Steel Making

Dr. Trinath Talapaneni

Assistant Professor
Department of Metallurgical and Materials Engineering
OP. Jindal University
 Course Content
• Unit – I
• Introduction to steelmaking, acid Bessemer process and its limitations, basic Bessemer process and its
limitations, open hearth process and its limitation, introduction to basic oxygen furnace, LD design,
related refractory, oxygen lance, Raw materials for BOF, Oxygen lance characteristics, Jet action,
Foaming and Emulsion formation, Stabilization and collapse of emulsion, reactions in LD converter,
Evolution of Impurities in liquid steel, Evolution of slag composition, Thermodynamics of P removal,
Decarburization, gas cleaning system, bottom blowing process and its disadvantages, combined
blowing process, modern trends in BOF technology.
• UNIT –II
• Features of Induction Furnace, Steel making in electric arc furnace- raw materials for EAF process,
design and construction futures of EAF process, electrical considerations for AC/DC furnaces,
graphite electrodes, gas collection and cleaning system, fluxes and additives, Furnace operations,
refining process, developments in EAF steel making process, use of sponge iron as a charge, use of hot
metal and Fe3C as charge material, novel steel making technologies- EOF, CONARC.
• UNIT –III
• Ladle Metallurgy- Objectives of secondary steel making, inert gas stirring in ladles, ladle furnace,
deoxidation of liquid steel, deoxidation kinetics, injection metallurgy- desulphurization, kinetics of
desulphurization, design of synthetic slag and its practice, degassing techniques; clean steel-source of
inclusions, slag carry over and its consequences, effect of inclusions on properties of steel, types of
inclusions, properties of inclusions, control of inclusions, inclusion engineering, Stainless steel
Making Technology- AOD, VOD Process.

• UNIT –IV
• Ingot casting technologies- ESR, VAR processes, Tundish Metallurgy- role of tundish in the
continuous casting process, design and operation of tundish, flow control devices, role of tundish flux,
refractories, mould and its operation, electromagnetic stirring; mechanism of solidification, quality
control in continuous casting, recent trends in continuous casting, continuous casting defects and its
remedies.
• UNIT –V
• Finishing operations- Reheating of billets/blooms/slabs, hot rolling, cold rolling, galvanizing,
problems faced by domestic iron and steel industry, case study on defects occurred during processing
of final products, numerical related to steel making.
Unit- I
 Introduction to Steel Making
• Steel is as alloy of iron and carbon, along with this it contains many other elements such as
Al, Si, Mn, S, P, O, etc. which are not added specifically for any purpose but are inevitably
present because of their association in the process of iron and steelmaking and can not be
totally eliminated during iron and steel making process. These are known as impurities.
• The chemical composition of steels broadly divide them into two major groups, (i) plain
carbon steels and (ii) alloy steels.
• Plain carbon steels: these are essentially alloys of iron and carbon .
• Alloy steels: if one or more of elements other than carbon are added to steel in significant
amounts to ensure specific better properties such as better mechanical strength, ductility,
electrical and magnetic properties, corrosion resistance and so on it is known as an alloy
steel.
• These specifically added elements are known as alloying additions in steels.
• Plain carbon steels are broadly subdivided into four major types based on their carbon
contents.
(i) soft or low carbon steels – up to 0.15 % C
(ii) Mild steels – 0.15-0.35 % C
(iii) Medium carbon steel – 0.35-0.65 % C
(iv) High carbon steels – 0.65-1.75 % C
• Mild steels are widely used for constructional purposes. Flat product are generally produced
from low carbon steels because of their better malleability which enables their easy rolling
into thin sections. High carbon steels are used for making cutting tools because of their
better hardness.
• Alloy steels are broadly sub-divided into three groups on the basis of the total alloying
elements present
(i) low alloy steels – up to 5 % total alloying content
(ii) Medium alloy steels – 5-10 % total alloying
(iii) High alloy steels – above 10 % total alloying
Routes of Steel Making
 Classification of Steel Making Process

• Once upon a time steels were classified in terms of their process of manufacture, e.g. Bessemer,
acid open hearth, basic open hearth, electric and so on.
• In terms of uses, steels are often classified as structural, deep-drawing, rail, forging, flat etc.
• Modern steel making is supposed to have been begun with advent of Bessemer process of steel
making in 1860 in U.K. It uses air for refining.
• Prior to 1850s molten iron was refined to first produce wrought iron, a nearly impurity free
ferrous material containing a small amount of mechanically entrapped slag particles, which was
later recarburized in solid state to make steel. This was known as blister or cement steel and the
process as cementation process of steel making.
• It was Huntsman, in U.K., who in 1740 successfully melted the cement steel in a crucible and
thereby laid the foundation of crucible process of steel making.
• By 1860s Henry Bessemer perfected his process of steel making in U.K. by blowing cold air
through molten iron and thereby producing steel finally in molten condition.
• Soon the open hearth and electric furnaces were developed to melt steel scrap. The open
hearth used fuel like producer gas and the electric furnace used electric energy for melting
the scrap.
• Depending upon the impurities to be eliminated the slag nature has to be adjusted. When
only Si, Mn and C are to be removed as impurities from iron, the slag produced is
predominantly acidic, nearly silica saturated, and the furnace lining has to be acidic, of
silica, to contain the slag. Such a process came to be known as acid process of steel making.
• Around 1878 in Germany, Thomas modified the Bessemer process and made it applicable to
irons containing P and S, along with Si, Mn and C has to be removed the slag has to adjusted
by external addition of flux like limestone. The slag is basic in nature and basic lining of the
furnace becomes necessary. Such as process came to be known as Thomas process or basic
process of steel making.
• Modern steelmaking is carried out in basic lined furnaces or vessels making basic slag,
using oxygen as refining media. This is often called basic oxygen furnace steel making or
BOF.
 Bessemer Process
Acid Bessemer process:
• Modern steelmaking starts with the Bessemer steelmaking process.
• This process uses a pear shaped cylindrical steel vessel of approx. 6m height lined with silica
refractory (because that is the only refractory material which could able to withstand steel
making temperatures).
• It is the first economic tonnage liquid steel production from the molten pig iron. Vessel had a
capacity from 10 to 50 tons.
• By this time liquid pig iron were being produced through Stukofen but high temperature
furnace for large scale refining of liquid pig iron was not available. Bessemer invented the
autogenous refining furnace that was based on chemical heating by oxidation of impurities
and attained 1600oC required to attain the liquidus of low carbon refined iron.
• Liquid iron is charged into the convertor at around 1300ºC and air is blown from bottom
through tuyers for 15 min.
• Oxygen in air reacts with C, Si, Mn present in hot metal and forms oxides like SiO 2, MnO
along with FeO forms silica saturated acidic slag.
• Carbon reacts with oxygen and forms CO and CO2, which escapes into atmosphere from
mouth of the converter.
• Since the oxidation reactions are exothermic, the liquid bath temperature rise automatically
with out the need of using any external fuel.
• Oxidation of Si is the principle source of heat in acid Bessemer process.
• Refining took hardly 20 min.

Chemistry of refining:
• As soon as the blast is turned on, the oxygen in the blast starts reacting with the metal.
• Even though the free energy change involved in the formation of oxides of iron is much
higher than that of SiO2, MnO and CO (based on Ellingham diagram), iron is oxidized first
due to its large mass.
O2 (g) = 2 [O]
2 [Fe] +2 [O] = 2 (FeO)
• The FeO immediately reacts with Si in the metal.
2(FeO) + [Si] = (SiO2) + 2[Fe]
• In both acidic and basic process , Si oxidation occurs first . After Si oxidation, Mn reaction
starts.
[Mn] + (FeO) = (MnO) + [Fe]
• The SiO2 reacts with excess (FeO) and (MnO) forming a silicate slag
(SiO2) + 2 (FeO) = (2FeO.SiO2) (Fayalite, M.P. 1205 oC)
(SiO2) + 2 (MnO) = (2 MnO. SiO2)
• Major limitation of the process, however, was that it could not remove S and P present in the
metal. (P and S can only be removed effectively from the metal under a cover of basic slag)
• Oxygen content of the Bessemer steel was also increasing. In 1864 , Mushet found that
deoxidation of liquid steel with Ferro-manganese (FeMn) will lower the oxygen content in
steel. Also, this practice increases Mn content in steel, which reacts with S and forms MnS. S
can also reduced in the melt.
• But P cannot removed in Acid Bessemer process- because P removal requires basic slag, but
acid Bessemer process have acidic lining, also low P ores are expensive, so high P ores are
used for steel making.
• This leads to the invention of Basic Bessemer process.
Basic Bessemer (Thomas process):
• The P issues was tackled following the invention of Thomas process by Sidney G. Thomas in
1879 to accept the iron containing around 2 % phosphorous.
• The lining of the converter was changed to basic, made from dolomite (Ca Mg(CO3)2).
• Limestone was incorporated in the charge to make good basic slag capable of interaction
with metal to remove not only Si and Mn but P as well.
• In the basic process, P oxidation occurs after the carbon blow.
• The carbon oxidation is indicated by the appearance of long blue flame over the mouth of the
converter. The flame lengthens as the rate of carbon-oxygen reaction increases and it drops
after the completion of C-O reaction.
• When the C-O reaction slow down (i.e. carbon content reached to minimum value) FeO
content in the slag increases.
2 [P] + 5 (FeO) = (P2O5) + 5 [Fe]
• Limestone is also added to make basic slag and it is capable of removing P in the form of
calcium phosphate.
(P2O5) + 4 (CaO) = (4CaO. P2O5)
• The basic slag also reacts with S in the metal to some extent
[FeS] + (CaO) = (CaS) + (FeO)
[Mn] + [FeS] = (MnS) + [Fe]
• However, both acid and basic Bessemer process suffered from the presence of high level of
nitrogen (around 200 ppm), which got dissolved in the bath due to purging of air through
bottom tuyers.
• Problem with nitrogen in steel: nitrogen in steel forms stable nitrides of Al, Si, Cr etc. this
effects toughness and ageing characteristics of steels as well as enhancing the tendency
towards stress-corrosion cracking. Also, it strain hardens the material and does not allow
cold working- steel will become brittle.
 Open Hearth Process

• The Bessemer was incapable of producing low nitrogen steel. Furthermore, it could not able
to melt the cold charge, scraps generated from casting and forming processes were being
piled up during that time.
• A furnace that could attain high temperature to melt steel scrap was not available. To fill-up
this need open hearth furnace (OHF) came into existence.
• These problems are resolved with the advent of open hearth process. It was introduced in
1868 by Karl Wilhelm Siemens and Martin brothers. This process is dominated till late 1950.
• The open hearth furnace is a shallow fireclay refractory lined rectangular tray with a roof
above it.
• Charge consist of steel scrap, hot metal, lime and iron ore were introduced into the furnace
through a number of doors that were provided in the front wall of the furnace .
• These doors were also used for additions, inspection and sampling of the liquid metal bath
during the course of heat making.
• Heat was provided to the open hearth furnace by the combustion of gaseous (coke oven gas)
and liquid fuels ( fuel oil and tar) with preheated air, through burners positioned in the side
walls of the furnace.
• Air preheating was done through regenerative principles. In one cycle, the hot off gas from
the furnace was allowed to pass through a checker brick works to exchange heat with the
brick works. In the next cycle, the cold air was passed through the hot checker bricks to get
preheated before it join the fuel for combustion in the furnace. Two brick structure were used
and while one brick structure were on hot furnace gas and the other was on air. Through this
regenerative principles the air was preheated utilizing the hot gas from the furnace.
• OHF was the first fuel fired furnace to melt the steel scrap using chemical fuel. Another
unique feature of the furnace was the wide and shallow liquid bath to facilitate the heat
transfer to the liquid bath from the furnace atmosphere. The wide hearth liquid surface was
covered with a refractory-lined hood. The open hearth furnace derived its name from such
open structure.
• Oxygen for oxidation of C, Si, Mn and P was supplied by iron ore as well as atmospheric
oxygen. Almost, all grades of steels can be made in open hearth furnace.
• But the large refining time (takes 6-8 hr for each heat) and it is not an autogenous process,
heat is supplied from external source, became a major drawback for this furnace. To improve
the kinetics, the furnace was converted to twin hearth furnace. Here, the furnace was divided
into two parts; one part was put on preheating and other part was on the melting and this
increased the melting efficiency. Inspite of all these improvements, the furnace took atleast 6
hr for a heat.
• This lead to the development of Basic Oxygen furnace (BOF/BOS/LD).
 Basic Oxygen Furnace (BOF/BOS/ LD)

• Attempts were made to reduce the nitrogen content in Bessemer steel by oxygen enrichment of
the air blast blown through the bottom of the converter. But this could not progress beyond a
point, because the oxygen enriched blast damaged the refractory, overheating and melting of
tuyers (tuyers shrouding).
• Attempts were therefore made to lance oxygen onto the bath through the throat of the convertor.
As a result top-blown basic oxygen converter process popularly known as LD process was
developed.
• First BOF process was the LD process, which derived its name after the name of the cities Linz
and Donawitz in Austria where it was invented.

• Advantage of using oxygen in place of air:

• Pure oxygen by far is the most powerful oxidizing agent.
• During refining exothermic reactions occurs which makes it possible to melt scrap or DRI into
the charge.
• Refining rates are much higher with no nitrogen contamination of the melt.
• A supersonic jet provides a greater depth of jet penetration and stronger bath agitation due
to higher momentum of the jet. This promotes better refining reactions by improving the
kinetics by way of increased availability of surface area due to more droplet generation,
foaming (gas-slag-melt emulsion) and the mixing of the metal bath.
• LD process was introduced in India in Rourkela steel plant in 1956. steel can be produced in
two routes (i) BOF (ii) EAF
• BOF constitutes – 45 % , EAF route constitutes 28% and IF route constitutes – 27%.
• BOF vessel is equipped with:
• Rotating device that allows proper positioning of the vessel
• Lance carriage to keep the water cooled lance in the vertical position
• Nose cone section through which gases exit
• Tap hole for draining metal/slag
• Overhead bins for adding iron ore, fluxes etc. are required during the blow.

• LD vessel Design:
• The bath depth is in the range of 110-180cm depends on capacity. The depth should be maximum to
prevent damage of bottom during lancing.
• Height to dia ratio- 1.5
• Total lining thickness- 600-1000 mm.
• Height if the vessel – 7-10m
• The nose dia & angle – 1/3(shell dia) & 67 o
• Refractory Lining of BOF:
• The lining of oxygen converter is usually made of three layers:
• First an inner layer (safety lining) is made of magnesite or burnt dolomite bricks.
• Gaps between the bricks and the shell is filled with tar-dolomite ramming mass.
• The same ramming composition is used for making up the second intermediate layer.
• The upper working layer is made of magnesia carbon bricks.
• The performance or life of the refractory depends on various factors:
(i) furnace atmosphere (ii) composition of slag (iii) mechanical stresses (iv) thermal shock (v)
effect of high temperature (vi) blowing technique (vii) quality of hot metal and (viii) quality of
refractories.
• Modern LD converters are therefore lined with magnesia-carbon refractories. The presence
of submicroscopic carbon particles in magnesia carbon refractories control penetration of
slag into the refractory.
• The lining of LD converter lasts between 3000 to 10,000 heats. Most of the plants have LD
furnaces of 150 ton capacity.

• Raw materials for BOF:

• Hot metal, coolant & source of Fe (scrap, DRI), oxide additions, Flux (lime, dolomite),
oxygen.
• Scrap, charged from a scrap box, is the first material to be charged into the furnace. The hot
metal is then poured into the vessel from a ladle, after which the oxygen blow is started.
• Iron ore is usually charged into the BOF as a coolant and it is often used as a scrap
substitute. Iron ores are available in the form of lumps or pellets. The cooling effect of iron
ore is about three times higher than scrap. The reduction of the iron oxide in the ore is
endothermic and higher amounts of hot metal and lower amounts of scrap are required when
ore is used for cooling.
• The fluxes, usually in lump form, are charged into the furnace through a bin system after the
start of the oxygen blow. In most BOF shops limestone (CaCO3) or dolomitic stone,
(CaCO3•MgCO3) is frequently used as a coolant rather than as a flux. Limestone is
commonly used to cool the bath if the turndown temperature is higher than the specified aim.
When limestone is heated, the endothermic calcining reaction occurs producing CaO and
CO2, causing a temperature drop in the furnace.
• In a 300 ton heat, 450 kg of limestone will drop the temperature of the bath by about 6°C
• Charging sequence in LD process :

• First, the scrap is charged directly on the vessel from the scrap box. It has two advantages:
(1) If we charge the scrap first and then you put the hot metal over it, then hot metal does not
directly hit the refectory wall and avoids chemical erosion of the wall. Thus, scrap provides a
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cushioning effect over the refractory.
(2) Secondly, charging the hot metal over the scrap helps in the scrap melting. Scrap melting is
heat and mass transfer controlled and when liquid falls over scrap, its inertia may be utilized
for scrap melting. It may be noted that besides steel scrap, other coolants like DRI/briquettes
of iron bearing solid waste could also be utilized.
• After charging, Oxygen is lanced from the top at supersonic velocity that creates gas-slag-
metal emulsion with tremendous increase in surface area for superfast refining. Impurity
oxidation generates heat that is more than sufficient to self-sustain this process. Surplus heat
is generated such that coolant is required to maintain the bath temperature at 1600oC.
Around 25% scrap is added to control the temperature to the desired limit.
• Then sampling is done by turning the vessel to check whether the desired steel composition
has been achieved or not.
• The final step is tapping the metal. Metal is tapped by tilting the furnace directly to the ladle.
Draining of slag to the metal at the end of tapping is a concern because carryover slag
interferes with subsequent deoxidation of bath by reversion of impurities from slag to metal
when bath oxygen is lowered to very small value. To arrest the slag, some kind of float with
density between that of slag and metal is used, which block the taphole when metal has been
drained. some sensors have also been used which indicates the traces of slag in metal flow
through the nozzle when the tapping could be stopped. Inspite of all efforts some carryover of
slag could not be avoided with due consideration to the metal yield.
• Deoxidation and alloying is also sometimes done in the ladle by adding blocks of aluminum
and ferroalloy at the vessel bottom to utilize the inertia of the falling stream.
• For low carbon scrap, the scrap melting is mass transfer controlled and for high carbon
steel scrap, scrap melting could be heat transferred controlled.
• For low carbon steel scrap, the scrap liquidus is very high; it is higher than that of hot
metal. So, to melt the scrap, it needs to be carburized first to lower its liquidus, such that
scrap liquidus goes below the hot metal temperature enabling hot metal to melt it. Now the
transfer of carbon from hot metal to scrap surface is controlled by mass transfer of carbon
through the concentration boundary layer at the scrap-hot metal interface. Such boundary
mass transfer is facilitated by turbulence in the boundary layer, which could be derived from
the falling stream over the scrap.
• When the scrap liquidus is lower than hot metal temperature, then heat transfer across the
boundary layer might also control the scrap melting. In this case also liquid inertia derived
from falling stream will be helpful in enhancing heat transfer across the boundary layer.

• Oxygen lance:
• 99.99 % pure O2 is sent through water cooled lance (steel tube)
• Lance tip is made of Cu
• Lance height = 8-10 m, dia- 20-25 cm.
• Water requirement = 50-70 m3/hr at a pressure of 5-7 kg/cm3
• The supersonic jet is used to penetrate the bath adequately and
the area of its impact will be maximum.
• In modern oxygen steelmaking processes a water-cooled lance is used to inject oxygen at
very high velocities onto a molten bath to produce steel. With the increasing demands to
produce higher quality steels with lower impurity levels, oxygen of very high purity must be
supplied. Therefore, the oxygen for steelmaking must be at least 99.5% pure.
• In top-blown converters, the oxygen is jetted at supersonic velocities with convergent-
divergent nozzles at the tip of the water-cooled lance. A forceful gas jet penetrates the slag
and impinges onto the metal surface to refine the steel. Today, most BOFs operate with lance
tips containing four to five nozzles and oxygen flow rates, (in 230 to 300 ton converters), that
range from 640 to 900 Nm3/min.
• The tip is made of a high thermal conductivity cast copper alloy. The nozzles are angled
about 12° and equally spaced around the tip. The tip is welded to a 12 inch seamless steel
pipe (lance barrel) about 60 feet long.
• Cooling water is essential in these lances to keep them from burning up in the furnace. As the
oxygen passes the converging section it is accelerated and reaches sonic velocity (Mach =1)
in the cylindrical throat section. Then it expands in the diverging section and its temperature
and pressure decreases while its velocity increases to supersonic levels (Mach > 1).
• The supersonic jets are at an angle of about 12° so that they do not interfere with each other.

• The lance barrel is a series of concentric pipes consisting of an outer pipe, an intermediate
pipe and the central pipe for the oxygen. Oxygen lance is to be designed to compensate for
thermal expansion and contraction.
• The important components of a lance are the water cooling channels where the cooling water
flows through the center of the nozzle and exits through the outer pipe of the lance.
• With cylindrical nozzle it is not possible to produce a supersonic jet as it interact with the
ambient atmosphere generating shock wave.
• In case of the convergent divergent nozzle, oxygen can be
accelerated to supersonic speed and it will emit at a pressure
close to that of ambient atmosphere without making any energy
dissipation through shock wave generation; and it will
propagate through atmosphere retaining its energy until it
interacts with the liquid bath.
• When the supersonic jet moves through the atmosphere it
entrains atmosphere along with it and velocity in the entrained
region drops to subsonic velocity. Therefore, the fully expanded
jet contains a supersonic core with subsonic extended region.
• The supersonic core has a Mach number of 2.5; that is the
velocity of oxygen jet is 2.5 times that of the velocity of the
sound. The length of this supersonic core might be 15 times to
that of the nozzle exit diameter.
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• How Convergent-Divergent can accelerate the gas at supersonic velocity without any shock
wave generation at the nozzle exit?

• The nozzle has three portions; one is called the convergent section (CS), where nozzle
converges to throat; then you have a throat that is basically a cylindrical section, and then
there is a diverging section (DS), where nozzle is diverging out.
• Equation of momentum for one dimensional compressible flow is presented by
• Following Bernoulli’s equation, only the pressure head and the kinetic head is considered.
Here pressure drop across the line accounts for the increase in kinetic energy of the gas. For
incompressible fluid, the equation of continuity can be written as

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• Incorporating velocity of sound through pressure, density correlation, the combined equation by
amalgamating momentum and continuity equation, can be given as

• In the converging section, dA is negative. So, if you want to accelerate the gas, then du has to be
positive, meaning M2-1 is negative, or, M<1; that is the gas velocity will remain in subsonic
range.
• At cylindrical portion dA is 0, since du can not be zero, M2-1=0; so M=1and the velocity of the
gas will attain the velocity of sound.
• Now, in the diverging section, dA is positive; to accelerate the gas du has to be positive; then M2-
1 has to be positive. So, M is greater than 1, or the gas will attain supersonic velocity.
• As the velocity of the gas through Divergent section increases, the pressure of the gas will
decrease and Divergent section length could be designed in such a way that when the supersonic
jet emerges from the nozzle, it pressure become comparable to that of the ambient pressure, such
that no shock wave generates. Roy-KGP
• Jet Action:
• When the oxygen jet interacts with the liquid bath it forms some crater in the bath. The
strength of the jet is characterized by Jet force number (JFN), defined as

• Upstream gas pressure that is approximately 1 mega Pascal and fixed. Nozzle throat
diameter is also fixed by design of nozzle. What actually could be varied is the height of the
nozzle from liquid bath. So, by pushing the nozzle up and down, the nozzle height (H) can be
varied and so the JFN. JFN increases when lance is lowered, or H is decreased, and vice
versa.
• Depending on jet force number, you can produce the three regimes of jet penetration in the
bath: one is called the dimpling with a slight surface depression, when JFN is low. It causes
lot of splashing of the liquid droplets on the refractory; not good for refractory life. Roy-KGP
• On increasing the Jet Force Number (JFN), splashing with shallow depression happens.
Here ejected droplets is mostly directed towards the emulsion phase above and some droplets
might hit the refractory directly.
• With further increase in JFN, or further lowering the lance, a distinct crater is formed and
droplets are directed vertically towards the emulsion phase. It forms a significant penetration
of the jet into the bath; so it is also called the penetration regime and industrial vessel
usually operate in this regime.
• With increase in JFN, oxygen partial pressure become more, so decarburization rate also
become high.
• Under extreme case of JFN, preferential decarburization might occur where rate of carbon
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removal might exceeds the rate of generation of FeO and the slag might dry off in depleting
FeO in slag. The condition is called the hard blow.
• On the other hand, soft blow is defined a situation when JFN is moderate such that FeO
formation much exceeds the decarburization. With soft blow it is possible to build the FeO in
the slag without sacrificing much carbon from the metal bath at initial stage of blowing.
• During soft blow, for better slag formation, a high lance height (1.5-2m) is used at the
beginning of the blow and the lance is lowered (0.8-1.2m) for decarburization, called as hard
blow.
• The starting lance distance (Xi) for specific oxygen blow is :
Xi = 0.541 (db)1.04 , where db = bath dia in meters.
• Instead of single nozzle, use of multi-hole nozzles increase the bath impact area for large
capacity furnace.
 Refining Reactions in BOF Steel Making
• In the oxygen steelmaking process, impurities such as carbon (C), silicon (Si), and manganese
(Mn) dissolved in the hot metal are removed by oxidation to produce liquid steel.
• Hot metal and scrap are charged into the furnace and high-purity oxygen gas is injected at high
flow rates, through a lance, to react with the metal bath.
• The oxygen injection process, known as the blow, lasts for about 16 to 25 minutes and the
oxidation reactions result in the formation of CO, CO2, SiO2, MnO, and iron oxides.
• Most of these oxides are dissolved with the fluxes added to the furnace, primarily lime (CaO), to
form a liquid slag that is able to remove sulfur (S) and phosphorus (P) from the metal.
• The gaseous oxides, composed of about 90% CO and 10% CO2, exit the furnace carrying small
amounts of iron oxide and lime dust.
• Typical oxygen flow rates during the blow range between 2–3.5 Nm3 per minute per ton of steel.
• The commercial success of oxygen steelmaking is mainly due to two important characteristics.
• First, the process is autogenous meaning that no external heat sources are required. The
oxidation reactions during the blow provide the energy necessary to melt the fluxes and
scrap, and achieve the desired temperature of the steel product.
• Second, the process is capable of refining steel at high production rates. The fast reaction
rates are due to the extremely large surface area available for reactions.
• When oxygen is injected onto the metal bath a tremendous amount of gas is evolved forming
an emulsion with the liquid slag and with metal droplets sheared from the bath surface by the
impingement of the oxygen jet.
• Emulsion Formation:
• Formation of emulsion requires energy, with increase in the jet velocity distinct crater is
formed. So, peripheral liquid of the crater is teared off and oxygen jet is continuously
pumping the energy for generating the liquid droplets and these are splashed into the slag
phase.
• Slag metal reaction will take place at the ejected metal droplet slag interface and mostly it is
the decarburization that will initiate first because carbon is the major impurity in steel and
forms a stable gaseous product at steelmaking temperature.
• So in-situ CO generation will take place that will form slag foam. With progress of refining
such foam will increase in height. Continuously ejected metal droplets into the foam will
form slag-gas-metal emulsion.
• When a full fledged emulsion forms other impurities also starts removing. Phosphorus
removal starts when the basic slag forms. Carbon content of the bath is judiciously
controlled by proper blowing practice such that carbon stays in the bath and supports
emulsion and impurity removal till the end of the process.
• [C] + [O] = {CO} ------------ (i)
• FeO + [C] = [Fe] + {CO} ------ (ii)
• When this CO gas bubbles are unable to escape through the slag, the slag is said to be
foaming (gas bubbles entrapped in liquid).
• Samples of emulsion from LD converter revealed that metal droplets are hollow and through
eq-(ii) it is confined that CO enters the metal droplets and forms emulsion.
• Increase in height of emulsion indicates high amount of decarburization. As the C content in
the bath decreases (= 0.3 % C) emulsion decreases, results in end of decarburization.
• foaming of slag has to be controlled to avoid ejection of slag, which can be controlled by
controlling C reaction with FeO in slag.
(FeO) + [C] = [Fe] + {CO}
• Reaction between C and FeO of slag, in slag , will not allow CO bubble to grow. Smaller
size gas bubbles can be trapped easily in slag as compared to larger sizes. Slag may foam
and may be eject from the converter.

• Formation and Stability of emulsion:

• Formation of emulsion requires energy because the metal droplet are formed, by tearing the
liquid metal and creating a new surface. So, the formation of emulsion requires energy and
oxygen jet is continuously pumping the energy for generating this liquid droplets, and
throwing them into the slag phase.
• But collapse of emulsion is spontaneous, because the emulsion contains small bubbles with
lots of surface area and associated surface energy. So, emulsion is a very high energy
product; and always it will try to collapse and go to the nominal slag metal interface by
minimizing its energy.
• So how to stabilize this emulsion? What are the factors that can stabilize the emulsion?

Roy-KGP
• Factors that can stabilize the emulsion:
• There are three factors:
(1) surface tension at different interfaces like slag-metal interface, slag-gas interface, metal-
gas interface. And if these surface tension forces are higher, then the surface energy also will
be higher and emulsion will be much less stable. So, the aim should be to reduce the surface
tension at all interfaces.
(2) viscosity of slag, If slag viscosity is higher, then the gas bubbles and the liquid droplets will
have more residence time due to enhanced drag force.
(3) The most important thing is the gas generation by the decarburization; because when the
bath gets decarburized CO bubbles forms and that CO bubbles basically stabilizes the foam by
buoyancy.

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• Surface Tension of different interfaces:
• slag-metal interface, the value of surface tension is 800 to 1200 ergs/cm2.And if we compare
this value with water- mineral oil system, a low temperature analogue of metal-slag system,
it is only 40 ergs/cm2.
• slag-metal interface is most important, as it concerns the formation and destruction of metal
emulsion; because if surface tension is less, then it is easier to generate the droplets, and
also the total energy in emulsion will be less and intern stability of the emulsion will also be
higher.
• Presence of the FeO and SiO2 in the slag has been found to emulsify the iron better in the
slag. Both FeO and SiO2 are surface active compounds and modify the slag-metal interface
for better emulsification of iron in slag.
• And most importantly, it has been found by experiment that the surface tension decreases
significantly during the impurity transfer across the slag-metal interface. This phenomena is
observed by considering a metal droplet in an alumina crucible and then slag is allowed to
fall on it. Thereafter the contact angle of the metal slag interface is monitored.
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• Figure (b) shows the evolution of contact angle at slag-metal interface with time. It is found
that initially the metal droplet is round with high contact angle between metal-slag interface.
When slag poured over it and time passes, the contact angle at slag-metal interface decreases
and the interface flattens and it becomes almost horizontal at peak mass transfer and then
onwards again the contact angle starts increasing. Finally when the mass transfer Roy-KGP
is over the metal droplet regains its spherical shape.
• So, during the refining process, the surface tension at slag-metal interface decreases
significantly, that helps in reducing the emulsion surface energy and helps in stabilizing it.
Besides, presence of FeO and SiO2 also enhances the emulsification of iron in slag.

• Gas-Slag interface:
• For slag-gas interface also interfacial tension not very low and of the order of 400 to 600
ergs/cm2. If you compare this value to 72 ergs/cm2 for the water-gas system; this is also quite
high. And it concerns the formation and stability of the foam.
• So, in case of the LD refining carbon has to be preserved to the end of the process, such that
decarburization continue to the end and it sustain the foam as well as emulsion. Once the
supply of CO bubbles ceases, foam collapse, emulsion collapse and refining comes to a halt.

Roy-KGP
• Metal-Gas interface:
• For pure iron, the surface tension is 1800 ergs/cm2. The surface tension at metal-gas
interface can be reduced significantly by using the surface active element.
• The figure shows the variation of surface tension at the
liquid iron-gas interface in presence of oxygen and
sulphur dissolved in liquid iron.
• Oxygen and Sulphur are surface active elements and in
their presence surface tension at liquid iron-gas interface
decreased from 1800 to 1300 & 1200 dynes/cm
respectively with concentration of (0.1 atomic %) each.

variation of surface tension of liquid iron-gas interface in presence of surface active elements like oxygen and Sulphur
Roy-KGP
• Kinetics of Decarburization:
• The figure depicts the variation of decarburization rate
with the progress of blowing.
• There are three distinct regimes; in the first regime,
decarburization rate increases progressively; in the 2nd
regime, it is stabilized to a steady state value and in the
remime-3, decarburization decreases.
• In regime-1, the decarburization is controlled by the
oxygen mass transfer. In this regime, there is plenty of
carbon in the bath and the supply of oxygen controls the
rate of decarburization. Here, the rate of
decarburization is controlled by oxygen mass transfer;
that means blowing practice has a role to play.
• Controlling decarburization using hard and soft blow
through blowing practice is possible. So, the slope of the
line can be tailored as par the requirement.
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• In regime-2, i.e., in the steady state regime, the carbon in the bath has decreased
significantly. Under this condition the rate of decarburization depends both on the rate of
supply of oxygen and carbon. Rate of supply of oxygen just match the rate of supply of
carbon from the bath and attains somewhat constant rate of decarburization. Some
unevenness in the curve is due to local segregation of carbon and oxygen due to insufficient
mixing.
• Finally in the regime-3, the bath carbon becomes very lean and the reaction does not
depends on the oxygen supply and it solely become dependent of the rate of supply of carbon.
So, this regime is controlled by mass transfer of carbon and the blowing practice has no role
to play.
• So, only regime-1, i.e., at initial stage of blowing, blowing practice has a role to play in
controlling decarburization. For superfast decarburization, one can adopt hard blowing by
increasing JFN, or, lowering the lance. Or, for building FeO in the slag at mild
decarburization rate, one can adopt soft blowing with lower JFN, or moving up the lance.

Roy-KGP
• Decarburization & Slopping:
• slopping is an important phenomenon in LD furnace
and it is very much related to decarburization. In LD
furnace, slopping is the phenomena, where the emulsion
emerges out of LD mouth. slopping is undesirable
because it causes loss of iron.
• The figure depicts two industrial heats where in one of
the two heats slopping has taken place due to improper
blowing practice.
• In heat A, during the first stage, in regime-1, decarburization is normal; that is the
decarburization rate progressively increases till it comes to steady state regime.
• In heat B, the first stage of decarburization appears to be abnormal; you can find here the
decarburization rate does not increase for a certain blowing period and there is a sudden
jump in the decarburization rate to catch up the steady state regime. And in this case the
slopping has taken place. Because due to sudden increase in the decarburization rate; the
foam height increases suddenly to reach the vessel top and then emulsion comes out of the
vessel mouth, causing slopping.
Roy-KGP
• Slopping might also happen due to improper mixing in the bath. Usually the upper part of
the LD vessel is nicely mixed up; but the lower part of the vessel is not properly mixed up;
because the momentum of the oxygen jet does not reach significantly to the lower part of the
bath. So, as a result the carbon may be accumulated into the lower part and they do not
participate in the reaction too much. And suddenly when some carbon rich liquid from the
lower part comes up and join the upper part that triggers a spurt in decarburization, and
cause slopping.

Evolution of impurities in Steel Making Process

• x-axis represents the percentage of blowing, while total

blowing time could be only 20 minutes. Weight
percentage of phosphorus and Sulphur are given in two
different y-scale. The main y-scale represents the
percentage of C, Mn, and Si
• The figure shows the typical evolution of the impurities
during LD refining. It is found that Si depletes the fastest
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and within 20 percent of blowing time (4 minutes) silicon
goes down to zero almost; because silicon oxide is the
most stable oxide and chemical potential for formation of
the silicon oxide is very high.
• In basic steel making conditions, the Si can be reduced
to around 30 to 50 ppm; that means, 0.005 or 0.003 wt
%. [Si]+[O] = (SiO2);(FeO)+[Si] = [Fe] + (SiO2)
• The conditions for silicon oxidation are :
(i) low temperature (ii) A basic slag
• Mn decreases initially but it may also noted that at the
later stage of blowing there is a reversion of
manganese. Mn is a unique impurity in the steel in the
sense that it produces an oxide that is basic in nature.
So, when the basic slag forms at later stage, activity of
manganese oxide increases in the slag and it becomes
unstable in the basic slag and reverts back to metal
phase. As a result the manganese in the metal phase
increases and shows a hump on its evolution curve.
Roy-KGP
• Thereafter, again manganese content in the metal bath decrease. At the later stage when
most of the impurities have left the bath, the FeO content and the oxygen potential in the
slag increases, which facilitates manganese oxidation, reducing the bath manganese
content.
• Manganese Reaction:
• Manganese in metal is oxidized by FeO in slag to form MnO in slag: (1)
• This reaction is a slag-metal reaction, FeO is formed due to oxygen enrichment of the bath
by oxygen lancing. When the activity of FeO in slag is decreased, i.e. the concentration of
FeO in the bath gradually falls below the equilibrium limit, and then the reaction will start in
the back-ward direction.
• MnO in slag is decomposed and Mn gets back into the metal. This is known as Mn-reversion
that creates the Mn-hump, which take place at the pick period of carbon–oxygen reaction:

Basic concepts of Iron and steel making

• When the rate of carbon–oxygen reaction decreases, enough FeO will be present in the bath,
then again, the Mn reaction processed to the forward direction.
• During the initial period of slag formation, when the temperature is not yet high enough to
dissolve the lime completely, so MnO combines with SiO2 to form slag.

• With an increase of the temperature, lime is dissolved in slag phase; hence, basicity of the
slag is increased; high acidic oxide, SiO2 is now strongly bonded with high basic oxide, CaO.

• By the above reaction, the activity of MnO in the slag is increased. The content of FeO in the
slag phase is drastically decreased on that time due to reduction reactions of FeO by Si, P
and particularly with C. MnO is reduced by C in iron or iron itself:

• This behavior of Mn is responsible for the characteristic of Mn-hump. The content of FeO in
the slag increases, once again reaction (1) goes forward direction; hence, again curve
goesdownward.
• Phosphorous Reaction:
The conditions for de-phosphorization as follows:
1. Basic slag,
2. Low temperature,
3. Oxidizing atmosphere,
4. Low viscosity and high fluidity of the slag,
5. Good slag-metal contact.
• Oxidation of phosphorous begins from the beginning of the blowing. The phosphorous is
oxidized by the following reactions:

• phosphorus oxide does not become stable in absence of basic slag; temperature rise also makes
it further unstable; and so phosphorus again reverts back to metal phase. But, by the time when
FeO build-up in slag is high and temperature is also high; lime starts dissolving in the slag and
form the basic slag. Basic concepts of Iron and steel making
• It may be noted that fine lime dissolves faster but lumpy lime stone dissolution is stopped in
the initial period itself by the formation of solid adherent di-calcium silicate layer over the
lumpy limestone. FeO helps in breaking the adherent silicate layer by forming low melting
liquid product like CaO-FeO-SiO2.
• Now, slag becomes basic (FeO–MnO–SiO2–CaO) in nature, which helps phosphorous
oxidation reaction at the early stage. For the removal of phosphorous from the metal to slag
the amount of free lime dissolved in the slag must be sufficiently high.
• when CaO is dissolved in the slag then P2O5 reacts with it and the activity of P2O5 is lowered
down. If the slag does not contain dissolved CaO, then product P2O5 (by P–O reaction) is not
entrapped by CaO; and it is highly unstable due to its high free energy and starts
decomposed into phosphorous and oxygen. This newly formed phosphorous again absorbed
by the metal. This is known as reversion of phosphorous.
• The aim is to complete dephosphorization before emulsion collapse, or till decarburization
continues; such that de-phosphorization could be carried out in emulsion phase most
effectively.
• Decarburization starts at the beginning and continues till the end of the refining. Therefore,
to treat hot metal of different phosphorus content, blowing practice and slag evolution is
tailored in such a way such that decarburization continues till all other impurities, especially
phosphorus (which starts later in the process when basic slag forms) removal is complete.

• Sulphur Reaction:
• The sources of sulphur in the metal are hot metal and lime.

• But the major part of sulphur transfer from metal to slag phase by the following reactions:

Basic concepts of Iron and steel making

• The condition for de-sulphurization:
1. Basic slag,
2. High temperature,
3. Reducing atmosphere,
4. Low viscosity and high fluidity of the slag,
5. Good slag-metal contact.
• In LD converter, the slag is basic right from the beginning, the basicity also of the order of
2.3–2.8, it is much higher (i.e. viscosity is low and fluidity is good); so sulphur removal is
good. Since temperature, at the oxygen penetration zone, is higher and turbulence in the bath
is more which ensure a good slag-metal contact.
• Because of these reasons, although the condition of (3), i.e. reducing atmosphere, is not
fulfilled; hence, the sulphur reaction occurred nicely in LD converter.
• Metal de-sulphurization reaction proceeds slowly because it is a diffusion process. It may be
faster by improving the bath mixing, increasing temperature, fluidity and basicity of the slag,
as well as the activity of sulphur.
• At the initial stage of the heat, when the metal is rich in carbon and silicon, the activity of
sulphur is high. A part of sulphur is removed at the initial stage of the process when the
temperature of the melt is still relatively low through its reaction with manganese in metal:

• Increasing the concentration of FeO in slag promotes dissolution of lime, and therefore
favors de-sulphurization. Most intensive de-sulphurization occurs at the end of the heat when
the lime dissolves completely in slag phase and slag basicity increases to 2.8 and more. With
an increase of slag basicity, the residual concentration of sulphur in the metal becomes
lower, so that the coefficient of sulphur distribution between slag and metal can be increased.
• Sulphur partition coefficient,

• For LD process, this value is 12–14.

• Evolution of slag Composition:
• The figure shows the evolution of the slag constituents with
progress of blowing.
• The FeO initially increases and attains a maximum. As
oxygen is charged in the bath, iron being the major
constituents, by law of mass action(the rate of a chemical
reaction is proportional to the concentrations of the reacting
substances), iron first get oxidized to FeO. Subsequently,
impurity is transported from the bulk to the slag metal
interface and it consumes FeO by forming more stable
oxides.
• So initially FeO builds up in the slag. Since Si is depletes first in the bath SiO 2 in the slag
also increases in the bath initially.
• After certain blowing of oxygen, when FeO is sufficient in the slag and temperature also
high in the slag due to exothermic Si/Mn/C oxidation, then CaO start dissolving and its
amount progressively increases. Then the other constituents of the slag like FeO, SiO2, MnO
Roy-KGP
starts decreasing due to dilution effect of CaO.
• Another reason for FeO decrease in the slag is due to addition of phosphorus load (in
addition to the carbon load) as soon as basic slag forms and phosphorus starts transporting
to the slag phase. In this period, rate of generation of FeO by oxygen charging fall short of
the combined effect of phosphorus oxidation and dilution effect of lime dissolution, which
results in FeO decrease in slag.
• And, at the end of blowing period, FeO again starts increasing when the impurity load
diminishes.

• Slag practices used for treating hot metal of different composition:

• The Figure shows the evolution of slag composition in a
ternary CaO-FeO-SiO2 diagram, for two heats treating low
and high phosphorus hot metal.
• Heat I represents treating low phosphorus hot metal
(<0.1wt% P); while Heat II represents treating hot metal of
high phosphorus (>1wt%) hot metal.
• For low phosphorus hot metal we have lot of carbon in to the hot metal (~4wt%), but we
have phosphorus at a very low level (<0.1 wt%). In this case, the slag practice represented
by heat I is used.
• Since, phosphorus is very low and comparatively large carbon is available, we need not to
bother about preservation of the carbon; rather we need to concern about removing the
carbon from the beginning such that refining time does not prolong for carbon removal. So,
we should start removing carbon from the beginning at moderate rate.
• After certain blowing period, when the basic slag forms, phosphorus will be removed in a
short span of decarburization period, which will still persists even after all phosphorus is
removed.
• The slag starts with large FeO, which can be achieved by adding mill scale. Large FeO at
the start ensures faster decarburization from the beginning. Thereafter, along the slag curve,
FeO decreases and both CaO, and SiO2 in the slag increases, so also the basicity increases.
Then dephosphorization starts. Subsequently again the FeO in the slag starts increasing as
the phosphorus and carbon load is removed.
• The heat 2, hot metal with higher phosphorus (>1wt%). In this case phosphorus is very high
from the beginning, then plant operator has to be very economic in consuming the carbon
from the beginning of the heat.
• For heat II, slag starts with comparatively low FeO (say 25%), where decarburization is
comparatively low. It may be noted lime and silica are also present in the slag both to the
tune of 40%. Subsequently, the slag enriches in FeO, with decrease in SiO2.
• FeO build up in the slag can be achieved by soft blow practice, where JFN is decreased or,
lance is moved up to reduce the partial pressure of oxygen on the bath that decreases
decarburization rate and allows smooth build-up of FeO in the slag, and temperature
through impurity oxidation. Thereafter, CaO starts dissolving in the slag. When the basic
slag forms, the lance is lowered, to carry out both decarburization and dephosphorization
simultaneously at moderate rate and FeO further decreases. At the end of blow again the
curve turns showing increase in FeO in slag when the impurity load diminishes.
 Thermodynamics of Phosphorous Removal

• In Basic oxygen steel making like LD, oxygen is lanced from top and oxidation of iron is
preferred kinetically, because it constitute 95% of the liquid iron. So, by law of mass action it
is the iron that will get oxidized first; subsequently FeO will oxidize the impurities which
forms more stable oxides. These reactions could be written as:

• If we examine the Ellingham diagram with oxides

relevant to steelmaking, it may be observed that SiO2,
MnO are more stable oxides compared to the FeO,
even at high steelmaking temperature. CO is also much
more stable compared to the FeO at high temperature.
• So, all these right hand side impurity oxides that are
more stable compared to the iron oxide. So, even
though the iron oxide form first, the impurity will
reduce the iron oxide to iron and they themselves will
Roy-KGP
be oxidized to SiO2, MnO and CO.
• Out of these oxides, CO is a gas gaseous product. So, CO will go away from the system; but
SiO2 and MnO have to be arrested into the slag, such that these reactions move in the
forward direction.
• From the above Figure, it may be observed that phosphorous line is very close to the FeO
line and even cross the FeO line at higher temperature; so when both are pure, FeO becomes
more stable compared to P2O5. Therefore, unlike above three reactions, the reaction given
below is not feasible when both FeO and P2O5 are in their standard state, or are in their pure
state:

• So, it is difficult to oxidize phosphorous selectively over iron under the standard state. Now,
if the activity of P2O5 in the slag can be reduced significantly by fluxing it with lime, the
reaction can move forward. The phosphorus line (indicated by dotted line) will move down in
the Ellingham diagram. To understand this, let us consider the phosphorus oxidation, its
equilibrium constant and apparent standard free energy change.
• Since, equilibrium constant (K) is constant at a particular temperature; a decrease in activity
coefficient of P2O5, will cause partial pressure of oxygen in equilibrium with P-P 2O5 to
decrease. Consequently, the chemical potential of oxygen, or standard free energy change
will decrease, lowering the position of the line P-P2O5 in the Ellingham diagram.
• So, under basic slag condition, the apparent P-P2O5 line will move down w.r.t. Fe-FeO line
making it feasible to oxidize phosphorus preferentially under basic slag condition.

• So, it may be concluded that for de-phosphorization, a basic slag is a must. But for removing
silicon, manganese, carbon basic slag is not a must; but obviously, the silicon removal will
be facilitated in presence of basic slag because activity silica in basic slag decreases
significantly.
• So, basic slag obviously helps the silicon oxidation or the silicon removal, but for
preferential removal of silicon fluxing of slag is not a must because silica itself is more stable
oxide compared to the iron oxide.
• In case of manganese, it is a basic oxide. So, basic slag does not help much. But manganese
oxide itself is more stable oxide compared to the FeO. So, manganese also can be removed
preferentially over iron under steel making condition.
• And, for carbon it is also not a problem because CO is a stable oxide, especially at high
temperature; So preferential carbon removal is also not a problem.
• But for removal of phosphorus, a basic slag is a must; such that activity of P2O5 decreases,
and it can be selectively removed over iron. Activity coefficient of P 2O5 decreases
significantly with increase in basicity of slag.
• Activity of P2O5 in slag at different temperatures:

• The Figure shows the variation of activity coefficient of P 2O5 in slag with basicity at three
different temperatures. It may be found that activity coefficient decreases with decrease in
temperature and increase in basicity. Basicity is defined as summation of various basic oxides
with different weighting factors. CaO being the most influential, its weighting factor is 22,
followed by MgO with weighting factor of 15, subsequently MnO with a factor of 13 and FeO
with 12.
• Effect of FeO on De-Phosphorization:
• According to ionic theory the reaction can be represented as:
• The equilibrium constant may be expressed as:

• The partition coefficient of phosphorus may be represented as:

• So, partition coefficient of phosphorus depends on dissolved oxygen, basicity and

equilibrium constant or, temperature.
• From the figure it is seen that the de-phosphorization reaction is favored when FeO in slag
increases (increasing oxidation potential of the slag) , or CaO increases (increasing the
basicity of the slag), or, both increases. But, if you go on increasing the FeO progressively,
then CaO in slag get diluted; similarly, if you increase the amount of CaO progressively in
the slag, then FeO get diluted. So, a higher value of one in the slag dilutes the other.
• An optimum amount of FeO should be required that does not dilute the CaO, maintaining
proper slag basicity. From figure it is seen that optimum FeO in the slag is around 15% and
it is found to be true at various basicity values; and partitioning being maximum at basicity
(V-ratio) of 4.

• So based on above expression, the favorable conditions for Dephosphorization is:

• Basic slag (V ratio > 2.2)
• Optimum FeO in slag (approx. 15%)
• Low Temperature
 Hybrid Processes

• The combined blowing is an example of a hybrid process. In LD furnace the bath stirring is
not uniform. Since the bath is stirred from the top; a clear stratification between upper and
lower layers takes place with respect to heat, mass and momentum transfer. There exists a
steep gradient in terms of velocity, concentration and temperature between two layers as
shown below.
• So, upper part liquid is strongly stirred while the lower part liquid is weakly stirred (shown
by dotted circles). While the upper part regularly interacts with emulsion and its impurity
concentration decreases progressively; the lower part rarely interact with emulsion phase
and remain rich in impurities. So, when a packet of impurity rich liquid from the lower part
of the furnace joins the upper part and subsequently join the emulsion phase, there could be
a sudden rise of decarburization; causing foam and emulsion height to rise suddenly and
leading to slopping.
• An improper mixing in the lower part of the furnace also keeps the process away from the
equilibrium; consequently, the partitioning of the impurity, and yield of the process remains
low. So, the process will not be very efficient. So, two problems are there in conventional LD
namely, the irregularity like slopping, and poor partitioning of impurities and lower yield
due to improper mixing of the lower parts of the furnace.
• So, inert gas purging from the bottom, alleviates this problem by mixing the lower part of the
furnace; and thus giving birth to the process of combined blowing, or hybrid blowing. Thus
in hybrid blowing, in addition to conventional oxygen lancing from the top in LD, inert gas is
also purged from the bottom.
• There are several other variants of hybrid processes. Below Table presents various existing
hybrid processes.
• After classical LD, the second process in the table is called the LDAC, or OLP (oxygen Lime
Powder), where lime powder is blown with oxygen from top. Lime powder is added to
enhance the lime dissolution rate and to form the basic slag early to treat high phosphorus
hot metal.
• And then, LD with additional bottom gas purging, i.e., the hybrid blowing. One of the variant
of hybrid blowing is called the LBE (ladle bubbling equilibrium) process; here inert gas is
purged from the bottom at a moderate rate to eliminate the stratification at the lower part of
the LD furnace. And the process in the vessel move closer toward the equilibrium, improving
the partition coefficient.
• Then, LD-AB LD-KG, are the other process variants of the LD with the additional inert gas
purging from the bottom.
• In some hybrid process oxidizing gas (oxygen/Air) is blown along with or without inert gas
from the bottom. There some process variants like LD-OB, BAS_BAP.
• There are some processes where oxygen is purged both from top and bottom, along with lime
powder either from top or from bottom. Depending on that some process variants are there;
like LD-HC, STB-P for lime injection from top and K-BOP for lime injection from bottom.
• When 100 percent oxygen is blown from the bottom; that is called the classical OBM (oxygen
bottom blowing method). Oxygen blowing from the bottom has been found to be very good
from the mixing point of view and the process is also very close to equilibrium, with a
minimum iron loss, maximum yield and with maximum impurity partitioning.
• But the major problem is the nozzle maintenance. When oxygen is purged from the bottom,
the impurity oxidation takes place at the nozzle tip leading to its rapid erosion, especially
when large amount of oxygen is purged.
• Such nozzle is designed to pass hydrocarbon gas through annular section and when the
hydrocarbon exposed to liquid steel it leads to endothermic cracking, giving a partial
protection from excess heat generation at the nozzle tip. Such protection might be okay for
moderate oxygen purging like 20% along with other inert gases. When full load of oxygen is
purged from the bottom, like in OBM, hydrocarbon protection is not sufficient and nozzle has
to be replaced at regular interval, which makes the process cumbersome and costly. This is
the reason, in-spite of very good impurity partitioning and yield, the process could not
compete with LD with moderate bottom purging.
• Various process variants have also emerged based on nozzle design. The below Figure
depicts the various process variant based on nozzle design.
• straight pipe nozzle as in LD-KG, LD-OTB. There are directed porosity through the channel
bricks, NK-CB process. Other designs are porous plug in BSC-BAP, permeable membrane as
in LBE. The process where oxidizing gases are introduced from the bottom have slight
variations in nozzle design or, process could vary in terms of combination of gas and solid
powder injection.
• In STB process, oxidizing CO2 is purged along with air and nitrogen both through central as
well as annular section of the nozzle. CO2 serves both the purpose of oxidation as well as
cooling. It oxidize carbon through an endothermic solution loss reaction that helps in
reducing the temperature near the nozzle.

• In case of LDHC and LD-OB process, oxygen is purged through central tube with a
protective hydrocarbon through annular section as in OBM process. In case of K-BOP and
KMS process, they have similar nozzle design but lime powder also accompany oxygen from
the bottom.
• Various process originated from the intensity of bottom stirring. The below Figure shows the
extent and type of gas injection from the bottom for various processes.
• There exists three regimes of gas injection from the bottom. When the gas injection from
bottom is less than 1 percentage of the total gas (including oxidizing and inert) charged in
the vessel, bottom stirring may be characterized as weak. 1 to 5% gas injection from the
bottom may be considered as standard, because several hybrid process operate in this
regime. When the gas purged from the bottom ranges between 5 to 10%, stirring may be
characterized as moderate and when more than 20% gas injection may be termed as
vigorous.
• We can find LD-OB in the moderate regime and K-BOP and KPS in vigorous regime. In
moderate and vigorous regime oxygen from bottom is purged with hydrocarbon protection.
Most of the standard processes including LBE (the most popular method) only purge inert
gas from the bottom in the range 1 to 5%. STB, BSC-BAP, which inject oxidizing gases like
air and CO2 along with inert gas also operate in this regime (1-5%).
• In hybrid blowing, mixing rate is decreased significantly compared to conventional LD
process. Mixing time provides an estimate of the time required to homogenize the bath.
Average time required to attain the 95% of the average concentration in the bath, is defined
as the mixing time. It is measured by introducing a trace in the bath and monitoring the
temporal evolution of concentration in the bath using a suitable probe.
• Since mixing time will also depends on the locations, mixing time could be measured in some
representative location; or it could be measured at several locations and their average could be
taken. The below Figure shows the spectrum of mixing time for different processes.

• It may be observed from the above figure that in case of the LD, the mixing time is maximum; you
can find it ranges from 100-120 seconds; while it is less than 20 seconds for OBM process where
mixing is fastest among the hybrid processes. In case of LBE, it is around 50 secs.
• The performance of hybrid process can be assessed based of residual dissolved oxygen in the
bath, and the iron loss through slag.

• It is observed from the figure that for a certain dissolved carbon in the bath, residual dissolve
oxygen in tapped steel is maximum in the LD process and it is minimum in the OBM process.
• It is also observed that iron loss is also maximum in LD and minimum in OBM. Because of lower
mixing in the bath, the slag in LD get over oxidized, which keeps the bath as well as
slag at higher level of oxygen.

Modern Trends in BOF Technology

• Slag splashing:
• The life of a BOF converter is an important parameter and has considerable bearing on the
economics of steel making.
• Refractory consumption in steel making has always been an issue of concern and therefore
considerable efforts are being made to reduce refractory wear and tear and in turn, achieve
prolonged lining life which is essential for sustained and smooth BOF operation.
• Steel is tapped and slag is retained in the vessel. Now, in the same top oxygen lance, nitrogen
is blown at 2-4 bar pressure for 2-4 min. The lance is lowered to around 1 m above the
bottom of the BOF converter. As a result the slag is splashed on the walls of the BOF vessel.
• In order to have a good slag splashed coated refractory lining, the slag should have MgO
content around greater than 13 %, because MgO will react with Fe2O3 and it will form a high
temperature phase.
• At the same time, FeO content of the slag should also be approx. around 20 % because it
forms good adhesion between slag and refractory.
• If FeO content is more in the slag, coke is added to reduce FeO content in slag.
• So, both are combined together, then a very good coating of the slag results on splashing of
slag.
• Based on area to be splashed, the height of the lance is adjusted.
• In this way the furnace lining can with stand up to 8,000 heats.
• Post combustion:
• The oxidation of carbon to CO in BOF steel making is the principle reaction.
• In converter steel making process CO produced during refining exits the furnace in exhaust
system, where it is combusted with the ambient air.
• Combustion of CO to CO2 produces large amount of thermal energy. Thus post combustion of
CO in BOF and transferring the heat of combustion to the slag and metal offers an
additional amount of energy. The amount of post combustion taking place in the furnace can
be represented by post combustion ratio (PCR)
PCR =
[C] + 0.5 O2 = CO (g) ; CO (g) + 0.5 O2 = CO2 + heat

Advantages:
High melting rates can be achieved.
Reduced green house gas emission.
• Technology of post combustion:
• The technology is required which can inject oxygen in the converter just above the slag so
that CO can be combusted to CO2.
• The supply of oxygen for the post combustion must be well distributed above the slag surface
for an efficient combustion of CO.
• One possible way is to add several small orifices around the main supersonic nozzle tip.
Lance tip is adjusted such that oxygen through the orifice is available for combustion of CO
and CO2 above the slag surface.
• Another method could be a lance with double flow of oxygen. In the main lance, a separate
oxygen inlet and oxygen control system can be provided which is solely dedicated to post
combustion.
• This design may provide better control of oxygen for post combustion with out affecting the
oxygen flow through the main lance.
BOF Steel Making Process
Thank You