Metals and Metallurgical process

Syllabus: 6 Teaching Hours

 Characteristics of Metals, Non metals and Metalloids
 Minerals ,ores & Important mineral deposits in Nepal
 Different steps involved in metallurgical process
i) Crushing and pulverization of ores
ii) Concentration of ores : a) Gravity separation b) Froth floatation c) Electro-
magnetic separation d) Leaching
iii) Calcination and roasting
iv) Reduction of ores
a) Smelting (Reduction by using C )
b) Alumino thermic process (reduction by using Al metal)
c) Electrolytic reduction method (reduction by free electrons)
v) Refining of metals
 Elements

Non-Metals Metals Metalloids

Active metals Less active Metals

(Reactive metals) (Less Reactive metals)

 Lies above H-in ECS and

 Lies below H-in ECS and cannot
displace H2 gas from mineral acids. (dil.
displace H2 gas from mineral acids. (dil.
HCl or dil. H2SO4)
HCl or dil. H2SO4)
 eg: Li, Na, Mg, K, Fe, Zn , Pb etc..
 eg: Cu, Hg, Ag, Au, Pt etc..
Non-Metals
Metalloids
Non-Metals

Metals

Metals
 Characteristics
Properties Metals Non- metals
1. Physical state Solid, hard Exists in Solid (Carbon)
Except –Hg (liquid) liquid (Bromine) or gas
(Oxygen, Nitrogen)
Except- diamond( Carbon)
2. Appearance Lustrous when freshly cut Non lustrous

3. Electrical conductivity good conductor poor conductor

Except – Graphite (carbon)
4. Thermal (heat) Good conductor Bad conductor
conductivity
5. Mechanical Malleable (can be hammered Neither malleable nor ductile
into thin sheets)
(Ductile can be drawn into
wires)
 Characteristics conti..
Properties Metals Non -metals
6. General chemical Metallic (can loose electrons) Non metallic (can gain
behavior electrons)
7. Ionization energy Low Vey high

8. Electronegativity Low High

9. Oxides Generally Basic, sometime Generally Acidic some

acidic ( Oxides of Cr or Mn) times neutral
or amphoteric (ZnO & Al2O3)
10. Oxidizing or reducing Reducing Oxidizing

11. Periodic classification S-block , d-block, f-block and Only in p-block

some metals are in p-block
12. Examples Na, K , Mg, Ca, Zn, Cu, Fe, C, N, O, S, F, Cl, Br, I
Au, Ag, Al etc
Relative abundance of elements on earth crusts
Occurrence of Metals on earth crust
Occurrence of metals in nature

Free or Native state Combined state

Au, Pt, Ag, Hg As Oxide- Fe, Al, Zn, Sn, Cr etc .
As carbonate- Ca, Mg, Zn, Fe etc
As sulphide- Ag, Cu, Zn, Hg, Pb etc
As halide- Na, K, Rb, Cs, Mg Ag, Pb
etc

Halite or Rock Salt-NaCl

Native Gold ( ore of Na)
Occurrence of metals in Nepal

Fe, Au, Ca, Mg, U

Fe, Cu, Pb, Zn, Ca, Au

Co

Ca, Bi, Cu, U

Mg Cu, Mg, Ca
 Occurrence of metals in Nepal
Iron (Fe) As hematite(Fe2O3) and magnetite (Fe3O4)

Copper (Cu) As copper pyrite (CuFeS2) or malachite Cu2CO3(OH)2

Calcium (Ca) As lime stone (CaCO3)

Magnesium (Mg) As dolomite (MgCO3.CaCO3)

Zinc(Zn)/lead(Pb) As sulphide i.e. ZnS and PbS) etc….

 Metalloid : they show the properties of metal as well as non metal. For
example As, Bi, Sb ( they are lustre but formed acidic oxide)

 Alloy : alloy is a homogenous mixture of two or more metal or non metal.

alloy are usually harder than their compound but less ductile and malleable.
Alloy are generally classified into two type: i) ferrous alloy ii) non-ferrous
alloy
for example : steel = Fe +C , stainless steel : Fe + Cr + Ni
Brass = Cu + Zn Bronze = Cu + Sn
 Amalgams : Alloy made from metal and mercury. They may be solid or
liquid. Na + Hg NaHg
Sodium amalgum

Zn + Hg ZnHg
Znic amalgum
 Differences between minerals and ores
Ores Minerals
1. The natural occurring substance in which 1. The naturally occurring substances from
contains significant amount of metal & which metal cannot be extracted profitably
from which metal can be extracted and economically are called minerals .
profitably and economically are called
ores.

2. All the ores are minerals. 2. All minerals are not ores.
3. Example : 3. Example :
i) Bauxite (Al2O3.2H2O) is ore of Al metal i)Clay ( Al2O3. 2SiO2. 2H2O) is mineral of Al
ii) Copper pyrite( CuFeS2) is ore of Cu ii) Copper pyrite( CuFeS2) is minerals of Fe
Classification of ore:
Native ore Au, Ag

Oxide ore Bauxite (Al2O3.2H2O) ,Zincite(ZnO)

Carbonate ore Magnesite (MgCO3)

Limestone (CaCO3)
Sulphate ore Epsom salt (MgSO4.7H2O)
Gypsum(CaSO4.2H2O)
Halide ore Rock salt(NaCl)
Horn silver(AgCl)
Silicate ore China clay (Al2O3.2SiO2.2H2O)

Suphurised ore Copper pyrite(CuFeS2) Iron pyrite

(FeS2)
Cinnabar(HgS)
Other type(Nitrate, Borate ores) Saltpetre(KNO3)
Borax (Na2B4O7.10H2O)

Process by which metal is extracted (obtained) in pure and free state from their respective
ores is called metallurgy.
Pyro metallurgy
Extraction of ore by using fire or
heating ore at high temperature in
suitable reducing agents
e.g. Extraction of Fe, Zn , Cu,
Hg
Metallurgy
Hydro metallurgy Electrometallurgy
Extraction of metal from their
respective ores by dissolving Extraction of metal is from their
respective ores by electrolysis in
metal ores in suitable solvent
molten or aqueous state
and then followed by
e.g. Extraction of Na, K,
precipitation of metal by
suitable chemicals. Ca
e.g. Extraction of Ag, Au
Steps involved extraction of metal from their ores
( Metallurgical process)
Big lumps of ores are crushed by using jaw crusher and pulverized
1. Crushing & Pulverization into powder form by using ball mills.

Big lumps of ore

Rolling steel balls

Pulverized ore

Jaw crusher Ball Mill

Crushed ore
2. Concentration or dressing
The process of removing gangue particles ( or unwanted earthy impurities-like mud,
sand etc) from powdered ore is called concentration of ore. Based on nature of ore,
the concentration is carried out by following processes:

Gravity separation Froth Floatation Electro Magnetic

Leaching
process separation

Ore particles

Gangue or matrix
i. Gravity separation
The oxide ores like tin stone(SnO2), hematite (Fe2O3), bauxite (Al2O3.2H2O) etc are
concentrated by this process.

Working Principle Based on the difference in densities of the ore and the impurities
(gangue).

Procedure The powdered or pulverized ore is washed with running water

by which the lighter impurities washed away and heavier ore
particles are settled down at the bottom.
i. Gravity separation conti..

Fig. Gravity separation

 ii. Froth Floatation
The sulphide ores like Zinc blend (ZnS), Galena (PbS), Copper pyrites (CuFeS2) Silver
glance (Ag2S) , Cinnabar (HgS) etc are concentrated by this process.

Working Principle Based on the differences in the wetting property or affinity of the
ore towards oil and impurity or gangue towards water

The powdered ore is mixed with pine oil and water in the
Procedure
floatation tank. The mixture is then agitated by blowing air. The
sulphide ore which is wetted by oil comes to surface with froth
while the impurities settled at the bottom of tank with water.
ii. Froth Floatation conti..

Fig. Froth Floatation

 iii. Electromagnetic separation
The non magnetic ore like tin stone (SnO2) containing wolfram (iron-tungsten) as
magnetic impurities or magnetic ore like Chromite [Fe (CrO2)2] non magnetic
impurity like silicon oxide (SiO2)etc are concentrated by this process.

Working Principle Based on the difference in magnetic properties of ore particles&

gangue particles.

The powdered ore is dropped over a conveyer belt moving

Procedure
around two electromagnetic rollers. The magnetic particles (ore
or gangue) is attracted towards magnetic rollers and collected
nearer to magnets and the non magnetic particles (ore or
gangue) drops away from the roller.
iii. Electromagnetic separation conti..

Powdered ore

Magnetic
roller

Moving conveyer belt

Non Magnetic Magnetic

Fig. Electromagnetic separation

 iv. Leaching
It is used when ores are soluble in such solvent in which impurity( gangue) can not
dissolve . Example :Bauxite (Al2O3.2H2O).

Based on difference in the solubility of ore and impurity (gangue)

Working Principle in suitable solvent.

The powdered ore such as bauxite containing impurities such as

Procedure Fe2O3, Fe(OH)3 etc is dissolved in hot concentrated NaOH
solution. In this process the impurities will undissolved which is
removed by filtration process. The filtrate contains sodium meta
aluminate gets hydrolyzed to give precipitate of Al(OH)3
which is then dried and heated to convert it into Al2O3. This is
an example of alkaline leaching process.
 iv. Leaching conti..
Reaction involved Al2O3. 2H2 O + 2NaOH 2NaAlO2 + 3 H2O
Sodium meta aluminate
NaAlO2 + 2 H2 O Al(OH)3 + NaOH

2Al(OH)3 Al2O3 + 3H2O



Hot Conc. NaOH

Dissolved Sodium meta aluminate

Undissolved Gangue

Fig. Leaching
 3. Preliminary Heating-Calcination and Roasting
The calcination is usually carried out in reverberatory furnace and roasting is usually
carried out in rotary hearth furnace or in Multiple hearth furnace .

Purpose The main purpose of preliminary heating of concentrated ore

is to convert the ore into respective oxide which is later
reduced into metal. Other purposes are

i) To remove moisture
ii) to remove volatile impurities like S, As, P etc in the form of
their respective oxides ( i.e. SO2, As2O3, P2O5).
iii) To decompose organic impurities if present along with
concentrated ore
Fig. Preliminary heating of ore in reverberatory furnace
 i) Calcination

Definition  The process in which concentrated ore of metal is converted

into its oxide by heating the ore below its melting point in
limited supply of air or in absence of air is called calcination.

 The ore obtained in calcination process is called calcined ore.

 It is usually carried out for oxides & carbonates ores

(i.e. oxygen rich ores)

Effect of calcination In this process

i) moisture is removed,
ii) water of crystallization is lost,
iii) carbonates and hydroxides are converted into their oxides.
 i) Calcination conti…

Reactions involved
 Fe2O3.2H2O Fe2O3 + 2H2O
(Hematite)
 Al2O3.3H2O Al2O3 + 3H2O
(Bauxite)
 CaCO3.MgCO3 CaO + MgO + 2CO2
(Dolomite)

 ZnCO3 ZnO + CO2

(Calamine)

 CuCO3.Cu(OH)2 2CuO + H2O + CO2

(Malachite)
 ii) Roasting

Definition  The process in which concentrated ore of metal is converted

into its oxide by heating the ore below its melting point in
excess supply of air is called roasting.

 The ore obtained in roasting process is called roasted ore.

 It is usually carried out for sulphide ores (i.e. oxygen

deficient ores)

Effect of roasting In this process

i) moisture is removed,
ii) Volatile impurities like S, As, P are removed in the form of
their oxides SO2, As2O3 and P2O5 respectively.
iii) Sulphide ores are converted into their oxides.
 ii) Roasting conti…

Reaction involved Removal of volatile impurities

 S +O2 SO2 Note : To avoid sulphate
formation, the roasting is done
 4P + 5O2 2P2O5
at high temperature (900OC) in
 4As + 3O2 2As2O3 regular supply of air. At very
Reaction involved oxidation of sulphide ore high temperature, the sulphate
if formed is decomposed into
 ZnS+ O2 ZnO + SO2
respective oxide.
(Zinc Blende) Example:
 PbS + O2 PbO + SO2 ZnS +2O2 ZnSO4
(Galena)
 HgS + O2 HgO+ SO2 2ZnSO4 2ZnO + SO2 + O2
(Cinnabar)
 4. Reduction
The process in which the calcined or roasted ore is reduced by using suitable
ucing agent in order to get metal in free state is called reduction. The reduction is
ried out by any of following process:
Smelting- Reduction by using carbon

Gold-Schmidt’s Alumino Thermic( or thermite)

process- reduction by using Aluminum

Electrolytic reduction- reduction with electron

 i. Smelting
The process in which the calcined or roasted ore is reduced by using carbon (in the form
of coke or charcoal) as reducing agent is called smelting.

Procedure In this process the oxides of metal obtained after calcination or

roasting are mixed with carbon along with suitable flux to
remove impurities(gangue) in the form of slag and heated at
high temperature to reduce metal oxide into metal. Smelting is
usually carried out in blast furnace.

Reactions ZnO + C Zn + CO

CuO + C Cu + CO
Fe2O3 + C 2Fe + 3CO
 i. Smelting cont....
Sometime CO produced in the reaction may also acts as reducing agent.
Fe2O3 + 3CO 2Fe + 3CO2

During smelting process the impurities(gangue) present in ores are also removed in the
form of fusible mass called slag.

Flux + impurities (gangues) slag

CaO + SiO2 CaSiO3

(Basic flux) (acidic gangue) (slag)

CaO + P2O5 Ca3(PO4)2

(Basic flux) (acidic gangue) (slag)
 i. Smelting conti..
Flux is chosen on the basis of nature of the impurities present in ore.

Flux The chemical substances added to ore which reacts with non-fusible
impurity (gangue) to convert it into fusible mass(slag) is called flux.

 If the impurities are acidic (P2O5, SiO2) then basic flux (CaCO3,
CaO, MnO ) is used.

SiO2 + CaCO3 CaSiO3 + CO2
Acidic impurity Basic Flux Slag
 If the impurities are basic ( CaO, MgO, MnO, FeO) then acidic
flux (SiO2 ) is used.

CaO + SiO2 CaSiO3
Basic impurity Acidic flux Slag
Note : Neutral flux such as Fluor Spar (CaF2) is used to increase the fluidity of the molten metal
 i. Smelting conti..

Slag  The fusible substance obtained after the reaction of flux with
impurity(gangue) is called slag.

Slag = Flux + impurities (gangues)

 Slag is lighter than molten metal and float over the surface of
molten metal and can be easily removed.

 Slag is used as Fertilizer.


CaO + SiO2 CaSiO3
Basic impurity Acidic flux Slag
 i. Smelting conti..

Fig. Smelting in Blast Furnace

 ii. Alumino Thermic( or thermite) process- reduction by using Aluminum
The process in which the calcined or roasted ore is reduced by using Al
powder as reducing agent is called Gold Schmidt’s Alumino Thermic
process.

Procedure The oxide of metal is mixed with Al powder and little barium
peroxide (BaO2). The mixture is then transferred into crucible as
shown in fig below. The charge is then ignited, a vigorous reaction
takes place and oxide of metal is reduced into metal. The melted
metal is collected at the bottom of the crucible under alumina.

Reactions Cr2O3 + 2Al Al2 O3 + 2Cr + heat

3MnO2 + 4Al 2Al 2O3 + 3Mn + heat

ii. Alumino Thermic( or thermite) process conti…

Fig. Alumino thermic process

 iii. Electrolytic reduction- reduction by electrons
The process in which the metal is obtained in free state by electrolysis of
their molten or fused salt is called electrolytic reduction. The pure metal is
reduced at cathode.

Example Na metal is obtained from electrolysis of fused or molten NaCl by

using Down’s Process.

NaCl  Na+ + Cl-

Reactions
At Cathode (at –ve terminal- Reduction)
Na+ + e - Na

At Anode (at +ve electrode -Oxidation)

2Cl- Cl2 + 2e-
 iii. Electrolytic reduction- reduction by electrons conti..

Important Note:
 Highly electropositive or active metals like
Na, Mg , Al etc can be obtained by this
process.
 Aqueous solution can’t be used because
active metal produced reacts with water to
give H2
2Na + H2O  2NaOH + H2
 Carbon cannot be used for the reduction of
such ore because at high temperature such
active metal forms carbides.
Ca + 2C  CaC2

Fig. Electrolytic reduction of fused or molten NaCl for extraction of Na metal

iii. Electrolytic reduction- reduction by electrons conti..

NaCl  Na+ + Cl-

Fig. Down’s process for extraction of sodium Metal

 5. Purification or refining of crude metal
The metals obtained from any of the above process (except electrolytic method)
contain many types of impurities ( trace of other metal, Si, P , unreacted oxides &
sulphide etc) which can be removed by any of the following process:

 Impure molten metal in tank is stirred constantly with green pole of wood.
Poling During the poling, the hydrocarbons (CH4, C2H6 etc) of green pole are
oxidized into their oxide and metallic oxide are reduced to metal.
 This method is employed for those metals which contains their own oxide as
impurities.
 Pb, Cu metals can be purified by this method.

Reaction 3Cu2O + CH4 6Cu + CO + H2O

(from green poles)
 5. Purification or refining of crude metal conti..

Green pole

Poling
 5. Purification or refining of crude metal conti..

Liquation  Impure metal is placed in a sloping hearth furnace and heated then metal
melts and flow away leaving behind the impurities in grooves.

 This method is employed for easily fusible metals like Sn , Pb, Bi, Hg etc
containing non-fusible impurities.
 5. Purification or refining of crude metal conti..

Liquation
 5. Purification or refining of crude metal conti..

Distillation  Impure metal is heated in a vertical retort (for Zn) or Shaft

furnace ( for Hg) and its vapor are separately condensed in a
receiver. The pure metal collected as distillate and impurities left
behind.

 This method is done for purification of volatile metal (metals

with low boiling point i.e. Zn , Cd, Hg etc..
 5. Purification or refining of crude metal conti..

Electrolytic Refining  Impure metal is made anode and the cathode consists of
piece of pure metal in soluble salt of metal as electrolyte.
When the current is passed, then crude metal dissolves from
anode and pure metal is deposited at cathode while
impurities are settled at the bottom of the tank near anode
( which is called anode mud) .
 Cu, Sn, Pb, Al, Ag , Zn etc are purified by this method.

Reactions At Anode (Impure Cu)

Cu Cu + + + 2e-

At Cathode (pure Cu)

Cu + + + 2e- Cu
5. Purification or refining of crude metal conti..

Fig. Electrolytic refining of crude Cu

 5. Purification or refining of crude metal conti..

Zone Refining  Principle: when an impure metal in a molten state is

allowed to cool, only the metal crystallizes while the
impurities remain present in the molten state (mass) or melt.

Process  The impure metal converted into a rod which is heated at

one end with a circular heater. A narrow zone of metal is
melted. The heater is slowly moved along the rod. The pure
metal recrystallizes out of melt while the impurities remain
in the melt which moves along with the melted zone of the
rod with the movement of heater. The process is repeated
several times. The end of rod where impurities have
collected is cut off. This method is employed for the
purification of germanium, silicon, gallium etc, which are
used in semi – conductors.
 5. Purification or refining of crude metal conti..
Zone Refining
Moveable Circular
Pure Metal Heater
Impure Metal

Molten Zone containing Direction of movement of

impurities molten zone & impurities
The End