Ferrous Extractive Metallurgy

Dr. / Amr Basuony Saad Eldeeb

Lecturer of Metallurgy
Mining and Petroleum Department
Faculty of Engineering,
Al-Azhar University

Cairo
2022
13-11-2021
 Blast Furnace Reactions
Blast furnace reactions can be divided
according to different sections of the furnace:-

1. Tuyere reactions (combustion zone reactions),

2. Stack reactions (reduction zone reactions),
3. Bosh reactions,
4. Hearth reactions.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 1 Tuyere Reactions or Combustion Zone Reactions
* The combustion of the coke is one of the most important reactions in the BF process.
* The air enters the furnace through tuyeres situated just above the hearth.
* Air is pre-heated to a temperature 800 – 1200°C.
* The combustion of coke takes place in front of tuyeres in the presence of air.
* In this process, the oxygen in the blast and carbon in the coke are transformed into gaseous carbon monoxide.
* The resulting gas has a high flame temperature between 2100 and 2300°C.
* Coke in front of the tuyeres is consumed, thus creating voidage; this is known as tuyere raceway zone.
* Figure 1 shows combustion taking place as a balloon-like space in front of each tuyere.
• There are two zones at the tuyere raceway zone:
• (i) zone A, the gas phase, consists primarily of O2, CO2 and N2,
• (ii) zone B, the gas phase, consists of CO2, CO and N2.

Fig. 1: Tuyere raceway zone

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 Zone A:
Carbon in coke reacts with oxygen in air to form CO2.
exothermic
This reaction is strongly exothermic and releases a large amount of heat to the process, and temperature increases above
1650°C.
Zone B:
As the gases enter the zone B, the oxygen is depleted, and CO2 reacts with carbon because:
(i) There are present large amount of carbon particles,
(ii) CO2 is not stable at above 1000°C. endothermic
For this reason, if any CO2 forms it reacts immediately with carbon to form CO gas.
This reaction is endothermic and has great importance for producing a lot of reducing gas, although this reaction absorbs a
large proportion of the heat.
This reaction is called the solution loss reaction because carbon, which would otherwise be burned at the tuyeres to produce
heat, is lost by reacting with CO2 gas. This means increase in coke consumption to overcome the loss of carbon as well as
loss of large amount of heat. This reaction is also known as Boudouard reaction or gasification reaction.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 The net result of the combustion process is the sum of the two reactions:

This reaction is exothermic and may be the overall combustion reaction taking place in the blast furnace.
Any moisture present in the blast will also react with carbon in coke:

• The hydrogen, which is formed by the last reaction, and any unreacted water vapour join the gas stream and pass
upwards through the furnace.
• This reaction is endothermic, and it may be thought that the presence of water vapour in the blast would be
detrimental to the process.

* Therefore, the theoretical analysis of the gases at the combustion zone should be 35% CO, 1% H2 and 64% N2.
- When the very hot gas ascends through the furnace, it carries out a few important functions as follows:
• Heats up the coke in the bosh/belly region. exam

• Melts the iron ore in the burden, creating voidage. function of blast

• Heats up the material in the shaft zone of the furnace.

• Removes oxygen of the ore burden by chemical reactions.
IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 2. Reactions in the Stack
In the stack region, ores are heated and started reduction due to direct contact with ascending hot gases (which contain
55–60% N2, CO, CO2, H2, H2O and traces of hydrocarbon like CH4 etc.).
(i) Gas–solid reduction reactions:
* The velocity of the descending raw materials is much slower than that of the ascending hot gases.
* As these solids descend, they are gradually pre-heated.
• At the top of the furnace, where the temperature may vary from 200 to 300°C, the moisture and any combined water
are removed from raw materials.

• The reduction of Fe2O3 took place in

stages (above 570°C),

where 0.92 < x < 0.98. The two last reactions are reversible and a function of temperature.

* The reduction of Fe2O3 took place in stages (below 570°C),

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 ii) Dissociation reactions:
At about 700–800°C, the following reactions take place:

* This reaction, which is endothermic, is accelerated by increasing temperature.

* At the lower part of the stack, the temperature is about 900 °C, and this reaction is practically completed at 900°C.
* Calcium carbonate should completely decompose at this level. But this does not happen because of kinetic limitations, and
significant decomposition occurs only at 1000–1100°C.

(iii) Carbon deposition reaction:

Since below 1000°C, CO2 gas is more stable than CO gas, at low temperature (200–300°C), CO gas is transformed into CO2
gas and carbon, and this take place at the upper stack region in the presence of Fe and FeO

The temperature, at the bottom of stack, is 1100–1200°C. Charge begins to soften and fuse at the bottom of stack region.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 Fig. 6. Reaction zone and inner state of a blast furnace.
IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 Bosh Reactions:-
* The reduction of iron ore is completed, and the oxides and metal are partially melted down.

* Since the direct reduction of iron oxide is highly endothermic, it requires high temperature.

Besides iron oxide, other oxides entered in the BF bosh region, such as (i) P2O5, MnO and SiO2 and (ii) Al2O3, MgO and CaO.

(i) These oxides are easily reducible by BF gas (CO) at 1300–1400°C and by direct carbon of the coke at the higher T.

* Since all above reactions are endothermic, these reactions are favoured by a high temperature and proceed in the hotter zones
of the furnace.
* At bosh region, melting of charge, except coke, takes place; gangue and calcined flux combine to form basic slag.
IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 (ii) These oxides (Al2O3, MgO and CaO) are not easily reducible. So, at 1300–1400 °C, Al2O3, MgO, CaO, SiO2 (partly)
and MnO (very small amount) are the remaining oxides present.
* SiO2, MnO and FeO are dissolved in each other because these are producing a highly acidic slag which is very rich in
silica at the upper bosh region, so the viscosity of the slag is also very high.
* Gradually when the slag travels to the lower bosh region, it dissolves the higher melting oxides like CaO, MgO and
Al2O3 making it more and more basic and more fluid.

Hearth Reactions:-
Molten metal and slag are collected in the hearth.
Since the specific gravities of slag and molten metal are 2.5 and 7.0, respectively, slag is floated on the top of the
molten metal layer.
* Metal contains (3.5– 4.0% C, 0.5–2.5% Si, 0.4–2.0% Mn, 0.05–2.5% P and 0.04–0.1% S).
* Slag contains (CaO, MgO, Al2O3, SiO2 and MnO and traces of P2O5 and FeO).
(i) Carbon dissolution: Although most of the carbon in coke burns at the tuyere region, a certain fraction is descent into
hearth.
IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 Hot metal contains 3.5 - 4.0% C; this is less than maximum carbon (6.67%) present in Fe–C phase diagram; why?
There is no shortage of carbon in BF, but due to the presence of other elements (e.g., Si, P, S, etc.) in hot metal, solubility
of carbon in iron is decreased, and the activity of C is increased by Si, P, S which form stronger bonds with iron than with
carbon.
Carbon content in hot metal depends upon, in general, Si, P, S, etc.
(ii) Mn reaction:

As the basicity of slag increases, there is sharp increase in activity of MnO, so more Mn goes to the metal phase; i.e.,
forward reaction proceeds.
(iii) Si Reaction:

(iv) S Reaction:

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 BF Slag
Major constituents of BF slag are CaO, Al2O3, SiO2 and MgO. Minor constituents of BF slag are MnO, TiO2, FeO
and alkali oxides.

Liquid slag should have as low viscosity as possible, lower than 0.2 kg m−1 s −1.

There are difficulties in viscous slag as follows:

1. Pose difficulties during slag-metal separation in hearth.
2. Slow down the rates of slag-metal reactions.
3. Do not flow down properly from the bosh to the hearth.
4. Hinder smooth upward flow of gas through the burden.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 Modern Trends of BF Practice
Main developments are as follows:
exam
1. Large capacity of furnaces,
2. Better prepared burden (including better quality coke),
3. Better distribution of charge materials in the furnace,
4. Higher blast rate and temperature,
5. Oxygen enrichment of blast,
6. Humidification of blast,
7. Auxiliary fuel injection through the tuyeres,
8. Pulverized coal injection (PCI),
9. Lime dust injection through the tuyeres,
10. High top pressure.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 1. Large capacity of furnaces:-

The operational costs of a large capacity BFs are lower than smaller capacities BFs.

2. Better prepared burden (including better quality coke):-

Large capacity of BF requires better quality of coke.
The quality of coke can be improved by the following:
• Better preparation and more extensive blending of coals,
• The use of low volatile additives,
• Pre-heating of coal blend (30–40% with other low ash coal) before carbonization,
• Faster rates of carbonization at higher temperature,
• Partial briquetting of charges,
• Manufacture of formed coke (synthetically prepared coke),
• Mechanical stabilization of oven coke,
• Compacted coke oven charge, stamps charging,
• Dry quenching of coke in nitrogen or CO2 atmosphere.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 3. Better distribution of charge materials in the furnace:-
* After charging, materials are rolled due to (i) size and (ii) density of the material.
* The course size materials are more rolling tendency than small size.
* Densities of ore, coke and limestone are 5–6 g/cm3 , 1.5 g/cm3 and 3.0–3.5 g/cm3, respectively.
* Hence, rolling tendency of coke particles is more due to low density, and ore has less tendency of rolling due to high
density.
* Since densities of materials cannot be altered but sizes can be changed.
Hence, sizes of materials may be chosen in such a way that rolling tendencies can be offset to some extent.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 4. Blast Temperature:-
Since part of the fuel energy in the outgoing gases is pumped back into the furnace in the form of pre-heated blast, the
thermal efficiency of the process could be improved by increasing the rate of blowing of hot blast as well as its temperature.
The direct effect of blast temperature is to save coke and thereby improve productivity.

5. Oxygen Enrichment of Blast:-

* For every unit weight of coke burnt at the tuyere by the blast, nearly 4/5part weight of nitrogen of the blast are also
heated to nearly 2000°C.
• The presence of 79% nitrogen by volume in the blast restricts the temperature generated in the combustion zone.
• This temperature can be increased by decreasing the nitrogen content of the blast, i.e., by oxygen enrichment of
the blast.
• An enrichment of only 2% (by weight) oxygen reduces the nitrogen burden by about 4 units per unit weight of coke,
and a higher temperature would be possible.
• For every percent increase in oxygen content of blast, there is increase in production rate of about 3–4% and a
marginal saving in coke rate.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 6. Humidification of Blast:-
The endothermic reaction between steam and carbon as follow:

The presence of moisture in the blast generates double the volume of reducing gas per mol of carbon burnt. For every
carbon burnt one mol of CO and an additional mol of H2 will be available. More moisture the more will be this additional
hydrogen available.
• Kinetically, hydrogen reduction of iron ore is faster than by CO.
• The presence of moisture helps to burn coke at a faster rate.
• Some of the endothermic heat of moisture disintegration is compensated by exothermic reduction of iron oxide by
hydrogen.
• For an increase of 20 g/N m3 moisture in blast, endothermic heat can be compensated by a rise of 200 °C in the blast
pre-heat.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 7. Auxiliary Fuel Injection:-
* The necessity to adopt fuel injection in a BF arises from the fact that coke is not only costlier but also scarce and hence it
should be replaced by other cheaper and readily available fuels.
• The heat-producing function of coke is partially replaced by injection auxiliary fuels in the tuyeres. They are readily
available for combustion in front of the tuyeres.
• The auxiliary fuels are solid, liquid or gaseous. Solid fuel is pulverized coal, and liquid fuels are light oils, naphtha or
heavy oil; gaseous fuels are natural gas, coke oven gas or BF gas that are injected through the tuyeres.

These injections affect the following furnace parameters:

1. Flame temperature,
2. Bosh gas composition and volume,
3. Top gas temperature and CO/CO2 ratio and hence the efficiency,
4. Operational efficiency, i.e., the proportion of direct and indirect reduction,
5. Slag volume and its basicity,
6. Overall production efficiency.
IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 8. Pulverized Coal Injection (PCI) :-
* Injection of pulverized coal into the BF is one of the most promising options to reduce the coke consumption.
* Injection of coal dust through tuyeres of BF is for partial substitution of coke by non-coking coal.
* Higher PCI rate helps in reducing operational costs and at the same time increases productivity

• Coals are injected via lances into the tuyeres and gasified and ignited in
the raceway.
• Coal at a level of 175 kg/thm has been injected steadily.
• The raceway can be classified into three main zones:
(i) PC devolatilization zone,
(ii) Oxidation or combustion zone,
(iii) Solution loss reaction zone.
Fig. 7. Coal injection in the tuyeres.
The concentration of oxygen sharply decreases in the oxidation zone
due to its reaction with carbon of coke and coal to produce CO/CO2.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 Figure 8 shows a schematic representation of the PC injection
and the subsequent reactions in the raceway.
* The replacement ratio:- The ratio of the amount of coke which is
replaced by unit weight of coal powder.

* The higher the replacement ratio, the better will be the results of
coal injection. The replacement ratio depends on the varieties
and qualities of the coals using the fineness of the coal powder
and on the operational techniques of the furnace and injection
system.

* To obtain a high replacement ratio, a high quality of coal is

required preferably with a low ash content, which also reduces
the coke rate and a fine particle size to increase the specific
Fig. 8. Schematic diagram for pulverized coal
surface area of coal and hence accelerate the combustion. reactions in raceway.
IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 The most important reasons for the pulverized coal injection (PCI) in a blast furnace are as follows:-
• Lower consumption of expensive coke.
• Cost savings by lowering the coke rates.
• Increased productivity from using oxygen-enriched blast.
• Greater flexibility in BF operation; PCI allows the flame temperature to be adjusted, and the thermal condition in the
furnace can be changed much faster.
• Improved consistency in the quality of the hot metal.
• Decrease of the CO2 footprint, i.e., the amount of CO2 produced per tonne of steel.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 9. Lime Injection :-
Lime injection can control the quality of bosh slag, which produced in the bosh region has direct effect on the
productivity of the furnace.
If the slag is more viscous, then it affects the aerodynamics adversely, and as a result the productivity falls.
* Increase of bosh slag viscosity by even 1 poise may decrease the productivity by about 0.5%.

* Such highly viscous slag poses several problems :-

(i) It comes down slowly through the coke bed,
(ii) It interferes with the aerodynamics adversely and decreases the rate of reduction of ore and rate of heating of the
charge in the stack,
(iii) It decreases the productivity.

All such slag-related problems can be solved to a great extent if part of the total lime requirement can be injected
through the tuyeres in a way like fuel injection. Lime will be available where it is needed most, i.e., flux to ash of coke.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 10. High Top Pressure:-
* The gaseous reduction in a blast furnace would increase if the static pressure in the furnace is increased by throttling
back of the discharge gas pressure.
* This increase in the furnace top gas pressure is known as high top pressure.
* The adoption of high-top pressure in a furnace provided with standard two-bell top leads to a differential pressure
across the big bell.
* The pressure below the bell is high and that above the bell is practically atmospheric pressure. As a result, the bell
would get pressed against its hopper seat and would not lower down.
* The big bell can be lowered only after admitting gas under pressure in the chamber above the big bell (i.e., between
the two bells) to develop zero pressure differential across the big bell.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb
 Advantages for high top pressure are as follows:
1. Increasing production rate due to increase time of contact of reducing gas and solid, because of decrease velocity of
gases in the furnace.
2. Increasing the reduction rate of iron oxide.
3. Improving the efficiency of utilization of reducing gas results in saving of coke.
4. High top pressure may be applied at constant blowing rate to obtain fuel saving with lesser increase in output.
5. High top pressure markedly decreases channelling and dust losses in the effluent gases.
6. At high top pressure, the Boudouard equilibrium moves to left due to decreasing the coke consumption.

IRON AND STEEL MAKING 2022 Dr. /Amr Basuony Saad Eldeeb