Department of Metallurgical Engineering

• About 50 to 75% of the manganese in the burden gets

reduced along with the pig iron resulting its manganese
content between 0.5 to 2.5%.

• During steelmaking major amount of manganese is lost

into the slag and very little is utilized to meet the
specifications.

• Some manganese is required to control the deleterious

effects of sulphur and oxygen and also for improvement of
mechanical properties of the steel.
 From the equation it is apparent that the conditions for
the highest possible recovery of Mn i.e. minimum slag-
metal distribution ratio are
i) min (χFe2+), requiring a low FeO content in the slag.
ii) min K’ requires a low SiO2 content and a high
temperature as evident from the relation showing effect
various anions in the slag.

log K  = 3.1 SiO 4 − + 2.5  PO 3 − + 2.4 O 2 − +1.5  F − (26)

4 4
From the figure it is evident
that for slags containing
about 20% MnO, a
maximum of 0.1% Mn is
found in metal.

The slag containing 50%

SiO 2 (the rest being FeO
and MnO), with increasing
Mn content of the metal the
(MnO) content of the slag
increases whereas the
oxygen content of the metal
decreases and silicon
content increases.
 Oxidation and Reduction of P
In all cases, the oxidation of dissolved phosphor us is
associated with heat evolu tion. Especially much heat is
liberated when it is oxidized by gaseous oxygen. In some
processes based on the conversion of high-phosphor us pig
iron (such as the basic Bessemer process), phosphorus is the
main 'fuel', i.e. the element that produces on oxidation the
required heat for metal heating.
With an increase in the temperature, favourable conditions
may appear for the reduction of phosphorus. A higher oxygen
content of the slag promotes the pro cesses of phosphor us
oxidation , and on the contrary, a lower activity of iron oxides
in the slag inhibits these processes.
Despite its very low boiling point significant
amount of P gets dissolved in pig iron due to
strong attraction for iron.
Making use of the interaction coefficients for the
effect of various elements on the activity
coefficient of phosphorus in iron, the activity of P
can be estimated by the expression:
logfP = 0.13×%C + 0.13×%O + 0.12×%Si + 0.062×
%P + 0.024×%Cu + 0.028×%S + 0.006×%Mn –
0.0002×%Ni – 0.03×%Cr
A very close stability of FeO, Fe2O3 and P2O5 is evident
from the iron and phosphorus lines in the Ellingham
diagram.
Hence practically all the phosphorus present in the ore
gets reduced along with iron in the blast furnace and
joins pig iron.
During steelmaking the activity of P2O5 in the slag of
basicity 2.4 is reduced drastically to 10-15-10-20.
Activity of P2O5 in steelmakig slag is very low even if it
contains 25% P2O5.
Phosphorous React ion TempePatu Pe ,°C
500 10 0 0 15 0 0

.lJG
k cal

-100 -

- 2 0 0 L -- e .:: L _ - -- -- - I .
o
-=-- - 2000
0 500 10 0 0 150
Temp era t u re ,°K
 •i.e. 2[P] + 5[O] + 3(O2-) = 2 (PO 43-) (12)

 Thus for effective removal of phosphorus basic steelmaking

processes have to employ slags of high basicity.
 The distribution of phosphorus between slag and metal can be
dessribed as
2[P] + 5(FeO) + 3 (CaO) = (3 CaO.P2O5) + 5[Fe]
i.e. 2[P] + 5[O] + 3(O 2)- = 2 (PO 43)-
2
aPO 3−
K= 2 5 3
4
ApplyingTemkin rule : (13)
aP .aO .a(O 2− )

 PO
2 3−
=
4

f %P2 f %O5  3
P O O 2−
(14)

The dephosphorising index, DP which is the ratio of phosphorus in slag to that in metal,is given as
(  PO )
= K  %O5 / 2 (  ) 3 / 2
3− 1/ 2

DP =
4
(15)
%P
2−
O
From the figure it is clear that D P
increases with increase in the (FeO)
content upto 15% due to the high
oxidizing power.

Beyond this D P decreases due to

decrease in the lime proportion.

Dephosphorisation is more effective

at lower temperature because D P
increases with decrease of
temperature.
The soda ash is 100 times more effective compared to lime
on molar basis but it is avoided in practice due to its severe
corrosive action on furnace lining.
The magnesia content of a basic steelmaking slag reaches
equilibrium with the lining hence not under control and MnO
depends on charge and hence not much adjustable.
The steel maker has the option of controlling lime, silica and
FeO.
For charges containing high % P more than one slags are
made to dephosphorise metal bath to the desired level.
In brief ,high basicity, low temperature, and FeO content
around 15% favour dephosphorisation of metal by basic
slags.
The optimum conditions for dephosphorisation can be
derived from the equation defining the index:
(  PO 43− )
%O 5 / 2 (  O
1/ 2

DP = = K )3/ 2
% P 
2−

1. Basic slag gives a high value of χO2-

2. High lime content – lime is the divalent oxide making the
largest contribution to K’ (log K' = 21N'Ca+++ 18 N'Mg+++
13N'Mn+++ 12 N'Fe++
3. Ferrous oxide close to 15% .
4. Low temperature gives a high value of K‘.
In refining of steel oxidation of Si, Mn and P takes place
at the slag-metal interface.
The oxidation of carbon practically does not take place
at the slag-metal interface because of the difficulty of
nucleation of CO bubbles there.
C-O reaction takes place at the gas –metal interface
since it eliminates the necessity of nucleating gas
bubbles.
During refining of steel oxygen has to dissolve first in the
bath before it reacts with the dissolved impurities.
In the absence of other slag forming constituents at
1600oC liquid iron can dissolve oxygen up to at 0.23 wt.
%
 In steel making the reaction between carbon
and dissolved oxygen is of utmost importance.
Generally pig iron contains about 4 wt% carbon.
The solubility of carbon in steel is effected by the
presence of impurities and alloying elements.
Presence of Nb, V, Cr, Mn and W increase
solubility of carbon in iron where as presence of
Co, Ni, Sn and Cu decrease it.
 Oxidation of Carbon can be discussed according to
the reaction:
C + O = CO, ΔG0= -5350 – 9.48T cals.
p p
K = CO = CO
a c aO [ fc%C][ fo%O]
pCO pCO
[%C ][%O] = =
K fc fo K

At any chosen pressure of CO, % C vs % O indicates

inverse hyperbolic relationship
During oxidation period oxygen is continuously transferred from
the slag to the bath, where it continuously reacts with carbon to
give CO.
The main resistance to the oxygen flow is the slag–metal and the
metal–gas interfaces, whereas inside the steel bath the transfer
of dissolved oxygen is very fast.
The activity coefficient of
carbon in iron increases with
increasing carbon content
and that of oxygen
decreases with increasing
carbon content.

The net result is that the

product [% C] [% O] for a
given pCO decreases slightly
with increasing carbon
content as shown in Figure.
Since steel making is a dynamic process, the
concentration of carbon and oxygen in the bulk metal
phase is not in equilibrium with the prevailing CO-
pressure in the bubbles.

At the gas bubble–metal interface the reaction is close to

equilibrium.

The experimentally observed excess oxygen and carbon in

the bulk metal phase is thus helpful in transfer of the
reactants by diffusion to the gas-metal interface in the
violently stirred metal bath.
As [% O] increases with (aFeO) in slag and [% O]
decreases with [% C] in the bath.

it follows that the iron oxide contents of the slag increases

with decreasing carbon in steel during refining.

Hence there is a general trend in the variation of slag

composition with the carbon content of the metal.

For a given total iron oxide in a slag, a lower carbon in

the steel corresponds to a higher sum of (% SiO2 + %
P2O5) in the slag.
Within the range of basic slags, for a given sum of % CaO + %
MgO + % MnO the carbon content of steel does not vary much
with the FeO content of the slag.
High carbon steels like rail steels (0.65%-0.74% C, 0.6%-1.0%

Mn, 0.27-0.30% Si), ball-bearing steel (1.0% C, 1.2% Cr), etc. are
also manufactured in the LD converter by the catch carbon
technique. In this technique, dephosphorization is accelerated
and completed before decarburization. Extra lime and fluorspar
are charged and the lance is raised to a higher position for
maintaining a soft blow condition till phosphorus removal is
completed. Thereafter, decarburization is continued by a harder
blow till the bath carbon content drops to the desired level.
Alternatively, blowing may be continued to complete both
dephosphorization and decarburization. Required amount of
carburizer is then added to the low carbon steel bath to raise
the carbon content to the desired level. However, this method
involves a risk of increasing the inclusion and nitrogen
contents in the steel. These are picked up from the carburizer
(e.g., petroleum coke or graphite). For production of low alloy
steel, the alloying elements are usually added in the ladle
during tapping the steel.
As will be evident from the discussion [Mn] from the bath is
lost in the slag. (MnO) thus formed quickly combines with (SiO2
to form (2MnO· Si02). Thus, there is a reduction in the Mn
content in the bath in the initial period of the blow. As the slag
basicity increases due to lime dissolution, (MnO) is gradually
released and is reduced by carbon during intensive carbon
oxidation according to the following reactions:
(MnO) +[C] → [Mn]+{CO}
[Mn] content in the bath increases again. As the intensity of the
carbon-oxygen reaction decreases towards the end of the
blow,. manganese is reoxidized from the bath. As a result, the
bath manganese content drops again. This accounts for the
characteristic 'manganese hump' in the LD converter reaction
diagram.
A basic and highly reactive slag is necessary to attain desulphurization
and dephosphorization in LD steel making at the turndown stage.
Hence the physical and chemical characteristics of the lime used are
of utmost importance.

Some common quality criteria for steel making lime are listed below:

 Chemical composition
Size distribution Reactivity

 Loss on ignition
Moisture content

 Si02 in the lime reduces the CaO activity due to the formation of
larger amount of slag by fixing up about two times its mass of CaO.
This is detrimental both from "yield" and "cost" points of view.
The sulphur content in lime should be as low as possible.

An MgO content of approximately 3.5% in lime is thought to be

beneficial because an MgO content of around 5% in the slag
has been found to hinder the formation of dicalcium silicate,
thereby ensuring a faster lime dissolution in the slag. However,
lowering of melting point and the viscosity of slag due to
increased proportion of MgO can result in early slopping. An
adequate level of MgO in slag also ensures less corrosion of
the vessel refractories because of its known properties of
neutralizing the FeO level of the bath.
 Formation of slag as early as possible during the blow requires a
uniform and rapid dissolution of lime. A size range of +8 to -40 mm,
minimum proportion of fines in the lime charge and soft burnt lime
promote early slag formation. A soft burnt lime is highly porous,
having a large specific area. This results in its favorable reactivity.

Thermal dissociation reaction of unreacted CaC0 3 is

endothermic. It adversely affects the heat balance of the
converter and leads to operating problems. Similarly, a moisture
content in lime directly
affects the heat balance of the vessel because of temperature
losses during its disintegration. It also acts as a potent source of
hydrogen in steel. Hence both loss on ignition (LOI) and moisture
content of lime should be low.
LD refractory lining life has been greatly enhanced in recent
years by adopting the slag splashing technology. In this
technology, a portion of the slag is retained in the vessel after
tapping. A low FeO and a high MgO slag is desirable for slag
splashing. Such improvement in slag condition is achieved
through addition of dolomite lime after tapping. Slag splashing
is accomplished by injecting nitrogen into a conditioned slag at
a given flow-rate and lance height. The existing oxygen-lancing
equipment is used.
By varying lance height and nitrogen flow-rates, slag can be
selectively targeted and blown into particular areas of the furnace.
This is schematically illustrated in Figure given below. The process
time for slag splashing is between 1 and 4 minutes. A well-
designed nitrogen slag splashing programme can extend furnace
lining life to 8,000 heats. Once slag splashing is started, it would be
done on a regular basis. Slag splashing presents some operating
challenges like lance shell
 Refractory lining Slag coating

FIGURE 4.3 Schematic diagram of slag splashing in LO converter.11

(Reproduced with permission of the Institute of Materials, Minerals and Mining).