National Institute of Technology, Durgapur

Department of MME
STEEL MAKING CODE: MMC601
Assignment-2
Instruction: Questions are based on perception of the topic. It is suggested to
stick to your own thoughts Answer all questions. Answers are to be precise
and short. Write the questions prior to the answers
Instruction for submission : Answers to be sent by mail. The file name will be
rollnumber_assignment2 and send to steelmaking2020@gmail.com.
For example : Sourav Dutta -16BT8001 for Sourav the file name will be
16BT8001_Assignment2
1) How can you remove Phosphorus from LD Slags?

The principal methods for removing phosphorus from LD slags for its
application as a flux for steelmaking involved:

 P2 evaporation in reduction and floating. The recovery of

crystalline phase containing phosphorus element has been
attempted using strong magnetic field. The results indicated that
50% of phosphorus in the initial slag can be recovered by a
magnetic field gradient of around 2 Tesla. In a recent test work
conducted at 0.5–2.5 tesla magnetic intensity, it has been reported
that recovery of phosphorus decreases with an increase in particle
size of the ground slag. It has been reported that phosphorus in LD
slag can be reduced below 1% by adopting physical separation
techniques like spiral concentration.

 The phosphorus removal studies have also been carried out using
bioleaching and chemical leaching. Bioleaching is a time
consuming process and chemical leaching is very costly.
Bioleaching is a time consuming process and chemical leaching is
very costly. Bio-dephosphorization of the LD slag was attempted
using bacterium Frateuria aurentia to remove insoluble phosphorus.
In 13 and 30 days of leaching under appropriate conditions, about
72% and 90%, respectively, of the phosphorus could be leached
from the LD slag in the presence of the bacteria at 20% pulp
density. The amount of carbon source seems to be important for
 phosphorus solubilization by bacteria. This is a novel method for
dephosphorization of LD slag and subsequent waste utilization.
The dephosphorized slag can thus have application as a fluxing
material in iron and steel production.

 A cost-effective technique that can achieve a phosphorus level of

less than 1% in LD slag adopting centrifugal jigging technique has
been expored at different grind sizes.

2) What is the utilization of worn up refractory from a steel making

vessel?

The steel industry consumes mostly magnesitic, dolomitic and silico-

aluminous refractories. There is a great variety of types, manufacturing
ways, vessels or furnaces to be lined, and broad scope of operating practices.
All this makes recycling a complex issue. During use, part of the material is
dissolved in slag, hot metal and steel. After use, the remains may be recycled
internally or externally, or may be deposited. Internal recycling may imply
the use of the waste refractory within the steel plant. For instance, as a slag
conditioner in the blast furnace, BOF or EAF. External recycling means that
waste refractory is sent back to the refractory plant or to specialized
recyclers. Landfilling refers to material being sent to deposit directly by the
steel industry.
The steel industry consumes about twothirds by weight of refractory
production. It is estimated that the refractory material remaining after use is
30% of the material applied. This means that around 9 millions tons of spent
refractories per annum are available for recycling or land refilling.
BaoSteel has given some steps. For many years, they recycled MgO-Cr2O3
bricks from RH lining for gunning material for repairing of the same
equipment, in a proportion of 20%.
Reuse and recycling of some types of spent refractories has been shown in
the table:
Fig: Flow diagrams of refractory recycling at steel plants. Top: integrated
mill. Bottom: minimill

3) Why is the shape of a refractory important for steel making furnaces?

The choice of shape and size of the refractory has significant impact on
the useful life of the refractory, the stability of the steel making furnace
and ensure good fittings to minimize joints.
Shaped
 These have standard size and shapes. These may be further divided into
standard shapes and special shapes. Standard shapes have dimension that
are conformed by most refractory manufacturers and are generally
applicable to kilns or furnaces of the same types. Standard shapes are
usually bricks that have a standard dimension of 9 × 4 1⁄2 × 2 1⁄2 inches
(230 × 114 × 64 mm) and this dimension is called a "one brick
equivalent". "Brick equivalents" are used in estimating how many
refractory bricks it takes to make an installation into an industrial furnace.
There are ranges of standard shapes of different sizes manufactured to
produce walls, roofs, arches, tubes and circular apertures etc. Special
shapes are specifically made for specific locations within furnaces and for
particular kilns or furnaces. Special shapes are usually less dense and
therefore less hard wearing than standard shapes.
Unshaped (monolithic refractories)
These are without definite form and are only given shape upon
application. These types are better known as monolithic refractories. The
common examples are plastic masses, Ramming masses, castables,
gunning masses, fettling mix, mortars etc.
Dry vibration linings often used in induction furnace linings are also
monolithic, and sold and transported as a dry powder, usually with a
magnesia/alumina composition with additions of other chemicals for
altering specific properties. They are also finding more applications in
blast furnace linings, although this use is still rare.

4) Which property of the Refractories is important for steel making?

Properties required in a refractory
The diversified applications of refractory materials in several different
types of industries require diversified properties to meet the physico-
chemical and thermal requirements of different phases. In some industrial
units more than one phase are present e.g. in steel-making vessels slag
/metal /gases are simultaneously present in the vessel at high
temperatures. In the heat treating furnaces solid/reducing or oxidizing
gases are simultaneously present. Below are briefly described the
properties of the refractory materials:
1. Refractoriness
Refractoriness is a property at which a refractory will deform under its
own load. The refractoriness is indicated by PCE (Pyrometric cone
equivalent). It should be higher than the application temperatures.
Refractoriness decreases when refractory is under load. Therefore more
important is refractoriness under load (RUL) rather than refractoriness.
2. Porosity and Slag permeability
Porosity affects chemical attack by molten slag, metal and gases.
Decrease in porosity increases strength and thermal Conductivity.
3. Strength
It is the resistance of the refractory to compressive loads, tension and
shear stresses.
In taller furnaces, the refractory has to support a heavy load; hence
strength under the combined effect of temperature and load, i.e.
refractoriness under load is important.
4. Specific gravity
Specific gravity of the refractory is important to consider the weight of a
brick. Cost of bricks of higher specific gravity is more that of lower
specific gravity. But strength of bricks of higher specific gravity is greater
than one with lower specific gravity.
5. Spalling
Spalling relates to fracture of refractory brick which may occur due to the
following reasons:
• A temperature gradient in the brick which is caused by sudden heating
or cooling.
• Compression in a structure of refractory due to expansion
• Variation in coefficient of thermal expansion between the surface layer
and the body of the brick
• Variation in coefficient of thermal expansion between the surface layer
and the body of the brick is due to slag penetration or due to structural
change.
6. Permanent Linear change (PLC) on reheating
In materials certain permanent changes occur during heating and these
changes may be due to
• Change in the allotropic form
• Chemical reaction
• Liquid phase formative
• Sintering reactions

PLC (%) linear = ((Increase /decrease in length)/original length )×100

PLC% (volume) = ((Increase /decrease in volume)/original volume) ×100
These changes determine the volume stability and expansion and
shrinkage of the refractory at high temperatures.
7. Thermal conductivity
Thermal conductivity of the bricks determines heat losses. Increase in
porosity decreases thermal conductivity but at the same time decreases
strength also.
 8. Bulk density:
Decrease in bulk density increases volume stability, heat capacity.

5) Why is refractory important for steel making vessels? Which form –

bricks, Coating along the wall, or a thin sheet fixed on the wall of the
vessel can be used and why?
Refractory materials have a crucial impact on the cost and quality of steel
products. The diversification on steel products and their cleanliness
requirement in recent years have increased the demand for high quality
refractory. Steelmaking requires high temperatures of the order of 1600
degree centigrade. In addition steelmaking handles high temperature
phases like molten steel, slag and hot gases. These phases are chemically
reactive; refractory materials are required to produces steels. High quality
refractory at a cheaper cost is the main requirement because cost of
refractory adds into the cost of product.

Why required?
• To minimize heat losses from the reaction chamber
• To allow thermal energy dependent conversion of chemically reactive
reactants into products because metallic vessels are not suitable.

Broadly speaking refractory materials are either bricks or monolithic.

Shaped refractories are in the form the bricks of some standard dimensions.
These refractories are machine pressed and have uniform properties. Special
shapes with required dimensions are hand molded and are used for particular
kilns and furnaces. Different types are:
i. Ramming refractory material is in loose dry form with graded particle size.
They are mixed with water for use. Wet ramming masses are used
immediately on opening.

ii. Castables refractory materials contain binder such as aluminate cement

which imparts hydraulic setting properties when mixed with water. These
materials are installed by casting and are also known as refractory concretes.
iii. Mortars are finely ground refractory materials, which become plastic
when mixed with water. These are used to fill the gap created by a deformed
shell, and to make wall gas tight to prevent slag penetration. Bricks are joined
with mortars to provide a structure.
 iv. Plastic refractories are packed in moisture proof packing and pickings are
opened at the time of use. Plastic refractories have high resistance to
corrosion.

Monolithic refractories
Monolithic refractories are replacing conventional brick refractories in
steelmaking and other metal extraction industries. Monolithic refractories are
loose materials which can be used to form joint free lining. The main
advantages of monolithic linings are
• Grater volume stability
• Better spalling tendency
• Elimination of joint compared with brick lining
• Can be installed in hot standby mode
• Transportion is easier

Monolithic refractories can be installed by casting, spraying etc.

Ramming masses are used mostly in cold condition so that desired shapes can
be obtained with accuracy.

6) What is the composition of LD gas and utilization of it?

During the process of steel making in the basic oxygen furnace (BOF),
significant amount of gases, rich in carbon monoxide content, are generated
during the blow time at a temperature of 950 deg C. This gas is termed as
converter gas or BOF gas. Converter gas is also known as LD gas. It is a
byproduct gas produced during the production of liquid steel in a basic
oxygen furnace (converter), where impurities of hot metal are oxidized with
oxygen gas.

Composition: The gas consists of about 64% carbon monoxide, 17% carbon
dioxide, 18% nitrogen and small amounts of hydrogen and methane (1%).
The main constituents of converter gas are carbon mono oxide (CO), carbon
di oxide (CO2), oxygen (O2) and nitrogen (N2).  Composition wise it is
similar to blast furnace gas but with lesser percentage of nitrogen in it. The
composition of the gas varies from start to the end of the blow and this is a
function of the blow time. In the oxygen rich phase (air ratio= 1) at the
beginning and at the end of the blowing period the primary gas is burned
completely and no gas is recovered during this period. During CO rich phase
(air ratio less than 1) only partial oxidation takes place and a combustible
waste gas is formed containing CO, H2, CO2 and N2. The maximum CO and
 H2 content in the waste gas corresponding to the minimum air ratio (air
ratio= 0.1) is present during the main decarburization period (middle part of
the blowing period) and maximum gas is recovered during this phase.

Utilization: The CO leaving the furnace is allowed to combust by letting

large amounts of air to enter the exhaust hood. The resulting hot gas from
the combustion is then used in a heat recovery boiler to produce high
pressure steam. (Combustion method);The CO- rich off-gas is first
recovered in a waste heat boiler, generating high pressure steam. The gas
is subsequently cleaned and stored and used as a fuel by mixing with
other by- product gases (coke oven gas, blast furnace gas). This method
recovers about 70% of the latent heat and sensible heat. (Non-
Combustion method). LD gas and electrical melting processes can be
used in Jenbacher gas engines.
Advantages of Steel Gas Utilisation in Gas Engines:
Independent power supply, Reduced energy costs, and greater predictability and
stability, Efficient and economic combined heat and electricity supply, High
electrical efficiency compared to other power generation technology (i.e. steam
or gas turbines),
Best suited for an electrical output range of a few hundred kW up to 20-30MW,
Considerably low gas pressure required, Alternative disposal of a problem gas
while simultaneously harnessing it as an energy source, Substitute to
conventional fuels,
Environmental benefits by greenhouse gas reduction

7) Regular shapes are casted by Continuous casting such as billets, blooms

slabs and rounds. Can you predict of casting shapes like angles and
channels in CC machine? Explain.
It may be predicted by strain analysis and microsegregation method. The tensile
strains at the solidifying front caused by bulging, unbending, and misalignment
of supporting rolls in a four-point-unbending bow caster were calculated. The
roll gap in the caster was measured for the calculation of the strains caused by
the misalignment of the supporting rolls. The calculated strain status near the
solidifying front was used to predict the internal cracks. Critical strains based on
some experimental data were adopted as the crack criteria.
Usually billets, blooms, slabs and rounds are casted using the Continuous
casting machine and further shapes like angles and channels are made from it.
However it is possible to make angles and channels using the continuous casting
machine but this technique is not good from the economic point of view
because the productivity of the process is quite less, the quality of the products
obtained is not very good, the tendency of crack formation in the products is
higher and proper shaping of the mould to cast angles and channels is difficult.

8) Explain the refining process in secondary steel making.

BASIC PROCESSES OF STEEL SECONDARY METALLURGY AND
THEIR EFFECTS
Inert gas blowing: - Only blowing (floatation of inclusions, temperature
and chemical homogenization of steel)
- Blowing under the active slag (a reaction between the slag and metal;
steel desulphurization)
Injection of additives: - Blowing of pulverized substances using an inert
gas (steel desulphurization, inclusion modification + steel deoxidation,
steel alloying, steel carburization)- Inputting additives in a form of cored
steel wires (accurate and economy alloying of steel, inclusion
modification)
- Aluminium wire feeding (controlled deep deoxidation of steel)
Steel refining by synthetic slags (steel deoxidation, controlled
desulphurization, absorption of non-metallic inclusions)
Vacuum steel refining: - Ladle degassing
- Stream degassing
- Chamber degassing (recirculating RH, lift DH)
- (H2 and N2 content reduction, vacuum carbon deoxidation, steel
additional alloying)
- Vacuum oxygen decarburization – VOD (stainless steel production
-deep decarburization by chromium of high alloyed steels)
Steel refining by gas mixture O2 – Ar, or O2 - H2O in a converter AOD,
CLU, K-OBM-S (stainless steel production – deepdecarburization under
the atmospheric pressure)
Steel temperature raising in ladle: - Electric arc under the atmospheric
pressure
- Electric arc with a possibility of steel vacuum degassing – ASEA, VAD
- Chemical temperature raising – by Al or FeSi oxidation under the
atmospheric pressure – IR-UT, CAS-OB
- Chemical temperature raising – by Al or FeSi oxidation in vacuum –
ISSM
INERT GAS PURGING: All secondary steel ladles have provision for gas
purging. Purging is carried out by porous plug shown in the next slide. The
rising gas bubbles create a central two phase gas-liquid region, known as
PLUME. The upward motion in the plume causes recirculatory flow .
STEEL REFINING BY INERT GASES: Argon is the most frequently used gas
for steel refining. However, carbon dioxide bubbles at occurring reaction of
carbon with oxygen fulfil the same function.
STIRRING AND HOMOGENIZATION OF THE MOLTEN METAL: Buoyant
energy of floating-out gas bubbles is used for stirring and homogenization of the
molten metal.
INCLUSIONS FLOTATION AT INERT GAS BLOWING AND THEIR
ABSORPTION BY SLAG: Non-metallic inclusions are floated-out from liquid
steel by a steel flow towards the phase interface with slag, where they are
caught and subsequently absorbed by the liquid slag. This process requires
laminar flow of the melt, which does not cause entrainment of particles of the
slag into the steel, and a negative value of the Gibbs energy in the process of
inclusion absorption by slag.
TECHNOLOGY OF STEEL REFINING IN VACUUM: Reduction of contents
of hydrogen and nitrogen during steel vacuum degassing in a ladle is caused
particularly by separation of these gases from the bath surface and partially also
by their diffusion to gas bubbles of blown argon or carbon monoxide bubbles
near the metal surface. The oxygen, or carbon, content decrease is caused both
by CO bubbles nucleation in pores of ladle lining as well as on the surface of
existing non-metallic inclusions and by transfer of CO into the gaseous phase
above the bath surface or to bubbles of blown argon.
PHYSICAL-CHEMICAL BASICS OF PROCESSES OCCURRING DURING
STEEL VACUUM PROCESSING: Favourable effects of steel vacuum
processing consist above all in reduction of contents of gases dissolved in steel
and in affecting the carbon reaction process, the product of which is a gaseous
phase – carbon monoxide. The process of steel vacuum degassing occurs
through two mechanisms:
(a) Formation of gaseous bubbles in molten metal, their growth and
precipitation from the melt volume.
(b) Metal degassing through diffusion of dissolved gas atoms to the melt
surface and their transfer into the outer atmosphere.
BASIC METHODS OF STEEL REFINING IN VACUUM COVER:
1. Steel vacuum refining in a melting furnace (EAF, induction
furnace)
 2. Steel vacuum refining in a ladle placed in a caisson
3. Steel stream vacuum refining during pouring from a ladle into a
ladle in a caisson or during pouring of steel into a mould (in a
caisson)
4. Steel vacuum refining in a chamber
5. A lift method DH (Dortmund-Hüttenunion)
6. A circulation method RH (Ruhrstahl-Heraeus)

9) The stainless steel is refined in AOD and VOD. How can carbon gets
oxidized preferentially with respect to Chromium in this reactors?
The major issue in stainless steelmaking is the difficulty of oxidising carbon
from molten steel without also oxidising large proportions of expensive
chromium. This can, however, be achieved by reducing the partial pressure of
the gaseous product of carbon oxidation, carbon monoxide, by dilution with
argon. Modern stainless steelmaking is dominated by duplex processes which
prepare a high carbon melt in an electric arc furnace, and then decarburise it in
an argon–oxygen decarburisation (AOD) converter. The activity of Cr2O3 was
taken by Dennis and Richardson to be unity, while the activity of chromium in
an 18 wt-%Cr stainless steel was taken as 0.2. When the carbon monoxide
partial pressure is 100 kPa, reducing the carbon content to 0.03 wt-% without
chromium oxidation is only possible above 1940°C. At a carbon monoxide
partial pressure of 10 kPa, the required temperature drops to 1610°C and at 1
kPa, it is only 1370°C. Lowering the carbon monoxide partial pressure enables
the necessary extent of decarburisation to be achieved without chromium loss at
much more favourable temperatures, where refractory erosion is not excessive.

Diluting the oxygen blown into the AOD converter with increasing amounts of
argon allows very low carbon contents in the stainless steel bath to be reached
without excessive chromium oxidation.
Additions of silicon in the form of ferrosilicon were also shown to be effective
in reducing chromium oxides from the slag, but the extent of reduction is
limited by the accompanying increase in the silicon content of the steel.

10) What is sequence of removal of elements in molten metal (from Blast

Furnace) during steel making?
The sequence of removal of elements in molten metal (from Blast
Furnace) during steel making:

Silicon is the first element to get oxidized because of SiO2 as compared to

other oxides. So, Si dissolved in iron gets eliminated in the form of silica
right from the start of the blow. Lime is also added from the start of the
blow so that SiO2 does not attack the basic lining and goes into the slag.

Once silicon is removed, the still impure molten iron is mixed with scrap
iron (from recycling) and oxygen is blown on to the mixture. The oxygen
reacts with the remaining impurities to form various oxides. The carbon
forms carbon monoxide. Since this is a gas it removes itself from the iron.
This carbon monoxide can be cleaned and used as a fuel gas. This process
continues throughout the blow.

Removal of phosphorus occurs towards the end of the blow. It reacts

with the oxygen to form acidic oxides. These are removed using
quicklime (calcium oxide) which is added to the furnace during the
oxygen blow. They react to form compounds such as calcium phosphate
which form a slag on top of the iron.

Most of the Mn and Fe also gets oxidized initially.

Sulphur has to be removed first in a separate process before the molten

metal is added to the steelmaking converter. In maximum cases, external
desulphurization occurs in the blast furnace runner. Magnesium powder is
blown through the molten iron and the sulfur reacts with it to form
magnesium sulfide. This forms a slag on top of the iron and can be
removed.

Mg+S→MgS