BENEFICIATION OF IRON ORES
Regardless of the process of mining, the consistency of the product of the mine is
improved, after screening and crushing, by blending, and re-claiming. The outputs of
similar but not identical deposits may be blended already at the crusher. Almost
invariably bedding is applied, whether the run-of-mine is to be beneficiated or not; the
ore is laid on the ground in one direction, and the subsequent layer is laid on top of and
perpendicular to the previous one. When the ore is reclaimed for shipment or further
operation, this cris-crossing of the layers has already smoothed out mainly chemical and
physical variations.
Concentration Processes
Earliest attempts to upgrade iron ores come under the general heading of “washing”
processes in which clay and fine sand are removed as suspended solids in a flowing
stream of water that overflows the washer. The heavier iron-bearing particles sink to the
bottom of the separating vessel and are removed as a concentrate. Modern gravity
separation methods use the same principles and involve the use of heavy media. In this
case, relatively coarse ore (5-40mm) is fed to an oscillating trough containing a
suspension of finely ground magnetic material, usually ferro-silicon, in water. By varying
the concentration of solids, suspensions of different densities can be obtained and
although the physics governing their behaviour is complex, they do exhibit properties
that are remarkably similar to those of real liquids with same density. Thus light materials
such as quartz (s.g = 2.65) can be separated from haematite (s.g = 5.0) by employing a
‘liquid’ of intermediate density (say s.g= 3.00).
Differences in the gravitational attraction forces experienced by minerals forms the basis
of a number of other concentration methods, but only two have relevance to iron ores.
These are jigs and spirals.
In jigging, closely-sized ore is fed to a jig containing water that is mechanically agitated,
causing heavier minerals to accumulate on the bottom of the jig, from which they are
continuously removed.
Spirals consist of an inclined launder whose cross-section is curved. Ore in the size
range 0.1-1.5mm is washed down the concave surface and stratification occurs with the
heavier minerals collecting at the lowest point of the launder, whilst the lighter minerals
are to be found nearer to the rim. Separation is a slow process so that the launder has to
be a considerable length. For this reason, it is constructed as a spiral and it is usual for a
number of spirals to be needed to effect a sufficient degree of concentration.
Nevertheless, it is attractive method, not least because the driving force is gravity, which
leads to low operating costs. Much of the low-grade ore from the great lakes area of
North America is treated by use of spirals.
Froth flotation is a concentration technique that was widely applied to other metal ores
before being adapted for use with iron ores. Briefly, in this method fine iron is fed to a
flotation cell where it is agitated with air, and by the use of suitable collectors and
frothers, the iron oxides are floated and collected as a concentrate.
1
Magnetic separation is, in principle, one of the simplest beneficiation methods and when
applied to iron ores, either a wet or dry process can be employed, from less magnetic or
non-magnetic materials, a low intensity wet separator consisting of a rotating drum and a
stationery, internal magnet is used when the particle size is small (0.1mm). Magnetite
adheres to the drum as it passes through a suspension of iron ore particles in water, but
when the adherent solids are carried out of the magnetic field they are scrapped off the
drum and transferred to a receiving vessel. When the particle size is larger (>5mm), a
dry process is possible. For example Hematites are naturally less easy to concentrate by
magnetic methods, but some success has been achieved using dry, high-intensity
machines, a related practice, which has limited attractions, is to give hematite ore a
magnetizing roast by heating it to a temperature of 600-800oC in a reducing atmosphere.
This is followed by magnetic concentration, but the heat requirements of roasting
represent a heavy expenditure on energy, which detracts from the usefulness of the
overall operations.
Pelletizing
The manufacture of fired pellets having diameters in the range 10-15mm can be
accomplished in a number of ways, but once the concentrate is prepared there are four
processing stages.
These are as follows:
1. Balling – This refers to the formation of soft, wet spherical agglomerates, known
as ‘green’ balls, from the initial concentrate feed. The mechanism of ‘green’ ball
formation requires that the ore particles be subjected to compressive forces by
rolling in drums or discs in the presence of water. The progressive changes that
occur during balling are illustrated schematically in figure 3.
Firstly, there must be sufficient water to cover the surface of the particle, so that
when two of them come into contact a liquid bridge is formed under the influence
of surface tension. Capillary forces are therefore created (figure 4) so that
capillary suction effectively provides bonding.
2. Drying – Ultimately, the temporary bonds created during balling are to be
replaced by permanent bonds brought about by fusion at elevated temperatures,
so after it has fulfilled its function in assisting with ball formation, gradual removal
of water by heating to a temperature of around 300 to 350oC is essential. This
must be done carefully to avoid destroying the weak ‘green’ balls. In most cases
a binder such as bentonite is needed to ensure adequate dry pellet strength.
Bentonite is a naturally – occurring clay mineral consisting mainly of
montimorillonite, which has the ability to absorb water between certain crystal
planes causing it to swell. In this way, the voids in pellets are partially filled and
adhesion between particles is maintained.
3. Firing – When the dried pellets are heated to a temperature in the range 1250 –
1350oC, consolidation occurs by means of the same partial fusion processes
which give sinter its strength.
4. Cooling – Finally, fired pellets must be cooled at a controlled rate in order to
minimize cracking and consequently adverse effects on pellet strength. Pellets
need to be able to withstand the forces imposed on them during handling and
transportation and must withstand the pressure of 21 to 30m high burden of a
blast furnace. The product has a crushing strength of 35 to 70 kg/sq cm.
2
Pelletizing plants utilize equipment that enables these basic requirements to be
fulfilled. For example, balling cab be carried out either in rotating drums or discs
and the operating principles and appropriate dimensions are illustrated in fig 5.
Figure 1.2 The Grate Kiln Process of firing pellets
Sintering
Sintering consists of mixing a ferrous feed, which is coarser than that required for
agglomeration, with about 5% coke powder or pulverized coal and 5 to 10% water, and
igniting the mixture with an external burner. This process produces partial fusion (fig 6)
of edges of the particles causing them to stick together. The sinter leaving the machine
has somewhat lower density than pellets have and is usually much more irregular in
shape. Fig 7 shows an example of a sintering machine. In practice, the feed for a
sintering machine may include raw, or more often, beneficiated ore fine, but most
various other ferrous materials are sintered, including 10 to 30% of return sinter fines. A
bed up to 30cm thick is normal.
A recent development is the addition of a basic flax, lime or limestone to the feed. The
limestone addition to the raw mix can be varied, thereby influencing the basicity ratio
(%CaO + %MgO)/(%SiO2 + % Al2O3) of the agglomerated product.
Sinter containing just enough lime to flux its own gangue is said to be self-fluxed, but
Silica (SiO2) and alumina (Al2O3) are also present in both coke ash and in the gangue
associated with any lump ore that is charged to the furnace. When all the lime required
to flux the sum of the burden materials is incorporated in the sinter, the latter is said to
be super-fluxed. The principle advantage of pre-fluxing is that limestone decomposition,
which is a highly endothermic reaction, is transferred from the blast furnace to the sinter
strand.
CaCO3 = CaO + CO2 H = +177 kJ/mole at 25oC.
3
Consequently, there is a reduction in the thermal load during blast furnace smelting and
less fuel needed to be used. In addition, the evolution of CO2 from limestone occurs
outside the furnace so that its effect on the Bourdouard equilibrium is eliminated.
In present-day rich ore practice, there will often be no urgent requirement to use
superfluxed sinter because because slag volumes are so small (300-350kg/tonne) and
the sensible heat in the furnace top gas should be sufficient to dry the charge and
decompose moderate amounts of carbonates and hydrated oxides.
Figure 2.2. Thermal Processes during sintering.
Briquetting
Is carried out in presses usually with the addition of a binder. The binder may be
inorganic lime, cement, clay, or metal-salts; or it may be organic: oil, tar, or pitch. When
cement is used as a binder the briquettes may be hardened at room temperature. When
clay is used as a binder the briquets are hardened by firing.
Due to the heavy wear on the briquetting press, briquetting is a relatively expensive
process and it has not found wide apllication in extractive metallurgy.
4
5
FLUXES IN IRON –STEELMAKING
It is not possible to conduct any smelting or refining operation without slag. Slag is the
medium that floats on the surface of the metal and acts as the receptacle, flux, for
impurities, except for those that escape as gases. In the production of iron and steel, the
flux is lime, CaO.
Lime absorbs and holds unwanted impurities, mainly silicon oxidized to silica,
phosphorus oxidized to phosphorus pentoxide, sulphur as calciumsulphide, and
magnesia and alumina. Some other often valuable oxides are unavoidably also removed
by slags: iron and manganese oxides are always present.
Since the melting point of pure lime is far higher than temperature obtainable during iron
and steel making, lime must be liquefied to act as a flux and its melting temperature
lowered by other components. In other words this flux must be fluxed itself. The oxides
mentioned all lower the melting point of CaO.
Ternary system for blast furnace slag
Slag is always composed of several more components, most of them acting in the
direction of lowering the melting temperature so that direct application of numerical
temperature and composition data is somewhat uncertain.
Slag chemistry is a complex subject, complicated in practice by impurities, varying
degrees of dissociation, and other factors.
Limestone and Lime
Limestone for direct use in a blast furnace or for calcining to lime for steel production
must be low in impurities, mainly sulphur, silica, and alumina. The presence of impurities
in limestone results in some of the lime being used up for fluxing of its own impurities,
hence results in a decrease of the “available lime”. Lime containing significant amounts
of magnesia or silica, about 5% each, may be acceptable in the absence of a purer
grade. Some dolomitic limestone containing 30 to 40% magnesia (MgO), after being
calcined to dolomitic lime is actually desired for steelmaking in basic oxygen process.
Limestone is used in the blast furnace where it is calcined in the process of ironmaking.
Calcination or burning, if it is done in a specific installation, is used to remove the carbon
dioxide and retain the oxide.
CaCO3 = CaO + CO2
This reaction is strongly endothermic, starting at about 900oC, but proceeding well above
1100oC.
6
FUELS
Coke and coking:
Coking is a process of dry destructive dry distillation of coal to convert it from a dense,
weak material to a strong, porous one; valuable by products are recovered in the
process.
Not all coals yield a satisfactory coke. The non-coking coals yield either porous coke
with a low crushing strength or a powder residue. Out of the three classes of coal
recognized in the industry, high, medium, and low volatile, only one subclass in the high
volatile class, yield coke suitable for blast furnaces.
Blending of coal is of major importance. High volatile coals may be blended with medium
or low volatile coals. The reason for blending is the chemistry, not the structure of the
coal. Many coals contain large amounts of ash: Siliceous sand, aluminous clays, iron
sulphide etc. Therefore almost all coals are washed. Coals with sulphur contents above
3% have poor coking properties.
As mentioned previously, coking is the process of destructive distillation using external
heat. Cokes are broadly classified according to the final temperature of the coking
process – low, medium, and high temperature coke. Only the high temperature coke,
finished at 930 to 1100oC is suitable for blast furnaces.
Coking is done in long, tall, and narrow chambers, about 15m long, 6m tall and 0.6m
wide. The chambers are externally heated by combustion chambers, called flues of the
same length and height, adjacent to the external walls of the ovens. The ovens and flues
alternate forming a battery, with 40 to 100 flues and ovens. The fuel used to heat coke
ovens is either coke oven gas or by-products recovered earlier. The combustion air is
always preheated to improve fuel utilization.
Coking is a slow process. Because of the low thermal conductivity of coal and slow rate
of distillation, atypical coking rate is only about 13mm per hour. This puts a limit on the
oven thickness. A typical oven, perhaps 12x15m long and 4 to 6m high is only 450mm
wide. Such an oven typically holds 18 tons of coal or a little more. Since coking
progresses from both sides of the oven (from both adjacent flues) inward, only 230mm of
coal must be coked, hence it takes about 18 hours to coke a 450mm wide oven
containing 18 tons of coal. (fig. 9).
Once coking is completed the doors at both ends of the long oven are taken off and a
pusher ram forces the coke out onto a quench car (fig. 10).
The car rapidly moves under a quench tower where a predetermined amount of water
floods the hot coke. Enough water is added to stop the burning, with excess water to
evaporate under the influence of the heat contained in the coke, although dry quenching
with heat gas is a recent innovation.
Required properties of coke:
Coking is carried out in a constant striving to improve the quality and quantity of coke
against decreasing qualities of coals. The blast furnace operates with a burden about 21
to 30m high, and uses a gas flow as its reactant. Hence the requirements of coke are:
1. High strength, especially compressive (crushing) strength.
7
2. Controlled porosity, for good passage of gases and good burning of coke.
3. High hardness and abrasion resistance; fines choke off flow of gases.
4. Minimum ash content; we must be satisfied with upto 8 to 10% ash.
5. High melting point of ash; to ensure good passage of gases.
6. Low sulphur and phosphorus, because they enter the iron and exert a
detrimental effect on steel productivity and steel quality. Preferred sulphur
maximum is 2%, although much lower contents are desirable; phosphorus
seldom reaches 0.05%.
Natural gas
This is by far the richest, most desirable gaseous fuel. It is mainly (75-96%) methane,
CH4. The remainder consists of other hydrocarbons and nitrogen.
Natural gas burns with a highly luminous, strongly radiating flame that is easy to control
both because of its excellent visibility. It has a high ignition temperature.
Tar
Tar is a by-product of coking. Occasionally used with or without removal of its
constituents. The flame is well-radiating. It must be “atomized”. Users have to be careful
not to burn a refractory close to it.
Fuel Oil
“Heavy” Fuel Oil (HFO) containing up to 2% and 3% sulphur is often injected into blast
furnaces where it serves as an excellent substitute for coke. Up to 90kg oil per ton of
iron can be used this way. Whenever external desulphurization of iron is practiced, there
are no objections to the use of higher sulphur, cheaper oils. The quality of oils can be
readility checked. Chemical analysis, except for sulphur, ash, and moisture, is of only
minor importance.
Oil’s combustion properties are most important. Specific gravity, viscosity, and flash
point (lowest ignition temperature) are always checked and well-specified in any
contract.
Fuel oil must be atomized for use (only fine subdivision into a mist which mixes well with
the combustion air, is achieved).
Fuel Economy
Many important facets of fuel conservation are the result of technological needs, for
instance, the impossibility of running an open hearth furnace without preheating the
combustion air.
Examples of such energy serving features are:
1. Recuperation or regeneration of combustion air and combustion gases.
Recuperation is done in vessels in which there is a continuous counter current
flow of air in one direction, through a set of tubes, while hot, spent combustion
gases flow in the opposite direction.
2. Use of oxygen for decarburization – this not only speeds up the progress of steel
production, but also heats up the furnace; the basic oxygen steelmaking process
does not use any fuel except that consumed by the oxygen production plant.
3. Combustion controls intended to improve production productivity and/or reduce
furnace wear: air/fuel ratio controllers aimed at minimizing excess air, furnace
8
pressure controllers which activate dampers, to minimize or prevent infiltration of
cold air into a furnace are a few examples.
4. Computerized control fuel demand.
Other techniques aimed at the reduction of energy consumption regardless of the
process, include the following:
1. Use of insulation on outside furnace walls and lagging of piping.
2. Increased use and improved efficiency of waste heat boilers fired only by spent
combustion gases. The fuel and combustion departments of each mill are now
equipped with good sensors (instruments) and read outs (computers) to achieve
the highest efficiencies possible.
9
10
IRON PRODUCTION
Introduction to Iron and Steelmaking:
Iron and steelmaking is concerned with the reduction of iron ores, and the production of
steel, an alloy containing iron, carbon and other alloying elements. The ore is either
hematite (Fe2O3) or magnetite (Fe3O4).
The major process for ironmaking is to carbon reduce the ore, with coke, in a blast
furnace. This produces a carbon saturated liquid iron. The product of the blast furnace is
called pig iron or hot metal.
This now has to be refined to give steel, normally a low carbon alloy iron. The
steelmaking process is one of oxidation, and in general ends up towards FeO saturation in
liquid.
If this alloy was to solidify it would precipitate large amounts of the oxide phase,
detrimental to the mechanical properties of the steel, or the dissolved oxygen would react
with dissolved carbon, as the temperature decreases towards solidification temperature, to
produce CO2 gas, which would cause the solidifying metal to foam up, or rim. To prevent
this we must deoxidize the steel by the addition of a strong oxide former, such as
aluminium, and the precipitation of an oxide, this case Al2O3.
The conventional method of steelmaking firstly is high reducing (A to B) in fig. 11), the
highly oxidizing (B to C), and finally reducing again (C to D).
Alternative routes that are in production are to partially reduce the iron ore in the solid
state, to about 96 -98% reduction. This is the so called direct reduction route. The solid
product is then melted and turned into steel.
11
MAIN OPERATING PARTS OF BLAST FURNACE
Complexity of structure can be reduced to few basic considerations based on fact that
furnace works in counter current mode: Solid charge slowly descends and gases
generated at bottom quickly ascend. The charge is progressively reduced chemically,
the iron oxides becoming at first sponge and then liquid iron. At first charge “burden”
swells, (hence stack of furnace slopes outward); as solid coke is increasingly burned,
iron changes from sponge to liquid, (volume of charge decreases and bosh slopes
inward).
The entire furnace is built of welded thick plates. The construction is discussed starting
from the lowestmost level (figure 12).
The hearth, sometimes called crucible, used to be constructed of high grade aluminous
firebrick, is now constructed with carbon blocks. The hearth is filled with molten iron, slag
and in all probability coke. Hearths of modern furnaces are 9 to 15m in diameter. The tap
holes reaches to within 30-60 cm from the hearth bottom; it is drilled open periodically to
12
cast the iron and closed with clay plug pushed by a mud gun. A cast will last 30 to 90
minutes.
Above iron level are one or more slag notches: They draw off the slag that accumulates
during operation and prevent slag reaching tuyeres where it would interfere with the
blowing into the furnace of air necessary for combustion. Slag is usually taken off
intermittently.
The section above the hearth of the furnace is the tuyere zone. There are from 12 – 40
tuyere uniformly distributed about the furnace circumference. Tuyeres are water-cooled
copper castings, which are really blast nozzles, directing the air needed for the
combustion of coke into the hearth. The hot air (“wind”, hot “blast”) is supplied to the
tuyeres via individual “blow pipes” which get the air from the main bustle pipe
surrounding the furnace. Up to 4250 m3/min is common. Tuyeres are critical for furnace
operation operations. Despite their water-cooling, their life may be anywhere from a few
hours to several months. Since the blowpipes are vertical and join the horizontal tuyeres
perpendicularly to their axes, it is possible to look into a tuyere from its back through a
dark blue glass enabling the descending lumps of coke to be seen.
The next section above the tuyere zone is the bosh. The highest quality firebrick is used
in thicknesses up to 1.5m. These are used to withstand the chemical and physical
erosion resulting from the melting of slag and abrasion by nonplastic components of the
burben. Boshes become narrow toward the hearth, the usual angle being 10 degree off
vertical. This is caused by the mentioned reduction of stock volume as it softens and
liquifies. Above the bosh, the stack extends from the widest part of the furnace to its
throat at the top. Here reduction of the iron oxides to metallic, sponge iron takes place.
The top of the solid charge should be held at a fairly steady level called the stock line.
The furnace top includes the charging devices and the waste gas off-takes, usually four,
terminating in downcomers.
Above the offtake are the bleeder valves, which open in case of a sudden increase of
gas pressure (a “kick”). Every opening results in clouds of dust particles discharged into
the atmosphere.
13
14
The furnace is charged by skip cars, which travel from the stockhouse on the ground
level to the furnace top along the hoist. Contents of the car are dumped into a stationery
receiving hopper and on to the small bell (upper bell). (Fig. 13). This small bell rests on a
gas-tight sealing ring. After each drop of the skip car the bell states as preprogrammed.
The small bell is lowered after each charge cycle is completed and it drops load onto the
large bell. The two bells are never open simultaneously. The large bell is dropped (open)
when its circumference is loaded by the small bell.
Chemical and physical uniformity of the burden is of paramount importance to the
smoothness of the operation, and therefore the quality and productivity.
Modern, large capacity furnaces are designed for continuous belt charging. The skip car
and its hoist are replaced with one inclined belt that charges the furnace. The slope of
the belt cannot exceed 12 degrees since burden consists of easily rolling pellets; thus a
large amount of space is needed to elevate the stock to about 34m.
Blast furnace auxiliaries:
Fig.14 shows some blast furnace “auxiliaries” i.e. stoves, gas clearing plant and
stockhouse without which iron could not be made (except cleaning plants).
15
16
Stoves preheat the combustion air, working on the regenerative principle. The stoves,
usually three per furnace, are cylindrical structures almost as tall as the furnace itself.
They consist of two internal chambers. One is for the combustion of cleaned blast
furnace gas. An air fan and burner are located at the base of the combustion burner. Hot
combustion gases travel through the second chamber stacked with a checker work of
bricks, thus preheating them. Mullite bricks 60 to 70% Al2O3 and pure SiO2 are used for
high temperature stove.
A stove is put “on blast” for an hour or two and the temperature of its checker work
gradually drop, thus lowering the blast temperature. Then a second stove is put “on
blast” and the first stove is depressurized and put “on gas” to again reheat the bricks in
the checker chamber. The air is always carried to the furnace via a blower.
The docks are holding facilities for raw materials storage. Different types of materials
have to be kept separately. The stockhouse consists of a series of bins, which carry
materials intended to be charged. Hot metal rail cars are used to transport the molten
iron to the steelmaking shops. The cars are lined with high-quality tarred fire brick. In
modern practice iron is often desulphurized outside of the blast furnace. This practice
has been growing because of the increased amounts of sulphur in the raw materials
resulting in its increasing content in the iron.
Principles of reduction
It is easier to regard free energies of formation of oxides as affinities of these metals to
oxygen. The greater the negative free energy of formation of oxide, the higher its
stability. Graph with data for some selected oxides is shown in fig.15. Not slope of CO
opposite to that of other oxides. Carbon only known element with affinity for oxygen,
which increases with temperature. The lower position of oxide for given temperature
(from fig. 15), the more likely it is to be formed under oxidizing conditions and less likely
to be reduced under reducing conditions.
For instance:
Both iron oxides tend to be reduced by CO to CO2 at all temperatures shown. Above
1500oC carbon will tend to reduce silica, but below this temperature silica will be stable,
i.e. will not be reduced by CO to form CO2. Note that phosphorus pentoxide is unstable
under reducing conditions, thus 100% recovery of phosphorus in blast furnace. Some
oxides will remain in their oxidized state: magnesia, titania, alumina, and lime will not be
reduced and will pass into slag floating on the iron.
Some volatile metals, zinc and alkalies (sodium and potassium) from highly volatile
oxides. These will be eliminated from hearth and bosh by volatilization into the stack.
Reactions in the blast furnace (figure 15b). Reactions (2) becomes noticeable from
980oC. The net thermal result of the reactions is a strong generation of heat.
17
18
Reduction chemistry:
Reduction can be effected by CO or by solid carbon but hydrogen resulting from oil or
gas injection through tuyeres also act as a reductant. Let us begin with formation of
reducing gas coke contains about 90% carbon. Carbon forms two oxides:
C + O = CO2 H = -393.5 kJ/mole at 25oC (1.1)
2C + O2 = 2CO H = -110.5 kJ/mole at 25oC (1.2)
Enthalpy changes at 25oC give indication of the potential heat release during combustion
in furnace. Composition of combustion gas in the presence of excess carbon is
controlled by C-CO-CO2 equilibrium known as Bourdouard equilibrium:
C + CO2 =CO (1.3)
Gaseous reduction of iron oxides:
Carbon monoxide capable of reducing hematite to iron, with magnetite and wustite as
intermediates at temperature above 570oC.
Relevant reactions are:
3Fe2O3 + CO = 2Fe3O4 + CO2 H = -52.8 kJ/mole of CO at 25oC (1.4)
Fe3O4 + CO = 3FeO + CO2 H = +36.3 kJ/mole of CO at 25oC (1.5)
FeO + CO = Fe + CO2 H = -17.3 kJ/mole of CO at 25oC. (1.6)
In each case reaction is reversible and equilibrium is established when gas attains
composition that, at constant pressure, is dependent only on temperature. Equilibrium
relationships in reactions (1.5) and (1.6) are shown in fig. 16 together with those for low
temperature reduction of magnetite to iron (reaction 1.7).
Fe3O4 + 4CO = 3Fe + 4CO2 H = -15.7 kJ/mole of CO at 25oC. (1.7)
Reduction of hematite to magnetite takes place at such low levels of CO that different
gas scale is required to represent equilibrium in equation 1.4. In the blast furnace stack,
reduction complicated by presence of coke which causes CO concentration to be
influenced by Bourdouard reaction. Consider changes experienced by element of gas as
it enters stack at initial temperature of 1000oC and rises to throat reducing and heating
burden on its way. From fig.16 in which Bourdouard line is superimposed on oxide
reduction equilibria following can be seen:
- Gas consisting of 100% CO capable of reducing oxide to metallic iron with Fe xO
would be established at 70% CO + 30% CO2.
- Element of gas might be supposed to come in contact with coke, if temp fell
again, this to 800oC, CO would be regenerated and its concentration raised to 90%, so
that it is again possible to reduce FexO to metallic iron.
Oscillation between gas compositions shown in the figure could continue until temp had
fallen to 700oC, when influence of Bourdouard would be such that reduction rate of
hematite to magnetite world be slow. Reactions represented by equations 1.4 to 1.7 are
sometimes known as “indirect reduction” because reducing agent CO is derived from
combustion of carbon (eqn 1.2). Thus iron oxides are indirectly reduced by carbon.
19
Reduction by solid carbon:
Burden entering bosh is pre-heated and partially reduced, but remaining oxygen must be
removed by reduction with solid carbon as
FeO + C = Fe + CO H = +155.2 kJ/mole of C.
Carbon reduction is highly endothermic and requires combustion of coke to make good
the heat it consumes. Use of carbon as reductant is often referred to as “direct
reduction”, because carbon is used directly.
High temperature reactions:
Reduction in bosh and hearth is not confined to iron oxides. Virtually all P2O5 contained
in burden is reduced to phosphorus, which dissolves in metal and must be removed in
steelmaking process that follows.
Phosphorus content of iron ore is important in determining commercial value, since
phosphoric iron takes longer to refine to finished steel.
P2O5 + 5C = 2P + 5CO (1.8)
Normal phosphorus content of iron for Basic Oxygen Furnace (BOF) is around 0.1 –
0.2%.
Other oxides such as silica (SiO2) and manganese oxide (MnO) are only partly reduced,
with the result that silicon and manganese partition themselves among between slag and
metal.
SiO2 + 2C = Si + CO G = +713900 – 367.95 T
MnO + C = Mn + CO G = +290300- 173.22T
A number of factors influence this process, including slag composition and temperature.
Increasing temperature displaces equilibrium to the right in both cases, leading to higher
silicon and manganese contents in metal. For BOF steelmaking, silicon and manganese
contents might each be expected to about 0.8%.
Remaining elements entering metal phase are sulphur and carbon. Carbon dissolves
readily and its concentration will be of the order of 4%. There is no way of exercising
control over carbon content.
Removal of sulphur from burden, sulphur originating maily from the ash in the coke, is
possible only by free lime, that means the excess lime remaining after neuralization of
acid oxides. If ratio of CaO/(SiO2 + Al2O3) (basicity or V-ratio) is greater than 1.1, the
desulphurization reaction may take place:
FeS + CaO + C = CaS + Fe + CO endothermic (1.1)
The reaction is inefficient for the following reasons:
- affinity of sulphur for lime is high, but solubility of resulting calcium sulphide in
blast furnace slag is low (2 to 3% sulphur maximum).
- Solubility of sulphur in iron is high at high temperature.
- High heat requirements of this endothermic reaction requires charging large
amounts of coke, thus lowering productivity of the funace.
20
21
Figure 15c
Blast furnace slags:
Minerals such silica (SiO2) and alumina (Al2O3) are present in commercial ores.
Collectively known as gangue are the basis of slag that collects in hearth of furnace. Ash
resulting from combustion of coke finds its way in slag. Formation of fusable slag
encouraged by inclusion of fluxes containing lime (CaO) and magnesia (MgO). Factors
determining optimum composition of slag are physical, chemical and commercial and
choice is a compromise.
22
Slag must be sufficiently fluid to run freely from furnace while at same time must have
high capacity for absorbing sulphur.
Buyers of slag may impose compositional requirements relating particularly to MgO
content, depending on whether slag is to be used for cement or concrete aggregate.
Major constituents of blast furnace slags are four oxides CaO, MgO, SiO2, and Al2O3 and
sum of their concentrations usually exceeds 95%. Compositions typically lie in following
ranges with only minor amounts of other oxides:
38 – 44% CaO
8 – 10% MgO
12-34% SiO2
10-12% Al2O3
0.5-1.0%MnO
1-2% S
0.1-0.6% FeO
Melting temp vary between 1200 and 1400oC hi general, chemical character of an oxide
slag is determined by its composition and various constituents are classified as either
acid or basic, e.g.
Acidic oxides : SiO2, P2O5, B2O3
Basic oxides : CaO, MgO, MnO, FeO, Na2O, K2O
Intermediate oxides : Al2O3, Fe2O3
Slags high in lime are therefore basic and those of high silica content are acidic. The
distinction between acids and bases is made on the grounds of their behaviour in slag
solution, since whilst acid oxides remove oxygen anion e.g.
CaO = Ca++ + O--
SiO2 + 2O-- = SiO4-4
It is normal to express composition of a slag as a simple ratio, thereby giving a number
that is called the basicity. Typical expressions are as follows:
CaO ; CaO + MgO ; CaO + MgO
SiO2 SiO2 SiO2 + Al2O3
Values of basicity are frequently linked to distribution of elements between slag and
metal in order to demonstrate the influence of slag on hot metal composition.
For example, Turkdogan has summarized factors affecting silicon, manganese, and
sulphur distributions as follows;
(i) The ratio [%Si]/(SiO2) decreases with increasing slag basicity and decreasing
temperature (figure 16a. A close approach to equilibrium in reaction (1.9)
appears to be achieved in a number of operating furnaces.
(ii) The ratio [%Mn]/(%MnO) increases with increasing slag basicity and
temperature, but equilibrium in reaction (1.10) is not achieved in practice (fig
16b).
(iii) The ratio [%Si]/(%S) increases with increasing slag basicity and temperature,
but equilibrium in equation (1.11) is not achieved in practice (fig 16c).
23
Summary of blast furnace reactions is shown in fig 18. Limestone calcinations occurs in
the stack, although in morden practice raw limestone is a small component of the
burden, the major part of the flux being incorporated in the sinter.
24
25
