaction 2.31: 𝐶+𝐶𝑂2→2𝐶𝑂
Reaction 2.32: 𝑍𝑛𝑂+𝐶𝑂→𝑍𝑛+𝐶𝑂2
Reaction 2.33: 𝑃𝑏𝑂+𝐶𝑂→𝑃𝑏+𝐶𝑂2
Carbon does not reduce ZnO until 1120°C, since at this temperature Zn gets vaporized.
After reduction complete the molten slag and Pb are taken out from the furnace hearth at
the melting point of the slag. Hence, Zn gets collected. So the reaction (2.31) may
backward as due to the difference.
Lead Bullion (Rich 70-80% Pb):
It is the mixture of Pb and precious metal, where preheated coke 8000C and sinter 21%
Pb are charged from the top of ISP furnace. So at bottom collect precious metals such as
Au, Cu etc. and this liquid is known as Lead Bullion.
Advantages of ISP:
• Economical production of Zn.
• Efficiency overall high but Zn recovery expensive.
• Entire amount of Au, Sb etc. recover.
• Capacity large.
• Complete mixed charge of Zn and Pb simultaneously charged and recovered.
• Operational cost is low.
• No additional C required.
Purification:-
Zinc spelter contains Pb, Fe, Cd, As, etc. as impurities. Impure zinc can be purified by
following methods.
a. By fractional distillation:-
The bpt of Pb, Fe are higher than that of zinc while that of cadmium, arsenic are lower
than that of zinc. When distillation is carried out around 1000°c, zinc, Cd, As, etc. distill
off leaving Pb and Fe the distillate is then heated to 800°c where cd and as distill off
leaving pure zinc. This sample of Zn is about 99% pure.
b. By electrolysis:-
Zinc of higher purity can be obtained by electrolysis. Pure zinc rod is used as cathode
while a block of impure zinc is used as anode. A mixture of ZnSO4 and dill H2SO4 is used
as electrolyte. On passing current impure zinc dissolves and equivalent amount of pure
zinc is deposited at cathode.
Zinc is extracted from the purified zinc sulfate solution by electrowinning, which is a
specialized form of electrolysis. The process works by passing an electric current through
the solution in a series of cells. This causes the zinc to deposit on the cathodes
(aluminium sheets) and oxygen to form at the anodes. Sulfuric acid is also formed in the
process and reused in the leaching process. Every 24 to 48 hours, each cell is shut down,
the zinc-coated cathodes are removed and rinsed, and the zinc is mechanically stripped
from the aluminium plates.
Hydrometallurgical Process
(a) Hydrometallurgical processes are used for the extraction of zinc from the low grade
ores. These processes produce high purity zinc and also lead to a higher rate of recovery
of valuable by-products. Figure 9.2 shows the flow sheet of hydrometallurgical process.
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Before leaching, the zinc sulphide concentrate is first roasted. Roasting for leaching must
be very carefully controlled to produce the right proportions of zinc oxide and zinc
sulphate. The zinc sulphate must be present in sufficient amount to make up for the
sulphuric acid lost in dissolving the oxide and processing the residues. The roasted zinc
concentrate is dissolved in sulphuric acid and the valuable by-products are precipitated
out.
ZnO + H2SO4 → ZnSO4 H2O 9:11
Zinc dust is added to the leach zinc sulphate solution to precipitate cadmium (i.e.
cementation process) for recovery of Cd; Co and Cu are also precipitated out.
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Precipitation of cobalt from leach solution is done by adding a-nitroso-b-napthol. Then
electrolysis of the purified leach solution (ZnSO4 + H2SO4) of 5.3 pH is done by using a
cell with an anode of cast Pb-Ag (1%) alloy and rolled high-purity aluminium sheet as
cathode. Metallic zinc is deposited at cathode and oxygen gas is released at anode. Cu
and Fe present in solution reduce the current efficiency of the electrolyte bath.
Electrolytic zinc smelters contain as many as several hundred cells. A portion of the
electrical energy is converted into heat, which increases the temperature of the
electrolyte. Electrolytic cells operate at temperature ranges from 30 to 35 °C (86 to 95 °F)
and at atmospheric pressure. A portion of the electrolyte is continuously circulated
through the cooling towers both to cool and concentrate the electrolyte through
evaporation of water. The cooled and concentrated electrolyte is then recycled to the
cells. This process accounts for approximately one-third of all the energy usage when
smelting zinc.
There are two common processes for electrowinning the metal: the low current density
process, and the Tainton high current density process. The former uses a 10% sulfuric
acid solution as the electrolyte, with current density of 270–325 amperes per square
meter. The latter uses 22–28% sulfuric acid solution as the electrolyte with a current
density of about 1,000 amperes per square metre. The latter gives better purity and has
higher production capacity per volume of electrolyte, but has the disadvantage of running
hotter and being more corrosive to the vessel in which it is done. In either of the electrolytic
processes, each metric ton of zinc production expends about 3,900 kW•h (14 GJ) of
electric power.
Today over 90% zinc is produced hydrometallurgically in electrolytic plants
Electrolysis Process: Pure zinc is made anode and pure aluminium as anode. Zinc
sulphate solution is acidified by sulphuric acid is taken as electrolyte. When electricity is
passed through the electrolytic solution, pure zinc gets deposited at cathode whereas
impurities remain as anode mud. Following electrolytic reaction occurs here:
At anode: Zn – 2e ⟶ Zn++ At cathode: Zn + 2e ⟶ Zn

Applications
After cold work, tensile strength is drastically increased; hence, zinc is not used where
high stresses are likely to be encountered; but it can be used for ordinary applications
such as roofing, metal linings, dry batteries etc. By rolling, the metal is easily worked to

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make foil, due to ductility of zinc. High purity zinc (99.99%) is used for manufacturing of
die casting parts, wire, foil and anodes. High grade zinc (99.95%) is used for production
of wire, zinc oxide, and high grade brasses. Foundry grade zinc (98.5%) is used for
making sheet and strip by rolling; foundry work for brass and other alloys castings. Zinc
(98%) is used for galvanizing, formation of zinc dust and brass. Zinc acts as an alloying
element in brass and bronze. The bulk of the metal is consumed as an alloying element
of brass and in the form of galvanized steel sheet.
Small articles are exposed to zinc dust at elevated temperatures (350–400 °C); zinc
diffuses at the surface, and this method is known as sherardizing. This process is used
for steel windows. Springs, aeroplane components, bolts, nuts and small castings of
intricate design can be made from zinc and its alloys. Almost any metal may be applied
by spraying, since zinc has a low melting point (420 °C) and corrosion prevention
property, hence being used to a greater extent than any other metal. Anti-corrosion paints
based on metallic zinc powder form, a convenient alternative to metal spraying.
On account of low melting point and prevention of corrosion, zinc is used to spray on the
other metals. Zinc in the form of wire or powder is loaded into a pistol, where it is melted
and atomized by compressed air; then is projected at the target object. The main
applications of sprayed zinc coating are for steel bridges, ships, storage tanks etc.
The most widely used of these zinc die-casting alloys contain up to 4% Al with small
amounts (0.02%) of Mg.
Zinc oxide is used for high grade pigments and pharmaceutical use. Zinc oxide is
extensively used in the manufacture of oil and other types of paints owing to its white
colour and high covering power.
Uses of zinc:
– It is used for galvanization of iron.
– It is used in making alloys like Brass. German metal, German silver, etc
Galvanization
The process of applying a coat of zinc on base metal like iron is galvanization Iron is
galvanized to protect iron from resting the galvanization is done in following steps.
i. cleaning and picking: Before applying zinc coat on iron, the surface of iron should be
clean. The cleaning is done first by sand blast and then washed by dipping in diluted acid.
The process of cleaning iron by using dil. acid is called picking.
ii. Applying of zinc coat:
The coat of zinc can be applied on iron surface by 3 methods.
a. By electroplating:-
Zinc can be electroplated on iron by keeping iron article as cathode, zinc as anode
and znso4 solution as electrolyte. On passing current a layer of zinc is coated on
iron article.
b. By metallizing:-
Zinc can be directly applied by dipping iron article in molten zinc this process is
generally used for galvanization of iron sheets. Iron sheets are dipped in molten
zinc bath & then passed through huge rollers that distributes zinc coat equally.
c. By sherardizing:-
The process is used for galvanization of small iron articles like nail, screws etc. In
this process iron article are mixed with zinc dust and then heated in enclosed
vessel for few hours when coat of zinc is applied on iron

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Which one is better at reducing ZnO,C or CO2?
Solution:
ZnO is reduced to Zn at around 1673 K. From the figure above, we observe that beyond
1073 K the Gibbs free energy of formation(ΔfG0) of CO from C and beyond 1273 K, the
Gibbs free energy of formation of CO2 from C is less than the Gibbs free energy of
formation of ZnO. Thus, C can reduce ZnO to Zn. However, the Gibbs free energy of
formation of CO2 from CO is greater than the Gibbs free energy of formation of ZnO.
Thus, CO is not able to reduce ZnO. Therefore, out of C and CO, C is a better reducing
agent than CO for ZnO.

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In some particular case, the thermodynamic factor dictates the choice of the reducing agent. To
what extent do you believe this statement to be true? Provide two examples to back your opinion.
Solution:
From the above Ellingham diagram, we observe that metals for which the standard free energy
of formation of their oxides is more negative can reduce the metal oxides for which the standard
free energy of formation of their respective oxides is less negative.

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Example 1
Let me illustrate material balance through a problem
Consider a blast furnace, which is charged with iron ore coke and flux of the following
composition:

The coke rate is 900kg/ton of pig iron. (Modern blast furnace operates with much lower
coke rate)
During smelting 99.5% of Fe is reduced and 0.5% is slagged. The CO/CO 2 ratio in the
top gas is 2/1
Calculate
a) Weight of iron ore
b) Weight and composition of slag
c) Volume of air required
d) Volume and% composition of exit gas.
Solution:

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Volume of air required calculation to consider the top gas. All the carbon charged except
that dissolves in iron will be available in the top gas. Air is required in the blast furnace to
combust carbon of coke at the tuyere level. From the amount of coke and the oxygen
available through the reduction of oxides, volume of air can be determined.
Oxygen available from the charge = Decomposition of CaCO3 and MgCO3 + oxygen
released through the reduction of the oxides

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Also important is the amount of carbon burnt at the tuyere level.
In order to find amount of carbon, burnt at the tuyere, volume of blast can be used.
N2 of blast is inert and O2 react with carbon only.
All oxygen of blast reacts with C and forms CO
Charge calculation problems
Hints for effective material balance: 1 – Read the question to understand the process
and materials
2 – Draw a diagram
3 – Define a base
4 – Write down the reactions
5 – Do stoichiometric and materials balance calculations
6 – Check your calculations
Example – Combustion of coal in furnace

145
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Roasting furnace analysis
Pyrometallurgical extraction of ores rich in CuS, FeS2, ZnS is uneconomical due the
difficulties involved in concentrating the ore
Roasting is needed to remove all of the sulfur and subsequently to leach the ore in dilute
sulfuric acid for the recovery of copper and zinc by hydrometallurgical methods

Copper, iron and zinc of the ore oxidize to CuO, Fe2O3 and ZnO
Reactions
CuS + 3/2O2 = CuO + SO2
2FeS2 + 11/2O2 = Fe2O3 + 4SO2
ZnS + 3/2O2 = ZnO + SO2
SO2 + 1/2O2 = SO3 Rational Analysis wt%

149
150
Roasting furnace analysis:- Pyrometallurgical extraction of ores rich in CuS, FeS2, ZnS is
uneconomical due the difficulties involved in concentrating the ore. Roasting is needed to remove
all of the sulfur and subsequently to leach the ore in dilute sulfuric acid for the recovery of copper
and zinc by hydrometallurgical methods

151
Examples –In a copper ore, chalcopyrite (CuFeS2) is 34%, pyrite (FeS2) is 30% and
SiO2 is 36%
a) Determine the % Cu and % gangue in the ore
b) What % Fe in the ore concentrate is to be removed to make 40% matte? Consider
Cu2S
c) If only excess S is eliminated in the ore concentrate, what is the composition of the
resulting matte?
Solution
AW Cu= 64, AW Fe= 56, AW S= 32

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154
Steel converter analysis
A basic pneumatic steel converter is charged with 25 tons of pig iron with the given
composition
In addition to the removal of all of the C, Si, Mn and P, iron equivalent to 5% of the weight
of charged iron oxidizes at a constant rate throughout the bessemerizing operation
Enough lime is added to obtain a slag containing 35% CaO
2/3 of the carbon in steel oxidizes to CO and 1/3 goes to CO2
Air compressor delivers air at a rate of 500 m3/min for specific periods of time
Should air blowing into the furnace be heated, to what temperature?

155
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157
158
Copper converter analysis
40 tons of matte carrying 34% Cu is charged in a bessemer converter
The flux is added in batches of 3000 kg, the converter is blown after each addition to
obtain slag of the given composition
Blister copper is produced after the removal of slags formed using partially added fluxes
Air is blown at a rate of 100 m3/minute

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161
Iron blast furnace analysis
Consider an iron blast furnace charged with iron ore, limestone and coke of following
analyses:

The ultimate analysis of the pig iron gives 93.8% Fe, 4% C, 1.2% Si, 1% Mn
For every ton of pig iron produced, 1750 kg of iron ore and 500 kg limestone are used
and 4200 m3 of flue gas is produced
The rational analysis of flue gases gives 58% N2, 26% CO, 12% CO2, 4% H2O

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for Zn to reduce MgO but Mg can reduce ZnO to Zn.

163