MODULE FOR EXTRACTIVE

METALLURGY

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 CHAPTER 1
MINERAL PROCESING
Mineral is a substance having definite chemical composition and internal atomic structure and formed by
the inorganic processes of nature. Minerals are broadly classified into two types:

1. Metallic minerals: are the minerals from which a metal is extracted

2. Non-metallic minerals: are the minerals used for industrial purposes for making cement,
refractories, glass and ceramics, insulators, fertilizers etc. These minerals are also called
industrial minerals.
IMPORTANT TERMINOLOGY
Minerals do not occur singly in the earth’s crust. They occur in association with several other
minerals. The following important terminology is used in describing the mineral deposits and
related terms.

Rock is an aggregation of several minerals as occurred in the earth’s crust.

Ore is also an aggregation of several minerals from which one or more minerals can be
exploited/separated at profit.

All Ores are Rocks, but all Rocks are not Ores. An Ore at one place may be a Rock at other place
Ore Minerals or Valuable Minerals are those minerals which contain an economically exploitable
quantity of some metal or non-metal.
Ore Deposits are the natural deposits of ore minerals. Ore is an aggregation of valuable and
gangue minerals.
Gangue Minerals are usually the non-metallic minerals associated with ore minerals which are
worthless as a source for that metal or otherwise. These are usually unwanted, waste or useless
minerals.
Simple Ore is one from which a single metal can be extracted. For example, only Iron is
extracted from Hematite ore, Aluminum is extracted from Bauxite ore, Chromium is extracted
from Chromite ore, etc.
Complex Ore is one from which two or more metals can be extracted. Lead, Zinc and Copper
metals are extracted from Lead-Zinc-Copper Ore
Metal Content of a mineral is generally expressed in percent of metal present in the mineral.
It is calculated by taking the atomic weights of the elements present in the mineral.

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Assay Value or Tenor is the percent metal, percent valuable mineral, or ounces precious metal
per ton depending upon the type of ore involved. Grade is a relative term used to represent the
value of an ore.

High Grade Ore is an ore having a high assay value and Low Grade Ore is an ore having a low
assay value. The Ore having an assay value between that of high and low value is called Medium
Grade Ore.
Rich Ore and Lean Ore are the other terms of common usage where an ore with a high assay
value is rich ore and an ore with low assay value is lean ore.

MINERAL BENEFICIATION

Mineral Beneficiation can be defined as processing of raw minerals to yield marketable products
and waste by means of physical or mechanical methods in such a way that the physical and
chemical identity of the minerals are not destroyed. It follows that mineral beneficiation is a
process designed to meet the needs of the consumer of minerals. Run-of-mine Ore is an ore
directly taken from the mine, as it is mined

Smelting operation, for the extraction of a metal, requires:

• Uniform quality of the ore.
• Appropriate size of the ore.
• Minimum tenor of the ore.

The reasons for the increasing importance of Mineral Beneficiation are;

1 Reserves of good quality ore (high grade ore) are depleting day by day as much of
such ore is continuously mined and utilized for extraction of metal and hence it is
unavoidable to use low grade ores (which need beneficiation) for metal extraction
to meet the demands.

2 In order to use un-mined reserves of a particular mine, switching over from Selective
mining to a cheaper mining method, Bulk mining, is found to be more Economical wherein
beneficiation is a must.

3 When compared to metallurgical processes Mineral Beneficiation is inexpensive.

The principal steps involved in beneficiation of Minerals are:

1. Liberation: Detachment or freeing of dissimilar particles from each other i.e. valuable
mineral particles and gangue mineral particles.
Liberation is the first and the most important step in Mineral Beneficiation.
Liberation: It can be defined as the freeing or detachment of dissimilar mineral grains.
The operation employed to liberate the dissimilar mineral grains is Size reduction or
Comminution.

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  Operations
 Crushing
 Grinding
 Screening

2. Separation: Actual separation of liberated dissimilar particles i.e., valuable mineral particles
and gangue mineral particles.
 Operations
 Gravity concentration
 Flotation
 Magnetic separation
 Electrical separation
 Miscellaneous operations like hand sorting

Free particles: If the particles of ore consist of a single mineral, they are termed as Free
particles.
Locked particles: If the particles of ore consist of two or more minerals, they are termed as
locked particles. If the locked particles contain valuable minerals at considerable quantity, they
are termed as middling particles.
Grain size: It is the size of a mineral as it occurs in the ore.
Particle size: It is the size of any particle whether free or locked particle.

Liberation size: It is the size of a mineral particle at which that mineral is completely liberated.
It is the size of a free particle of required (valuable) mineral.

COMMINUTION OPERATIONS
The operation of applying a force on the particle to break it is called size reduction.
Comminution is a general term for size reduction that may be applied without regard to the
actual breakage mechanism involved The run-of-mine ore is quite coarse and cannot be reduced
to fine size in one stage. It may require three or more stages. Each stage requires separate
equipment.
The comminution operations are divided into two broad groups as follows:

1 Crushing; is a size reduction operation wherein large lumps are reduced to fragments
or smaller particles.
2 Grinding; is considered as size reduction of relatively coarse particles to the ultimate
fineness.

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 OBJECTIVES OF COMMINUTION
The following are some of the objectives of comminution:
1. Reduction of large lumps into small pieces.
2 .Production of solids of desired size range.
3 .Liberation of valuable minerals from gangue minerals.
4 .Preparation of feed material for different beneficiation operations.
5 .Increasing the surface area for chemical reaction.
6 .Convenience in handling and transportation.
Crushing is that operation or group of operations in a Mineral Beneficiation plant whose object is
to reduce large lumps to fragments, the coarsest particles in the crushed product being 1/20 inch
or more in size. The size of coarsest particles is 1/2 inch in many cases. The crushing action in
all crushing machines (crushers) results from forces applied to the particles by some moving part
working against a stationary or some other moving part. It is the first stage of size reduction. The
crushing action in all crushing machines (crushers) results from forces applied to the particles by
some moving part working against a stationary or some other moving part. It is the first stage of
size reduction.

Reduction ratio is a convenient measure for comparing the performance of different crushers.
The crushing is performed in stages, crushing may be divided into primary, secondary, tertiary
and quaternary stages based on the particle size.
Correspondingly, the crushers can be classified into five groups according to the size of the
product they produce.
1 Primary Crushers: Jaw crusher, Gyratory crusher.
2 Secondary Crushers: Reduction gyratory, Cone crusher, Rolls crusher.
3 Tertiary Crushers: Short-head cone crusher.
4 Fine Crushers: Impact crushers.
5 Special Crushers: Bradford Breaker, Toothed Roll crusher.
Lumps of run-of-mine ore usually of 1 m size is reduced to 100–200 mm size in heavy duty
primary crushers. The usual size of feed to secondary crushers is 600 mm and the product is
usually 10–100 mm size. In tertiary crushers, particles of 250 mm size are reduced to 3–25 mm
size.

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JAW CRUSHERS
Jaw crushers consist of two jaw plates set at an acute angle, called angle of nip, to each other
which forms a crushing chamber. One jaw is fixed and kept vertical, the other jaw is a movable
or swing jaw and is moved to approach and recede alternately from the fixed jaw. Motion to the
swing jaw is transmitted by pitman working on an eccentric and toggles. The material is fed
between the jaws and is alternately nipped and crushed. Single and Double Toggle Jaw crushers
are shown in Figure below.

a) Single toggle jaw crusher; (b) Double toggle jaw crusher.

GYRATORY AND CONE CRUSHERS

Gyratory and Cone crushers are of similar in construction and working. They consist of two
vertical truncated conical shells of which the outer hallow conical shell is stationary and the
inner solid conical shell is made to gyrate. In a gyratory crusher the inner conical shell is
pointing up and outer conical shell is pointing down. The reduction ratio varies from 3 to 10. The
cone crusher is a modified gyratory. Both the outer and inner conical shells are pointing up.

Figure ; Cut section of Fuller-Traylor gyratory crushers

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ROLL CRUSHERS
Roll Crusher consists of two smooth heavy horizontal cylinders revolving towards each other
and the feed material is nipped between the rolls and pulled downward through the rolls by
friction. The distinguished feature of a roll crusher is that the material is crushed one time only
whilst it is passing through the crushing chamber. Due to this fact, the reduction ratio of a roll
crusher varies from 2 to 4, the lowest among all the crushers. Production of fines is minimum.
They can handle friable, dry, wet, sticky, frozen, and less abrasive feeds well.

Roll crusher

IMPACT CRUSHERS
Impact crushers reduce the particles by impact forces applied through sharp blows of fixed or
free swinging hammers revolving about central rotor at high speed to the free falling particles
against stationary surfaces. They are used for relatively soft, friable, and sticky ores such as
phosphates, limestone, clay, graphite and coal. Hammer mill is one type of impact crusher.

Hammer mill.

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Grinding
Grinding is the last stage of the comminution process. The particles are reduced from a
maximum upper feed size of 3/8 inch, to some upper limiting product size ranging between 35
mesh and 200 mesh (420 microns and 74 microns). Grinding is performed in rotating steel
vessels knows as tumbling mills or grinding mills. They are free to move inside the rotating
shell making the particles break by repetitive blows and by rolling and sliding one over the other.

Attrition, or shearing, forces which result from the application of forces by rolling and sliding
bodies tend to produce more fine particles than impact forces applied on particles by repetitive
blows. Grinding mills can be operated wet or dry, batch-wise or continuously.

Grinding mills are classified as Ball mill, Rod mill, Tube or Pebble mill, and Autogenous mill on
the basis of grinding medium and shell proportions. In ball mills, the grinding medium is steel
balls; in rod mills, steel rods; in tube or pebble mills, pebbles of hard rock or other nonmetallic
material; in autogenous mills, coarse ore particles.

BALL MILL
Ball mill uses steel or iron balls as grinding medium. Ball mills usually have a length to diameter
ratio of 1.5 to 1.0. According to the shape of the mill, the ball mills are classified as
cylindroconical and cylindrical mills. As the mill rotates, the balls are lifted to certain height and
then dropped. Grinding of ore particles takes place due to simple rolling of one ball over the
other (cascading) and by the free fall of balls (cataracting).

Cascading leads to fine grinding whereas cataracting leads to coarse grinding. As the speed of
the mill increases, the balls are lifted higher and a stage is reached where the balls are carried
around the shell and never allowed to fall. That means centrifuging occurs. The balls will rotate
as if they are part of the shell. The speed at which centrifuging occurs is known as critical speed.
An expression for the critical speed is given by

Where D and d,are the diameter of the Mill and the ball in meters

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 Figure Motion of the charge in a ball mill.

ROD MILL
A rod mill uses rods as a grinding medium. Length to diameter ratio is between 1.5 and 2.5. Rods
are a few centimeters shorter than the length of the mill to avoid any jamming of rods in the mill.
The rods are kept apart by the coarsest particles. The grinding action results from line contact of
the rods on the ore particles and is exerted preferentially on the coarsest particles. Smaller and
fine particles do not grind till the coarsest particle is reduced in size. Thus the rod mill produces
a more closely sized product with little oversize or slimes. Hence the rod mills may be
considered as coarse grinding machines.

Figure ; Grinding action of rods.

TUBE OR PEBBLE MILL

A tube mill is a grinding mill where length to diameter ratio is 3 to 5. It is also known as a
pebble mill as it uses ceramic pebbles made of flint or porcelain as the grinding media. As
pebbles are fragile, pebble mills are smaller in diameter. Because of low specific gravity of
pebbles, large quantity of pebbles has to be used to attain required grinding for equivalent duty
as compared with ball mills. Pebble mills are used when iron contamination in the product is
highly objectionable such as in the manufacture of paints, pigments, cosmetics, etc.

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AUTOGENOUS MILL
Autogenous mill use coarse ore particles as grinding medium. Grinding is achieved by the action
of ore particles on each other when particles of ore of different sizes are rotated together in a
tumbling mill. The mill is of very large in diameter. The larger particles in the feed must be
sufficient in size and number to break the smaller particles as fast as they themselves are broken
down in the mill. Autogenous grinding greatly reduces metal wear and also reduces the number
of crushing and grinding stages as compared to conventional size-reduction operations, thus it
offers the possibilities of large savings in capital and operating costs. However, it is practical for
only a limited number of ore types.

WET AND DRY GRINDING

The grinding may be wet or dry depending on the subsequent process and the nature of the
product. Wet grinding is generally used in mineral beneficiation plants as subsequent operations
for most of the ores are carried out wet. Wet grinding is usually carried out with 20–35% water
by weight. The chief advantages of wet grinding are increased capacity (as much as 15%) for a
given size of equipment and less power consumption per ton of the product.

Low power consumption is due to the penetration of water into the cracks of the particles which
reduces the bond strength at the crack tip.

Dry grinding is used whenever physical or chemical changes in the material occur if water is
added. It causes less wear on the liners and grinding media. Dry grinding mills are often
employed to produce an extremely fine product. This arises from the high settling speed of solids
suspended in air as compared with solids suspended in water.

SCREENING
Screening is an operation used for the separation of particles according to their sizes. Sieving and
screening are distinguished by the fact that sieving is a batch process used almost exclusively for
test purposes, whereas screening is a continuous process and is used mainly on an industrial
scale. Sieves are manufactured with definite dimensions and standard aperture sizes.

Screens can be manufactured with any dimension and any aperture sizes as per the requirement.
In industrial screening, the particles of various sizes are fed to the screen surface. The material
passing through the screen aperture is called underflow (undersize or fines) while the material
retained on the screen surface is called overflow (oversize or coarse).

PURPOSE OF SCREENING
Industrial screening is used:
1. To remove oversize material before it is sent to the next unit operation as in closed
circuit crushing operations.
2. To remove undersize material before it is sent to the next unit operation which is
set to treat material larger than this size.
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 3. To grade materials into a specific series of sized (finished) products.
4. To prepare a closely sized (the upper and lower size limits are very close to each
other) feed to any other unit operation.

Screening is generally used for dry treatment of coarse material. Dry screening can be done
down to 10 mesh with reasonable efficiency. Wet screening is usually applied to materials from
10 meshes down to 30 mesh (0.5 mm) but recent developments in the Sieve Bend Screen have
made the wet screening possible at the 50 micron size.
Screen sizes are classified according to the number of openings per inch square and are referred
to as mesh sizes.
SEPARATION OF ORE PARTICLES ACCORDING TO THEIR SIZE

Separation of ore particles according to a property where valuable mineral particles are different
from gangue mineral particles in that property Operations:

 Gravity Separation or Concentration

 Classification
 Flotation
 Magnetic Separation
 Electrical Separation
 Dewatering

Gravity Concentration is a method of separating the mineral particles based on their specific
gravities when they are allowed to settle in a fluid medium. Some idea of the type of separation
possible can be gained from the ratio, called concentration criterion, and is defined as:

Where; ρh ,is the density of the heavy mineral,

ρl is the density of the light mineral, and
ρf is the density of the fluid medium.

This ratio is a comparison of the buoyancy forces which are at work. In general, when this ratio
is greater than 2.5, whether positive or negative, then gravity separation of particles down to 75
micron size is possible. As the value of this ratio decreases, the efficiency of separation
decreases, and if it is below 1.25, gravity concentration is not commercially feasible in general.

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Another (heavier) fluid, or a pseudo fluid medium heavier than H2O, is needed. An alternative is
to alter the effective particle density by causing it to adhere to an air bubble as in flotation.
The motion of a particle in a fluid depends not only on its specific gravity but also on its size;
large particles will be affected more than smaller ones. The efficiency of gravity concentration
operation, therefore, increases with particle size. Smaller particles respond poorly because their
movement is mainly dominated by surface friction. In practice, close size control of feeds to
gravity processes is required in order to reduce the size effect and make the particles move
depending on their specific gravities.

FLOAT AND SINK

Float and sink, also called Heavy Liquid separation (HLS), is an operation where particles of
different specific gravities are separated by using a suitable heavy liquid. The principle of float
and sink is: When two particles of different specific gravities are introduced in a liquid having
specific gravity intermediate between that of the two particles, the lighter particle would float
and the heavier particle would sink.

CLASSIFICATION
Classification is a method of separating mixtures of particles of different sizes, shapes and
specific gravities into two or more products on the basis of the velocity with which the particles
fall through a fluid medium i.e., settling velocity.
Generally classification is employed for those particles which are considered too fine to be
separated efficiently by screening. The basic principle of classification is: The coarser, heavier
and rounder particles settle faster than the finer, lighter and more angular particles In
classification, certain particles are only allowed to settle in the fluid medium in order to separate
the particles into two fractions.

CLASSIFIERS
The units in which the separation of solids in fluid medium is carried out are known as
classifiers. These classifiers may be grouped into three broad classes as:
1. Sizing classifiers.
2. Sorting classifiers.
3. Centrifugal classifiers.
1. Sizing classifiers.
A typical sizing classifier consists of a sloping rectangular trough. Feed slurry is introduced at
point 1 as shown in Figure 13.2 fines overflow at point 2. The rate of feed and distance between
point 1 and point 2 is selected in such a way that the rate of travel of required fine particles must
be more than the rate of their settling so that all the required fine particles overflow at point 2.
The coarse particles settle to the bottom. To remove these coarse particles, a mechanical means

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such as spiral or rake is placed at the bottom of the trough. Figure below shows how the particles
are separated in Spiral and Rake classifiers.

Figure ;Principle of a mechanical classifier

Sizing classifiers are the mechanical classifiers. Since the stream of slurry consists of fines flow
horizontally from the feed inlet to the overflow weir, these are also called as horizontal current
classifiers. They are also called pool classifiers as the classification takes place in the pool. These
classifiers are extensively used in closed circuit grinding operation with a ball mill where
underflow coarse product is directly fed to the inlet of the ball mill.

Figure; (a) Spiral classifier; (b) Rake classifier

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2. Sorting classifiers
Sorting classifiers employ the hindered settling conditions to increase the effect of density in
order to separate the particles according to their density rather than size. The feed slurry is
introduced centrally near the top of the first sorting column. A current of water known as
hydraulic water is introduced at the bottom of the sorting column at a velocity slightly less than
the smallest heavy particle among the particles required to be discharged in the first sorting
column. All those particles having settling velocity less than that of rising water velocity will not
settle and rise to the top of the column and fed to the second column.

The particles, having a settling velocity more than that of the rising water velocity, settle to the
bottom of the first sorting column and get discharged through the spigot. The velocity of the
hydraulic water in the second sorting column is less than that of the velocity in the first sorting
column so that the particles of low settling velocity settle to the bottom of the second sorting
column and get discharged through the spigot. Similarly the particles with still low settling
velocity are obtained through the spigot of third sorting column and remaining particles are
obtained as overflow from the third sorting column.

Figure Principle of sorting classifier

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 Figure Hydraulic classifier with sizing effect

3. Centrifugal classifiers

Under gravity force, the settling rate of a particle varies as its effective mass. If a centrifugal
force is applied, the effective mass increases and therefore settling rate increases. As particles are
ground smaller they reach a size where the surface drag against the surrounding fluid almost
neutralizes the gravitational pull, with the result that the particle may need hours, or even days,
to fall a few inches through still water. This slowing down of the settling rate reduces the
tonnage that can be handled and increases the quantity of machinery and plant required. By
superimposing centrifugal force, the gravitational pull can be increased from 50 to 500 times
depending on the pressure at which the pulp is fed and the size of the vessel. The hydro cyclone
is one which utilizes centrifugal force to accelerate the settling rate of particles. Hydro cyclone
has no moving parts. It consists of a cylindrical section with a tangential feed inlet.

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 Figure; Hydro cyclone operation

Froth flotation
In a beaker of water, if air is introduced from the bottom, air bubbles are produced and rise to the
surface of the water as the density of an air bubble is much less than that of water. Similarly air
bubbles also rise if air is introduced in a pulp containing mineral particles. If a mineral particle of
high density adheres to the air bubble, the air bubble along with the mineral particle rises to the
surface because the apparent density of the air bubble and the adhered mineral particle is less
than that of water. If many mineral particles are adhered to the air bubble, still the air bubble
rises to the surface as the apparent density of the air bubble and adhered mineral particles is less
than that of water due to the relatively large volume of the air bubble. This concept is the basis
for froth flotation operation.
The required mineral particles after adhering to the air bubble float to the surface along with the
air bubble. The aggregation of several such mineral adhered air-bubbles forms the froth on the
surface of the pulp. Hence this operation of mineral separation is named Froth flotation.
Flotation is a method of separating the minerals in a relatively finely divided state. It utilizes the
differences in physico-chemical surface properties of particles of various minerals. This method
can only be applied to relatively fine particles (less than 150 µm). If the particles are too large,
the adhesion between the particle and the bubble is less than the weight of the particle and the
bubble drops the mineral particles. The air bubbles can only stick to the mineral particles if they
can displace water from the mineral surface. This can only happen if the mineral is water
repellent or hydrophobic. Air bubbles, after reaching the surface, can continue to hold the
mineral particles if they can form a stable froth. If not, air bubbles will burst and drop the
mineral particles.

In order to achieve the favorable conditions for froth flotation, the pulp is treated with various
chemical reagents known as flotation reagents. The chemicals used for treating the mineral

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particles to make them to adhere to the air bubbles are called collectors and the chemicals used
to increase the life of the air bubbles are called frothers.

Figure Process of rising air bubbles and forming froth.

Magnetic separation
Magnetic separation is a physical separation of particles based on the magnetic property of the
mineral particles. The property of a material which determines its response to a magnetic field is
the magnetic susceptibility. According to the Weber’s theory of magnetism, molecules of all
substances are basically magnets in themselves, each having a north and south pole. In a magnet,
these molecular magnets lie in line so that north poles of molecular magnets are on one end and
south poles on the other. Thus, two definite poles N and S are developed at the ends.
TYPES OF MINERALS
Based on magnetic susceptibility, minerals are classified into three broad groups as
Ferromagnetic, Paramagnetic and Diamagnetic.
Ferromagnetic minerals have a very high susceptibility to magnetic forces and retain some
magnetism when removed from the magnetic field. They are strongly attracted by the magnetic
field. They can be concentrated by low-intensity magnetic separators. The principal
ferromagnetic mineral separated is magnetite (Fe3O4).
Paramagnetic minerals are weakly attracted by magnetic field. They can be concentrated by
high-intensity magnetic separators. Examples of paramagnetic minerals are ilmenite (FeOTiO2),
rutile (TiO2), wolframite ((Fe,Mn)WO4), hematite (Fe2O3), siderite (FeCO3), chromite
(FeOCr2O3), pyrrhotite (FeS) and manganese minerals. Hematite and siderite can be roasted to
produce magnetite and can be separated by low-intensity magnetic separators.
Diamagnetic minerals are repelled along the lines of magnetic force to a point where the field
intensity is smaller. The forces involved here are very small. They cannot be concentrated
magnetically. Examples are quartz (SiO2) and feldspar (KAlSi3O8 or NaAlSi3O8

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MAGNETIC SEPARATORS

The machines used for magnetic separation are called magnetic separators. The principle
operation of a magnetic separator is: When a stream of ore particles is continuously passed
through a field of magnetic force, the magnetic particles are attracted towards the source of
magnetic force while the non-magnetics travel unaffected.
Magnets used in magnetic separators are of two types; Permanent magnets and Electromagnets.
Permanent magnets are magnetized steel bars which retain magnetism indefinitely. Bars of soft
wrought iron, soft steel or cast iron are magnetized by electric currents through the insulated
copper or aluminum wireindings around the iron bars. These iron bars form electromagnets as
long as the current flows through the windings.

Magnetic separators, can be classified into two groups based on their function:
1, Tramp iron magnetic separators ;are those used to remove tramp iron and protect
the handling and processing equipment.
2, Concentrators; are those used to separate the bulk of magnetic materials from a
stream of ore.

Magnetic separators that are used to remove small quantities of deleterious magnetic material
from a product (e.g. from china clay) are termed as purifiers. The concentrators that remove
magnetic material from a product and return to the process are termed as reclaimers.

ELECTRICAL SEPARATION
Electrical separation is a physical separation of particles based on the electrical properties of the
mineral particles. The following are the three important electrical separation processes:

1. Electrostatic separation.
2 .Electro dynamic (High Tension) separation.
3 .Dielectric separation.

1. Electrostatic separation.
The basis of any electrostatic separation is the interaction between an external electric field and
the electric charges acquired by the various particles. Particles can be charged by:
A. Contacting dissimilar particles. In charging by contacting dissimilar particles,
particles placed on surface are made to repeatedly contact one another as well as the
surface; the surface will acquire electrons from one type of particles and give electrons to
another type so that two types of particles are charged with opposite charges.
B. Conductive induction. In charging by conductive induction, the particles are placed
on a ground conductor in the presence of an electric field. Then the particles will rapidly
develop a surface charge by induction. Both conducting and non-conducting particles will

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 become polarized, but conducting particles will have an equi-potential surface through its
contact with the grounded conductor. The non-conducting particle will remain polarized.

In an electrostatic separator ), a large single electrode produces a strong electric field. When a
particle is placed on the grounded rotor in the region of the electrostatic field influence, the
particle rapidly develops a surface charge by induction. Whether the particle is a conductor or
non-conductor, it will be polarized. However, a conducting particle rapidly becomes an equi-
potential surface and has the same potential as the ground rotor. Therefore it is attracted towards
the electrode, drawn away from the surface, and falls by gravity. The non- conducting particle
continues to adhere to the rotor until it falls by gravity.

Figure Electrostatic separator

DEWATERING
Dewatering is the separation of pulp(Slurry) into two parts, one is relatively solid-free and the
other is relatively liquid-free, with respect to original pulp. As most of the mineral beneficiation
operations are conducted by the use of substantial quantities of water, the products are obtained
in the form of pulp. Hence water has to be removed from the Slurry to get the final product in
dry form. The removal of water from the pulp is called dewatering. If the solid particles in the
pulp are relatively coarser, screening the pulp results in removal of water by passing the water
through apertures and retaining the solid particles on the screen. Draining is a fairly effective
method to remove water from coarse sands, but if fine sands and slimes are present, they tend to
run off with the water.

Dewatering usually in the following three stages:

1 Sedimentation.
2 Filtration.
3 Drying.

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Sedimentation means gravity settling or subsidence of solids suspended in liquid. This
operation, coupled with continuous overflow of water and withdrawal of partially dewatered
solids (thick pulp) from the bottom, is called thickening. Much of the water is first removed by
the thickening operation and the thick pulp so obtained is then filtered to produce moist filter
cake. The filter cake, in many cases, is subjected to further processing directly. When it is
required to eliminate the moisture, the filter cake is dried thermally to about 95% solids by
weight. Removal of water by drying is the most expensive operation. Hence it is usual practice to
eliminate as much water as possible by filtration, leaving only the moisture contained in the filter
cake for removal by thermal drying.

Thickening is an operation of concentrating a relatively dilute slimy pulp into a thick pulp by
allowing solid particles to settle under the influence of gravity force. Thickening is also
considered as a classification with a difference that in thickening all the 130 Mineral
beneficiation solid particles are allowed to settle whereas in classification only certain solid
particles are allowed to settle

Figure Batch sedimentation test.

Filtration is the separation of finely divided solid particles from a fluid by driving the pulp to a
membrane or septum (commonly called as the filter medium), porous to the fluid but impervious
to the solid, through which the fluid called filtrate passes.

The volume of filtrate collected per unit time is termed as the rate of filtration. As the filtration
process proceeds, solid particles accumulate on the filter medium forming a packed bed of solids
called filter cake. Pressure difference between two sides of filter medium, more pressure at the
upstream side and less pressure at the downstream side, is the driving force.

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 CHAPTER 2
PYRO METALLURGY
The basic premise of most pyro metallurgical operations is simple: high-temperature chemistry
is employed to segregate valuable metals in one phase while rejecting gangue and impurities in
another phase. In most instances, both phases are molten. The gas phase may also be used to
advantage, either as a means of separating valuable volatile constituents or for removing
unwanted volatile impurities. These separation techniques form the basis of thermal smelting and
refining operations.
Pyro metallurgy is a branch of extractive metallurgy. It consists of the thermal treatment of
minerals and metallurgical ores and concentrates to bring about physical and chemical
transformations in the materials to enable recovery of valuable metals. Pyro metallurgical
treatment may produce saleable products such as pure metals, or intermediate compounds or
alloys, suitable as feed for further processing. Examples of elements extracted by pyro
metallurgical processes include the oxides of less reactive elements like Fe, Cu, Zn, Chromium,
Tin, and Manganese.
Pyro metallurgical processes are generally grouped into one or more of the following categories:

 Calcining
 Roasting
 Smelting
 Refining

Most pyro metallurgical processes require energy input to sustain the temperature at which the
process takes place. The energy is usually provided in the form of fossil fuel combustion,
exothermic reaction of the material, or from electrical heat. When enough material is present in
the feed to sustain the process temperature solely by exothermic reaction (i.e. without the
addition of fuel or electrical heat), the process is said to be “autogenous.”
In metal extraction, a vast majority of metallurgical reactions are made to take place at elevated
temperatures because than the ore compounds become relatively unstable, facilitating the release
of the metal. This is the basis of pyro metallurgy. Pyro metallurgy deals with the methods of
extraction of metals from their ores and their refining and is based on physical and chemical
changes occurring at high temperatures, i.e. 500-2000°C.

21
Pyro metallurgical methods of metal production are usually cheaper and suited for large scale
productions. Some of the noteworthy advantages of pyro metallurgy are:

 Reaction rates are greatly accelerated at high temperatures. So small units can achieve
high production rates.

 Some reactions which are not thermodynamically possible at low temperature become
possible at high temperatures.

 At high temperatures the products get melted or vaporized which makes easy, the
physical separation of product metal from the gangue. Example; Meta-Slag separation.

 Pyro metallurgy can bring about the reduction of a compound, which cannot take place in
presence of water i.e. it has got ability to extract the reactive metals which can’t be
reduced from aqueous solutions. Ex. Alkaline earth metals, zirconium, titanium etc.

Drying
Drying is thermal removal of liquid moisture (not chemically bound) from a material. Drying is
usually accomplished by contacting the moist solids with hot combustion gases generated by
burning fossil fuels.
In some cases, heat for drying can be provided by hot air or inert gas that has been indirectly
heated. The amount of heat required for a given drying operation corresponds to the heat
required to vaporize the liquid moisture, the heat required to raise the temperature of the products
(dry solids and water vapor) to the final drying temperature, and heat required to offset radiant
heat losses. Usually, the drying temperature is set at a nominal value above the boiling point of
water, often about 120°C. Drying of moist solids is carried out in several types of industrial
dryers, including rotary dryers, fluidized bed dryers, and flash dryers.

Rotary Dryer: The rotary dryer is a type of industrial dryer employed to reduce or
minimize the liquid moisture content of the material it is handling by bringing it into
direct contact with a heated gas. A rotary dryer is suitable to dry metallic and non-
metallic mineral, clay in cement industrial and coal slime in coal mine, etc. Rotary dryers
can be widely used to dry various materials, and are simple to operate.

Fluidized bed dryer (also called fluid bed dryer) is a kind of equipment to reduce the
moisture content. In fluidization process, hot air is introduced at high pressure through a
perforated bed of moist solid particulate. The wet solids are lifted from the bottom and
suspended in a stream of air (fluidized state). Heat transfer is accomplished by direct
contact between the wet solid and hot gases. The vaporized liquid is carried away by the
drying gasses. Sometimes to save energy, the exit gas is partially recycled.

22
 Flash Dryers: Wet material is dispersed into a stream of heated air (or gas) which
conveys it through a drying duct. Using the heat from the airstream, the material dries as
it is conveyed. Product is separated using cyclones, and/or bag filters. Typically, cyclones
are followed by scrubbers or bag filters for final cleaning of the exhaust gases to meet
current emission requirements.

Calcining
Calcining is thermal decomposition of a material. Calcining is
 Process of heating the ore at a temperature not sufficient to melt the ore, in the
absence of air; and
 In calcination, we use the process of heating the ore because this is a thermal
treatment process at the same time. All of these are thermal treatment process. But
we do it in the absence of air.
 Air is mixture of different gases. Nitrogen has the most percentage followed by
oxygen. Between nitrogen and oxygen, we only need oxygen to generate fire. .
 Exothermic reactions materials or the chemicals produce their own heat as the
process is being continued. Complete opposite of endothermic wherein we need
heat from the outside to generate heat to the material.
 Converts carbonate ores into oxides.

CaCO3 CaO + CO2 Calcite/Aragonite

MnCO3 MnO + CO2 Manganese Carbonite

In calcination, we heat the ore in a temperature without melting [Link] of

heating the ore at a temperature not sufficient to melt the ore, in the absence of
air; and o In calcination, we use the process of heating the ore because this is a
thermal treatment process at the same time. All of these are thermal treatment
process. But we do it in the absence of air. o Fuel, Air, Heat. o Air 3 mixture of
different gases. Nitrogen has the most percentage followed by oxygen. Between
nitrogen and oxygen, we only need oxygen to generate fire. o Exothermic
reactions 3 materials or the chemicals produces their own heat as the process is
being continued. Complete opposite of endothermic wherein we need heat from
the outside to generate heat to the material.

 Converts carbonate ores into oxides.

CaCO3 CaO + CO2 Calcite/Aragonite
MnCO3 MnO + CO2 Manganese Carbonite
In calcination, we heat the ore in a temperate without melting it.

23
Roasting
Roasting consists of thermal gas-solid reactions, which can include oxidation, reduction,
chlorination, sulfation, and pyro hydrolysis. The most common example of roasting is the
oxidation of metal sulfide ores.

 The metal sulfide is heated in the presence of air to a temperature that allows the
oxygen in the air to react with the sulfide to form sulfur dioxide gas and solid
metal oxide.

2Cu2S+3O2 2Cu2O+2SO2 -Chalcocite

 The solid product from roasting is often called “calcine.” In sulfide roasting, if the
temperature and gas conditions are such that the sulfide feed is completely
oxidized, the process is known as “dead roasting.”
 Sometimes, as in the case of pre-treating reverberators or electric smelting furnace
feed, the roasting process is performed with less than the required amount of
oxygen to fully oxidize the feed.
 In this case, the process is called “partial roasting,” because the sulfur is only
partially removed.
 Finally, if the temperature and gas conditions are controlled such that the sulfides
in the feed react to form metal sulfates instead of metal oxides, the process is
known as “sulfation roasting.”
 Sometimes, temperature and gas conditions can be maintained such that a mixed
sulfide feed (for instance a feed containing both copper sulfide and iron sulfide)
reacts such that one metal forms a sulfate and the other forms an oxide, the
process is known as “selective roasting” or “selective sulfation.”

Smelting
Smelting involves thermal reactions in which at least one product is a molten phase. Metal
oxides can then be smelted by heating with coke or charcoal (forms of carbon), a reducing agent
that liberates the oxygen as carbon dioxide leaving a refined mineral.
Concern about the production of carbon dioxide is only a recent worry, following the
identification of the enhanced greenhouse effect. Carbonate ores are also smelted with charcoal,
but sometimes need to be calcined first. Other materials may need to be added as flux, aiding the
melting of the oxide ores and assisting in the formation of a slag, as the flux reacts with
impurities, such as silicon compounds.
Fluxes are added to facilitate slag formation, it also breaks down and lowers the melting point of
all the other materials Fluxes are added to facilitate slag formation, it also breaks down and
Lowers the melting point of all the other materials Fluxes are added to facilitate slag formation,
it also breaks down and lowers the melting point of all the other materials

24
Fluxes are added to facilitate slag formation, it also breaks down and lowers the melting point of
all the other materials Fluxes are added to facilitate slag formation, it also breaks down and
lowers the melting point of all the other materials. Fluxes (i.e. limestone, borax, silica, dolomite)
- Is any substance that you introduce in the smelting of ores to promote fluidity and to remove
(pro jectionable) impurities in a form of slag.

25
 CHAPTER 3
HYDROMETALLURGY

Hydrometallurgy is part of the field of extractive metallurgy involving the use of aqueous
chemistry for the recovery of metals from ores, concentrates, and recycled or residual materials.
Hydrometallurgy is typically divided different general areas.

LIQUID–LIQUID OR SOLVENT EXTRACTION

Liquid–liquid or solvent extraction is a common process for selectively concentrating metals.

Liquid–liquid extraction is performed using an organic extractant that is dissolved in an organic
phase. The organic phase is allowed to contact an aqueous phase containing the dissolved metal
or metal ion complex. Thus, two liquids are used, hence the term liquid–liquid extraction. The
aqueous and organic phases are immiscible in each other.
The organic phase contains an extractant and a diluent. The diluent effectively dilutes the
extractant. The diluent commonly consists of paraffins, naphthenes, and alkyl aromatics.
Diluents are needed to facilitate pumping, processing, and settling of the extractant, which is
often viscous and difficult to manage without a diluent. The diluent also helps to distribute the
extractant more effectively in organic phase droplets. The diluent effectively extends the
presence of extractant at the droplet interface. Thus, the diluent is also referred to as the
extender. Solvent extraction is carried out using a mixer. The mixer disperses the organic phase
in the aqueous phase as small droplets. Small droplets enhance the extraction kinetics. A
schematic diagram of small-scale and industrial-scale solvent extraction systems are presented in
below.

Figure; Schematic diagram of a laboratory solvent extraction mixer and settler in

the loading stage.

26
 Figure; Schematic diagram of an industrial solvent extraction mixer and settler in
the stripping stage.

Types of Liquid–Liquid or Solvent Extractants

Two main events are required for liquid–liquid metal extraction. One event is dehydration. The
other event is charge neutralization. Because the extractants are organic, they do not have a high
tolerance for hydrated ions. The charge on the ions cannot be accommodated by the nonpolar
nature of most organic molecules. As oil and water do not mix, it is evident that ions that are
surrounded by water molecules do not mix in oil. The organic phase is essentially oil and does
not easily accommodate water. Thus, dehydration is an important liquid–liquid extraction step.
Three basic types of solvent extractants are used: ion-exchange, solvation, and coordination
extractants. Each type facilitates dehydration and charge neutralization. Coordination extractants
typically undergo ion exchange as part of the overall extraction process. Solvation extractants do
not formally exchange ions.

1. Ion-Exchange Extractants. Ion-exchange extractants include both basic and acidic

compounds. The basic extractants often have a net excess of hydrogen ions. These ions
are attracted to hydroxyl or other anions in solution. Some of these extractants are used in
the basic or alkaline pH range. Acidic extractants have a net excess of negative charge
that attracts cations. Acidic extractants are generally used in the acidic pH range. In acid,
hydrogen ions occupy active sites until exchanged with a metal cation. Some common
acidic
extractants are carboxylates, sulfonates, and phosphates. The basic extractants are nearly
always primary, secondary, tertiary, or quaternary amines.
2. Solvating Extractants. Solvating extractants are effectively neutral. Consequently, they
are sometimes referred to as neutral extractants. Solvating extractants remove metal ions
and complexes by first replacing solvating water molecules. The replacement of water
molecules with organic solvent molecules facilitates organic solubility. Next, ion
associations (usually through protonation) are made. These associations effectively
neutralize the overall charge. Most solvating extractants contain polar oxygen atoms that

27
 accept hydrogen ions. The accepted hydrogen ions associate with negatively charged
metal complexes.

Many metals form anionic complexes with chloride ions. The most common functional
groups in solvating extractants include ketones, ethers, esters, and alcohols. Examples of
solvating extractants are tri-n-butyl phosphate (TBP) and trioctyl phosphine oxide
(TOPO).

3. Coordination Extractants. Coordination extractants are often very selective for specific
ions because of the steric (atomic position constraints within a molecule) effects in the
extractant that limit extraction to ions within a very narrow range of size.

Coordination extractants act by spatially coordinating metal-bearing ions. The most

common type of coordination extractant is a chelating extractant. Chelating extractants
utilize ion dissociation and association to form a coordinated complex. Coordinating
extractants often have excess electron pairs on nitrogen or oxygen atoms. These pairs are
separated from each other at the ends of heterocyclic organic rings. The proximity of the
nitrogen and oxygen atoms on the ends of the rings aids in complex formation. Other
factors that assist in extraction include an easily removed hydrogen atom. The
hydrogenvoid creates a stable negative charge. The special arrangement between
nitrogen, neutral oxygen, and anionic oxygen is designed for specific metals. The
resulting structure is very selective. Typically, two of the extractant molecules coordinate
and bond with one divalent metal ion in a very specific manner. Coordinating
extractants for copper solvent extraction are often hydroxyoximes. Other general
extractants such as carboxylates are also effective.

General Principles of Solvent Extraction

Most extractants involve ion exchange. Hydrometallurgical extractions typically utilize ion-
exchange extractants. Often, extraction takes place in acidic media. Thus, acidic extractants are
commonly used. A typical extraction reaction can be expressed by

Note

 Solvent extraction is based on the chemical reaction or exchange of ions between

aqueous and organic phases.
 Maximum extraction is based on the thermodynamic equilibrium constraints for the
interaction of ions in aqueous and organic phases.

28
PRECIPITATION
Precipitation is a very common method for removing or recovering specific species from
solution. Precipitation is a common method for concentrating metal content and purifying
solutions. Iron is commonly removed from solution by precipitation. Ferric ions have low
solubility above pH 3. Many divalent metal ions such as ferrous ions are relatively soluble at low
and intermediate pH levels. This difference in solubility’s as a function of pH facilitates
separations. The differences in precipitation of metals at specific pH levels facilitate separations.
As an example, ferric ions are often separated from other divalent metal ions at pH values of 3–4
by selective precipitation.

The ferric ions are generally precipitated as ferric hydroxide. One industrially important example
of iron precipitation is found in zinc metal production. Precipitation can also be accomplished
using gasses and/or water. Ferrous iron, for example, can be precipitated as hematite by the
addition of oxygen and water.

In zinc metal production from zinc sulfide ore concentrate, the concentrate is often first calcined.
Calcined concentrate is leached in sulfuric acid to dissolve

the zinc. Iron also dissolves in the leaching process. Iron is separated from thezinc by
precipitation using hydroxide compounds. The resulting iron precipitate (jarosite [NH4, Na
Fe3(SO4)2(OH)6] or goethite [FeO·OH]) is removed from the zinc-bearing solution. The reactions
are as follows:

Precipitation is also practiced through contact reduction to produce metal. Precipitation is also
used to recover by-products from process solutions.

ADSORPTION
Carbon adsorption is a common method of species removal. Carbon is particularly adept at
removing low levels of dissolved ions. The activated carbon can be made from a wide variety of
organic starting materials. Items such as peach pits, coconut shells, and wood are used
for activated carbon. The material is converted into activated carbon by heating it in a low
oxygen environment.

29
Initially, the carbon source is carbonized by heating it to 500 ◦C with dehydrating agents to
remove water and impurities The carbon is then heated to 700–1000 ◦C with steam, carbon
dioxide, and/or air to volatilize residues, develop pore structures, and form functional groups.
Different types of carbon surfaces also provide active adsorption sites for dissolved ions.
Extraction using carbon adsorption is most often diffusion controlled.

There are several processing options for activated carbon use.

 The process of loading carbon from leaching solution without ore or concentrate
particles is known as carbon-in-column (CIC). The carbon is commonly partially
fluidized by the flow of leaching solution upward through CIC columns. Locating
columns at different elevations often creates the head pressure for solution flow.
CIC utilization requires particle/liquid separation after leaching, before CIC
loading.
 Exposure of the carbon to a gold leaching slurry or pulp with particles present
after leaching is known as the carbon-in-pulp (CIP) process. This process is often
operated similarly to CIC. However, the particles must be ground to fine particles
to facilitate a screen separation of the carbon from the pulp after adsorption.

Note;

 Activated carbon performance decreases with use unless it is regenerated.

Regeneration is often performed by thermal activation in a rotary kiln at 600–900
◦C (usually around 650 ◦C) in steam to remove organic debris. Thermal activation
is often preceded or followed by hydrochloric acid washing to remove inorganic
precipitates such as carbonates.

METAL DISTILLATION

Metal distillation is the thermodynamics process using the difference of boiling points of metal
alloy to separate them from each other. Usually, the metal of low boiling points is evaporated
from the liquid alloy and later the vapor is condensed in a separate container. In a distillation
system, by setting up condensing elements along the evaporation passage, the metal of high
boiling point gets condensed before taking away by the vapor. Consequently, low boiling point
metal are purified.

Distillation technology is applied for many industrial sectors to treat scrap/waste generated from
industrial production and daily use household, especially favored by high purity product
application. Certain metals such as Zinc and Mercury have a very low boiling point. So
on heating them they very readily vaporize. And of course, they leave behind their impurities. The
impure metal is heated beyond its melting point in a furnace and the vapors are reconverted to metals
once the impurities are separated.

30
 CHAPTER 4
ELECTROMETALLURGY
Electrometallurgy is the science of producing metals from metallic ores through the use of
electricity. It deals with both the use of electricity for various heating processes and the use of
electricity to produce chemical changes (a process called electrolysis). Electrometallurgy
involves the use of electric and electrolytic processes to purify metals and is commonly
employed at the end of the metals extraction chain, resulting in final product recovery. The two
most common processes are electrowinning and electrorefining

ELECTROWINNING
Electro winning is the electrolytic process of “winning” or recovering dissolved metal using an
applied potential. Electro-winning is the most common method of recovering metal from
solution in its metallic form.

An external power source supplies the potential and the current. An inert anode is
used to complete the circuit and the necessary counter reaction to metal recovery. Metal is
recovered at the cathode. Ions or molecules are reduced at the cathode. Molecules or ions are
oxidized at the anode. An electrolyte or ion-conducting medium must exist between the anode
and cathode. Water containing dissolved ions is a common electrolyte. Commercial electro-
winning in aqueous solutions often involves acid. The hydrogen ions in the acid as well as the
counter ions (usually sulfate) provide most of the solution conductivity. The primary electro-
winning parameters are potential and current.

Figure; Schematic diagram of a typical hydrometallurgical electro winning process.

31
Note that the anodic reaction occurs for the half-cell reaction with the highest equilibrium
potential. The anodic reaction is often the decomposition of water to hydrogen ions and oxygen.
The cathodic reaction is generally the reduction of metal to its metallic state. If the applied
potential is greater than the difference between the two half-cell reactions, electro-deposition of
the metal will occur. The rate of electrodeposition depends on the applied potential and the
associated electrochemical reaction kinetics. A significant overvoltage, η, is needed to allow the
water decomposition to occur at a reasonable rate. The over potential for the metal deposition is
generally not large.

Figure; Schematic diagram for electrowinning (E versus log|i|)

The applied voltage is related to the rate of the electro-winning as indicated in the diagram. If
the voltage is not greater than the difference between the half-cell voltages plus the reaction over
potentials and solution and contact resistance voltage drops, no electro-winning occurs. The
applied potential can be expressed mathematically as

ELECTROREFINING
The electro-refining of metals is similar to electro-winning. However, electro-refining utilizes
the desired metal of intermediate purity (95–99.5%) as the anode. Electro-refining is used to
purify metal such as smelted copper to achieve desired high purity levels. Electro refining
consists of electrolytically dissolving the desired metal from the anode. The dissolved metal is
electrodeposited on the cathode as shown in Figure below. Electro refining results in deposited

32
metal of higher purity than the anode. Much of the high purity copper produced in the world is
produced by electro-refining.

Electro refining is less energy intensive than electro winning.

 The potential difference between the two half-cell reactions is zero in electro
refining. Consequently, no energy is consumed to overcome differences in half-
cell potentials.
 In addition, the normally large water hydrolysis over potential is eliminated. The
over potentials for dissolution and plating of the metal are generally small. The
net outcome of these factors in copper electro refining is a 5- to 10-fold decrease
in the energy requirement.
 The applied voltage is generally between 0.2 and 0.35 V. The current efficiency is
often above 98%.

Figure; Schematic diagram of the electro refining process.

Figure; Schematic diagram of the relationship between electro-refining potentials and the
absolute value of the logarithm of the current density or rate of electro-refining per unit area.

33
 CHAPTER 5
TYPICAL FLOW SHEETS FOR EXTRACTIO OF
COMMON METALS
EXTRACTING COPPER FROM ITS ORES

The method used to extract copper from its ores depends on the nature of the ore. Sulfide ores
such as chalcopyrite (CuFeS2CuFeS2) are converted to copper by a different method from
silicate, carbonate or sulfate ores. Chalcopyrite (also known as copper pyrites) and similar
sulfide ores are the commonest ores of copper. The ores typically contain low percentages of
copper and have to be concentrated before refining (e.g., via froth flotation).

Figure : Chalcopyrite

The Process

The concentrated ore is heated strongly with silicon dioxide (silica) and air or oxygen in a
furnace or series of furnaces.
 The copper (II) ions in the chalcopyrite are reduced to copper(I) sulfide (which is reduced
further to copper metal in the final stage).
 The iron in the chalcopyrite ends up converted into an iron(II) silicate slag which is
removed.
 Most of the sulfur in the chalcopyrite turns into sulfur dioxide gas. This is used to make
sulfuric acid via the Contact Process.

34
An overall equation for this series of steps is:
2CuFeS2+2SiO2+4O2→Cu2S+2FeSiO3+3SO2 (1)

The copper(I) sulfide produced is converted to copper with a final blast of air.

Cu2S+O2→2Cu+SO2(2)

The end product of this is called blister copper - a porous brittle form of copper, about 98 -
99.5% pure.

Exploring the redox processes in this reaction

It is worthwhile spending some time sorting out what the reducing agent is in these reactions,
because at first sight there does not appear to be one! Or, if you look superficially, it seems as if
it might be oxygen! But that's silly! We'll start by looking at the second reaction because it is
much easier to see what is happening.

Cu2S+O2→2Cu+SO2(3)

Let's look at the oxidation states of everything.

 In the copper (I) sulfide, the copper is +1 and the sulfur -2.
 The oxidation states of the elements oxygen (in the gas) and copper (in the metal) are 0.
 In sulfur dioxide, the oxygen has an oxidation state of -2 and the sulfur +4.

That means that both the copper and the oxygen have been reduced (decrease in oxidation state).
The sulfur has been oxidized (increase in oxidation state). The reducing agent is therefore the
sulfide ion in the copper (I) sulfide.

The other reaction is more difficult to deal with, because you can't work out all of the oxidation
states by following the simple rules - there are too many variables in some of the substances.
You have to use some chemical knowledge as well.

2CuFeS2+2SiO2+4O2→Cu2S+2FeSiO3+3SO2 (4)

In the CuFeS2, you would have to know that the copper and iron are both in oxidation state +2,
for example. You would also have to know that the oxidation state of the silicon remains
unchanged at +4. So use that information to work out what has been oxidized and what reduced
in this case!

35
You should find that copper has been reduced from +2 to +1; oxygen (in the gas) has been
reduced from 0 to -2 (oxygen in the SiO2 is unchanged); and three of the four sulfurs on the
left-hand side have been oxidized from -2 to +4 (the other is unchanged). Once again, the sulfide
ions are acting as the reducing agent.

Extracting of Copper from Other Ores

Copper can be extracted from non-sulfide ores by a different process involving three separate
stages:

1. Reaction of the ore (over quite a long time and on a huge scale) with a dilute acid such as
dilute sulfuric acid to produce a very dilute copper (II) sulfate solution.
2. Concentration of the copper (II) sulfate solution by solvent extraction. The very dilute
solution is brought into contact with a relatively small amount of an organic solvent
containing something which will bind with copper (II) ions so that they are removed from
the dilute solution. The solvent must not mix with the water. The copper (II) ions are
removed again from the organic solvent by reaction with fresh sulfuric acid, producing a
much more concentrated copper(II) sulfate solution than before.
3. Electrolysis of the new solution. Copper (II) ions are deposited as copper on the cathode
(for the electrode equation, see under the purification of copper below). The anodes for
this process were traditionally lead-based alloys, but newer methods use titanium or
stainless steel. The cathode is either a strip of very pure copper which the new copper
plates on to, or stainless steel which it has to be removed from later.

Purification of copper

When copper is made from sulfide ores by the first method above, it is impure. The blister
copper is first treated to remove any remaining sulfur (trapped as bubbles of sulfur dioxide in the
copper - hence "blister copper") and then cast into anodes for refining using electrolysis.

Electrolytic Refining

The purification uses an electrolyte of copper(II) sulfate solution, impure copper anodes, and
strips of high purity copper for the cathodes. The diagram shows a very simplified view of a cell.

36
 At the cathode, copper (II) ions are deposited as copper.

Cu2+ (aq)+2e−→Cu(s)(5)

At the anode, copper goes into solution as copper (II) ions.

Cu(s) →Cu2+(aq)+2e−(6)

For every copper ion that is deposited at the cathode, in principle another one goes into solution
at the anode. The concentration of the solution should stay the same. All that happens is that
there is a transfer of copper from the anode to the cathode. The cathode gets bigger as more and
more pure copper is deposited; the anode gradually disappears. In practice, it isn't quite as simple
as that because of the impurities involved.

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.

37
EXTRACTION OF IRON

Iron, when extracted from iron ore such as hematite containing iron (III) oxide, Fe2O3, in a blast
furnace is called iron extraction blast furnace metallurgy. In this reduction reaction, oxygen is
removed from the iron (III) oxide to leave behind iron. Generally, the extraction of metals and
their isolation are based on three major procedures. The steps are:

1. Concentration of Ore

2. Extraction of metal from concentrated ore and

3. Purification of the metal

What is the Procedure of Extraction of Iron From its Ore?

Extraction of iron is a lengthy process which commences from Concentration through calcination
roasting. Water and other volatile impurities like sulfur and carbonates are removed by the
process of Concentration. The concentrated ore is blended with limestone (CaCO3) and Coke and
fed into a blast furnace from the top. Extraction of iron happens in the blast furnace. It is a very
lengthy and submissive procedure. The above process helps in separating the useful ingredients
from the waste materials like slag.

What is Calcination?
Calcination is the procedure of converting an ore into an oxide by heating it strongly. The
heating of ore is materialized below its melting point either in absence of air or in a controlled
supply. The carbonates and hydroxides are converted into their respective oxides by this
process. Calcination also separates the moisture and volatile impurities. Calcination may also be
termed as a thermal process which is used to convert ores and other solid materials by providing
thermal decomposition. decomposition of limestone (calcium carbonate) to lime (calcium oxide)
and carbon dioxide takes place by the method of calcination. The products from calcination are
termed as calcines.

CaCO3=CaO+CO2

What is roasting?
Roasting is a method of Metallurgy. It converts an ore into its oxide by heating it above the
melting point in the presence of excess air. While roasting is a process that is used for converting
sulfide ores, calcination is generally used in the oxidation of carbonates. Moisture and non-
metallic impurities in the volatile gasses are extracted during the process of roasting. Oxidation,

38
reduction, sulfation, chlorination and pyro-hydrolysis are included in the solid-gas thermal
reaction which is an important part of roasting.
The major drawback of the process is that roasting involves sulfides which are the main source
of air pollution. Apart from that, the process of releasing a large amount of metallic as well as
toxic and acidic compounds results in harm to the environment. When Zinc sulfide is converted
into zinc oxide that will be an example of roasting.
2ZnS+3O2=2ZnO+CO2
What are the Differences between Calcination and Roasting?
The major differences between the Calcination and Roasting are given in the following table:

Calcination Roasting

An ore is heated in the absence of air or air An ore is heated to higher than its melting
might be supplied in controlled way during the point in the presence of air or oxygen during
process of Calcination the process of Roasting

Thermal decomposition of carbonate ores occur Sulfide minerals are formed at the time of
in Calcination Roasting

Moisture is driven out from ore at the time of Roasting does not engross in any
Calcination dehydrating an ore

A large amount of toxic, metallic and acidic

Carbon dioxide is extracted at the time of
compounds are released at the time of
Calcination
roasting

What Happens in the Blast Furnace?

The concentrated ore is reduced to its liquid metal state in a chemical method in Blast Furnace. A
Blast Furnace is a giant, steel stack parallel with refractory brick where the concentrated ore,
coke and limestone are dumped from the top and a blast of steamy air is blown into the bottom.
All the three components are crushed into small round pieces and blended and put on a hopper
which regulates the input. Hot steamy air is blown from underneath and coke is burned to
capitulate temperatures up to 2200K. The maximum portion of heat for this process is produced
by burning coke.
Coke reacts with the oxygen in the hot air to generate Carbon Monoxide (CO) at such high
temperatures. After that, the CO and heat move in the upward direction to meet the raw material
coming down from the top. The temperature in the upper portion of the Blast Furnace is
eventually lower than the 2200K at the lower portion. Ferrous Oxide (FeO) is generated by
reducing Haematite (Fe2O3) and Magnetite (Fe3O4).The following reactions occur in the blast
Furnace at 500-800K in the upper portion with lower temperatures:

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 3Fe2O3+CO=2Fe3O4+CO2

Fe3O4+4CO=3Fe+4CO2

Fe2O3+CO=2FeO+CO2

In the lower portion of the Blast Furnace (at 900-1500K)

C+CO2=2CO
Fe+CO2= Fe+CO2
The limestone is also decomposed to CaO that separates the silicate impurity of the ore in the
form of Slag. It can be easily removed from the molten iron. Approximately 3-4% of Carbon and
little quantities of many other impurities like sulfur, Silicon etc are contained in the iron
manufactured in the Blast Furnace. The same is termed as Pig Iron. The strength is acutely
hampered by the impurities. Carbon plays a pivotal role in influencing the brittleness and
hardness balance in iron. The above component is melted again with scraps of iron and coke to
further reduce the carbon content in Pig iron. It is also subject to the blast of hot air. The above
kind of iron is termed as cast iron and contains slightly lower carbon content (2-3%). Cast iron is
harder than pig iron.

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 Figure; Iron Extraction Procedure
Iron extraction is considered as an extremely lengthy process that starts from concentration and
ends through calcination roasting. The process of concentration deals with the removal of water
and other volatile impurities like sulfur and carbonate. This is concentrated or is then blended
with limestone and coke and fed into the blast furnace from the top. The extraction of iron occurs
in the blast furnace. This process helps in separating the useful ingredients from the waste
materials like slag.
There are certain steps that are followed for the process of extraction and isolation of metals
from ores-

 Purification of metal

 Concentration of an ore

 Metal isolation from its concentrated ore.

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EXTRACTION OF STEEL

Much of the iron produced is refined and converted into steel. Steel is made from iron by
removing impurities and adding substances such as manganese, chromium, nickel, tungsten,
molybdenum, and vanadium to produce alloys with properties that make the material suitable for
specific uses. Most steels also contain small but definite percentages of carbon (0.04%–2.5%).
However, a large part of the carbon contained in iron must be removed in the manufacture of
steel; otherwise, the excess carbon would make the iron brittle. However, there is not just one
substance called steel - they are a family of alloys of iron with carbon or various metals.

Impurities in the iron from the Blast Furnace include carbon, sulfur, phosphorus and silicon,
which have to be removed.

 Removal of sulfur: Sulfur has to be removed first in a separate process. Magnesium

powder is blown through the molten iron and the sulfur reacts with it to form magnesium
sulfide. This forms a slag on top of the iron and can be removed.
Mg+S→MgS

 Removal of carbon: The still impure molten iron is mixed with scrap iron (from
recycling) and oxygen is blown on to the mixture. The oxygen reacts with the remaining
impurities to form various oxides. The carbon forms carbon monoxide. Since this is a gas
it removes itself from the iron! This carbon monoxide can be cleaned and used as a fuel
gas.

 Removal of other elements: Elements like phosphorus and silicon react with the oxygen
to form acidic oxides. These are removed using quicklime (calcium oxide) which is
added to the furnace during the oxygen blow. They react to form compounds such as
calcium silicate or calcium phosphate which form a slag on top of the iron.

Extraction of Zinc

Zinc Mining
The most commonly available ore used in the extraction of zinc is called zinc blende also known
as zinc sulphide (ZnS). Historically extraction of zinc has been more difficult than the extraction
of other metals because, at temperatures where metals such as iron typically begin to melt, zinc is
a gas. Due to its very low boiling point, at such temperatures, zinc will escape with exhaust
gases. Zinc blende does not contain a very high percentage of zinc and hence it needs to be
concentrated. The best concentration method for zinc ore is known as froth flotation.

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

Metal from Concentrated Ore

The next step in the extraction of zinc is called roasting. The concentrated ore is finely ground
into small pieces and then suspended in a rising stream of air. The sulphur content can be
reduced hugely with this process. This also converts the zinc blende to ZnO which is way more
reactive. The reaction occurring here is
2ZnS+3O2→2ZnO+2SO2

Zinc Oxide is then mixed with coke and ground into fine pieces and heated at 1673 K in fire clay
containers in a process which is also known as the Belgian process. Here the zinc oxide gets
reduced to metallic zinc. The carbon from coke acts as the reducing agent in this reaction. The
reaction of the final step of extraction of zinc is
2ZnO+C→2Zn+CO2

Since the boiling point of zinc is way back at 1180 K, the zinc formed immediately vaporises and
distils over leaving behind non-volatile impurities such as cadmium, lead and iron. This gas
containing zinc vapor’s is collected and cooled to yield solid zinc. This crude metal is called
Spelter. It can be further purified by fractional distillation.

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