Iron Making

Iron ore and its uses

• Iron accounts for approximately 95% of all
metals used by modern industrial society.
Elemental Iron (Fe) is ranked fourth in
abundance in the earth's crust and is the major
constituent of the Earth's core.
• Pure iron is silvery white, very ductile, strongly
magnetic and melts at 1530° C.
• Although iron is a common element, pure iron
is almost never found in nature.
Most iron is found in minerals formed by the
combination of iron with other elements.
Major iron compounds are:
Name Formula %Fe
Hematite Fe2O3 69.9

Magnetite Fe3O4 74.2

Goethite/Limonite HFeO2 ~ 63

Siderite FeCO3 48.2

Chamosite (Mg,Fe,Al)6(Si,Al)414(OH)8 29.61

Pyrite FeS 46.6

Ilmenite FeTiO3 36.81

• "Pig iron" is most
commonly produced
from the smelting of
certain iron compounds,
which is referred as
"iron ores".
• The most common process is
the use of a blast furnace to
produce pig iron which is
about 92-94% Fe and 3-5% C
with smaller amounts of
other elements, e.g., Si, Mn,
P and S.
• Pig iron has only limited uses,
and most of this iron goes on to
a steel mill where it is converted
into various steel alloys by
further reducing C content and
adding other elements, e.g., Mn,
Ni, Cr, …, to give the steel
specific properties.
 Pig-Iron Production
• The pig-iron is produced in a blast-furnace
which typically consists of a cylindrical steel
hull and a refractory lining on the inside. The
lower part of the furnace (crucible) has
openings (tuyeres) through which hot air is
injected. Two openings closer to the bottom are
used to tap the iron and an opening above that
is used to tap the slag. To tap the iron the
refractory clay plug is pulled out of the hole.
The raw materials are charged through two
openings. The blast-furnace gas is released
through another opening.
The blast furnace process.
1. Iron ore + limestone sinter 8. Removal of slag 14. Smoke outlet
2. Coke 9. Tapping of molten pig iron 15: Feed air for Cowper stoves (air
3. Elevator 10. Slag pot pre-heaters)
4. Feedstock inlet 11. Torpedo car for pig iron 16. Powdered coal
5. Layer of coke 12. Dust cyclone for separation of solid particles 17. Coke oven
6. Layer of ore, sinter and limestone 13. Cowper stoves for hot blast 18. Coke
7. Hot blast (around 1200 °C) 19. Blast furnace gas downcomer
1. Hot blast from Cowper stoves (heath) 5. Pre-heating zone (throat) 9. Removal of slag
2. Melting zone (bosh) 6. Feed of ore, limestone, and coke 10. Tapping of molten pig iron
3. Reduction zone of ferrous oxide (barrel) 7. Exhaust gases 11. Collection of waste gases
4. Reduction zone of ferric oxide (stack) 8. Column of ore, coke and limestone
 The Blast Furnace Charge (Raw Materials)
• Iron ores (source of iron) are mainly iron oxides and
many other rocks. The iron content of these ores
ranges from 70% down to 20% or less.
• Coke (fuel and reducing agent) is a substance made
by heating coal until it becomes almost pure carbon.
• Sinter (source of iron) is made of lesser grade, finely
divided iron ore which, is roasted with coke and lime
to remove a large amount of the impurities in the ore.
• Limestone (flux) occurs naturally and is a source of
calcium carbonate.
 Modern furnaces
• The largest modern blast furnaces
have a volume around 5580 m3 and can
produce around 80,000 tonnes of iron
per week.
• This is a great increase from the
typical 18th-century furnaces, which
averaged about 360 tonnes per year.
 Charging the blast furnace (B.F.)
After processing, the ore is blended with other ore
and goes to the blast furnace. A blast furnace is a
tower-shaped structure, made of steel, and lined
with refractory or heat-resistant bricks.
The mixture of raw material, or charge, enters at the
top of the blast furnace. At the bottom of the
furnace, very hot air is blown, or blasted, in through
nozzles called “tuyeres”. The coke burns in the
presence of the hot air. O2 in the air reacts with C in
the coke to form CO. Then CO reacts with the iron
ore to form CO2 and pure Fe.
 Separating the iron from the slag
The melted iron (Fe) sinks to the bottom of the
furnace. The limestone combines with the rock and
other impurities in the ore to form a slag which is
lighter than the Fe and floats on top. As the volume
of the charge is reduced, more is continually added
at the top of the furnace. The iron and slag are
drawn off separately from the bottom of the furnace.
The melted iron might go to a further alloying
process, or might be cast into ingots called pigs. The
slag is carried away for disposal.
 Treating the gases
The hot gases produced in the chemical reactions are
drawn off at the top and routed to a gas cleaning
plant where they are cleaned, or scrubbed, and sent
back into the “Cowper Stoves” and the furnace; the
remaining CO, in particular, is useful to the
chemical reactions going on within the furnace.
A blast furnace normally runs day and night for
several years. Eventually the brick lining begins to
crumble, and the furnace is then shut down for
maintenance.
 Quality Control
The B.F. operation is highly instrumented and is
monitored continuously. Times and temperatures
are checked and recorded. The chemical content of
the iron ores received from the various mines are
checked, and the ore is blended with other iron ore
to achieve the desired charge. Samples are taken
from each pour and checked for chemical content
and mechanical properties such as strength and
hardness.
 Byproducts /Waste
The process of extracting Fe from ore produces
great quantities of poisonous and corrosive gases. In
practice, “B.F. gases” are scrubbed and recycled as a
fuel. It is burned in the hot blast stoves, boilers, etc.
A main byproduct of Fe purification is slag, which is
produced in huge amounts. This material is largely
inert. Nowadays in most countries “iron slag” is
considered as a product not waste. “B.F. gases” is
used as a raw material for some industries, e.g.,
cement and fertilizer, and as building materials for
road construction.
 Byproducts / Waste
Iron-making uses up huge amounts of coal. The coal is
not used directly, but is first reduced to coke which
consists of almost pure carbon. The many chemical
byproducts of coking are almost all toxic, but they are
also commercially useful. These products include
ammonia, which is used in a vast number of products;
phenol, which is used to make plastics, and antiseptics;
cresols, which go into herbicides, pesticides,
pharmaceuticals, and photographic chemicals; and
toluene, which is an ingredient in many complex
chemical products such as solvents and explosives.
 Chemistry of the B.F. process
The main chemical reaction producing the molten pig iron is:
Fe2O3 + 3CO → 2Fe + 3CO2
This reaction might be divided into multiple steps, with the first
being that preheated blast air blown into the furnace through
tuyeres (at the hearth) reacts with C in the form of coke to
produce CO and heat:
C(s) + O2(g) → CO2(g)
C(s) + CO2(g) → 2 CO(g)
2 C(s) + O2(g) → 2 CO(g)
So, the gas composition in the hearth zone will be about 35% CO
and 65% N2. This produced gas rapidly ascends the stack, giving
up heat to the burden materials and reducing them (i.e., iron
oxides, moisture and other compounds).
C(s) + H2O → H2 + CO
Thus, reducing agents in the blast furnace: C , CO & H2.
Reduction of iron oxides:
Depending on the temperature in the different parts of the furnace
(warmest at the bottom) the iron oxide (Fe2O3) is reduced in several
steps, as follow:
 At the top, where the temp. usually is in the range between 200 °C
and 700 °C, “Fe2O3” is partially reduced to “Fe3O4”.
3 Fe2O3(s) + CO(g) → 2 Fe3O4(s) + CO2(g)
 At temps. around 850 °C, further down in the furnace, “Fe3O4” is
reduced further to “FeO”:
Fe3O4(s) + CO(g) → 3 FeO(s) + CO2(g)
 As “FeO” moves down to the area with higher temperatures, ranging
up to 1200 °C degrees, it is reduced further to “Fe” metal:
FeO(s) + CO(g) → Fe(s) + CO2(g)
 At temps. less than 572 °C, “Fe3O4” can be reduced by “CO” to “Fe”:
Fe3O4(s) + 4 CO(g) → 3 Fe(s) + 4 CO2(g)
In presence of H2 similar reduction reactions of iron
oxides occur:
3 Fe2O3(s) + H2 → 2 Fe3O4(s) + H2O(vap.),
Fe3O4(s) + H2 → 3 FeO(s) + H2O(vap.),
FeO(s) + H2 → Fe(s) + H2O(vap.),
and at temp. less than 572 °C,
Fe3O4(s) + 4 H2 → 3 Fe(s) + 4 H2O(vap.).
Hot “CO2”, unreacted “CO”, and “N2” from the air pass up through the
furnace as fresh feed material travels down into the reaction zone. As
the material travels downward, the counter-current gases both preheat
the feed charge and decompose the limestone (CaCO3) to “CaO” and
“CO2” (in the temperature range 500 - 850oC):
CaCO3(s) → CaO(s) + CO2(g)
The carbon dioxide formed in this process is re-reduced to “CO” by the
coke:
C(s) + CO2(g) → 2 CO(g)
The temp.-dependent equilibrium controlling the gas atmosphere in the
furnace is called the Boudouard reaction:
2 CO → CO2 + C
“CaO” formed by decomposition reacts with various acidic impurities
in the iron (notably silica), to form a molten slag which is essentially
calcium silicate (CaSiO3):
SiO2(s) + CaO(s) → (CaSiO3)
Reduction of other oxides:
 Manganese oxides are introduced into the charge with iron ore, and are reduced similar
to iron oxides:
2 MnO2(s) + CO(g) → Mn2O3(s) + CO2(g)
3 Mn2O3 + CO(g) → 2 Mn3O4(s) + CO2(g)
Mn3O4 + CO(g) → 3 MnO(s) + CO2(g)
 However, MnO is reduced by C only in the high temperature zone, i.e., at temp. above
1000°C:
MnO(s) + C → Mn + CO(g)
 About 1% only of SiO2 is reduced by C at high temp. > 1100°C.:
SiO2(s) + 2 C → Si + 2 CO
 The reduction of MnO, SiO2, … etc., in the blast furnace is facilitated by the fact that
the reduced product (Mn, Si, …) dissolves in molten iron:
e.g., (MnO) + [Fe] + CO → [Mn]Fe + CO2
 The reduction of phosphorous from calcium phosphate (which is introduced with the
iron ore) is facilitated by SiO2 at high temperature:
2 Ca3P2O8(s) + 3 SiO2(s) + 10 C → 3 (Ca2SiO4) + 10 CO + 4 [P]
 All phosphorous introduced into the blast furnace is reduced and enters the pig iron as
iron phosphide [Fe3P].
 Oxides of nickel (Ni) and cobalt (Co) reduced at low CO/CO2 ratio in the gas. Therefore,
all Ni and Co contained in the iron ore enter the produced pig iron.
 Formation of Pig Iron
 Reduction of the iron ore pieces (lumps, pellets, etc.) produces masses of solid
sponge iron (porous solid masses) which is carburized by CO according to the
following reactions:
2 CO → CO2 + C ……….…….… (1)
3 Fe + C → Fe3C ………….….… (2)
 Or an overall reaction:
3 Fe + 2 CO → Fe3C + CO2 …… (3)
 CO finds its way into the pores of sponge iron masses, decomposes on the surface of
the reduced iron, reaction (1), and the resultant C is absorbed by Fe, reaction (2).
 Carburized iron has a lower melting point, e.g., Fe-C eutectic (4.3% C) melts at
1130 oC.
 Carburized iron melts at the top of the bosh and drips between the coke lumps,
picking up some more C.
 The presence of carbide forming elements in pig iron, e.g., Cr and Mn, increases
total C in it. However, Si, P and S, which combine with Fe, decrease C in pig iron.
In addition, Si promotes the decomposition of Fe3C and precipitation of C as
graphite. This effect improves the mechanical properties of pig iron, therefore,
foundry pig iron is smelted so as to have more Si in it than in steel-making irons
(conversion pig iron).
 Slag formation
Slag formation in the blast furnace is a process by which the molten oxides of
the gangue and the ash in the fuel (coke) combine with the flux oxides to form
B.F. slag. It begins after iron has been reduced and carburized and the pig iron
has begun to melt.
The first drops of molten slag appear at the lower end of the stack as low-
melting eutectics. Its amount increases rapidly as it dissolves FeO and MnO,
forming fluid low-melting silicates of Fe and Mn.
The slag at the lower end of the stack and the top of the parallel bosh carries up
to 20% FeO. As the slag drops down, it gradually loses much of FeO and MnO
by reduction and pick up much CaO instead, which raises its melting point.
The gangue of the ore usually carries some Al2O3, which has a considerable
effect on the melting point and fluidity of the slag. The absence of Al2O3 in the
gangue retards slag formation.
The final composition of B.F. slag is directly dependent upon the composition of
the charge and the grade of pig iron being smelted.
 B.F. slag
 Essential composition of B.F. slag:
 30-40% SiO2 , 10-20% Al2O3 , 40-50% (CaO + MgO).
 Basicity of the B.F. slag (β) = (CaO + MgO) / SiO2 = 1.2 - 1.4 .
 B.F. slag must be sufficiently fluid at 1450 oC. A slag will be
sufficiently fluid when the ratio of (SiO2 + Al2O3) / CaO = 1.
 A dense and viscous slag hampers normal furnace working. It is
sticks to the bosh lining to form what is known as scaffolds,
which interferes with the descent of the burden, and is difficult
to flush from the furnace.
 B.F. slag may be utilized in the production of cement, fertilizer
and building materials (e.g., slag building blocks, mineral wool,
blocks for paving roads, etc.).
 Behavior of Sulfur in Blast Furnace
Sulfur is present in iron ore and coke as FeS2 (pyrite), FeS and stable sulfates
(e.g., FeSO4). In the sinter sulfur is present as FeS and sulfates. The pyrite is
decomposed before pig iron is produced:
2 FeS2 → 2 FeS + S2
and half of produced sulfur is carried away in the gases.
Most of sulfur is introduced into the burden with coke. When coke burns, S is
oxidized forming SO2 which is reduced by C. The resultant gas combines with
some Fe and Mn and enter pig iron as FeS and MnS.
Desulfurization of pig iron requires a basic slag and is effected when molten
metal (pig iron) drips the slag bed and at the metal/slag interface owing to the
formation of CaS which is insoluble in pig iron and soluble in the slag:
[FeS] + (CaO) → (FeO) + (CaS)
[MnS] + (CaO) → (MnO) + (CaS)
The two previous reactions are endothermic, thus, the solubility of S in slag
increases with increasing temperature and basicity (CaO/SiO2) of the slag, and
with reduction of (FeO) and (MnO) contents. The overheating of high-lime slags
raises their fluidity and reactivity.
For slag of high basicity, desulfurization reaches 60 - 80% of total S introduced
with the B.F. charge.