Introduction to Metallurgy

Mineral is a naturally occurring homogeneous inorganic substance

of definite chemical composition and with certain characteristic
physical properties; e.g. galena PbS, chalcopyrite CuFeS2.
The natural material in which the metal or their compounds occur
in the earth is known as mineral. Thus a mineral is a naturally
occurring material present in earths crust which contains metal in
the native (or free state) or in combined state.
Earths crust refers to the outer siliceous shell of the Earth which
is about 35 km thick. The original source of all metals is the Earths
crust.
Oxygen, silicon, aluminum and iron are the four most abundant
elements in earth.
A mineral may be a single compound or a complex mixture of
various compounds. When a mineral contains sufficient amount of a
metal in combined state, from which it can be readily and profitably
separated on commercial scale, then the mineral is said to be an ore
of the metal. Thus all ores are minerals, but all minerals are not
ores. A mineral from which a metal can be profitably extracted is
called an ore. For example, clay (Al2O3 2 SiO2 2 H2O) and bauxite
(Al2 O3 2H2O) are two minerals of aluminium, but aluminium, can
be profitably extracted only from bauxite and not from the clay.
Hence bauxite is an ore of aluminium, while clay is a mineral.
The biggest source of metal is the earths crust and the process of
taking out the ores from the earth crust is called mining.
Table. Classification of ores
Gangue or matrix
Metals occur in nature sometimes in free or native state, but most of
these occur in nature in the form of chemical combination, i.e., in the
form of their stable compounds which are associated with gangue or
matrix. The earthy impurities such as sand, clay, rocks etc.
associated with ore are collectively known as gangue or matrix.
Mineral Dressing
Since most ore minerals are usually finely disseminated (dispersed)
and intimately associated with gangue minerals, the various minerals
must be broken apart (freed) or liberated before they can be
collected in separate products. Therefore, the first part in any ore
dressing process will involve the crushing and grinding (which is
also known by a common name called comminution) of the ore to
a point where each mineral grain is practically free.

Ore dressing (ore beneficiation) is a process of mechanically

separating the grains of ore minerals from the gangue minerals, to
produce a concentrate (enriched portion) containing most of the ore
minerals and a tailing (discard) containing the bulk of the gangue
minerals.
Comminution
Comminution is the reduction of the size of ores. Crushing and
grinding are usually carried out in a sequence of operations by which
the lump size is reduced step by step. There are 3 stages of crushing
and 2 stages of grinding.
Primary Crushing (coarse crushing): In primary crushing,
ore (up to 1 m in size) is crushed down to about 10 cm and it is
done in a jaw or gyratory crusher.
Secondary Crushing (intermediate crushing): In this case, ore
is crushed from 10 cm to less than 1 2 cm size; for this
purpose jaw, cone or roll crushers are used.
Tertiary Crushing (fine crushing): By tertiary crushers ore is
crushed from 1 2 cm to less than 0.5 cm. Short head cone
crushers, roll crushers, hammer mills can be used for this
purpose.
The two stages of grinding are:
Coarse Grinding: Rod mills are generally used as coarse
grinding machines. They are capable of taking feed as large as 50
mm and making a product as fine as 300 microns.
Fine Grinding: Fine grinding, which is the final stage of
comminution, is performed in ball mills using steel balls as the
grinding medium. The ball mill, after feeding 0.5 mm material
may give a product that is less than 100 microns. Grinding is
usually done wet.
The principle purposes of grinding are:
To obtain the correct degree of liberation in mineral processing.
To increase the specific surface area of the valuable minerals
for hydrometallurgical treatment; i.e. leaching.
Rod mill Ball mill
Mineral processing combines a series of distinct unit operations.
The flowsheet shows diagrammatically the sequence of unit
operations in the plant.
Concentration

The second fundamental (main) operation in mineral processing,

after the release or liberation of the valuable minerals from the
gangue minerals, is the separation of these values from the gangue,
i.e. concentration.
Concentration is usually accomplished by utilizing some specific
difference in physical (or chemical) properties of the metal and
gangue compound in the ore.
In concentration the following terms are used:

Head is the feed to a concentrating system.

Concentrate is defined as the valuable mineral(s) separated from
ore undergoing a specific treatment.
Tailing is the fraction of ore rejected in a separating process. It is
usually the valueless portion, i.e. discard or waste.
Middlings are the particles of locked valuable mineral and
gangue, i.e. liberation has not been attained. Further liberation can
be achieved by further comminution.
Recovery is the percentage of the total metal, contained in the ore
that is recovered in the concentrate.
Physical Concentration Methods
(1) Gravity separation process or hydraulic washing
This method is especially suitable for heavy oxide ores like
haematite, tinstone, etc. In this, the powdered ore is placed on a
sloping floor (or platform) and washed by directing on it a strong
current of water. The lighter sandy, and earthy impurities are
washed away; while the heavier ore particles are left behind.
(2) Froth flotation process

This method is especially suitable for sulphide ores like zinc blende
(ZnS), and copper pyrites (CuFeS2). This process is based on the fact
that the sulphide ore particles are only moistened by oil; while those
of oxide, and gangue particles are moistened only by water. In this
process, the powdered ore is mixed with water and a little pine oil (a
foaming agent) and the whole mixture is then stirred vigorously by
blowing compressed air. The oil forms a foam (or froth) with air. The
ore particles stick to the froth, which rises to the surface; while the
rocky, and earthy impurities (gangue) are left in water as shown in the
Figure. The froth is skimmed off, collected, and allowed to subside to
get concentrated ore.
Fig. Froth flotation process
(3) Electromagnetic separation process

This method is meant for separating magnetic impurities from

nonmagnetic ore particles, e.g., tinstone (a tin ore) in which
tinstone is non- magnetic; while impurities iron, manganese and
tungstates are magnetic. The powdered ore (containing the
associated magnetic impurities) is made to fall (from a hopper) on a
belt moving over electromagnetic roller. The magnetic impurities
fall from the belt in a heap near the magnet, due to attraction; while
the non-magnetic concentrated ore falls in separate heap, away from
the magnet, due to the influence of centrifugal force as shown in the
Figure
Fig. Electromagnetic separation method
(4) Chemical method
This method is employed in case where the ore is to be in a very
pure form, e.g., aluminium extraction. Bauxite (Al2O3), an ore of
aluminium, contains SiO2 and Fe2O3 as impurities. When bauxite
ore is treated with NaOH, the Al2O3 goes into solution as sodium
meta aluminate leaving behind the undissolved impurities [Fe 2O3,
SiO2, Fe(OH)3,etc.], which are then filtered off.
The filtrate (containing sodium meta-aluminate) on dilution, and
stirring gives a precipitate of aluminium hydroxide, which is
filtered, and ignited to get pure alumina.
Pretreatment Processes

Ores are not always in the optimum chemical or physical state for
conversion to metals.
Oxides are more conveniently reduced to metals than sulfides.
The metal might be more readily leached from the ore if it were
present as a sulfate, a chloride, or an oxide.
Sulfide ores or concentrates, for example, usually are heated in an
oxidized atmosphere (roasted) to convert them to an oxide or
sulfate.
The physical state of an ore may be too fine for charging to a
process. Fine ores often are agglomerated by sintering prior to
charging to a blast furnace, the principal smelting unit for lead and
iron.
Pyrometallurgy
Pyrometallurgy 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. Pyrometallurgical treatment may
produce pure metals, or intermediate compounds or alloys, suitable as
feed for further processing.

Examples of elements extracted by pyrometallurgical processes include

the oxides of less reactive elements like Fe, Cu, Zn, Cr, Sn, Mn etc.
Pyrometallurgical processes are generally grouped into one or more of
the following categories:
Drying
Calcining
Roasting
Smelting
Refining
 1. Drying
Drying usually means the removal of mechanically held water or
moisture from concentrate, or other solid materials by evaporation,(i.e.
expensive operation) usually done in a drying furnace (fixed or fluidized
bed, or kiln) and usually accomplished by passing hot combustion gases
through or above the substance.
Drying may be accomplished either at atmospheric pressure by
heating the substance above the normal boiling point of water, or
under reduced pressure where the atmospheric pressure is brought
below the vapor pressure of water at the temperature in question.
H2O(l) H2O(g) H298oK = +10.5 Kcal / gram-mole (Endothermic
process)
Therefore, in addition to the heat needed to bring the substance to
the drying temperature, the heat of evaporation must be supplied at
that temperature.
2. Calcination
Calcination is the thermal treatment of an ore or a concentrate to
effect its decomposition and the elimination of a volatile product,
usually CO2, water vapor, or other gases.

Method of conversion of ore into metal oxide (oxidation) is called

calcination.
The process in which the ore is subjected to the action of heat at
high temperature in the absence of air below its melting point.
The process of calcination is carried out in the case of carbonate and
hydrated ore.
 As a result of calcination
(a) The moisture is removed.
(b) Gases may be expelled.
(c) Volatile impurities are removed.
(d) The mass becomes porous.
(e) Thermal decomposition of the ore takes place.
Therefore, by contrast with drying, calcination involves the
removal of H2O, CO2, etc., which are chemically bound as e.g.
hydrates or carbonates.
For example,
CaCO3 (limestone) CaO + CO2
MgCO3 (Magnesite) MgO + CO2
MgCO3.CaCO3 (Dolomite) MgO + CaO + 2CO2
 CuCO3.Cu(OH)2 (Malachite) 2CuO + H2O + CO2
ZnCO3 (Calamine) ZnO + CO2
2Fe2O3.3H2O (Limonite) 2Fe2O3 + 3H2O
The name calcination originated from the ore calcite which on
thermal decomposition gives quick lime. Calcination is usually
carried out in reverberatory furnace.
Calcination Furnaces
Shaft furnace For the calcination of coarse limestone
Rotary kiln For the calcination of materials with mixed particle
size or lumps which disintegrate during the process
Fluidized bed For materials of uniform, small particle size
Fuels used in calcination furnaces are gas, oil, coke, pulverized coal,
etc.
Fig. Temperature of gas and solids during calcination of limestone in
a coke-fired shaft furnace, i.e. temperature profiles
3. Roasting
Roasting is one of the oxidation method where ore is converted into
metal oxide.
In the process of roasting, the ore either alone or with the addition of
suitable material, is subjected to the action of heat in excess of air at
temperature below its melting point.
Roasting is usually carried out in a reverberatory furnace or in a blast
furnace.
During roasting
(a) Volatile impurities like S, As, Sb etc. get oxidized and escape out
as volatile gases SO2, As2O3 and Sb2O3
(b) The sulphide ores decompose to their oxides evolving SO2
(c) The moisture is removed. Mass becomes porous and thus it can
easily be reduced.
Oxidising Roasting In this type of roasting S, As, and Sb
impurities are removed in the form of their volatile oxides as SO 2,
As2O3 and Sb2O3 etc. due to combined action of heat and air. The ore
is simultaneously converted into its oxides. This type of roasting is
carried out for ores like copper pyrites, zinc blende and lead ores
(PbS) etc.
2ZnS + 3O2 2ZnO + 2SO2
2PbS + 3O2 2PbO + 2SO2
Blast Roasting
Oxidation is carried out for by hot blast.
 Reducing Roasting
Oxidized metallic inerals are subjected to the action of reducing
agents such as H2, C at a temprature below fusion point.
Fe2O3 + C FeO + CO
FeO + C Fe + CO
Sulphating Roasting

In this type of roasting, the sulfide ore is not converted to oxide but
to a suitable and soluble sulphate.
ZnS + O2 ZnSO4 + SO2
Chlorodizing Roasting
In this process, Metals or ores are converted into chlorides by
heating the ore with NaCl in the presence of air.
Ag2S + NaCl 2AgCl + Na2S
 Smelting
Smelting uses heat and a chemical reducing agent to change the
oxidation state of the metal ore; the reducing agent is commonly a
source of carbon such as coke, or in earlier times charcoal.
Fe2O3 + C FeO + CO
FeO + C Fe + CO
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, a
reducing agent that liberates the oxygen as carbon dioxide leaving a
refined mineral.
Carbonate ores are also smelted with charcoal, but are 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.
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 into three general areas:

Leaching
Solution concentration and purification
Metal recovery
Leaching
Leaching involves the use of aqueous solutions containing a
lixiviant which is brought into contact with a material containing
a valuable metal. The lixiviant in solution may be acidic or basic
in nature. The type and concentration of the lixiviant is normally
controlled to allow some degree of selectivity for the metal or
metals that are to be recovered.
In the leaching process, oxidation potential, temperature, and
pH of the solution are important parameters, and are often
manipulated to optimize dissolution of the desired metal
component into the aqueous phase.
The three basic leaching techniques are in-situ leaching, heap
leaching, and vat leaching.
In-situ leaching
In-situ leaching is also called "solution mining." The process initially
involves drilling of holes into the ore deposit. Explosives or
hydraulic fracturing are used to create open pathways within the
deposit for solution to penetrate into. Leaching solution is pumped
into the deposit where it makes contact with the ore. The solution is
then collected and processed. The Beverley uranium deposit is an
example of in-situ leaching.
Heap leaching
In heap leaching processes, crushed (and sometimes
agglomerated) ore is piled in a heap which is lined with an
impervious layer. Leach solution is sprayed over the top of the
heap, and allowed to percolate downward through the heap. The
heap design usually incorporates collection sumps which allow
the "pregnant" leach solution (i.e. solution with dissolved valuable
metals) to be pumped for further processing.
Vat leaching
Vat leaching involves contacting material, which has usually
undergone size reduction and classification, with leach solution in
large tanks or vats. Often the vats are equipped with agitators to
keep the solids in suspension in the vats and improve the solid to
liquid contact. After vat leaching, the leached solids and pregnant
solution are usually separated prior to further processing.
Solution concentration and purification

After leaching, the leach liquor must normally undergo

concentration of the metal ions that are to be recovered.
Additionally, some undesirable metals may have also been taken
into solution during the leach process. The solution is often
purified to eliminate the undesirable components. The processes
employed for solution concentration and purification include:
Precipitation
Solvent Extraction
Ion Exchange
Precipitation
Precipitation is the formation of a solid in a solution during a
chemical reaction or by diffusion in a solid.
When the reaction occurs in a liquid,
the solid formed is called the
precipitate, or when compacted by a
centrifuge, a pellet. The liquid
remaining above the solid is in either
case called the supernate or
supernatant.

Natural methods of precipitation include settling or sedimentation,

where a solid forms over a period of time due to ambient forces
like gravity or centrifugation.
Solvent extraction

A mixture of an extractant in a diluent is used to extract a metal

from one phase to another. In solvent extraction this mixture is
often referred to as the "organic" because the main constituent
(diluent) is some type of oil.
The PLS (pregnant leach solution) is mixed to emulsification with
the stripped organic and allowed to separate. The metal will be
exchanged from the PLS to the organic they are modified. The
resulting streams will be a loaded organic and a raffinate. The
organic stream is recycled through the solvent extraction process.
Ion exchange

Chelating agents, natural zeolite, activated carbon, resins, and

liquid organics impregnated with chelating agents are all used
to exchange cations or anions with the solution. Selectivity and
recovery are a function of the reagents used and the
contaminants present.

Metal Recovery

Metal recovery is the final step in a hydrometallurgical process.

Metals suitable for sale as raw materials are often directly produced
in the metal recovery step. Sometimes, however, further refining is
required if ultra-high purity metals are to be produced. The primary
types of metal recovery processes are electrolysis, gaseous
reduction, and precipitation.
Electrolysis
Electrowinning and electrorefining respectively involve the
recovery and purification of metals using electrodeposition of
metals at the cathode, and either metal dissolution or a competing
oxidation reaction at the anode.

Electrowinning, also called electroextraction, is the

electrodeposition of metals from their ores that have been put
in solution or liquefied. Electrorefining uses a similar process
to remove impurities from a metal. Both processes use
electroplating on a large scale and are important techniques for
the economical and straightforward purification of non-ferrous
metals.
 Sintering
Sintering is a method for making objects from powder, by heating
the material in a sintering furnace below its melting point until its
particles adhere to each other. Sintering is traditionally used for
manufacturing ceramic objects, and has also found uses in such
fields as powder metallurgy.
Advantages
Particular advantages of this powder technology include:
1.Very high levels of purity and uniformity in starting materials
2.Preservation of purity, due to the simpler subsequent fabrication
process (fewer steps) that it makes possible
3.Stabilization of the details of repetitive operations, by control of
grain size during the input stages
4.Absence of binding contact between segregated powder particles
or "inclusions" (called stringering) as often occurs in melt processes
5.No deformation needed to produce directional elongation of grains
6.Capability to produce materials of controlled, uniform porosity.
 Agglomeration
When the particle size of an ore or concentrate is too small for use
in a later stage of treatment, i.e. in the blast furnace, it must be
reformed into lumps of appropriate size and strength that is
agglomerated.
Agglomeration is used particularly if the ore is to be smelted in a
shaft furnace where fine-grained material would plug up the gas
passage, i.e. decrease gas permeability.
Sintering (one type of agglomeration process) may be defined as a
process in which relatively coarse materials, e.g. for iron ore
concentrate 8mm + 0.15mm (100 mesh), are converted into coarse
agglomerates by partial melting and fusion.
The sinter product has a porous structure.
Flux
In metallurgy, a flux is substance which is added to the furnace
charge, during the process of smelting, to remove the non-fusible
impurities of earthy matter present in the roasted or calcined
oxide ore.
Example
SiO2 + MgCO3 MgSiO3 + CO2
Acidic Basic flux Fusible slag

impurity
The role of flux is typically dual: dissolving of the oxides on
the metal surface, which facilitates wetting by molten metal,
and acting as an oxygen barrier by coating the hot surface,
preventing its oxidation. In some applications molten flux
also serves as a heat transfer medium, facilitating heating of
the joint by the soldering tool or molten solder.
Slag

During smelting, flux combines with the non-fusible impurity

to convert it into a fusible material, then it is called slag.
SiO2 + CaO CaSiO3 + CO2
Acidic Basic Fusible slag

flux impurity
Being light, slag floats over the molten metal from where
it can be removed.
At high temperature, the slag is a liquid which is
insoluble in the molten matter.
The density and viscosity of slag is low.