Extraction of Metals

Module 3
 module3

Principles of metal extraction.

Principles of pyrometallurgy-calcination,
roasting, smelting
Hydrometallurgy-leaching, solvent extraction,
ion exchange, precipitation
Electrometallurgy-electrolysis, electrorefining
Stress strain behaviour of metal
 Difference between ORE and MINERAL
• A naturally occurring inorganic compound of one or more
metals in association (chemical or physical) with nonmetals e.g.
Oxygen, sulphur, silica, carbon and the halogens, having well
defined physical and chemical properties, is called a MINERAL .
• A naturally occurring aggregate or combination of minerals
from which one or more metals or minerals may be extracted
economically is called as ORE. Thus all ores are constituted with
minerals but all minerals are not ores.
• Most active metals- highly electropositive and therefore exist
as ions.
• So most of the important ores of these metals occur as (i)
oxides (ii) sulphides (iii) carbonates (iv) halides and (v) silicates.
Some sulphide ores undergo oxidation by air to form sulphates.
• The rocky or earthy impurities accompanying the ores are
termed as gangue or matrix.
Some Important Ores
 Some metal ores in INDIA

Metal State
Al MP,AP,J&K,Raj,Orissa,UP,Karnataka,Bihar,Goa,
Guj
Cu Bihar,MP,Raj
Fe Goa, MP,Maharastra,Bihar,Karnataka, Orissa
Sn Jharkhand
Ag Karnataka, Raj
Ti Kerala, Tamil Nadu
Na Ladakh, Kashmir
Facts about Important Metals and Their Ores

1. The most common metal ores are oxides and

sulphides.
2. Sulphides are the oldest ores, formed in the Earth’s
history when there was a lot of sulphur from volcanic
activity.
3. Oxides formed later when photosynthesis in plants
released large amounts of oxygen into the atmosphere.
4. Iron ore is the most common element in the world
and makes up close to 5% of the Earth’s crust. This
makes it one of the most abundant rock elements.
5. Aluminum is one of the most common elements in
the Earth’s crust and is found in a variety of silicate ores,
which are often a type of clay.
Mo
sulfide
(BaSO4)
(W+Fe+Mn oxide)

FeTiO3
(Fe2+Fe3+2O4) CaTiO3

CaTiSiO5
FeTiO3
Bi2S3
 General Principles of Extraction
• Process of extracting the metals from their ores
and refining them is called metallurgy

• Unit Operations: Physical processes- Crushing,

Grinding, Concentration
• Unit Processes: Chemical Processes-
1. PYROMETALLURGY
2. HYDROMETALLURGY
3. ELECTROMETALLURGY
 Unit operations
• Crushing-JAW and Gyratory Crushing
• Grinding-(Ball ,Stump) milling
• Classification &Concentration-
• Magnetic, gravity, froth floatation, chemical
Unit Operations(physical Change)
Crushing and Pulverization

The ore is generally obtained as big rock pieces. These

big lumps of the ore are crushed to smaller pieces by
using 1. jaw crushers and 2.gyratory crusher (grinders)
 Feed

Blake jaw Crusher

It applies both friction and pressure
on the material-most commonly It applies only pressure and rarely used
used in industries only for very hard ores
The rapid action at the top of the crushing chamber tends to
crowd material into the lower zone i.e. choking
 Low or no
choking at the
bottom

Dodge Jaw Crusher

Choking at the bottom

Pivoted at bottom
 A gyratory crusher with material being crushed
between the gyratory head and the frame
concave

A cone crusher showing material being

crushed between the cone mantle and bowl
liner
 Pulverisation The crushed pieces of the ore
1 are then pulverized (powdered)
in a stamp mill shown in Fig. 2

Pulverization can be carried out in

a ball mill (fig1). The crushed ore is
taken in a steel cylinder containing
iron balls. The cylinder is set into
revolving motion. The striking balls
pulverize the crushed ore into fine
powder.
 Concentration or Dressing of the Ore
• The process of removal of gangue from
powdered ore is called concentration or
ore dressing.
• Various methods include:
Gravity separation (Hydraulic washing)
Magnetic separation method
Froth floatation method
Chemical method
 Gravity separation (Hydraulic washing)
•the light (low specific gravity) earthy impurities are
removed from the heavier metallic ore particles by washing
with water. It is therefore, used for the concentration of
heavier oxide ores, like haematite (Fe2 O3 )tinstone
(SnO2)and gold (Au).
The heavier ore settles
down rapidly in the grooves
in slopping table and the
lighter sandy and earthy
materials (gangue particles)
are washed away
 Magnetic separation method

•those ores can be concentrated which

either contain impurities which are
magnetic or are themselves magnetic in
nature.
•For example, tin ore ,tin stone
(SnO2)itself is non-magnetic but contains
magnetic impurities such as iron
tungstate(FeWO4 )and manganese
tungstate (MnWO4 )
•The finely powdered ore is passed over a
conveyer belt moving over two rollers,
one of which is fitted with an
electromagnet .
•The magnetic material is attracted by
the magnet and falls in a separate heap.
In this way magnetic impurities are
Froth floatation method
 Froth floatation method
•especially applied to sulphide ores, such as galena (PbS), zinc
blende (ZnS), or copper pyrites (CuFeS2)
•It is based on the different wetting properties of the surface of the
ore and gangue particles. The sulphide ore particles are wetted
preferentially by oil and gangue particles by water.
•In this process, finely powdered ore is mixed with either pine oil or
eucalyptus oil.
• It is then mixed with water.
• Air is blown through the mixture with a
great force.
• Froth is produced in this process which carries the wet ore
upwards with it.
•Impurities (gangue particles) are left in water and sink to the
bottom from which these are drawn off
 Chemical process
In this method, the ore is treated with a suitable
chemical reagent which dissolves the ore leaving
behind insoluble impurities.
The ore is then recovered from the solution by a
suitable chemical method. This is applied for extraction
of aluminium from bauxite (Al2 O3 .2H2O )
• Bauxite is contaminated with iron (III) oxide (Fe2O3 ),
titanium (IV) oxide (TiO2 )and silica (SiO2 ).
•These impurities are removed from the ore by Bayer
process(to be discussed later under “leaching”)
Unit Process (Chemical Change)
Pyrometallurgy
• Extraction of metals from their ores at very high
temperature through physical and chemical changes
• Four types :
• Calcination (often controlled within 1000~1100 °C )
• Roasting( 450-550oC and 3h,oxidation)
• Smelting (higher than melting temp of
metal,reduction)
• Refining-
 Advantages of Pyrometallurgy
• Higher rate of production
• Low cost process in view of low cost reagents
required
• Fast process as small activation energy at high
temperature-so
• Reactive alkaline earth metals can be extracted
• Brings about reduction which cannot happen in
presence of water
• Saving capital investment as large tonnage of
production from a compact space
 (Decomposition)
• Calcination involves heating of the concentrated ore in a
limited supply of air so that it loses moisture, water of
hydration and gaseous volatile substances.

• The ore is heated to a temperature so that it does not

melt but may undergo decomposition to lower
molecular weight (volatile and/or nonvolatile )products
• As most of the decomposition reactions are endothermic, heat
transferred from an external source to the particle plays the vital
role to determine the temperature of calcination inside a
kiln(furnace)
• Mainly applied for oxide , carbonate ores


 Roasting (oxidation)

• Roasting is a process in which the concentrated ore is heated

in a free supply of air at a temperature insufficient to melt it
and to form oxides from the impurities
• Mainly applied for sulphide ores
• Roasting is affected by the factors: availability of Oxygen,
temperature, duration, nature of mechanical device used for
roasting and physical condition of the ore
• Several Industrial roasting Units:
 Multiple hearth
 Flash Type
 Fluidized bed
 Sinter
Chemistry of sulphide ore roasting (oxidation roasting)

Roasting the sulfide

ore, until almost
complete removal of
the sulfur from the
ore, results in a dead
roast.
Quartz and gangue
materials act as
catalysts
Volatilizing roasting (dead /sweet roasting)

• involves oxidation at elevated temperatures of the

ores, to eliminate impurity elements in the form of
their volatile oxides. Examples of such volatile oxides
include As2O3, Sb2O3, ZnO and sulfur oxides.
• Chloridizing roasting
• metal compounds to chlorides, through oxidation or reduction.
metals such as uranium, titanium, beryllium and some rare
earths are processed in their chloride form.
• Magnetic roasting
• controlled roasting of the ore to convert it into a magnetic
form, For example, controlled reduction of haematite (non
magnetic Fe2O3) to magnetite (magnetic Fe3O4).
Thermodynamics of Roasting
 Types of roasting on the basis of duration :

• Blast : flash of time( seconds or minutes):Coarse and cellular

feed
• Hearth: hours
• Heap: Months
• Weather: year

Factors affecting Roasting:

Time
Temperature
Flow of Oxygen
Physical condition of ore(chemical
composition)
Nature of Mechanical Device used
 Industrial Roasting Units:
• Multiple hearth Roaster
• Flash Roasting
• Fluidized Bed Roasting
• Sinter Roasting
Multiple hearth roasting
Flash Roasting
Fluidized Bed roasting
Sinter Roasting/Sintering

Ore particle movement

Conveyer
belt
Mechanism of sintering

• 1st stage-Neck
growth
• 2nd stage-
Densification and
grain growth
• 3rd stage-Pore
shrinkage
 Kinetics of Roasting
• Exothermic
• Particle gets oxidized from outer most surface
to inner
• Unchanged inner core –possibility
• Reaction @ interface between these two
regions- if the gas ratio po2/pso2 is locally higher
than the equilibrium ratio for the reaction at
the temperature under consideration.
 Smelting (reduction)
• Process of melting and separation of the charge(ore) into two
or more immiscible liquid layers –slag, matte, speiss or metal
• Metal oxides/sulphides ,which are present in ore or which are
formed by partial oxidation during roasting , are converted to
elemental metal by reduction reaction at a high temperature
• The required temperature varies over a very large range, both
in absolute terms and in terms of the melting point of the base
metal.
• Example: Iron oxide is converted to metallic iron at roughly
1250 °C almost 300 degrees below iron's melting point of
1538 °C
• Mercuric oxide becomes vaporous mercury near 550 °C ,
almost 600 degrees above mercury's melting point of -38 °C
 Types
• 1.Reduction at high temperature :oxides and sulphates from
roasting converted to pure metal by carbon as reducing agent
and in presence of flux(basic/acidic oxide)
(Mineral + gangue)+ reducing agent+ flux = metal/matte + slag +
gas
• 2.Matte: fusion of sulphidic sources of metals with a flux and
no recuing agent reqd.
Sulphidic source concentrate + flux= matte + slag + gases
( smelting of Cu and Ni ores)
• 3.Flash :Combination of (Flash Roasting +Smlating operation)
The sulfide concentrate fines react with oxygen at high
temperatures. The oxidation process itself generates sufficient
heat for the smelting process to occur simultaneously.
 Salient Features

• Furnace used-
• Reverberatory furnace (matte smelting),
• Blast furnace(reduction),
• Electric arc furnace( Combination-reduction and
matte smelting)
• As gangue is less fusible than metal so flux(basic
oxide) must be added to form slag which is easily
fusible
 Flux
• for catalyzing the desired reactions and chemically
binding to unwanted impurities or reaction products.
• To lower the liquid’s temperature
• To lower the viscosity of slag
• Calcium oxide, in the form of lime (basic ), is used ,as it
can react with the carbon dioxide and sulfur dioxide
produced during roasting and smelting to keep them
out of the working environment.
• Flux and slag provide a molten cover on the purified
metal, preventing contact with oxygen while still hot
enough to readily oxidize. This prevents impurities from
forming in the metal.
 Slag

• What is it?
• A solution of metal oxides (in molten state) is used in metal extraction and
refining to collect all the gangue (waste) in the form of oxides (or sulphide
in small quantities) and remove the impurities into separate phase
• Slag is multicrystalline in solid state, lighter than molten metal and immiscible in
metal
• Both basic (FeO, MnO, CaO, MgO,Na2O) and acidic oxides(SiO2,P2O5) with small
amount of sulphide and phosphides
• Slag Basicity B= (wt% All Basic Oxides)/(wt% All Acid Oxides)
• Slag Volume ratio(V)=wt% CaO/wt% SiO2
• Why do we need it?
• At high temperature metallic carbides form which can be suppressed in presence of
a solvent metal.
• The solvent metal in which metal M dissolves causes reduction in chemical potential
of M and pushes th ereduction reaction to the right making reduction possible at
lower temperature
 Role of slag
•Acts as sink for impurities during refining of metal
•Controls oxidizing and reducing potential during refining
through variation of FeO content. Higher FeO makes the
slag oxidizing and vice versa.
•Prevents passage of N2 and H2 from atm to the molten
steel
•Absorbs oxide /sulphide inclusions
•Acts as a thermal barrier to prevent heat transfer from
molten steel to the surrounding
•Protects metal against reoxidation
•Emulsifies hot metal and promotes Carbon Oxidation
•In electric smelting ,slag prevents the radiation of heat
of arc to the walls of the furnace and roof.
 How does slag function?
• Slag contains Silica-which has hexagonal network and
possesses high viscosity in pure form
• When alkaline oxide (CaO) is added to it the hexagonal
network breaks and in molten state viscosity reduces ,as
depolymerization of silica happens

CaO=Ca2+ +O2-

Each mole of CaO introduces

one mole of oxygen ions in
the hexagonal network of
silica and can break two
vertices of the hexagonal
structure of silica
 Refining

• Involves adding some substances that can confer desirable

characteristics to pure metal
• Unwanted metals, nonmetals, unreacted oxide of a metal flux,
slag etc. –considered as impurities are eleminated by refining .
• Various types of refining processes are
1. Liquation
2. Polling
3. Distillation
4. Electrolytic refining
5. Zone refining
6. Chromatography
7. Cupellation
8. Vapour phase refining
Distillation
• Hydrometallurgy refers to production of metal or pure
compounds with the help of reaction in aqueous and organic
solution.
• confined to low grade ore, but it has been used to extract metals
from concentrate, matte, species and scrap.
• produce a pure compound which can later be processed by
pyrometallurgy to yield the metal.
• produce a metal directly from an ore or concentrate
• It is done by combining water, oxygen or other substances
in a pressurized or other vessel to dissolve a metal from its
ore, concentrate or an intermediate product .
 Steps in hydrometallurgical extraction process
1.After preparation of ore( for leaching) by grinding, roasting etc.
• 2-Leaching- by using a suitable liquid reagent the metallic values
in an ore are selectively dissolved and the process is controlled by
particle size, temperature, pressure, volume of leaching liquid,
leaching reaction
• 3-Separation of leach liquor – by settling, thickening, filtrations,
washing
• 4-Recovery of metallic values from leach liquor

• Most efficient leaching agent is acid as it can leach both basic and
precious metals-generally base metals are leached in nitric acid
 a) Bioleaching
b) Chemical

a)Solvent Extraction
b)Ion Exchange
c)Adsorption

a)Electrodeposition
b)Precipitation
 Types of Leaching
• Depending upon the processing unit
• In situ
• Vat
• Heap
• Agitation
• Depending upon type of leaching agent
• Bio leaching-microorganism
• Chemical
• Acid
• Base
• Thiosulphate
• Cyanide
• Halide
• thiourea
Permeable
rock

Nonpermeable rock
Heap leaching process
Vat leaching:
•Ore loaded into vats which are made of concrete
After leaching the residual solids are dugout of the vat and
replaced by a fresh batch of ore (batch process)
•Suitable for porous and sandy materials
•Commonly used for gold and silver ore
•In case of vat leach, we can control temperature, acidity (pH) and
solution flow rates and this provides significant advantages over
heap leaching.
This process is faster, more efficient and targeted leaching over
heap leaching process.
Agitation Leaching:
• Soil is slurred with the
extraction fluid for a period of
time
•When equilibrium between the
metal on the soils surface and the
metal contained by the solution is
approached , the solubilization of
the metal in the soil is slowed and
the extraction is considered to be
complete
 Bayer Process (leaching of Aluminum from Bauxite)
•These impurities are removed by digesting the powdered ore with
aqueous solution of sodium hydroxide at 420 K
under pressure. Aluminium oxide dissolves in sodium hydroxide,
whereas, iron (III) oxide, silica and titanium (IV) oxide remain
insoluble and are removed by filtration.

Sodium aluminate
Sodium aluminate is diluted with water to obtain precipitate of
aluminium hydroxide. It is filtered and ignited to obtain pure
alumina.
Reactions involved in the Three main steps of
“Cu”metal extraction in Hydrometallurgy
Types of Microorganisms used in bioleaching
 Solvent Extraction
• Transferring one solute(s) contained in a feed
solution to another immiscible liquid (solvent)
• The solvent that is enriched in solute is called
as extract and the feed which is depleted of
the solute is called as raffinate

Distribution coefficient,
KD=Concentration in organic phase(extract) / Concentration in
aqueous phase(feed)
 Salient Features
• An extractant is a substance primarily
responsible for the transfer of a solute from
one phase to another
• The extractant is dissolved in a suitable diluent
and together act as a solvent
• The diluent is immiscible with other phase
which is usually water
• The extractant reacts with the solute by
solvation/Chelation/ion pair formation etc. to
extract from the aqueous phase
 Commonly used solvents

• ethyl acetate (8.1 %), • diethyl ether (6.9 %), •

dichloromethane (1.3 %) and • chloroform
(0.8 %) dissolved up to 10 % in water.
• Water also dissolves in organic solvents:
• ethyl acetate (3 %), • diethyl ether (1.4 %), •
dichloromethane (0.25 %) • chloroform (0.056
%).
The distribution equilibrium between two phases is governed
by Gibbs Phase rule----
P+F=C+2
Where, P= number of phases F= the variance or degrees of
freedom and C= number of components
In solvent extraction, P=2 (Aqueous and organic);C=1 (Solute); F=1
at constant temperature and pressure…
So, 2+1=1+2 ie, P+F=C+2 ie, It follows Gibbs Phase rule
Distribution ratio:
D= [X]org/[X]aq
Where, X represents the stoichiometric or formal concentration of a substance
X and the subscripts 1 and 2 refer to the two phases
Separation of two solutes by solvent extraction is expressed by
the term separation factor (α) which is related to individual
distribution ratio α=DA /DB Where DA and DB are the respective
distribution ratios of solute A and B
Percent Extraction (%E):
%Extraction(E) =100D/( D+Vaq/Vorg )
Where, V represent solvent volume and the other quantities
remain as previously defined. The percent extraction may be
vary with the volume ratio of the two phases as well as with D
 Mechanism of solvent extraction
• Chelate formation – • Metal forms stable and neutral
complexes with chelating agents. • Such chelates are usually
water soluble • The chelating agents are usually bidentate or
multidentate organic ligands which provide hydrophobic
pocket to the metal ion. • The organic part of such ligands
strongly interact with organic solvent and thereby metachelate
become soluble into organic phase.
• Examples:
• N,N′-di-n-octadecyl ethylenediamine-N,N′-diacetic acid (DOED)
chelating agent in 2-ethylhexanol-cyclohexanol (1:1) solutions
shows extremely high chelating ability for Ni(II), Co(II), Cu(II),
Fe(III), Cr(III), and Cd(II) ions in neutral aqueous solutions.
• Extraction of Uranium with 8-hydroxyquinoline in chloroform
• Extraction of Iron with cupferron in carbon tetrachloride
 Mechanism of solvent extraction
• Solvation • It is the process in which metal ion gets
solvated by solvent molecule and trapped inside the
solvent cage.
• Extraction proceeds by the process of solvation of the
species which is extracted into organic phase •
Oxygenated organic solvents ( alcohols, ketone, ether,
ester) show some basicity therefore, directly solvate
protons and metal ions and cause extraction
• Carboxylic acids, ternary amines, alkyl substituted
phosphoric acids. etc. can be used as extractants
• Examples: 1. Extraction of Uranium with tributyl
phosphate from nitric acid 2. Extraction of Iron(III) with
diethyl ether from hydrochloric acid
 Extraction involving ion-pair formation:
• Metal ions form ionic complexes with certain ions.
In turn these ionic complexes get associated with
oppositely charged ions called as ion association
• Extraction proceeds with the formation of neutral
uncharged species which in turn gets extracted into
the organic phase • In this case an ion pair is
formed between complex of metal ion with high
molecular weight amine and anionic species of
mineral acids
• Examples: Extraction of Scandium and Uranium
with trioctyl amine from mineral acid
 Advantages of solvent extraction
• Compared with other separation methods, it
gives a better separation effect than chemical
precipitation, and a higher degree of selectivity
and faster mass transfer than the ion exchange
method.
• Compared with distillation, solvent extraction
has advantages such as low energy consumption,
large production capacity, fast action, easy
continuous operation and ease of automation.
 Advantages of hydrometallurgy

• ideally suited for lean and complex ores

• ensures great control than other conventional method over
every step in the processing of ore.
• Resulting in the recovery of valuable by products.
• ecofriendly, it does not create much pollution
• carried out at room temperature or slightly elevated
temperature.
• waste liquor from the final recovery step can be recycled to
the initial leaching operation
• hydrometallurgy can produce metal in a variety of physical
form such as powders, nodules, and
coherent surface deposit.
 Metal recovery

• At this point, the metal needs to be

recovered from solution in the solid form. This is
either achieved chemically, or electrochemically.
• Electrowinning: An electrochemical process for
precipitating metals from solution
The anode is made
out of a material
that will not easily
oxidise or dissolve,
such as lead or
titanium

Electrowining process
 Electrometallurgy
• Electrometallurgy is a process for refining
(electrorefining) and production (electrowinning,
electroplating, and electroforming) from a solution
containing metals throughout electrolysis
• uses electrical energy to produce metals by electrolysis
• Final step of metallurgy -preceded by pyro- and hydro-
metallurgy
• can be done on a molten metal oxide (smelt
electrolysis)
• Electrorefining-electrolysis used as a final refining stage
in pyrometallurgical metal production
• Electrowinning- used for reduction of a metal from an
aqueous metal salt solution produced by
hydrometallurgy
Electrowinning (smelt electrolysis) Electrorefining
• Nonmetal anions generally • Dissolution of anode metal
undergo oxidation at the itself occurs
anode to give gaseous
products
• Primary extraction of metals • Subsequent refining to high
from their ores purity
• Reactive metals such as • More noble metals e.g.
Aluminum and Magnesium Copper and zinc are
are electrolyzed from electrolyzed from aqueous
electrolytes of their fused electrolytes
salts
Electrowinning cell
• Processing steps before electrolysis:
• The concentrated ore is converted to an acid soluble form
• Leaching in acid(commonly sulfuric acid) to produce an acidic
solution of metal salts
• This solution is purified to remove the more noble metal ions
which will electrodeposit more readily than the metal of
interest
• Purification by solvent extraction or cementation or ion
exchange
• The purified solution is then fed to electrolysis cell
 Production of Sodium
• the electrolysis of molten sodium chloride
using ”Downs cell”
• Reaction:

Ions of metals of groups 1

and 2, along with aluminum,
are very difficult to reduce;
therefore, it is necessary to
prepare these elements by
electrolysis
 ElectroRefining (Preparation)of Aluminum

• Hall–Héroult cell is used as the electrolysis cell for the

production of aluminum.
Reaction of bauxite, AlO(OH), with hot sodium hydroxide forms
soluble sodium aluminate, while clay and other impurities
remain undissolved

After the removal of the impurities by filtration, the addition

of acid to the aluminate leads to the reprecipitation of
aluminum hydroxide:
•Precipitated aluminum hydroxide is removed by filtration.
• Heating the hydroxide produces aluminum oxide, Al2O3, which
dissolves in a molten mixture of cryolite,Na3AlF6, and calcium fluoride,
CaF2.
• Electrolysis of this solution takes place in a cell like that shown here
•Reduction of aluminum ions to the metal occurs at the cathode, while
oxygen, carbon monoxide, and carbon dioxide form at the anode