Iron Making MM 321

3 credits

Course Teacher: Dr. Natraj yedla

Source: IITM; Metallurgical and Materials Engineering Dept.
 Objectives of the course
What are the raw materials for iron making?

Burden preparation

Distribution of burden

Physical-thermal–chemical process in a blast furnace

Layout of blast furnace

Blast furnace products

Alternate routes of iron making

 History of iron making

Use of iron by Egyptians dates back to 6000 BC

Use of iron in Indian: 3000 years ago; WOOTZ steel: the oldest steel

What is an ore?
What is a mineral?

An ore is a type of rock that contains minerals with important elements
including metals and from which metal can be extracted economically
A mineral is an element or chemical compound that is normally crystalline and
that has been formed as a result of geological processes

Primitive iron making

Furnace: stone and clay

charged with ore and charcoal
Air was blown through the charge continuously until the operation was over.
Modern iron making

Iron was produced by reduction smelting of iron ores with coke

Smelting: It is a heating process for the production of metal or matte. It involves reduction of
the oxide of the metal with carbon/sulphur/sulphide in a suitable furnace

Mineral+ gangue + reducing agent + flux = metal+slag+gas

Furnace: Blast furnace

Elevation view of a blast furnace
Raw materials used in blast furnace

1. lump iron ore

2. Sinter/pellets
3. Coke
4. Fluxes (limestone/dolomite)

Iron ore deposits in India

1. India stands third in the world iron

ore reserves after Brazil and
Australia
2. Bihar and Orissa have 43% of total
iron ores reserves in India
(Singhbum, Keonjhar, Bolani,
Mayurbhanj and Cuttack districts)
3. Madhya pradesh-Bailadila
4. Karnataka-Mysore,
5. Goa
6. Andhrapradesh-Anantapur,
kurnool, Nizamabad
 ORES of Iron
1. Hematite- Fe2O3
2. Magnetite-Fe3O4
3. Limonite-FeO(OH)·nH2O
4. Carbonate-FeCO3
2300 million tonnes of iron ore reserves in India
85% is Hematite
8% is Magnetite
7% rest

Iron content of Hematite ores is >55%

Iron content of Magnetite ores is >30%
Reducing agent used: coke

Coke is obtained by destructive distillation of coal

coal reserves

Jharkhand, westbengal, bihar, orissa, MP, UP

Coking coal reserves (low ash content, volatile matter)

Jharia-Jharkhand
Bokaro-MP
Ramgarh-WB
Karanpura-Bihar

What are the different fluxes

1. Lime stone (CaCO3)
2. Dolomite (MgCO )
 Class-II
1. Crushing of the iron ores from ROM (Run off mine )
2. 10-40 mm size is used as lump ore in blast furnace
3. 6-8 mm and above 100 mesh is used for sintering
4. Below 100 mesh size ore is rejected or used to make
pellets
5. So iron ore is charged in the blast furnace in the form of
a) Lump iron ore
b) Sinter
c) pellets
 Ore beneficiation

Involves increasing the iron content of the ore from 55% to

65%

Why beneficiation is required?

a) To increase the production of iron
b) To decrease the coke consumption rate

The above will result in decrease in slag volume

 Sinter
Purpose of sintering : To utilize iron ore fines

What is the problem in charging iron ore fines in the blast

furnace?
Sintering is incipient fusion of iron ore particles at
temperature near the melting point resulting in the formation
of agglomerates.

The process requires heat

Charge is a) iron ore fines: 6-8mm

b) flux: 3 mm
Steps preceding sintering
 The raw materials are individually stored in bins.
The materials are discharged from the bins in the prescribed
amounts onto conveyor belt.
A shuttle type conveyor belt takes all the materials together to the
bedding and blending yard.
The discharge from the conveyor is heaped in the shape of
triangular piles of the mixed materials on the ground.
The mix is scooped and arranged in the form of long horizontal
layers.
 ~300 layers make one bed.
 Sintering process
Iron ore fines of size less than 10mm are
sintered to produce lumps of size range 5-
40 mm

Sintering machine : Dwight-lloyd

 It is 8 m in width, 500 m2 useful grate area
Production capacity: 24,000t/day
It is an endless band of pallets moving over rails
 there are two large pulleys, one of which is
driven by a motor through a reduction gear system
The raw materials are loaded at one end of the
machine and the top layer is ignited as it comes
under a fixed ignition hood
As the pallets move, the ignited portion comes
over a series of stationary wind boxes connected to
an exhaust blower.
 sintering of the charge is completed by the time
the pallet travels over nearly the whole useful
length of the machine.
The sintered cake drops out at the other end when the pallets turn upside down
The cake is broken, screened and the over size is cooled
The undersize usually -9mm is returned to the machine for resintering whereas the
oversize after rescreening goes to the blast furnace as charge
From the discharge end the pallets return to the feed end in inverted overhung
fashion on rails
The exhaust gases are let of into the atmosphere through a chimney after dust
extraction

So the important parts of the machine and its accessories

1. Storage bins, mixers, feeders

2. Charge leveller
3. Ignition hood
4. Band of pallets and rail for its movement
5. Drive mechanism
6. Sinter breaker, screen, cooler
 Class III

Storage bins, mixer and Feeder

• Raw materials: iron ore fines, coke breeze limestone
• The raw materials are stored in separate overhead
bins from where weighted amounts of these are
delivered to the mixer to prepare a homogeneous
feed mix (water is added to moisten the feed) .
• The mixer is a tromel or drum fitted with paddles
• The moist charge is rolled in a drum to nodulise the fines
and thereby decrease the size range of the particles and
improve the permeability of the sinter bed.
• The mix is then laid on to the pallet

What happens if bed permeability decreases?

 2. Charge leveler

For smooth working a uniform thickness of the bed is

necessary.
A flat plate is fitted immediately after the feeder to
level off the charge.
A cut of plate is adjusted to obtain a thickness of
300-400 mm
 3. Pallet
1. The pallet has to support the mix during its travel from the feed
end to the discharge end.
2. Withstand high temperature (1150 - 1250 °C ), efficient seal
with the stationary windboxes
3. The grate bars laid at the bottom of the pallet should provide
maximum openings without allowing excessive fine materials
being pulled into the wind boxes during suction.
4. The aperture in the grate <= 6mm to avoid excessive dust
losses.
5. Since the pallets move over static windboxes the pallets must
ensure leak proof seals.
 4. Drive mechanism
• The pallets move from feed end to the discharge end and after
discharging the sinter cake return back to the feed end in
overhung fashion on the lower rail track.
• The drive mechanism is responsible for smooth change over
from lower to upper rails.
• Reduction gear system: to control speed.
• Gap between the pallets 60-75 mm for allowing thermal
expansion.
 5. Ignition hood
• Ensure proper ignition of the top layer-why?
Effects the output and quality of the sinter

Two main types of ignition hoods are used

1. Combustion chamber type
two burners at the discharge half side of the hood
Heating of the charge takes place partly directly
and partly by the radiation from the hot roof
2. Nozzle or torch type

 One or more rows of burners are fitted into the

hood.
 The flame directly impinges into the charge and
radiation plays a relatively minor role.
 Source of heat: coke oven gas and blast furnace
gas.
 Product handling
• The sinter cakes are dumped at the discharge end in
the same shape as that of the pallet.
• The big pieces are broken by sinter breaker (prongs
or claws mounted on a shaft)
• The sinter is broken, crushed, screened and the
oversize is cooled and then transported to the blast
furnace by rubber conveyor belt.
 Spillage collector
• Bunker is installed below the bottom track to collect the
spillage
Waste Gas system
• Thickness of the bed
• Quality of the feed
• Ignition condition
• Amount and quality of the fuel in the mix
An exhaust blower is provided with the machine
Suction capacity: 45-500 m3/s
 Objectives of sintering
• To increase the size of the ore fines to a level acceptable
to the blast furnace.
• To form a strong agglomerate with high bulk reducibility.
• To remove volatiles like CO2 from carbonates;
H2O from hydroxides and sulphur from sulphide ores
• To incorporate flux in the burden
Formation of slag is easier
It forms at correct level in the blast furnace
 Types of sinter
• Acid sinter
 The sinter mix does not contain flux at all
• Fluxed sinter
 The amount of flux added in the mix is such that the basicity of the
mix = basicity of slag to be produced in the furnace.
 Additional flux is required when ore lumps are charged.
• Super-fluxed sinter
Flux added in sinter mix = flux added in the furnace
when run on 100% iron ore lumps
The basicity of the mix will be much higher than the basicity of the slag
produced in the furnace
No flux addition is required in the furnace if super-fluxed sinter is used
 Free energy

• Free energy = internal energy-energy that

cannot be used to perform work
• G= Gibbs free energy (at const temperature and
pressure) = H-TS
• Molar heat capacity at constant volume C v=
dqv/dt=?
• Constant pressure Cp = dqp/dt= �
H /�
T
Since q= E+Pv and H=E+Pv
• Absolute values of thermodynamic quantities such
as internal energy and enthalpy cannot be
obtained. The diference in their values in two
diferent states can always be determined.
• Standard heat of formation of a compound is
equal to the heat of reaction by which it is formed
from its elements
2 Al (1 atm, 298 K) + 3/2 O2 (1 atm, 298 K) Al2O3 (1 atm, 298 K)
∆H°298 = -400 K cal
 Second law of thermodynamics
 It is useful to process metallurgist because, it provides
a method of predicting the conditions under which a
process is thermodynamically feasible
ds=
�q /T

 For an isolated system entropy always increases

 Any spontaneously occurring change in an isolated

system is accompanied by an increase in entropy
• ∆H = +ve the reaction is ?
• ∆H = -ve the reaction is ?
• G=H-TS
• ∆G= ∆H-T∆S
• ∆H-T∆S=0 for reversible or equilibrium process
<0 for a spontaneous process
>0 for an impossible process
• A reaction always proceeds towards
equilibrium
• no reversible reaction can proceed beyond
equilibrium.
• To determine whether a reaction takes place
completely, we have to understand the factors
that control equilibrium.
• Standard free energy change
It is the free energy state when all the reactants
and products are in their standard state
∆G° (I atm, temperature)
Standard or reference state is the most stable form
of pure substance
The free energies of all the elements in their
standard state are assumed to be zero at all
temperatures
• aA+bB = cC+dD
∆G= cGC + dGD – (aGA +bGB )
∆G°= cG°C + dG°D – (aG°A +bG°B )
∆G-∆G°= RT ln a (a = activity)
∆G=∆G°+ RT ln (acC x adD )/ (aaA x abB )-----(1)
Reaction (1) will proceed until equilibrium is
attained so ∆G=?
∆G°=?
• ∆G° = -ve at a given temperature then forward
reaction is spontaneous provided that the
reactants and products are in their standard
states at unit activity
So K value will be large/small?
• ∆G° = +ve (forward reaction takes place)
So K value will be large/small?
 Gibbs free energy vs temperature
• Graphical representation of standard free energy vs
temperature for compounds such as oxides and
sulphides-ELLINGHAM diagram
• ∆G° can be calculated by the following equations
∆G°= A+BTlogT+CT (A,B,C are constants; T=temp)
∆G°= ∆H°-T ∆S°
Calculation of ∆G° from the above is tedious so
Ellingham diagram is the easiest and simplest method
for accurate calculation of ∆G°
∆G°= a-bT (a and b are the mean values of ∆H° and ∆S°)
• The free energies of formation of compounds
such as oxides and sulphides are represented
in the form of linear plots over wide range of
temperatures
• Why linear?
• ∆G°=a-bT
• In the ED For oxides, the free energy change ∆G°,
when one mole of gaseous oxygen at 1 atm
combines with a pure element to form oxide is
plotted against temperature.
• It is possible to compare relative reducing or
oxidizing tendencies of oxides and elements.
4/3 Al (l)+O2(g) = 2/3 Al2O3(c) ∆G° = -200 kcal at 1000
°C
2Ca (l) + O2(g) = 2 CaO (c) ∆G° = -243 kcal 1000 °C
• 2/3 Al2O3 (c)+2Ca (l) = 2CaO(c) +4/3Al
∆G° = -43 kcal at 1000 °C

Inference
Alumina can be reduced by calcium at 1000 °C to
Aluminum
• Highly stable oxides are found at the bottom and less
stable oxides occupy higher position
• An element occupying a lower position in the diagram
can always reduce the oxide of another metal lying
above it
Condition: when all the reactants and products are in their
standard state
∆G°= ∆H°-T ∆S°
slope of the equation: -∆S°
Intercept on y-axis= ∆H°
An increase in slope corresponds to the reactant undergoing
phase transformation.
Decrease in slope corresponds to product undergoing phase
transformation
Change in slope is related to the ? of transformation of the
reactants or products
A large change in slope suggests a transformation from
condensed state to the gaseous state
A small change in slope is expected for a melting or for a
transformation from one solid phase to other
All the lines are parallel
• Upward slopes of most of the lines indicate that
the oxides become less stable as the temperature
increases
• Downward slopes – oxides are more stable at
higher temperature.
Concept check
solid state liquid state---(1)
Solid stategaseous state---(2)
Entropy is higher in which case?
• 2M+O2= 2 MO
1 mole gas 0 mole gas
∆S= -ve ∆G°= +ve so slope will be +ve
2C+O2 (g) = 2 CO (g)
1 mole gas 2 mole gas
∆S= +ve ∆G°= -ve so slope will be –ve
C+O2 (g) = CO2 (g)
1 mole gas 1 mole gas
∆S= 0 ∆G°= ∆H° ; slope will be zero (no variation of free energy
with temperature)
• Concept check
• CO is more stable at higher/lower
temperatures
• 2C+O2 (g) = 2 CO (g)
∆S° increases and ∆G° decreases with increasing
temperature- this makes carbon act as a useful
reducing agent
The temperature at which a line of any M-MO intersects
with C-CO line indicates the MO reduction by C
Al2O3 gets reduced by carbon at 2000 °C
MnO gets reduced by carbon at 1400 °C
What is the reason for the above?
• 2C+O2 (g) = 2 CO (g) C-Co line
• C+O2 (g) = CO2 (g) C-CO2 line
These lines intersect at 723 °C so
Above 723 °C which is stable CO/CO2
So reduction of any MO by C at temp> 723 °C
will produce CO/CO2
• Reduction of MO by reducing agent other than C
• It is not always necessary that the two curves intersect
each other for reduction
Find whether reduction of Cr2O3 by Al or Pb at 1200 °C is
possible from the diagram as well as from ∆G° values
4/3 Cr+O2 =2/3 Cr2O3 ∆G° f = -120 kcal/mol of O2
4/3 Al+O2 =2/3 Al2O3 ∆G° f = -190 kcal/mol of O2
2 Pb +O2 = 2PbO ∆G° f = -40 kcal/mol of O2
Ascending order of stability of oxides?
 Why top charging is employed
• In order to clean the top gas for its utilization as
fuel
- It is necessary to have a top charging device by
which solids could be charged into the furnace
without significant leakage of the gas
- The above led to the invention of double bell
charging system
- Gas flows through uptakes continuously while
charging cycle goes on
Stage -I
• Small bell and large bell closed
• The charge is dumped in the hopper above small bell
Stage-II
• Large bell remains closed while small bell opens to
admit charge to large bell hopper
Stage-III
• Small bell closed to prevent escape of gas to atmosphere
and large bell will open to admit charge to the furnace
Stage-IV
• Both the bells are closed and are ready for
repeat charging cycle
• Both the bells are operated independently
• Material consisting of varying sizes, shapes
and densities fall inside the furnace with
various trajectories of individual particles
• How the distribution effects the permeability
of the bed
• What is permeability
Passage of reducing gas through the bed
 Factors affecting the distribution inside the
F/C
 Design of the B/F and its charging device
• Angle and size of the big bell
• Speed of lowering of the big bell
 Physical properties of the charge m/l’s
• Size range of charge m/l’s
• Angle of repose of raw m/l’s
• Density of charge m/l’s
 Level, system and sequence of charging
• The production rate of B/F is determined by

i) Rate of reduction of iron oxide

ii)Rate of heating of the burden

The above two factors are dependent on the quantity of blast that goes through the f/c

Rate of reduction of iron oxide: the degree and the time of contact of the reducing gases with the burden

Therefore the burden inside the furnace should have uniform and good bulk permeability

What we expect?

The uniform distribution of reducing gas throughout the horizontal and vertical cross-section of the f/c for efficient reduction and

heating of the burden.

What we achieve by better permeable burden?

The gas-solid contact will be uniform

Allows a large amount of blast to be forced through the furnace

Conclude:

The distribution of the charge in the throat of the furnace determines the performance of the f/c
 Size of the charge particles
• The packing density or bulk density increases and correspondingly the permeability
decreases with increase in the size range of the particles
• Permeability (gas flow through the burden) also decreases with increase in fines in the
bed
• Result of low permeability---
i) increase in gas blowing pressure for the same amount of gas.
ii) Decrease in reduction rate
Wider range of sizes in the charge is more prone to segregation and hence crest formation
Remedy
Screen of -5 mm size fraction before charging the materials in the furnace
For better stack permeability and adequate bulk reducibility
The following size ranges of ore are preferred
More reducible ore +10-37 mm
Less reducible ore +10-25 mm
Sinter +5-50 mm
Pellets +9-16 mm